JP2005049847A - Composition for optical film and optical film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide composition for optical film having high-grade near-infrared absorbing power and also excellent in light resistance, and optical film using the composition for optical film, having simple constitution and easily manufactured. <P>SOLUTION: The composition for the optical film contains a stabilized cyanine pigment consisting of cations and quencher anions selected from a group consisting of compounds expressed by formulae (I) to (III), and a diimmonium pigment as a quencher compound. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  INDUSTRIAL APPLICABILITY The present invention is a composition suitably used for an optical film having a near-infrared absorbing ability that absorbs near-infrared rays, and an optical film using the composition, particularly a viewing side of a plasma display panel (hereinafter abbreviated as PDP). It is related with the optical film used suitably for the optical filter installed and used for.

The principle of PDP is to generate visible light by applying a voltage to a rare gas (helium, neon, argon, xenon, etc.) enclosed between two glass sheets, and then applying the ultraviolet light generated at that time to the light emitter. It is.
PDP emits harmful light such as near infrared rays and electromagnetic waves simultaneously with visible light. For example, near infrared rays have a negative effect when data is transferred to a POS (point-of-sales information management) system by malfunctioning a near infrared remote control for home appliances such as home TVs, coolers, and video decks, or malfunctioning communication equipment. Effect. Therefore, it is necessary to install an optical filter for preventing harmful light such as near infrared rays on the front surface (viewing side) of the PDP.

Until now, as an optical filter, a method using an optical film that blocks near infrared rays having a wavelength of 850 to 1100 nm has been proposed.
As an optical film, for example, a pigment that absorbs near infrared rays is dispersed in a transparent resin and formed on a film made of polyethylene terephthalate (PET) or the like.
Various dyes such as polymethine, metal complex, squalium, cyanine, indoaniline, and diimonium have been reported as dyes that absorb near infrared rays. These dyes are generally used in combination of two or more in order to impart a high near infrared absorption ability. For example, Patent Document 1 proposes a near-infrared absorbing film having a near-infrared absorbing layer containing a cyanine dye and a diimonium dye.

  However, these dyes have a problem that they are low in light resistance and easily deteriorate. In particular, when two or more kinds of dyes are used in combination, one of the dyes may be noticeably deteriorated. For example, a cyanine dye and a diimonium dye as in the near-infrared absorbing film of Patent Document 1 described above. When used in combination with a dye, the deterioration of the diimonium dye is particularly large. Such deterioration of the dye changes the color of the film and deteriorates its optical characteristics.

In order to improve the light resistance of the dye, for example, Patent Document 2 describes an optical filter containing a cyanine dye stabilized by forming a salt of a cyanine cation with a quencher anion.
Patent Document 3 describes a near-infrared absorbing film having a layer containing a diimonium dye and a quencher compound and a layer containing a cyanine dye and a quencher compound.

However, for example, the stabilized cyanine dye described in Patent Document 2 is more stable than a general cyanine dye, but is insufficient in light resistance for practical use.
In addition, the near-infrared absorbing film described in Patent Document 3 is not preferable because a plurality of dyes are contained in separate layers, resulting in an increase in the number of steps and inferior productivity.
JP 2003-21715 A JP 2002-350632 A JP 2003-43244 A

  The present invention has been made in view of the problems of the above-described conventional technology, and has a high near-infrared absorbing ability and excellent light resistance, and an optical film composition that is easy to manufacture with a simple structure. An object is to provide an optical film.

  The present invention relates to the following general formulas (I) to (III):

［式中、環Ａおよび環Ａ’は、それぞれ独立にベンゼン環、ナフタレン環またはピリジン環を表し、Ｒ^１およびＲ^１’は、それぞれ独立にハロゲン原子、ニトロ基、シアノ基、炭素数６〜３０のアリール基、炭素数１〜８のアルキル基または炭素数１〜８のアルコキシ基を表し、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立に水素原子、ハロゲン原子、シアノ基、炭素数６〜３０のアリール基、ジフェニルアミノ基または炭素数１〜８のアルキル基を表し、ＸおよびＸ’は、それぞれ独立に酸素原子、硫黄原子、セレン原子、プロパン−２，２−ジイル基、ブタン−２，２−ジイル基、炭素数３〜６のシクロアルカン−１，１−ジイル基、−ＮＨ−または−ＮＹ_１−を表し、Ｙ、Ｙ’およびＹ_１は、それぞれ独立に炭素数１〜３０の有機基を表し、ｒおよびｒ’は、それぞれ独立に０〜２の整数を表す］
で表される化合物からなる群から選択されるカチオンとクエンチャーアニオンとからなる安定化シアニン系色素、およびクエンチャー化合物を含有することを特徴とする光学フィルム用組成物を提供する。
また、本発明は、前記光学フィルム用組成物が透明樹脂中に分散されてなる近赤外線吸収層を有する光学フィルムを提供する。

[Wherein, ring A and ring A ′ each independently represent a benzene ring, a naphthalene ring or a pyridine ring, and R ¹ and R ¹ ′ each independently represent a halogen atom, a nitro group, a cyano group, a carbon number of 6 to 30 represents an aryl group, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a cyano group or 6 carbon atoms. Represents an aryl group of ˜30, a diphenylamino group or an alkyl group of 1 to 8 carbon atoms, and X and X ′ are each independently an oxygen atom, sulfur atom, selenium atom, propane-2,2-diyl group, butane- 2,2-diyl group, a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms, —NH— or —NY ₁ —, wherein Y, Y ′ and Y ₁ each independently represent 1 to Table of 30 organic groups , R and r 'represent each independently an integer of 0 to 2]
A stabilized cyanine dye comprising a cation selected from the group consisting of compounds represented by formula (I) and a quencher anion, and a quencher compound are provided.
Moreover, this invention provides the optical film which has the near-infrared absorption layer by which the said composition for optical films is disperse | distributed in transparent resin.

  The optical film composition of the present invention provides an optical film that has a high near-infrared absorbing ability, is excellent in light resistance, and is easy to manufacture with a simple configuration.

Hereinafter, the present invention will be described in detail.
≪Composition for optical film≫
The composition for optical films of the present invention contains a stabilized cyanine dye and a quencher compound, and has near-infrared absorbing ability.

<Stabilized cyanine dye>
In the present invention, the stabilized cyanine dye is a cation selected from the group consisting of the compounds represented by the general formulas (I) to (III) (hereinafter sometimes referred to as cyanine cation) and a quencher anion. Is a salt compound consisting of

"Cyanine cation"
In the general formulas (I) to (III),
In R ¹ and R ¹ ′, examples of the halogen atom include fluorine, chlorine, bromine and iodine;
Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-vinylphenyl group, 3-isopropylphenyl group, 4-isopropyl Phenyl group, 4-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-octylphenyl group, 4- (2-ethylhexyl) phenyl group 4-stearylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5 -Dimethylphenyl group, 2,4-ditertiarybutylphenyl group, 2,5-ditertiarybutylphenyl group, 2,6-ditertiary Butylphenyl group, 2,4-ditertiarypentylphenyl group, 2,5-ditertiaryamylphenyl group, 2,5-ditertiaryoctylphenyl group, 2,4-dicumylphenyl group, cyclohexylphenyl group, Biphenyl group and 2,4,5-trimethylphenyl group are exemplified; examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group, and tertiary butyl. Group, isobutyl group, pentyl group, isopentyl group, tertiary pentyl group, hexyl group, cyclohexyl group, cyclohexylmethyl group, 2-cyclohexylethyl group, heptyl group, isoheptyl group, tertiary heptyl group, n-octyl group, isooctyl group , Tertiary octyl group, 2-ethylhexyl group;
Examples of the alkoxy group having 1 to 8 carbon atoms include methyloxy group, ethyloxy group, isopropyloxy group, propyloxy group, butyloxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, A 2-ethylhexyloxy group is mentioned.

In R ² , R ³ and R ⁴ , examples of the halogen atom, the aryl group having 6 to 30 carbon atoms, and the alkyl group having 1 to 8 carbon atoms include those exemplified for R ¹ above.

  In X and X ′, the cycloalkane-1,1-diyl group having 3 to 6 carbon atoms includes cyclopropane-1,1-diyl group, cyclobutane-1,1-diyl group, 2,4-dimethylcyclobutane- Examples include 1,1-diyl group, 3-dimethylcyclobutane-1,1-diyl group, cyclopentane-1,1-diyl group, and cyclohexane-1,1-diyl group.

Examples of the organic group having 1 to 30 carbon atoms represented by Y, Y ′ and Y ₁ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, a tertiary butyl group, an isobutyl group, Pentyl group, isopentyl group, tertiary pentyl group, hexyl group, cyclohexyl group, cyclohexylmethyl group, 2-cyclohexylethyl group, heptyl group, isoheptyl group, tertiary heptyl group, n-octyl group, isooctyl group, tertiary octyl group 2-ethylhexyl group, nonyl group, isononyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, peptadecyl group, octadecyl group and other alkyl groups, vinyl group, 1-methylethenyl group, 2- Methylethenyl, propenyl, butenyl, isobutenyl, pentenyl, Cenyl group, heptenyl group, octenyl group, decenyl group, pentadecenyl group, alkenyl group such as 1-phenylpropen-3-yl group, phenyl group, naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4- Methylphenyl group, 4-vinylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-hexylphenyl group, 4- Cyclohexylphenyl group, 4-octylphenyl group, 4- (2-ethylhexyl) phenyl group, 4-stearylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group Group, 2,4-ditertiarybutylphenyl group, alkylaryl group such as cyclohexylphenyl group, benzyl group, phenethyl group, 2-phenylpropan-2-yl group, diphenylmethyl group, triphenylmethyl group, styryl group, Arylalkyl groups such as cinnamyl groups, etc. in which these are interrupted by an ether bond or a thioether bond, for example, 2-methoxyethyl group, 3-methoxypropyl group, 4-methoxybutyl group, 2-butoxyethyl group, methoxyethoxy Examples include an ethyl group, a methoxyethoxyethoxyethyl group, a 3-methoxybutyl group, a 2-phenoxyethyl group, a 3-phenoxypropyl group, a 2-methylthioethyl group, and a 2-phenylthioethyl group. Group, alkenyl group, nitro group, cyano group, halogen atom, etc. It may be.

Among these, those in which R ² is a halogen atom are preferable because the near-infrared absorption effect of the optical filter is good, and X and X ′ are propane-2,2-diyl, butane-2,2-diyl groups, A group selected from a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms is preferred because of its high light stability.

  More specifically, as the above-mentioned preferable cyanine-based cation, the following cation Nos. 1-50 are mentioned.

"Quencher anion"
In the present invention, the quencher anion refers to an anion having a function of deexciting (quenching) an active molecule in an excited state (for example, singlet oxygen ( ¹ O ₂ )). The quencher anion is disclosed, for example, in JP-A-60-234893, JP-A-5-43814, JP-A-6-239028, JP-A-9-309886, JP-A-10-45767, and the like. It can be applied to optical recording materials.

  As the quencher anion, a benzenedithiol metal complex anion is preferable in order to give particularly excellent light resistance to the optical filter. Examples of the benzenedithiol metal complex anion include anions represented by the following general formula (A).

［式（Ａ）中、Ｍはニッケル原子または銅原子を表し、Ｒ^５およびＲ^５’は水素原子、ハロゲン原子、炭素数１〜８のアルキル基、炭素数６〜３０のアリール基、−ＳＯ_２−Ｑ基を表し、Ｑは炭素数１〜８のアルキル基、ハロゲン原子で置換されていてもよい炭素数６〜３０のアリール基、ジアルキルアミノ基、ジアリールアミノ基、ピペリジノ基、モルフォリノ基を表し、ａおよびａ’は１〜４の整数を表す］

[In formula (A), M represents a nickel atom or a copper atom, R ⁵ and R ⁵ ′ represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 30 carbon atoms, —SO ₂ represents a Q group, and Q represents an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 30 carbon atoms which may be substituted with a halogen atom, a dialkylamino group, a diarylamino group, a piperidino group, and a morpholino group. A and a ′ represent an integer of 1 to 4]

In the general formula (A), examples of the halogen atom represented by R ⁵ and R ⁵ ′, the alkyl group having 1 to 8 carbon atoms, and the aryl group having 6 to 30 carbon atoms include those exemplified for R ¹ above. It is done.
Examples of the alkyl group having 1 to 8 carbon atoms represented by Q include those exemplified for the above R ^1. Examples of the aryl group having 6 to 30 carbon atoms which may be substituted with a halogen atom include the above R ^1. Or those in which these benzene rings are substituted with 1 to 4 halogen atoms, and the dialkylamino group, the alkyl group contained in the diarylamino group, and the aryl group include those represented by R ¹ above. Illustrative examples include an alkyl group having 1 to 8 carbon atoms and an aryl group having 6 to 30 carbon atoms.

  As a specific example of the quencher anion represented by the general formula (A), when M is a nickel atom, anion No. 1 shown below is used. 1 to 11 and when M is a copper atom, anion No. 1 shown below is used. 12-22 are mentioned.

In the present invention, the stabilized cyanine dye is a salt of the above-mentioned cyanine cation and quencher anion, and can be produced according to a conventionally known method.
For example, by salt exchange between a salt compound of a cyanine cation with a corresponding structure and a halogen, an inorganic anion, an organic anion, etc., and a salt compound of a quencher anion with a corresponding structure and a tetraalkylammonium cation Can be easily obtained.

  In the composition for an optical film of the present invention, the blending amount of the stabilized cyanine dye is preferably 0.01 to 30% by mass, and preferably 0.1 to 10% by mass with respect to the total solid content contained in the composition. Is more preferable.

<Quencher compound>
In the present invention, the quencher compound refers to a compound having a function of deexciting an active molecule in an excited state, like the quencher anion.
In the present invention, the quencher compound used in combination with the above-mentioned stabilized cyanine dye is not particularly limited, and any compound used as a quencher compound in an optical film such as a near-infrared absorbing film can be used.
Examples of such quencher compounds include diimonium dyes, aminium dyes, dithiol nickel complexes (for example, see JP-A-2001-288380), dithiol copper complexes (for example, WO 98/34988) ), Dithiol metal complex dyes such as dithiol-based cobalt complexes, hindered amine dyes, nitroso compounds of diphenylamine (for example, see JP 2000-168233 A) and the like. One type of these quencher compounds may be used, or two or more different types may be used in combination.

(Near-infrared absorbing quencher compound)
In the present invention, among the above quencher compounds, near-infrared absorbing quencher compounds such as diimonium dyes, aminium dyes, and dithiol nickel complexes are preferably used. By blending a near-infrared absorbing quencher compound, a higher near-infrared absorbing ability can be obtained.

In the present invention, the “near infrared absorbing quencher compound” means the above-described quencher compound having a near infrared absorbing property.
Here, “having near infrared absorptivity” has an absorption peak in the wavelength range of 800 to 1100 nm when the absorption spectrum of the quencher compound is measured by the following measurement method, and the wavelength (maximum It means having a molar extinction coefficient (ε _m ) of 1.1 × 10 ³ or more at the absorption wavelength (λ _max ).
(Measurement method of molar extinction coefficient (ε _m ))
The quencher compound is diluted with chloroform so that the sample concentration is 20 mg / L to prepare a sample solution. The absorption spectrum of this sample solution, using a spectrophotometer, measured in the range of 300～1300Nm, read the maximum absorption wavelength (lambda _max), the molar extinction coefficient at said maximum absorption wavelength (λ _max) (ε _m ) Is calculated from the following equation.
ε = −log (I / I ₀ )
(Ε: extinction coefficient, I ₀ : light intensity before incidence, I: light intensity after incidence)
ε _m = ε / (c · d)
(Ε _m : extinction coefficient, c: sample concentration (mol / L), d: cell length)
One kind of these near infrared absorbing quencher compounds may be used, or two or more different kinds may be used in combination.

As the near-infrared absorbing quencher compound, a diimonium dye is preferably used because the color of the obtained optical film is particularly good.
Further, as described above, it is known that diimonium dyes are significantly deteriorated when used in combination with cyanine dyes as described in Patent Document 1. However, in the present invention, the combination of the diimonium dye and the stabilized cyanine dye prevents not only the stabilized cyanine dye but also the diimonium dye. Therefore, the obtained optical film has a high near-infrared absorbing ability and excellent durability.

  The diimonium dye is a compound represented by the following general formula (IV).

［式中、Ｒ^１７〜Ｒ^２４は、それぞれ独立に水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアリール基、または置換基を有してもよいアルキニル基を表し、Ｚ⁻は陰イオンを表す］

[Wherein R ^{17 to} R ²⁴ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, Or an alkynyl group which may have a substituent, and Z ⁻ represents an anion]

In R ^{17 to} R ²⁴ , examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a secondary butyl group, an isobutyl group, a tertiary butyl group, and an n-pentyl group. , A tertiary pentyl group, an n-hexyl group, an n-octyl group, or a tertiary octyl group. The alkyl group may have a substituent such as an alkoxycarbonyl group, a hydroxyl group, a sulfo group, or a carboxyl group.
Examples of the alkenyl group include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group. The alkenyl group may have a substituent such as a hydroxyl group or a carboxy group.
Examples of the aryl group include benzyl group, p-chlorobenzyl group, p-methylbenzyl group, 2-phenylmethyl group, 2-phenylpropyl group, 3-phenylpropyl group, α-naphthylmethyl group, and β-naphthyl. An ethyl group or the like is shown. The aryl group may have a substituent such as a hydroxyl group or a carboxy group.
Examples of the alkynyl group include a propynyl group, a butynyl group, a 2-chlorobutynyl group, a pentynyl group, or a hexynyl group. The alkynyl group may have a substituent such as a hydroxyl group or a carboxy group.

Z ⁻ represents chlorine ion, bromine ion, iodine ion, perchlorate ion, periodate ion, nitrate ion, benzenesulfonate ion, P-toluenesulfonate ion, methyl sulfate ion, ethyl sulfate ion, propyl sulfate ion, Tetrafluoroborate, tetraphenylborate, hexafluorate, benzenesulfinate, acetate, trifluoroacetate, propionate, benzoate, oxalate, succinate, malonate Oleate ion, stearate ion, citrate ion, monohydrogen diphosphate ion, dihydrogen monophosphate ion, pentachlorostannate ion, chlorosulfonate ion, fluorosulfonate ion, trifluoromethanesulfonate ion, hexa Fluoroarsenic acid It represents anions such as ON, hexafluoroantimonate ion, molybdate ion, tungstate ion, titanate ion, or zirconate ion.

  Among these anions, perchlorate ion, iodine ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, trifluoromethanesulfonate ion, etc. are preferable, and hexafluoroantimonate ion is particularly hot. It is preferable because it is most excellent in stability.

In the present invention, the diimonium dye preferably has a molar extinction coefficient ε around 1000 nm measured by the above measuring method of about 0.8 × 10 ^{4 to} 1.0 × 10 ⁶ .
Furthermore, a diimonium dye having a purity of 98% or higher, or a diimonium having a melting point of 210 ° C. or higher in order to suppress deterioration during processing of the optical film and to give practical durability after the optical film is formed. It is preferable to use a system dye. In particular, it is preferable to use a diimonium dye having a purity of 98% or more and a melting point of 210 ° C. or more.

  The blending amount of the quencher compound in the optical film composition of the present invention is preferably 10 to 5000 parts by weight, more preferably 50 to 2000 parts by weight, and more preferably 100 to 1500 parts by weight with respect to 100 parts by weight of the stabilized cyanine compound. Part is more preferable. When the blending amount is 10 parts by mass or more, the effect of improving durability such as light resistance and heat resistance is sufficient, and when it is 5000 parts by mass or less, the near infrared absorption layer formed using the composition is colored. Thus, an optical film having a good appearance can be obtained.

  When the quencher compound contains a near-infrared absorbing quencher compound, the ratio of the near-infrared absorbing quencher compound in all the quencher compounds is preferably 30 to 100% by mass, more preferably 50 to 100% by mass. 80 to 100% by mass is more preferable. When the ratio of the near infrared absorbing quencher compound is 30% by mass or more, sufficient near infrared absorbing ability can be obtained.

In the present invention, in particular, as described above, a diimonium dye is preferably blended as a near-infrared absorbing quencher compound, and the blending amount is 50 to 3000 with respect to 100 parts by mass of the stabilized cyanine compound. Mass parts are preferred, 100 to 2000 parts by mass are more preferred, and 50 to 1500 parts by mass are even more preferred.
When the blending amount is 50 parts by mass or more, the effect of improving durability such as light resistance and heat resistance is sufficient, and sufficient near infrared ray absorbing ability is obtained. When the blending amount is 3000 parts by mass or less, stabilized cyanine The interaction with the system dye is suppressed, and the dye stability is improved.

<Other optional components>
In the composition for optical films of the present invention, the maximum absorption wavelength other than the above-mentioned stabilized cyanine dyes and near-infrared absorbing quencher compounds is within the range of 800 to 1100 nm, as long as the effects of the present invention are not impaired. One or more near-infrared absorbing dyes may be blended.
As such a near-infrared absorbing pigment, general pigments such as inorganic pigments, organic pigments, and organic dyes can be used.

Examples of inorganic pigments include cobalt dyes, iron dyes, chromium dyes, titanium dyes, vanadium dyes, zirconium dyes, molybdenum dyes, ruthenium dyes, platinum dyes, ITO dyes, and ATO dyes. And pigments.
Examples of organic pigments and organic dyes include cyanine dyes other than stabilized cyanine dyes, merocyanine dyes, croconium dyes, squalium dyes, azurenium dyes, polymethine dyes, naphthoquinone dyes, and pyrylium dyes. , Phthalocyanine dyes, naphthalocyanine dyes, naphtholactam dyes, azo dyes, condensed azo dyes, indigo dyes, perinone dyes, perylene dyes, dioxazine dyes, quinacridone dyes, isoindolinone dyes, quinophthalone And dyes, pyrrole dyes, anthraquinone dyes, thioindigo dyes, metal complex dyes, indolephenol dyes, triallylmethane dyes, and the like.
Among these, metal complex dyes, phthalocyanine dyes, naphthalocyanine dyes, pyrrole dyes, anthraquinone dyes and the like are preferable.

  In addition, when a diimonium dye is blended as a quencher compound and a salt compound or metal complex salt containing an anion is blended as a near-infrared absorbing dye or a color correction dye, the salt compound or metal complex salt is the diimonium dye. It is particularly preferred to have the same anion as the anion in it. When the same anion is used, even when a salt exchange reaction with the anion of the diimonium dye occurs, the diimonium dye does not change, and the absorption performance, thermal stability, etc. do not change.

  Further, the composition for optical film of the present invention includes a color tone correction dye having a maximum absorption wavelength in the range of 300 to 800 nm, a leveling agent, an antistatic agent, a thermal stabilizer, an antioxidant, a dispersant, a flame retardant, and a lubricant. , A plasticizer, or an ultraviolet absorber may be contained.

≪Optical film≫
The optical film of the present invention is an optical film having a near-infrared absorbing layer in which the composition for an optical film is dispersed in a transparent resin.

In general, since such an optical film is disposed on the viewing side of a PDP or the like, an achromatic color is preferred. Therefore, in the C light source standard calculated in accordance with JISZ8701-1999, the chromaticity coordinates corresponding to the achromatic color are (x, y) = (0.310, 0.316). It is preferable to select the type and content of the dye as appropriate, and (x, y) = (0.310 ± 0.100, 0.316 ± 0.100).
Further, it is preferable that the luminous average transmittance is 45% or more.
In particular, it is preferable that the chromaticity coordinates (x, y) and the luminous average transmittance are simultaneously satisfied.

In the present invention, the transparent resin has a glass transition point in the range of 90 to 180 ° C. because it can maintain practical durability, has easy moldability, and suppresses deterioration of the dye during molding. It is preferable that it is in the range of 120-180 degreeC especially.
Preferable transparent resins include thermoplastic resins such as polyester resins, polyolefin resins, polycycloolefin resins, polycarbonate resins, and polyacrylic resins. This resin includes, for example, polyester resins such as Kanebo Co., Ltd., trade name “O-PET”, polyolefin resins such as JSR Corp., trade name “ARTON”, ZEON Corporation, trade name “ZEONEX”, etc. Use commercially available products such as polycycloolefin resins, polycarbonate engineering resins manufactured by Mitsubishi Engineering Plastics, trade name “Iupilon”, and polyacrylic resins such as Nippon Shokubai Co., Ltd., trade names “Hals Hybrid IR-G204”. Can do.

The near-infrared absorbing layer can be formed, for example, by dissolving the composition for optical film and the transparent resin in an organic solvent, coating the obtained coating liquid on a substrate, and drying.
It is preferable that the compounding quantity of the composition for optical films in a near-infrared absorption layer is 3-20 mass% with respect to transparent resin. If it is 3 mass% or more, sufficient near-infrared absorptivity can be given to an optical film, and if it is 20 mass% or less, sufficient visible light transmittance can be maintained. From these viewpoints, the content is particularly preferably 5 to 10% by mass.

  Examples of the organic solvent for dissolving the optical film composition and the transparent resin include alcohols such as methanol, ethanol, isopropyl alcohol, diacetone alcohol, ethyl cellosolve, methyl cellosolve, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, and the like. Ketones, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide, ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, methyl acetate, ethyl acetate, butyl acetate, etc. Esters, aliphatic halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, trichloroethylene, benzene, toluene, xylene, monochloroben Emissions, aromatics or n- hexane, such as dichlorobenzene, aliphatic hydrocarbons such as cyclohexanone ligroin, can be used a fluorine-based solvent such as tetrafluoropropyl alcohol or pentafluoropropyl alcohol.

  Coating liquid coating methods include dip coating, spray coating, spinner coating, bead coating, wire bar coating, blade coating, roller coating, curtain coating, slit die coater, gravure coater, A coating method such as a slit reverse coater method, a micro gravure method, or a comma coater method can be used.

  The thickness of the near infrared absorbing layer is preferably in the range of 0.3 to 50 μm. When the thickness is 0.3 μm or more, the near-infrared absorption ability can be sufficiently exhibited, and when the thickness is 50 μm or less, the residual organic solvent during molding can be reduced. From these viewpoints, the range of 0.5 to 20 μm is particularly preferable.

  Moreover, the optical film of the present invention may have one or more arbitrary functional layers other than the near-infrared absorbing layer. As functional layers, for example, an ultraviolet absorbing layer for preventing deterioration of pigments due to ultraviolet rays and improving light resistance, an antireflection layer for improving image visibility, and cutting electromagnetic waves emitted from display devices such as PDPs. Electromagnetic wave shielding layer, hard coat layer providing scratch resistance function or self-healing layer, or antifouling layer for preventing dirt on the outermost surface, adhesive or adhesive layer for laminating each layer Etc.

  The optical film of the present invention may be a near-infrared absorbing layer itself produced by being peeled after being formed on a peelable substrate, and may be a transparent support film (hereinafter referred to as a support film). A near-infrared absorbing layer may be formed thereon and integrated with the support film.

  The peelable substrate may be in the form of a film or plate, and the material is not particularly limited. In order to improve the releasability, it is preferable to perform a mold release treatment on the surface of the base material using a silicone or a low surface tension resin.

  Examples of the material for the support film include polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyolefins such as polyethylene and polypropylene, polyacrylates such as polyacrylates and polymethyl methacrylate (PMMA), and polycarbonate. (PC), polystyrenes, triacetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl acetate copolymer, polyvinyl butyral, polyurethane, cellophane, etc. Preferably, PET, PC, and PMMA are used.

  The thickness of the support film is preferable in terms of good workability in the range of 10 to 500 μm and low haze value. Moreover, before forming an optical film on a support film, it is preferable to give the surface of this support film a corona treatment or an easy-adhesion treatment.

Even if the optical film of the present invention is peeled off from a peelable substrate or integrated with a support film, a transparent substrate (hereinafter referred to as an adhesive layer) having a high rigidity is provided. , Described as a transparent substrate.).
The material of the transparent substrate can be appropriately selected from glass and a transparent and highly rigid polymer material, and preferably includes glass, tempered or semi-tempered glass, polycarbonate, or polyacrylate. If an optical filter having an optical film attached to a transparent substrate is used as an optical filter, it can also function as a protective plate for a display device such as a PDP.

Commercially available pressure-sensitive adhesives can be used as the pressure-sensitive adhesive for the pressure-sensitive adhesive layer. Preferred examples include acrylic acid ester copolymers, polyvinyl chloride, epoxy resins, polyurethane, and vinyl acetate copolymers. An adhesive such as styrene-acrylic copolymer, polyester, polyamide, polyolefin, styrene-butadiene copolymer rubber, butyl rubber, or silicone resin. Furthermore, when laminating the pressure-sensitive adhesive layer, it is preferable from the viewpoint of workability to attach a release film such as PET coated with silicone to the pressure-sensitive adhesive surface.
When using an adhesive, you may add the additive which has various functions, such as a ultraviolet absorber, to this adhesive.

The optical film of the present invention, or a film obtained by sticking the optical film on a transparent substrate, is a flat display device such as a PDP, a plasma addressed liquid crystal (PALC) display panel, a field emission display (FED) panel, and a cathode ray tube display. It can be used as an optical filter for a display device such as a device (CRT).
In this case, the optical film may be installed on the viewing side of the display device, may be installed away from the display device, or may be directly attached to the display device surface.

  The optical film of the present invention has a high near-infrared absorbing ability and is excellent in durability such as light resistance and heat resistance, so that it can be suitably used particularly for an optical filter such as a PDP that generates near-infrared rays. it can.

  Examples are given below to explain the invention in more detail. The present invention is not limited by these examples. Examples 1 to 6 and Examples 10 and 11 are examples, and examples 7 to 9 are comparative examples.

In addition, (lambda) _max and (epsilon) _m of the near-infrared absorptive pigment | dye (stabilized cyanine pigment | dye and near-infrared absorptive quencher compound) used in the following Examples 1-11 were measured in the following procedure.
The near-infrared absorbing dye was diluted with chloroform so that the sample concentration was 20 mg / L to prepare a sample solution. The absorption spectrum of this sample solution was measured in the range of 300 to 1300 nm using UV-3100 manufactured by Shimadzu Corporation, the maximum absorption wavelength (λ _max ) was read, and the molar extinction coefficient at the _maximum absorption wavelength (λ _max ). (Ε _m ) was calculated from the following equation.
ε = −log (I / I ₀ )
(Ε: extinction coefficient, I ₀ : light intensity before incidence, I: light intensity after incidence)
ε _m = ε / (c · d)
(Ε _m : extinction coefficient, c: sample concentration (mol / L), d: cell length)

(Example 1)
A transparent polyester resin (manufactured by Kanebo Co., Ltd., trade name “O-PET”) having a glass transition temperature of 140 ° C. is dissolved in a mixed solvent of cyclopentanone / toluene (6/4 volume ratio) to 15% by mass, A base solution was obtained. Diimonium dye (N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine-hexafluoroantimonic acid immonium salt): Nippon Kayaku Co., Ltd. Product name “IRG-022”, λ _max is 1090 nm, ε _m is 1.1 × 10 ⁵ ) 6.4 mass%, and cation no. No. 11 cyanine cation and anion no. Coating in which 0.5% by mass of a stabilized cyanine dye (λ _max is 855 nm and ε _m is 2.0 × 10 ⁵ ) consisting of 22 quencher anions is added to the main agent solution and dissolved. A liquid was obtained. This coating solution was coated on a 100 μm thick polyethylene terephthalate film (trade name “A4100”, manufactured by Toyobo Co., Ltd.) with a micro gravure so that the thickness of the dried coating film was 4 μm, and dried at 120 ° C. for 5 minutes. To obtain an optical film.

(Example 2)
The stabilized cyanine dye used in Example 1 was converted to cation no. No. 13 cyanine cation and anion no. An optical film was obtained in the same manner as in Example 1 except that a stabilized cyanine dye (λ _max was 818 nm and ε _m was 2.5 × 10 ⁵ ) consisting of 22 quencher anions was used.

(Example 3)
An optical film was obtained in the same manner as in Example 1 except that 0.5% by mass of the stabilized cyanine dye used in Example 2 was further added to the coating solution used in Example 1.

(Example 4)
The diimonium dye used in Example 3 was converted to N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine · -bis (bis (trifluoromethanesulfonyl) imidic acid) imonium salt (Japan) An optical film was obtained in the same manner as in Example 3 except that the trade name “CIR-1085” manufactured by Carlit Co., Ltd., λ _max was 1073 nm, and ε _m was 1.0 × 10 ⁵ ).

(Example 5)
Except for changing the main agent solution used in Example 3 to 15% by mass with MEK using acrylic resin paint (manufactured by Nippon Shokubai Co., Ltd., trade name “Hals Hybrid IR-G204”: glass transition temperature of resin = 89 ° C.) Obtained an optical film in the same manner as in Example 3.

(Example 6)
An optical film was obtained in the same manner as in Example 4 except that the main agent solution used in Example 4 was replaced with the main agent solution in Example 5.

(Example 7)
An optical film was obtained in the same manner as in Example 1 except that the stabilized cyanine dye used in Example 1 was replaced with an unstabilized cyanine dye (trade name “TW-1926” manufactured by Asahi Denka Co., Ltd.).

(Example 8)
To the main agent solution used in Example 7, a quencher dye (manufactured by Sumitomo Seika Co., Ltd., trade name “EST-5”, tetrabutylammonium salt of anion No. 22 quencher anion, no absorption peak at 800 to 1100 nm, ε _m <10 ³ ) An optical film was obtained in the same manner as in Example 7 except that 0.5% by mass was added.

(Example 9)
The diimonium dye used in Example 1 was replaced by a phthalocyanine dye (manufactured by Nippon Shokubai Co., Ltd., trade name “TX-EX-910”, λ _max of 978 nm, ε _m of 1.0 × 10 ⁵ ) 6.0 mass An optical film was obtained in the same manner as in Example 1 except that% was replaced.

(Example 10)
Acrylic resin paint (product of Nippon Shokubai Co., Ltd., trade name “Hals Hybrid IR-G204”: glass transition temperature of resin = 89 ° C.) was dissolved in MEK so as to be 15% by mass to obtain a base solution. Diimonium dye (N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine-hexafluoroantimonic acid immonium salt): Nippon Kayaku Co., Ltd. Manufactured, trade name “IRG-022”) 9.0% by mass, stabilized cyanine dye (manufactured by Sumitomo Seika Co., Ltd., trade name “SD-AG01”, λ _max is 877 nm, ε _m is 3.1 × 10 ⁵ ) 1.0% by mass, and hexafluoroantimonic acid / cyanine dye (manufactured by Nippon Kayaku Co., Ltd., trade name “CY-40MCS”, λ _max is 830 nm, and ε _m is 2.7 × 10 ⁵ ) 1.0 mass% was added to the main ingredient solution to obtain a coating solution in which these were dissolved. This coating solution was coated on a 100 μm thick polyethylene terephthalate film (trade name “A4100”, manufactured by Toyobo Co., Ltd.) with a micro gravure so that the thickness of the dried coating film was 4 μm, and dried at 120 ° C. for 5 minutes. To obtain an optical film.

(Example 11)
The diimonium dye used in Example 10 was replaced with N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediamine · -bis (bis (trifluoromethanesulfonyl) imidic acid) imonium salt (Japan) Instead of Carlit, trade name “CIR-1085”), hexafluoroantimonic acid / cyanine dye was replaced with trifluoromethanesulfonyl imido acid / cyanine dye (manufactured by Nippon Kayaku Co., Ltd., trade name “CY-40MCFI”, λ _max Was 830 nm, and an optical film was obtained in the same manner as in Example 10 except that ε _m was changed to 2.7 × 10 ⁵ ).

Test example 1
The optical characteristics (luminous average transmittance, chromaticity, near infrared transmittance) and durability (heat resistance, light resistance) of the optical films obtained in Examples 1 to 11 were evaluated by the following methods. The results are shown in Table 1.

(optical properties)
Using a spectrophotometer (manufactured by Shimadzu Corporation, UV-3100), the spectrum of a 20 × 20 mm square test piece cut out from each sample was measured in the range of 380 to 1300 nm. According to JIS Z8701-1999, the luminous average transmittance Tv and chromaticity coordinates (x, y) were calculated.
Moreover, the transmittance | permeability of 850 nm, 900 nm, 950 nm, and 1000 nm was measured, and the near-infrared transmittance was calculated | required by making the transmittance | permeability of indoor air into a comparison reference. The near-infrared transmittance at each wavelength was T850, T900, T950, and T1000, respectively.

(Heat-resistant)
Using a constant temperature thermostat (manufactured by Tokyo Rika Kikai Co., Ltd.), the temperature was set to 80 ° C., and the measured values of Tv, x, y of each sample after the 1000 hour test were compared with the measured values before the test. Yes, if the amount of change before and after the test is less than 3%, △ if any one is 3% to less than 5%, △, if any one is more than 5% X.

(Light resistance)
Using a light resistance tester (manufactured by Suga Test Instruments Co., Ltd., Xenon Fade Meter X-15F), the light of 380 nm or more was irradiated with 200 MJ / cm ² , and each measured value of Tv, x, y of each sample was measured before the test. Comparison with measured values. Yes, if the amount of change before and after the test is less than 3%, △ if any one is 3% to less than 5%, △, if any one is more than 5% X.

As shown in Table 1, the optical films of Examples 1 to 6 and Examples 10 and 11 (Examples) all had good optical characteristics, and both heat resistance and light resistance were good.
In contrast, the optical film of Example 7 using a cyanine dye instead of the stabilized cyanine dye used in Example 1 had poor light resistance.
In addition, the optical film of Example 8 in which a near-infrared absorbing quencher compound was further added to the main agent solution used in Example 7 was poor in both light resistance and heat resistance. Moreover, both x and y of chromaticity coordinates were high, and the appearance was not good. Furthermore, the near infrared transmittance was also high.
Further, the optical film of Example 9 in which no quencher compound was blended had poor light resistance and low luminous average transmittance.

Claims (4)

The following general formulas (I) to (III)

[Wherein, ring A and ring A ′ each independently represent a benzene ring, a naphthalene ring or a pyridine ring, and R ¹ and R ¹ ′ each independently represent a halogen atom, a nitro group, a cyano group, a carbon number of 6 to 30 represents an aryl group, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a cyano group or 6 carbon atoms. Represents an aryl group of ˜30, a diphenylamino group or an alkyl group of 1 to 8 carbon atoms, and X and X ′ are each independently an oxygen atom, sulfur atom, selenium atom, propane-2,2-diyl group, butane- 2,2-diyl group, a cycloalkane-1,1-diyl group having 3 to 6 carbon atoms, —NH— or —NY ₁ —, wherein Y, Y ′ and Y ₁ each independently represent 1 to Table of 30 organic groups , R and r 'represent each independently an integer of 0 to 2]
A stabilized cyanine dye comprising a cation selected from the group consisting of compounds represented by the above and a quencher anion, and a quencher compound.   The optical film composition according to claim 1, wherein the quencher compound contains a near-infrared absorbing quencher compound. The near-infrared absorbing quencher compound is represented by the following general formula (IV)

[Wherein R ^{17 to} R ²⁴ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, Or an alkynyl group which may have a substituent, and Z ⁻ represents an anion]
The composition for optical films of Claim 2 containing the diimonium dye represented by these. The optical film which has the near-infrared absorption layer by which the composition for optical films as described in any one of Claims 1-3 is disperse | distributed in transparent resin.