TW201510099A - Optical substrate and display device - Google Patents

Abstract

An optical substrate including a color material which has a significant effect on improving color purity and little reduction in brightness, and a display device using the optical substrate are provided. The invention relates to an optical substrate and a display device using the optical substrate, wherein in the display device containing a color filter formed by an arrangement of a multi-color colored layer and a light source, the optical substrate is disposed on an optical path from the light source to the color filter; the optical substrate contains at least one color material selected from the group consisting of a metal complex compound represented by a specific structural formula, a J-aggregate of a cyanine pigment represented by a specific structural formula, and a cyanine pigment represented by a specific structural formula, and the optical substrate has a maximum absorption wavelength of 580 nm or more and 610 nm or less.

Description

Optical substrate and display device

The invention relates to an optical substrate and a display device.

In recent years, display devices having color filters, such as monitors for personal computers, have been widely used in addition to television image receivers. In response to the development of large-scale, thinner, and lighter display devices, technologies for achieving more vivid images and more beautiful images have also been studied.

Such a display device includes, for example, a light source that emits white light, and a display panel having a plurality of pixels that display an image by modulating light emitted by the light source. In the display panel, a color filter in which each of the three colors of the red (R), green (G), and blue (B) colors is transmitted in order to perform full-color display is provided. Thereby, the light incident on the liquid crystal display panel from the light source is modulated by each pixel based on the image data, and the modulated light is taken out as light of R, G, and B by the color filter, respectively, and Display is performed by the extracted light.

However, in the image presented as described above, in addition to the light of R, G, and B which easily transmits the color filter, the color filter has a small amount of transmission, but Light having a wavelength of an intermediate color of R, G, and B.

5 is a characteristic diagram showing the spectral reflectance versus transmittance spectrum of each of R, G, and B of the color filter, and the curves R, G, and B show the transmission of light of each of R, G, and B colors. rate. As is apparent from Fig. 5, the light passing through the color filter also includes light of a wavelength of an intermediate color of R, G, and B. The color purity of light is lowered by the respective colors of R, G, and B of such a color filter, and it is difficult to obtain sufficient color reproducibility.

In addition to the Cold Cathode Fluorescent Lamp (CCFL), the white light source used in the liquid crystal display device is also available in the recent years in order to reduce the thickness or power saving requirements of the Light Emitting Diode (Light Emitting Diode, A white LED method in which a yellow, or red, and green phosphor is combined with an LED or an ultraviolet light emitting LED. These light sources include a sub-spectrum corresponding to an intermediate color of R and G or an intermediate color of G and B, and the spectrum itself is wide. Therefore, light having a wavelength corresponding to the intermediate color also emits a large amount of light, which causes a decrease in color purity. For example, the blue splitting light emitted by the blue LED is equivalent to the R and G in the spectrum of the relative intensity of the light, as shown in FIG. 5, as shown in FIG. 5 (Light Emitting Diode-Backlight, LED-BL). Light of a wavelength of 580 nm or more and 610 nm or less of the intermediate color.

In order to improve the color purity of an image displayed on a display device such as a liquid crystal display, a usual method is to increase the color purity of the color filter. Therefore, although there is a method of improving the coloring photosensitive composition of each pixel for forming a color filter, in order to maintain characteristics such as pattern formation property and reliability, the amount of colored material contained therein is limited, and it is not expected. The color purity is greatly improved.

Therefore, in order to solve this problem, it is being studied to increase the color purity of light of R, G, and B included in the light of the light source of the backlight, and to expand the color reproduction range. For example, a technique of using an optical substrate of a colored material containing light that absorbs unnecessary wavelength regions (wavelength regions of intermediate colors of R, G, B) has been proposed. Specifically, in a liquid crystal display device including a backlight unit, a method of using a sheet as a diffusion film in a backlight unit having a maximum absorption in a wavelength region of 420 nm to 530 nm or 530 nm to 630 nm is proposed. Peaked colored material. In particular, a tetraazaporphyrin having an absorption peak wavelength of 570 nm to 605 nm is proposed as a colored material contained in an optical substrate which absorbs a yttrium aluminum garnet-light emitting diode (Yttrium) as a light source. Aluminum Garnet-Light Emitting Diode (YAG-LED) emits light in a wavelength range of 530 nm to 630 nm corresponding to the intermediate color of G and R included in the backlight light (see Patent Document 1 to Patent Document 3).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-063195

[Patent Document 2] Japanese Patent No. 4250026

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-134349

The porphyrazine has a wide spectrum of light emission for absorbing only the intermediate color of R and G, and also absorbs a large amount of light other than the intermediate color. Therefore, there is a problem that the effect of improving the excellent purity is not sufficiently exhibited, or the brightness is greatly reduced. Can't reach practical.

As a colored material other than tetraazaporphyrin, research has also been conducted on colored materials such as xanthene, squary, cyanine, oxonol, azo, pyrrolethylene, etc., but no A material having satisfactory characteristics is desired to have a more desirable maximum absorption wavelength and a colored material that does not absorb sharp spectral characteristics of light other than the intermediate color.

The present invention has been made in view of the above problems, and an object thereof is to provide an optical substrate and a display device which not only maintain good brightness but also have excellent color purity.

The specific means for achieving the problem are as follows.

<1> An optical substrate disposed in a display device including a color filter and a light source configured by arranging a plurality of color-colored layers in a two-dimensional direction, from the light source to the color filter In the optical path of the light sheet, the optical substrate comprises a J-association selected from the group consisting of a metal-defect compound represented by the following formula (I), a cyanine dye represented by the following formula (II), and At least one colored material of the group consisting of the cyanine dye represented by the following general formula (III), and having a maximum absorption wavelength of 580 nm or more and 610 nm or less, and a formula of (Chemical Formula 1) I)

(In the formula (I), R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent substituent; and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic ring. And R ⁸ and R ⁹ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amine group; a metal atom or a metal compound; X ³ and X ⁴ each independently represent NR ^a (R ^a represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an aryl sulfonate) a mercapto group, an oxygen atom, or a sulfur atom; Y ¹ and Y ² each independently represent NR ^b (R ^b represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an anthracenyl group, an alkylsulfonyl group) Or an arylsulfonyl group, an oxygen atom, or a sulfur atom; X ⁵ represents a group bondable to Ma; a represents 0, 1 or 2; and R ⁸ and Y ¹ may be bonded to each other to form a 5-member, Ring of 6 or 7 members, R ⁹ and Y ² can be bonded to each other to form a ring of 5, 6 or 7 members)

[Chemical 2] General formula (II)

(In the formula (II), Z ¹ and Z ² each independently represent a group of non-metal atoms necessary for forming a nitrogen-containing heterocyclic ring of 5 or 6 members of the condensable ring; R ¹⁰ and R ¹¹ respectively Independently represents an aliphatic group; L ¹ represents a methine chain containing 1, 3 or 5 methine groups; X' ^- represents an anion; and b, c and d each independently represent 0 or 1)

(In the formula (III), R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an aryl group having 6 to 8 carbon atoms; U represents N or CH; W and Z each independently represent a group of atoms necessary for forming an aromatic ring; L represents a methine chain containing 3, 5 or 7 methine groups; X ^- represents Counter ion).

<2> The optical substrate according to <1>, which comprises at least one colored material selected from the group consisting of the metal-containing compounds represented by the formula (I) as a colored material.

<3> The optical substrate according to <2>, wherein, in the formula (I), R ² and R ⁵ represent a heteroaryl group.

<4> The optical substrate according to <3>, wherein the heteroaryl group is represented by the following formula (Ia),

(In the formula (Ia), HetAr ¹ represents a heteroaryl ring).

The optical substrate according to any one of <1> to <4> wherein, in the formula (I), R ³ and R ⁴ each independently represent an alkyl group or an aryl group, and Y ¹ and Y ² represents NH, X ³ and X ⁴ represent an oxygen atom, R ⁸ and R ⁹ represent an alkyl group, and Ma represents a metal atom.

The optical substrate according to any one of <1>, wherein the composition comprises a layer comprising the at least one colored material and having an ethylene property. A saturated polymerizable compound and a photopolymerization initiator.

<7> A display device comprising a color filter, a light source, and an optical substrate according to any one of <1> to <6>, wherein The optical substrate is disposed on an optical path from the light source to the color filter.

<8> The display device according to <7>, wherein the optical substrate is also a diffusion film.

<9> The display device according to <7>, wherein the optical substrate is also an adhesive layer.

According to the present invention, it is possible to provide an optical substrate and a display device which not only maintain good brightness but also have excellent color purity.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a spectroscopic transmittance spectrum diagram of four kinds of optical substrates of the present invention.

2 is a spectral transmittance spectrum diagram of two other optical substrates of the present invention and two conventional optical substrates.

3 is a spectrogram showing a relative luminance spectrum of light emitted from a blue LED and a spectrum of relative luminance of light passing through any of the four types of optical substrates of the present invention.

4 is a spectrum showing a relative luminance spectrum of light emitted from a blue LED and a spectrum of relative luminance of light passing through any of the other two optical substrates of the present invention and two conventional optical substrates. Figure.

Figure 5 is a graph showing the spectral relative transmittance of each of R, G, and B of a color filter. The spectrum, and the characteristic map of the blue spectral splitting relative to the luminous intensity spectrum emitted by the blue LED.

The optical substrate of the present invention is disposed on a light path from the light source to the color filter in a display device including a color filter and a light source configured by arranging a plurality of colored layers, and A J-association compound selected from the group consisting of a metal-defect compound represented by the following formula (I), a cyanine dye represented by the following formula (II), and a cyanine dye represented by the following formula (III) At least one colored material (hereinafter also referred to as "specific colored material") in the group of the composition, and the optical substrate has a maximum absorption wavelength of 580 nm or more and 610 nm or less.

Here, the optical substrate containing a specific colored material specifically means, and includes, a state in which a specific colored material is contained in a base body as a support; and an additional setting is made different from the base body. The layer on the base body (for example, the adhesive layer formed on the surface of the base body, the colored layer, the layer sandwiched between the two base bodies, and the like) contains a specific colored material.

<Specific colored materials>

The specific colored material of the present invention is a J-association selected from the group consisting of a metal-defect compound represented by the following formula (I), a cyanine dye represented by the following formula (II), and the following formula (III) At least one colored material in the group consisting of the cyanine dyes indicated.

[Chemical 5]

(In the formula (I), R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent substituent; and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic ring. And R ⁸ and R ⁹ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amine group; a metal atom or a metal compound; X ³ and X ⁴ each independently represent NR ^a (R ^a represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group (alkylcarbonyl group), an alkylsulfonyl group Or an arylsulfonyl group, an oxygen atom, or a sulfur atom; Y ¹ and Y ² each independently represent NR ^b (R ^b represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group) An alkylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group, an oxygen atom, or a sulfur atom; X ⁵ represents a group bondable to Ma; a represents 0, 1 or 2; R ⁸ and Y ¹ can be interlocked to form a ring of 5 members, 6 members, or 7 members, and R ⁹ and Y ² can be bonded to each other to form a ring of 5 members, 6 members, or 7 members.)

[Chemical 6]

(In the formula (II), Z ¹ and Z ² each independently represent a group of non-metal atoms necessary for forming a nitrogen-containing heterocyclic ring of 5 or 6 members of the condensable ring; R ¹⁰ and R ¹¹ respectively Independently represents an aliphatic group; L ¹ represents a methine chain containing 1, 3 or 5 methine groups; X' ^- represents an anion; and b, c and d each independently represent 0 or 1.

(In the formula (III), R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an aryl group having 6 to 8 carbon atoms; U represents N or CH; W and Z each independently represent a group of atoms necessary for forming an aromatic ring; L represents a methine chain containing 3, 5 or 7 methine groups; X ^- represents Counter ion.)

Hereinafter, the general formula (I) will be described in detail.

In the formula (I), R ² to R ⁵ each independently represent a hydrogen atom or a monovalent substituent.

In the general formula (I), examples of the monovalent substituent represented by R ² to R ⁵ include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) and an alkyl group (preferably, a carbon number of 1 to 2). 48. More preferably, it is a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, and examples thereof include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group and n-butyl group. Base, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, ring Butyl group, benzyl group, 1-norbornyl group, 1-adamantyl group, etc., alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms), for example, a vinyl group , allyl, 3-buten-1-yl, etc.), aryl (preferably a carbon number of 6 to 48, more preferably an aryl group having 6 to 24 carbon atoms, for example, substituted or unsubstituted a phenyl group, a substituted or unsubstituted naphthyl group, or the like, a heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms), for example, 2-thienyl group , 4-pyridyl, 3-pyridyl, 2-pyridyl, 1-pyridyl, 2-furyl, 2-pyrimidinyl, 2-benzothiazole , 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl, etc.), decylalkyl (preferably a carbon number of 3 to 38, more preferably a decyl group having a carbon number of 3 to 18, for example, : trimethyl decyl, triethyl decyl, tributyl decyl, tert-butyl dimethyl decyl, tert-hexyl dimethyl decyl, etc., hydroxyl, cyano, nitro, alkoxy The base (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms), for example, a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, and an isopropyl group. An oxy group, a third butoxy group, a dodecyloxy group, a cycloalkyloxy group (e.g., a cyclopentyloxy group, a cyclohexyloxy group), or an aryloxy group (preferably having a carbon number of 6 to 48, more) Examples of the aryloxy group having 6 to 24 carbon atoms include a phenoxy group and a 1-naphthyloxy group, and a heterocyclic oxy group (preferably having a carbon number of 1 to 32, more preferably a carbon number of 1 to 18). Examples of the heterocyclic oxy group include a 1-phenyltetrazole-5-oxy group and a 2-tetrahydropyranyloxy group, and a decyloxy group (preferably having a carbon number of 1 to 32, more preferably Examples of the decyloxy group having 1 to 18 carbon atoms include a trimethyl decyloxy group, a tert-butyldimethyl decyloxy group, and a diphenylmethyl decyloxy group. And an anthraceneoxy group (preferably a carbon number of 2 to 48, more preferably a carbon number of 2 to 24), and examples thereof include an ethoxy group, a trimethylacetoxy group, and a benzamidine group. And an alkoxycarbonyloxy group (preferably a carbon number of 2 to 48, more preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms), for example, an ethoxycarbonyloxy group a group, a third butoxycarbonyloxy group, a cycloalkyloxycarbonyloxy group (e.g., a cyclohexyloxycarbonyloxy group, etc.), an aryloxycarbonyloxy group (preferably having a carbon number of 7 to 32, more) Preferred examples of the aryloxycarbonyloxy group having 7 to 24 carbon atoms include a phenoxycarbonyloxy group and the like, and an amine methyloxy group (preferably having a carbon number of 1 to 48, more preferably a carbon number of 1). The amine methyl methoxy group of 24 may, for example, be N,N-dimethylamine methyl methoxy, N-butylamine methyl methoxy, N-phenylamine methyl oxy, N-ethyl- N-phenylamine methyl methoxy group, etc., and amine sulfonyloxy group (preferably, the sulfonyloxy group having a carbon number of 1 to 32, more preferably 1 to 24 carbon atoms, for example, N,N- a diethylsulfonyloxy group, an N-propylamine sulfonyloxy group, or the like, an alkylsulfonyloxy group (preferably an alkylsulfonate having a carbon number of 1 to 38, more preferably a carbon number of 1 to 24) Oxylate, for example Examples thereof include a methylsulfonyloxy group, a hexadecylsulfonyloxy group, a cyclohexylsulfonyloxy group, and the like, and an arylsulfonyloxy group (preferably having a carbon number of 6 to 32, more preferably a carbon number of 6) Examples of the arylsulfonyloxy group of ~24 include a phenylsulfonyloxy group and the like, and a mercapto group (preferably a fluorenyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms), and examples thereof include : a mercapto group, an ethyl fluorenyl group, a trimethyl ethane group, a benzamidine group, a tetradecyl group, a cyclohexyl group, etc.), an alkoxycarbonyl group (preferably a carbon number of 2 to 48, more preferably Examples of the alkoxycarbonyl group having 2 to 24 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a 2,6-di-tert-butyl-4 group. -methylcyclohexyloxycarbonyl or the like), an aryloxycarbonyl group (preferably, an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, a phenoxycarbonyl group) Aminomethyl sulfhydryl group (preferably an amine carbaryl group having a carbon number of 1 to 48, more preferably 1 to 24 carbon atoms, for example, an amine methyl sulfonyl group, an N,N-diethylamine methyl fluorenyl group, and N -ethyl-N-octylaminecarbamyl, N,N-dibutylaminecarbamyl, N-propylaminecarbamyl, N-phenylaminecarbamyl, N-methyl-N- Phenylamine An amine group (e.g., an N,N-dicyclohexylamine carbenyl group or the like) or an amine group (preferably having an alkyl group of 32 or less, more preferably 24 or less carbon atoms), for example, an amine group, a methylamino group, N,N-dibutylamino group, tetradecylamino group, 2-ethylhexylamino group, cyclohexylamino group, etc.), anilino group (preferably having a carbon number of 6 to 32, more preferably a carbon number of 6) Examples of the anilino group of ~24 include an anilino group and an N-methylanilino group, and a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms). For example, a 4-pyridylamino group and the like, and a carboguanamine group (preferably a carbon amide group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms), for example, an acetamino group, a benzylideneamine group, a tetradecylguanidinium group, a trimethylacetamidoguanidino group, a cyclohexaneguanidino group, etc.), a urea group (preferably having a carbon number of 1 to 32, more preferably a carbon number of 1) Examples of the urea group of -24 include a urea group, an N,N-dimethylureido group, and an N-phenylureido group, and a quinone imine group (preferably having a carbon number of 36 or less, more preferably a carbon number). Examples of the quinone imine group of 24 or less include, for example, N-butylenedimino group, N-phthalimido group, and the like, and alkoxycarbonylamino group (preferably, carbon number 2 to 48) More preferably, the alkoxycarbonylamino group having 2 to 24 carbon atoms may, for example, be a methoxycarbonylamino group, an ethoxycarbonylamino group, a third butoxycarbonylamino group or an octadecyloxycarbonylamine. An aryloxycarbonylamino group (preferably, an aryloxycarbonylamino group having a carbon number of 7 to 32, more preferably a carbon number of 7 to 24, for example, a phenoxy group) a carbonylamino group, etc., preferably a sulfonamide group having a carbon number of 1 to 48, more preferably 1 to 24 carbon atoms, and examples thereof include a methanesulfonamide group and a sulfonamide group. , benzenesulfonylamino, hexadecanesulfonylamino, cyclohexylsulfonylamino, etc.), aminesulfonylamino group (preferably a carbon number of 1 to 48, more preferably a carbon number of 1 to 24) Examples of the sulfonylamino group include an N,N-dipropylaminesulfonylamino group, an N-ethyl-N-dodecylaminesulfonylamino group, and the like, and an azo group. The azo group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, a phenylazo group or a 3-pyrazolylazo group, or an alkylthio group (preferably a carbon number) 1 to 48, more preferably an alkylthio group having 1 to 24 carbon atoms, for example, a methylthio group, an ethylthio group, an octylthio group, a cyclohexylthio group, or the like, and an arylthio group (for comparison) The arylthio group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, for example, a phenylthio group or the like, or a heterocyclic thio group (preferably having a carbon number of 1 to 32, more preferably a carbon number of 1 to 2) Examples of the heterocyclic thio group of 18 include a 2-benzothiazolylthio group, a 2-pyridylthio group, a 1-phenyltetrazolylthio group, and the like, and an alkylsulfinyl group (preferably carbon). The alkyl sulfinyl group having 1 to 32, more preferably 1 to 24 carbon atoms, for example, a dodecylsulfinyl group or the like, or an arylsulfinyl group (preferably having a carbon number of 6 to 32) More preferably, the arylsulfinyl group having a carbon number of 6 to 24, for example, a phenylsulfinyl group or the like, or an alkylsulfonyl group (preferably having a carbon number of 1 to 48, more preferably a carbon number) Examples of the alkylsulfonyl group of 1 to 24 include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, an isopropylsulfonyl group, and a 2-ethylhexyl group. a sulfonyl group, a hexadecylsulfonyl group, an octylsulfonyl group, a cyclohexylsulfonyl group, or the like, an arylsulfonyl group (preferably having a carbon number of 6 to 48, more preferably a carbon number of 6 to 24) Examples of the arylsulfonyl group include a phenylsulfonyl group and a 1-naphthylsulfonyl group, and an aminesulfonyl group (preferably having a carbon number of 32 or less, more preferably a carbon number of 24 or less). Examples of the group include an amine sulfonyl group, N,N-dipropylamine sulfonyl group, N-ethyl-N-dodecylamine sulfonyl group, and N-ethyl-N-phenylamine sulfonate. A mercapto group, a sulfo group or a phosphinium group (preferably a phosphinyl group having a carbon number of 1 to 32, more preferably a carbon number of 1 to 24), and examples thereof include a phenoxy group. a phosphinium group, an octyloxyphosphonium group, a phenylphosphonium fluorenyl group, a phosphinium group, preferably a phosphinium group having a carbon number of 1 to 32, more preferably a carbon number of 1 to 24. For example, a diethoxyphosphinylamino group, a dioctyloxyphosphinylamino group, etc. are mentioned.

In the case where the monovalent substituent represented by R ² to R ⁵ in the formula (I) is a group which may be further substituted, the monovalent substituent represented by R ² to R ⁵ may further have R ^{2 .} The substituents described in ~R ⁵ . When the monovalent substituent represented by R ² to R ⁵ has two or more monovalent substituents, the substituents may be the same or different.

In the formula (I), R ³ and R ^{4 are} preferably an alkyl group, an aryl group or a heterocyclic group in the group, more preferably an alkyl group or an aryl group.

In the formula (I), R ² and R ^{5 are} preferably an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbaryl group, an alkylsulfonyl group or an arylsulfonyl group in the group. a nitrile group, a quinone imine group, an amine mercaptosulfonyl group, or a heterocyclic group, more preferably an alkoxycarbonyl group, an aryloxycarbonyl group, an amine carbenyl group, a nitrile group, a quinone imine group, an amine formamidine A sulfonyl group or a heterocyclic group. Among them, it is preferred that at least one of R ² and R ⁵ represents a heteroaryl group described later.

Each of the groups shown in the preferred embodiment may be unsubstituted or may have the substituents already described.

In the general formula (I), when R ³ and R ⁴ represent an alkyl group, the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, more specifically, for example, Either methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl or benzyl, more preferably Further, it is a branched chain having 1 to 12 carbon atoms or a cyclic alkyl group, and more specifically, for example, isopropyl group, cyclopropyl group, isobutyl group, tert-butyl group, cyclobutyl group, cyclopentyl group Or a cyclohexyl group, particularly preferably a 2nd alkyl group or a 3rd alkyl group having 1 to 12 carbon atoms, and more specifically, for example, an isopropyl group, a cyclopropyl group, an isobutyl group, a tert-butyl group, or a ring. Butyl or cyclohexyl.

The alkyl groups shown in the preferred embodiment may be unsubstituted or may have the substituents already described.

In the formula (I), the aryl group in the case where R ³ and R ⁴ represent an aryl group is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, more preferably It is a substituted or unsubstituted phenyl group.

In the case of the formula (I), when R ³ and R ⁴ represent an aryl group, the aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

Each of the aryl groups shown in the preferred embodiment may be unsubstituted or may have the substituents already described.

In the case of the formula (I), when R ³ and R ⁴ represent a heterocyclic group, the heterocyclic group is preferably a 2-thienyl group, a 4-pyridyl group, a 3-pyridyl group or a 2-pyridyl group. , 1-pyridyl, 2-furyl, 2-pyrimidinyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl or benzotriazol-1-yl, more preferably: 2 -Thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl or 1-pyridyl.

Each of the heterocyclic groups shown in the preferred embodiment may be unsubstituted or may have the substituents already described.

In the formula (I), R ² and R ⁵ each independently represent a hydrogen atom or a monovalent substituent as described above. Among them, it is preferred that at least one of R ² or R ⁵ represents a heteroaryl group. The heteroaryl group may have a substituent. The substituent may be a monovalent substituent described in the above R ² to R ⁵ . When the heteroaryl group represented by R ² and R ⁵ is substituted with two or more substituents, the substituents may be the same or different.

From the viewpoint of firmness, R ² and R ⁵ are preferably a heteroaryl group. Further, when both of R ² and R ⁵ are heteroaryl groups, the structure of the heteroaryl group may be the same or different, but it is more preferably from the viewpoint of synthesizing suitability.

The heteroaryl group is not particularly limited as long as it contains one or more hetero atoms in the ring. For example, a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, a piperidine ring, a pyridine ring, a pyrimidine ring, a triazine ring, and a pyridyl group are mentioned. The azine ring, the oxazine ring and the like are preferably the structures represented by the following formula (Ia).

HetAr ¹ represents a heteroaryl ring. The heteroaryl ring may have one or more substituents. In the case of having a substituent, the substituent may be bonded to at least one of the carbon atoms constituting the heteroaryl ring, and together with the heteroaryl ring form a condensed ring. Further, the wavy line in the structure represented by the general formula (Ia) is bonded to a structure other than "R ² " or "R ⁵ " in the general formula (I).

The heteroaryl ring represented by HetAr ¹ may be any heteroaryl ring containing at least one nitrogen atom. In addition to the nitrogen atom, a hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom may be further included.

The heteroaryl ring represented by HetAr ¹ may be a heteroaryl ring of 5 members, 6 members or 7 members.

Examples of the heteroaryl ring represented by HetAr ¹ include a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, a piperidine ring, a pyridine ring, a pyrimidine ring, and a triazine. The ring, the pyrazine ring and the pyridazine ring are preferably a pyridine ring, a pyrimidine ring, a triazine ring, a thiazole ring, an oxazole ring, an oxadiazole ring or a thiadiazole ring.

The substituent which the heteroaryl ring has may be a monovalent substituent described in the above R ² to R ⁵ .

When the heteroaryl group represented by R ² and R ⁵ is substituted with two or more substituents, the substituents may be the same or different.

In the case of having a substituent, the substituent may be bonded to at least one of the carbon atoms constituting the heteroaryl ring to form a ring of 5 members, 6 members or 7 members.

Further, the ring formed has a saturated ring or an unsaturated ring. Examples of the saturated or unsaturated ring of the 5-, 6- or 7-membered members include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, and a pyrrolidine ring. The piperidine ring, the cyclopentene ring, the cyclohexene ring, the benzene ring, the pyridine ring, the pyrazine ring, and the pyridazine ring are preferably a benzene ring or a pyridine ring.

Further, in the case where the ring of the 5 members, 6 members and 7 members formed is a group which may be further substituted, it may be substituted with the monovalent substituent described in the above R ² to R ⁵ .

The structure represented by the formula (Ia) is preferably a structure represented by any one of the following formulas (Ib) from the viewpoint of synthesizing suitability and heat resistance.

Further, a substituent which is described as a monovalent substituent represented by the above R ² to R ⁵ may be contained at a substitutable position of the heteroaryl ring represented by the above formula (Ib). In the case of having two or more substituents, the substituents may be the same or different.

Further, in the case of having a substituent, the substituent may be bonded to at least one of the carbon atoms constituting the heteroaryl ring to further form a ring of 5 members, 6 members or 7 members.

Further, the ring formed here has a saturated ring or an unsaturated ring. Examples of the saturated or unsaturated ring of the 5-, 6- or 7-membered members include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, and a pyrrolidine ring. The piperidine ring, the cyclopentene ring, the cyclohexene ring, the benzene ring, the pyridine ring, the pyrazine ring, and the pyridazine ring are preferably a benzene ring or a pyridine ring.

Further, in the case where the ring of the 5 members, 6 members and 7 members formed is a group which may be further substituted, it may be substituted with the monovalent substituent described in the above R ² to R ⁵ .

In the formula (I), R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group.

In the case where R ⁷ is a halogen atom, an alkyl group, an aryl group or a heterocyclic group, R ⁷ represents a halogen atom, an alkyl group, an aryl group as illustrated in the substituent represented by the above R ² to R ⁵ or The same groups of the same heterocyclic group have the same preferred ranges.

In the case where the alkyl group, the aryl group or the heterocyclic group represented by R ⁷ in the formula (I) is a group which may be further substituted, the monovalent substituent represented by the above R ² to R ⁵ may be used. Substituted by the illustrated substituents. When the alkyl group, the aryl group or the heterocyclic group represented by R ⁷ is substituted with two or more substituents, the substituents may be the same or different.

Ma in the formula (I) represents a metal atom or a metal compound.

Any of Ma may be a metal atom or a metal compound which can form a complex compound, and may contain a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide or a divalent metal chloride.

Examples of the metal atom represented by Ma include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, and the like.

Examples of the metal compound represented by Ma include metal chlorides such as AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ , and GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si(OH) ₂ .

Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, and the like are preferable from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and manufacturing suitability of the complex. Ni, Co, TiO, B or VO, particularly preferably Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B or VO, most preferably Fe, Zn, Cu, Co, B or VO ( V=O). Among these, Ma is preferably Zn.

In the formula (I), R ⁸ and R ⁹ each independently represent an alkyl group (preferably a linear, branched, or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms). For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, 1,1-dimethylpropyl, hexyl, octyl, 2-ethylhexyl , dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl, etc.), alkenyl (preferably a carbon number of 2 to 24, more preferably an alkenyl group having 2 to 12 carbon atoms, for example Examples thereof include a vinyl group, an allyl group, a 3-buten-1-yl group, and the like, and an aryl group (preferably, an aryl group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms), and examples thereof include benzene. a heterocyclic group of a heterocyclic group (preferably a carbon number of 1 to 24, more preferably a carbon number of 1 to 12), and examples thereof include a 2-thienyl group and a 4-pyridyl group. 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl, etc., alkoxy (preferably) Examples of the alkoxy group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms, are exemplified by methoxy, ethoxy, propoxy, butoxy, hexyloxy and 2-ethylhexyloxy. Base, twelve A oxy group (e.g., a phenoxy group, a naphthyloxy group, etc.), and an aryloxy group (preferably an aryloxy group having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms) And an alkylamino group (preferably an alkylamino group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms), and examples thereof include a methylamino group, an ethylamino group, a propylamino group, and a butyl group. Amino, hexylamino, 2-ethylhexylamino, isopropylamino, tert-butylamino, trioctylamino, cyclohexylamino, N,N-diethylamino, N,N-dipropylamino group, N,N-dibutylamino group, N-methyl-N-ethylamino group, etc.), arylamine group (preferably carbon number 6 to 36, more preferably Examples of the arylamino group having 6 to 18 carbon atoms include a phenylamino group, a naphthylamino group, an N,N-diphenylamino group, an N-ethyl-N-phenylamino group, or the like. a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and examples thereof include 2-aminopyrrole, 3-aminopyrazole, and 2-aminopyridine. , 3-aminopyridinyl, etc.).

In the formula (I), an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amine represented by R ⁸ or R ⁹ In the case where the group is a group which may be further substituted, R ⁸ or R ⁹ may be substituted by the monovalent substituent described in the above R ² to R ⁵ and substituted by two or more monovalent substituents. In the case of these, the substituents may be the same or different.

In the formula (I), X ³ and X ⁴ each independently represent NR ^a (R ^a represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group (alkylcarbonyl group), an alkyl sulfonium group. a base, or an arylsulfonyl), an oxygen atom, or a sulfur atom.

The alkyl group of R ^a includes a linear, branched or cyclic alkyl group, preferably an alkyl group having 1 to 36 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, a dodecyl group, and a cyclopropyl group. Cyclopentyl, cyclohexyl, 1-adamantyl and the like.

The alkenyl group of R ^a is preferably an alkenyl group having 2 to 24 carbon atoms, more preferably an alkenyl group having 2 to 12 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, and a 3-buten-1-yl group.

The aryl group of R ^a is preferably an aryl group having 6 to 36 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms. Specific examples thereof include a phenyl group and a naphthyl group.

The heterocyclic group of R ^a contains at least one hetero atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom as a hetero atom, and preferably a heterocyclic group having 1 to 24 carbon atoms, particularly preferably a carbon number of 1 to 12 Heterocyclic group. Specific examples include 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, and 1-pyrazolyl. , benzotriazol-1-yl and the like.

The mercapto group (alkylcarbonyl group) of R ^a is preferably a mercapto group having an alkyl group having 1 to 24 carbon atoms, more preferably an alkyl group having 2 to 18 carbon atoms. Specific examples thereof include an ethenyl group, a trimethylethenyl group, a 2-ethylhexylcarbonyl group, a benzamidine group, and a cyclohexyl group.

The alkylsulfonyl group of R ^a is preferably an alkylsulfonyl group having 1 to 24 carbon atoms, more preferably an alkylsulfonyl group having 1 to 18 carbon atoms. Specific examples thereof include a methylsulfonyl group, an ethylsulfonyl group, an isopropylsulfonyl group, and a cyclohexylsulfonyl group.

The arylsulfonyl group of R ^a is preferably an arylsulfonyl group having 6 to 24 carbon atoms, more preferably an arylsulfonyl group having 6 to 18 carbon atoms. Specific examples thereof include a phenylsulfonyl group and a naphthylsulfonyl group.

The substitutable position of the alkyl group, alkenyl group, aryl group, heterocyclic group, mercapto group (alkylcarbonyl group), alkylsulfonyl group or arylsulfonyl group represented by R ^a may be substituted with a substituent. Further, the substituent may be substituted by the monovalent substituent described in the above R ² to R ⁵ , and when substituted with a plurality of monovalent substituents, the substituents may be the same or different.

X ³ and X ⁴ are each preferably an oxygen atom or a sulfur atom, and particularly preferably an oxygen atom.

In the formula (I), Y ¹ and Y ² each independently represent NR ^b , an oxygen atom or a sulfur atom, and R ^b has the same meaning as R ^a of NR ^a in the X ³ and X ⁴ .

Y ¹ and Y ² are each independently independently NR ^b , and R ^{b is} preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Y ¹ and Y ^{2 are} particularly preferably NH.

In the formula (I), R ⁸ and Y ¹ may be bonded to each other to form a 5-membered ring together with the carbon atom to which R ⁸ and Y ¹ are bonded (for example, a cyclopentane ring, a pyrrolidine ring, a tetrahydrofuran ring) , a dioxolane ring, a tetrahydrothiophene ring, a pyrrole ring, a furan ring, a thiophene ring, an anthracene ring, a benzofuran ring, a benzothiophene ring, etc.), a 6-membered ring (for example, cyclohexane) Ring, piperidine ring, piperazine ring, morpholine ring, tetrahydropyran ring, dioxane ring, pentamethylene sulfide ring, dithiane ring, benzene ring, piperidine ring, piperazine ring, hydrazine Or a 7-membered ring (for example, a cycloheptane ring or a hexamethyleneimine ring).

In the formula (I), R ⁹ and Y ² may be bonded to each other to form a ring of 5 members, 6 members or 7 members together with the carbon atom. The ring of the five members, the six members, and the seven members formed may be the same ring as the ring formed of R ⁸ , Y ¹ and a carbon atom.

In the formula (I), when R ⁸ and Y ¹ or R ⁹ and Y ^{2 are} bonded to each other, the ring of 5 members, 6 members and 7 members is a ring which may be further substituted, and the R may be passed through the R ^The monovalent substituent described in ² to R ⁵ is substituted, and when substituted with two or more substituents, the monovalent substituents may be the same or different.

In the formula (1), X ⁵ represents a group bondable to Ma, and particularly indicates a group necessary for neutralizing the charge of Ma. For example, it means a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxyl group, and an aliphatic quinone imide (for example, succinimide succinimide, maleimide, pentane quinone) The imine, the diethylamine, and the like are preferably a monovalent group of succinimide succinimide or maleimide, derived from an aromatic quinone imine or a heterocyclic quinone imide (for example). For example, phthalimide, naphthyl imine, 4-bromophthalimide, 4-methylphthalimide, 4-nitrophthalic acid Yttrium imine, naphthalenecarboximidamide, tetrabromophthalimide, etc., preferably phthalimide, 4-bromophthalimide, 4 a monovalent group of -methylphthalic imine) derived from an aromatic carboxylic acid (for example, benzoic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, 4-methoxyl) Benzoic acid, 4-chlorobenzoic acid, 2-naphthoic acid, salicylic acid, 3,4,5-trimethoxybenzoic acid, 4-heptyloxybenzoic acid, 4-third butyl Benzoic acid, etc., preferably benzoic acid, 4-methyl A monovalent group of oxybenzoic acid, salicylic acid, or the like is derived from an aliphatic carboxylic acid (for example, formic acid, acetic acid, acrylic acid, methacrylic acid, ethanoic acid, propionic acid, lactic acid) , trimethylacetic acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid, 2-hexadecyl The octadecanoic acid, 2-hexyl decanoic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 5-norbornene-2-carboxylic acid, 1-adamantanecarboxylic acid, etc., preferably include acetic acid, A monovalent group of methacrylic acid, lactic acid, trimethylacetic acid, 2-ethylhexanoic acid, stearic acid, etc., derived from dithiocarbamic acid (for example, dimethyldithiocarbamate, diethyl ether) A monovalent group of dithilylcarboxylic acid, dibenzyldithiocarbamic acid, derived from a sulfonamide (for example, benzenesulfonamide, 4-chlorobenzenesulfonamide, 4-methoxybenzenesulfonamide) And 4-methylbenzenesulfonamide, 2-methylbenzenesulfonamide, and methanesulfonamide, preferably a monovalent group of benzenesulfonamide or metosulfonamide, derived from hydroxamic acid (For example, acetoxy citrate (acet) Ohydroxamic acid), a monovalent group of octanohydroxamic acid, benzohydroxamic acid, derived from a nitrogen-containing ring compound (for example, hydantoin, 1-benzyl) 5--5-ethoxyethyl carbazide, 1-allyl carbendazim, 5,5-diphenylethylene carbazide, 5,5-dimethyl-2,4-oxazole pyridine Ketone (5,5-dimethyl-2,4-oxazolidine dione), barbituric acid, imidazole, pyrazole, 4,5-dicyanoimidazole, 4,5-dimethylimidazole, benzo Imidazole, diethyl 1H-imidazole-4,5-dicarboxylate, etc., preferably, 1-benzyl-5-ethoxyethyl carbazide, 5,5-dimethyl-2,4- A monovalent group of oxazolidinedione, 4,5-dicyanoimidazole, 1H-imidazole-4,5-dicarboxylate.

X ^{5 is} preferably a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic quinone imine group, an aromatic quinone imine group, a sulfonic acid group, a nitrogen-containing ring compound, more preferably a hydroxyl group or an aliphatic group. A carboxylic acid group, an aromatic quinone imine group, or a nitrogen-containing ring compound.

In the formula (I), a represents 0, 1, or 2.

In the case where a is 2, the two X ^{5 's} may be the same or different.

The metal-missing compound represented by the formula (I) may be a tautomeric compound. The tautomer compound in the present invention means a compound which can be formed by the movement of one hydrogen atom in the molecule, and includes, for example, a structure of the following formula (a) to formula (f).

Further, R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , X ³ , X ⁴ , X ¹ , Y ¹ , Y ^{2 in the} general formula (a) to the general formula (f) And Ma correspond to R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , X ³ , X ⁴ , X ⁵ , Y ¹ , Y ² and Ma in the formula (I).

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Specific examples of the metal-missing compound represented by the formula (I) are shown below. However, the present invention is not limited to these specific examples.

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[Chemistry 13]

[Chemistry 14]

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[Chemistry 16]

The metal-missing compound represented by the formula (I) can be used in the specification of the U.S. Patent No. 4,774,339, the specification of the U.S. Patent No. 5,433,896, the Japanese Patent Laid-Open No. 2001-240761, the Japanese Patent Laid-Open No. 2002-155052, and the Japanese Patent Laid-Open Japanese Patent No. 3,614,586, "Australian Journal of Chemistry, Aust. J. Chem" In 1965, No. 11th, page 1835 - page 1845, JH Boger et al., "Heteroatom Chemistry", Vol. 1, No. 5, p. 389 (1990), etc. synthesis.

Further, the metal-substituted compound represented by the formula (I) can also be obtained from a dipyrromethene compound represented by the following formula, and a metal or a metal compound.

(In the formula, R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent substituent; wherein, preferably, at least one of R ² or R ⁵ represents a heteroaryl group; and R ⁷ represents a hydrogen atom, a halogen atom, Alkyl, aryl or heterocyclic.)

Further, in the formula, R ² ~ R ⁵ and R ⁷ R of the formula (I) described in the same ² ~ R ⁵ and R ⁷ meaning, preferred range, etc. are also the same.

Further, R ¹ and R ⁶ represent a hydrogen atom or a monovalent substituent. The monovalent substituent has the same meaning as the monovalent substituent in R ² to R ⁵ described in the above formula (I), and the preferred range and the like are also the same.

The metal or metal compound has the same meaning as the Ma described in the above formula (I), and the preferred range and the like are also the same.

The method for obtaining a specific metal-substituted compound from the dipyrromethene compound represented by the above formula, and a metal or a metal compound is not particularly limited, and a known method can be used. For example, U.S. Patent No. 4,774,339, U.S. Patent No. 5,433,896, U.S. Patent No. Hei. No. 2001-240761, Japanese Patent Publication No. 2002-155052, Japanese Patent Application Publication No. 2008-076044, and Japanese Patent No. 3614586 No. Specification, "Australian Journal of Chemistry, Aust. J. Chem", 1965, No. 11, No. 1835 - page 1845, JH Boger et al., "Heteroatom Chemistry" The method described in Volume 1, Number 5, page 389 (1990), etc., is synthesized.

Hereinafter, the general formula (II) will be described in detail.

In the formula (II), Z ¹ and Z ² are each independently a group of non-metal atoms necessary for forming a nitrogen-containing heterocyclic ring of 5 or 6 members. The nitrogen-containing heterocyclic ring may also condense other heterocyclic rings, aromatic rings or aliphatic rings.

Examples of the nitrogen-containing heterocyclic ring and the condensed ring thereof include an oxazole ring, an isoxazole ring, a benzoxazole ring, a naphthoxazole ring, an oxazolocarbazole ring, an oxazolodibenzofuran ring, Thiazole ring, benzothiazole ring, naphthylthiazole ring, pseudoanthracene ring, benzofluorene ring, imidazole ring, benzimidazole ring, naphthoimidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring, A furopyrrole ring, a pyridazine ring, an imidazoquinoxaline ring, and a quinoxaline ring. The nitrogen-containing heterocycle is a 5-membered ring superior to the 6-membered ring. More preferably, a benzene ring or a naphthalene ring is condensed in a nitrogen-containing heterocyclic ring of 5 members. More preferably, it is an oxazolocarbazole ring and an oxazolodibenzofuran ring, and the most preferred is an oxazolodibenzofuran ring.

The nitrogen-containing heterocyclic ring and its condensed ring may have a substituent. Examples of the substituent include: a halogen atom, a cyano group, a nitro group, an aliphatic group, an aromatic group, a heterocyclic group, -OR ¹³ , -CO-R ¹⁴ , -CO-OR ¹⁵ , -O-CO-R ¹⁶ , -NR ¹⁷ R ¹⁸ , -NH-CO-R ¹⁹ , -CO-NR ²⁰ R ²¹ , -NH-CO-NR ²² R ²³ , -NH-CO-OR ²⁴ , -SR ²⁵ , -SO ₂ - R ²⁶ , -SO ₂ -OR ²⁷ , -NH-SO ₂ -R ²⁸ and -SO ₂ -NR ²⁹ R ³⁰ . R ¹³ to R ³⁰ are each independently a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Further, in the -CO-OR R ^{15 15} is a hydrogen atom (i.e., a carboxyl group) and the -SO ₂ -OR ²⁷ where R ²⁷ is a hydrogen atom (i.e., a sulfo group), a hydrogen atom may be dissociated, may also be The state of the salt.

In the present specification, the "aliphatic group" means an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group, and also includes a group in which a substitutable position of the group is substituted with a substituent.

The alkyl group may be cyclic or chain. The chain alkyl group may have a branch. The carbon number of the alkyl group is preferably from 1 to 20, particularly preferably from 1 to 12, most preferably from 1 to 8. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, cyclopropyl group, cyclohexyl group, and 2-ethylhexyl group. In the case where the alkyl group has a substituent, the alkyl moiety is the same as the alkyl group. Examples of the substituent of the alkyl group are the same as those of the substituent of the nitrogen-containing heterocyclic ring and the condensed ring thereof (excluding the cyano group, the nitro group and the aliphatic group). In the case where the alkyl group has a substituent, specific examples thereof include, for example, 2-hydroxyethyl, 2-carboxyethyl, 2-methoxyethyl, 2-diethylaminoethyl, 3-sulfonate. Propyl and 4-sulfobutyl.

The alkenyl group may be cyclic or chain-like. The chain alkenyl group may have a branch. The carbon number of the alkenyl group is preferably from 2 to 20, particularly preferably from 2 to 12, most preferably from 2 to 8. Alkenyl example It contains: vinyl, allyl, 1-propenyl, 2-butenyl, 2-pentenyl and 2-hexenyl. In the case where the alkenyl group has a substituent, the alkenyl moiety is the same as the alkenyl group. The substituent of the alkenyl group includes a group exemplified as the substituent of the alkyl group.

The alkynyl group may be cyclic or chain-like. The chain alkynyl group may have a branch. The alkynyl group preferably has a carbon number of 2 to 20, particularly preferably 2 to 12, most preferably 2 to 8. Specific examples of the alkynyl group include, for example, an ethynyl group and a 2-propynyl group. In the case where the alkynyl group has a substituent, the alkynyl moiety is the same as the alkynyl group. The substituent of the alkynyl group includes a group exemplified as a substituent of the alkyl group.

The alkyl portion of the aralkyl group is the same as the alkyl group. The aryl moiety of the aralkyl group contains the same group as the aryl group described later. Specific examples of the aralkyl group include a benzyl group and a phenethyl group. In the case where the aralkyl group has a substituent, the aralkyl moiety is the same as the aralkyl group. In the case where the alkyl moiety of the aralkyl group has a substituent, examples of the substituent include the same groups as the substituent of the alkyl group. In the case where the aryl moiety of the aralkyl group has a substituent, examples of the substituent include the groups exemplified as the substituent of the nitrogen-containing heterocyclic ring and the condensed ring thereof.

In the present specification, the "aromatic group" means a carbocyclic aryl group (hereinafter also referred to simply as "aryl group"), and also includes a group in which a substituted position of an aryl group is substituted with a substituent. The carbon number of the aryl group is preferably from 6 to 25, particularly preferably from 6 to 15, most preferably from 6 to 10. Specific examples of the aryl group include, for example, a phenyl group and a naphthyl group. When the aryl group has a substituent, the substituent includes a group exemplified as the substituent of the nitrogen-containing hetero ring and the condensed ring thereof.

In the present specification, the term "heterocyclic group" means self-contained from an oxygen atom, A group obtained by removing one hydrogen atom from at least one of a nitrogen atom and a sulfur atom and a cyclic compound of a carbon atom and a hydrogen atom, and a group which may be substituted with a substituent at a substituted position.

The heterocyclic group is preferably a group having a cyclic structure of a 5-membered ring or a 6-membered ring. An aliphatic ring, an aromatic ring or other heterocyclic ring may also be condensed in the hetero ring.

Specific examples of the heterocyclic group (including a condensed ring) include, for example, a pyridine ring, a piperidine ring, a furan ring, a furfuran ring, a thiophene ring, a pyrrole ring, a quinoline ring, or the like. Aromatic ring, anthracene ring, imidazole ring, pyrazole ring, indazole ring, phenothiazine ring, phenoxazine ring, porphyrin ring, thiazole ring, pyrazine ring, thiadiazine ring, benzoquinoline ring And a thiadiazole ring. When the heterocyclic group has a substituent, the substituent includes a group exemplified as the substituent of the nitrogen-containing hetero ring and the condensed ring thereof.

In the formula (II), R ¹⁰ and R ¹¹ are each independently an aliphatic group or an aromatic group. The aliphatic group and the aromatic group include a group described as a substituent of the nitrogen-containing hetero ring.

Preferably, R ¹⁰ and R ¹¹ are each an aliphatic group, and among them, an alkyl group having 1 to 4 carbon atoms is particularly preferable. Further, a group in which a terminal of an alkyl group is substituted with a sulfo group is also preferable. In this case, the sulfo group also contains a sulfo group which becomes an alkali metal salt such as a potassium salt.

In the formula (II), L ¹ represents a methine chain containing one, three or five methine groups. The methine chain may have a substituent. The substituent is preferably bonded to the central (median) methine group. Examples of the substituent of the methine chain are the same as those of the substituent of the nitrogen-containing hetero ring and the condensed ring thereof. The two substituents of the methine chain can be bonded to form a 5- or 6-membered ring.

L ^{1 is} preferably a methine chain containing 3 methine groups.

In the formula (II), b, c and d are each independently 0 or 1. Preferably, both b and c are zero.

The cyanine dye (trimethylene cyanine dye or the like) represented by the formula (II) preferably contains at least one substituent selected from the group consisting of a carboxyl group and a sulfo group as a substituent. In this case, the carboxyl group and/or the sulfo group may be a group which becomes an alkali metal salt such as a potassium salt.

In the formula (II), X' ^- is an anion. X' ^- is included in the case necessary to maintain the charge balance of the cyanine dye. Specific examples include, for example, halogen ions (chloride ions, bromide ions, iodide ions), p-toluenesulfonate ions, ethylsulfate ions, PF ₆ ^- , BF ₄ ^-, and ClO ₄ ^- .

Specific examples of the cyanine dye represented by the formula (II) are shown below. However, the invention is not limited to the specific examples.

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In the present invention, the cyanine dye (dye) represented by the formula (II) is a cyanine dye using the J associate. The dye in the associative state exhibits a sharp absorption spectrum peak due to the formation of a so-called J-band. The association of dyes and the J-band are described in detail in the literature (for example, "Photographic Science and Engineering", Vol. 18, No. 323-335 (1974)). The absorption maximum value of the dye in the J-associated state shifts to the longer wavelength side than the absorption maximum value of the dye in the solution state. Therefore, whether the dye contained in the filter layer is in an associated state or a non-associated state can be easily determined by measuring the absorption maximum value.

In the present specification, a state in which the absorption maximum value of the dye having a maximum absorption value is 30 nm or more toward the long wavelength side is referred to as an association state. In the dye in the associative state, the movement of the absorption maximum is preferably 30 nm or more, and particularly preferably 40. Above nm, the optimum is 45 nm or more. Among the dyes are compounds which form an association only by dissolving in water. However, in general, gelatin or a salt (for example, barium chloride, potassium chloride, sodium chloride, calcium chloride) is added to an aqueous solution of the dye to form an associate. Particularly preferred is a method of adding gelatin to an aqueous solution of a dye. The dye association can also be formed as a solid fine particle dispersion of the dye. In order to form a solid fine particle dispersion, a known dispersing machine can be used. Examples of the dispersing machine include a ball mill, a vibrating ball mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill, and a roll mill. The dispersing machine is described in the specification of Japanese Patent Laid-Open No. Sho 52-92716 and International Patent No. 88/074794. A media dispersion machine of a vertical or horizontal type is preferred.

The dispersion can be carried out in the presence of a suitable medium such as water or alcohol. It is preferred to use a surfactant for dispersion. The dispersing surfactant is preferably an anionic surfactant (described in the specification of Japanese Patent Laid-Open No. Sho 52-92716 and International Patent No. 88/074794). An anionic polymer, a nonionic surfactant or a cationic surfactant can be used as needed. After dissolving the dye in a suitable solvent, a poor solvent may be added to obtain a fine particle-like powder. In this case, the dispersing surfactant described above can also be used. Alternatively, it may be dissolved by adjusting the pH, and then the pH may be changed to precipitate the crystallites of the dye. The crystallite is also an association of dyes. In the case where the dye in the associative state is fine particles (or crystallites), the average particle diameter is preferably from 0.01 μm to 10 μm.

Hereinafter, the general formula (III) will be described in detail.

In the formula (III), R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an aryl group having 6 to 8 carbon atoms. U represents N or CH. W and Z each independently represent a group of atoms necessary for forming an aromatic ring. L represents a methine chain containing 3, 5 or 7 methine groups. X ^- represents a counter ion.

Among the compounds, a compound represented by the following formula (IIIa) is particularly preferred.

In the formula (IIIa), R ^4A , R ^4B , R ^5A and R ^5B are an alkyl group, an alkenyl group or an aryl group, and these groups may be the same as or different from each other. L ¹ is a substituted methine group or a trivalent group in which three, five or seven substitutable methine groups are bonded to form a conjugated double bond, and Z ^A and Z ^B are used. An atomic group forming an aromatic ring, X ^- is an anion.

In the above formula (IIIa), Z ^A , Z ^B , L ¹ , R ^4A , R ^4B , R ^5A and R ^5B each may further have a substituent. The substituent in the groups is preferably a substituent in the range of -1.0 to 15 in which the hydrophobic parameter promoted by C. Hansch et al.

Further, the hydrophobicity parameter π can be calculated based on the following documents.

(1) C. Hansch, J. Med. Chem., Vol. 16, p. 1207 (1973)

(2) C. Hansch, Journal of Medicinal Chemistry, Vol. 20, p. 304 (1977)

R ^4A , R ^4B , R ^5A and R ^{5B in} the formula (IIIa) are preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted lower alkyl group having 1 to 8 carbon atoms, Or a substituted or unsubstituted lower alkenyl group having 2 to 8 carbon atoms, and the substituent is preferably in the range of from -1.0 to 15 in the hydrophobic parameter π.

The substituents of R ^4A , R ^4B , R ^5A and R ^5B are preferably a halogen atom (F, Cl, Br, and I, etc.), a substituted or unsubstituted phenyl group (for example, a phenyl group, (m-chlorophenyl and p-methylphenyl), alkylthio (eg methylthio and butylthio), substituted or unsubstituted phenylthio (eg phenylthio, p-chlorophenylthio) And m-methylphenylthio group, and the like, and alkoxy groups (for example, ethoxy group, butoxy group, etc.). R ^4A , R ^4B , R ^5A and R ^{5B are} particularly preferably an unsubstituted alkyl group having 2 to 8 carbon atoms or an unsubstituted alkenyl group having 2 to 8 carbon atoms, and among these groups, the most preferred one is R. ^4A , R ^4B , R ^5A and R ^5B are the same group.

The atomic group represented by Z ^A or Z ^B in the formula (IIIa) is preferably an atomic group for forming a benzene ring, a naphthalene ring or an anthracene ring, and particularly preferably used for forming a benzene ring or a naphthalene ring. Atomic group. Further, Z ^A and Z ^B may have the substituents described as the substituents in the R ^4A , R ^4B , R ^5A or R ^5B . The substituents in Z ^A and Z ^B are preferably: a halogen atom (for example, F, Cl, Br, and I, etc.), a substituted or unsubstituted phenyl group (for example, phenyl, m-chlorophenyl, and para Phenylphenyl, etc., alkylthio (eg methylthio and butylthio), substituted or unsubstituted phenylthio (eg phenylthio, p-chlorophenylthio and m-methylphenylsulfonate) Alkyl, etc., substituted or unsubstituted alkyl (for example: methyl, trifluoromethyl, and tripentyl, etc.), cyano, alkoxycarbonyl (eg, propoxycarbonyl, butoxycarbonyl) , benzyloxycarbonyl, decyloxycarbonyl, 2-ethylhexyloxycarbonyl, etc.) and alkyl or arylsulfonyl (for example, butasulfonyl, phenylsulfonyl and octylsulfonyl) .

The atomic group represented by Z ^A or Z ^B preferably has a Hammett sigma constant of -0.2 to +0.7 to form a benzene having a weak electron supply substituent. The atomic group of the ring, particularly preferably an atomic group for forming a benzene ring substituted with a halogen atom such as F, Cl, Br or I.

Further, L ^{1 is} preferably a trivalent substituted or unsubstituted methine group or a conjugate of three, five or seven substituted or unsubstituted methine groups bonded by a conjugated double bond. The linking group is particularly preferably a group represented by the following formula (L-1) to formula (L-9).

[化35]

Y in the formula (L-1) to the formula (L-9) is a hydrogen atom or a monovalent group. Such a monovalent group is preferably a lower alkyl group such as a methyl group, a substituted or unsubstituted phenyl group, an aralkyl group such as a benzyl group, a lower alkoxy group such as a methoxy group, a dimethylamino group or a diphenyl group. a disubstituted amino group such as an amino group, a methylphenylamino group, a morpholinyl group, an imidazolidinyl group or an ethoxycarbonyl piperazinyl group; an alkylcarbonyloxy group such as an ethoxycarbonyl group; an alkylthio group such as a methylthio group; , a cyano group, a nitro group, and a halogen atom such as F, Cl, or Br.

Among the linking groups represented by L ¹ in the formula (IIIa), the groups represented by the formula (L-1), the formula (L-2), the formula (L-8) and the formula (L-9) are preferred. group.

X ^- in the formula (IIIa) is used to supply a negative charge of a quantity necessary for neutralizing the charge of the cationic moiety, and is a monovalent or divalent anion.

The X ^- is preferably: Cl ^-, Br ^- and I ^- like a halogen _{^{ion, SO 4 2-, HSO 4 -}} , CH 3 OSO 3 - and other alkyl sulfate ion, p-toluenesulfonate ion, naphthalene -1 , 5-disulfonate ion, mesylate ion, triflate ion, octanesulfonate ion, p-chlorobenzoate ion, trifluoroacetate ion, oxalate ion and succinate ion Ions, heteropolyacid ions such as PF ₆ ^- , BF ₄ ^- , ClO ₄ ^- , IO ₄ ^- , tungstate ions, tungsten phosphate ions, phenolate ions such as H ₂ PO ₄ ^- , NO ₃ ^- and picrate ions .

Among these ions, particularly preferred are: halogen ions such as Cl ^- , Br ^- and I ^- , CH ₃ OSO ₃ ^- , C ₂ H ₅ OSO ₃ ^- , p-toluenesulfonate, trifluoromethanesulfonate, p-chloro Perfluoroalkanesulfonate ion such as benzenesulfonate ion, mesylate ion, butanesulfonate ion, naphthalene-1,5-disulfonate ion, trifluoromethanesulfonate ion, PF ₆ ^- , BF ₄ ^- and ClO ₄ ^- Etc.; among these ions, trifluoromethanesulfonate ion, PF ₆ ^- and ClO ₄ ^- are preferable. The best is trifluoromethanesulfonate ion and PF ₆ ^{- in} terms of not worrying about the explosion.

Preferable specific examples of the cyanine dye (imidazoquinoxaline compound, etc.) represented by the above formula (III) or (IIIa) include the compounds shown below, but the present invention is not limited thereto. These compounds.

[化36]

[化37]

[化38]

[39]

[化40]

[化41]

[化42]

[化43]

[化44]

[化45]

[Chem. 46]

[化47]

[48]

The cyanine dye (imidazoquinoxaline compound, etc.) can be easily synthesized, for example, by the method described in the Large Organic Chemistry (Asakura Shoten) Nitrogen-containing Compound, Volume 1, page 432.

Among these compounds, a compound (pigment) having an imidazo(4,5-b) quinoxaline skeleton in particular can be easily synthesized by reference to the method described in U.S. Patent No. 3,431,111.

The specific colored material of the present invention may be contained alone or in combination of two or more.

The optical substrate comprising the specific colored material of the present invention has a maximum absorption wavelength of 580 nm or more and 610 nm or less. Therefore, a colored material which cannot obtain an optical substrate having a maximum absorption wavelength of 580 nm or more and 610 nm or less is contained in the metal complex compound represented by the above formula (I), or In the case of the J-association of the cyanine dye represented by the above formula (II) or the cyanine dye represented by the formula (III), it is also excluded from the specific colored material of the present invention.

The optical substrate of the present invention is preferably a substrate having a maximum absorption wavelength of 580 nm or more and 600 nm or less, and particularly preferably a substrate having a maximum absorption wavelength of 585 nm or more and 595 nm or less.

Further, the optical substrate of the present invention preferably has the following optical characteristics.

(1) The half value width at the maximum absorption wavelength is 80 nm or less, and particularly preferably 50 nm or less.

(2) The absorbance at 450 nm, 550 nm, and 650 nm (also referred to as ε _y , ε _{m ,} and ε _{c , respectively} ) is 5% or less, and particularly preferably 1% or less, with respect to the absorbance at the maximum absorption wavelength (ε _max ).

Specifically, the optical substrate containing the specific colored material of the present invention includes the following aspect: the aspect in which the base body as the support contains a specific colored material; and the base body is different from the base body, and is attached to the base body The layer (for example, the adhesive layer formed on the surface of the base body, the colored layer, the layer sandwiched between the two base bodies, and the like) contains a specific colored material, preferably having a specific content on the base. The aspect of a layer of a particular colored material of colored material.

<base body>

In the case where the specific colored material of the present invention is contained in the base body, the resin constituting the base body is preferably a resin having a transparency as high as possible when it is formed into a sheet or a film, and specifically, poly(p-phenylene terephthalate) Polyethylene terephthalate (PET), polyethersulphone (PES), polyethylene naphthalate, polyarylate, polyether ketone, polycarbonate, polyethylene, polypropylene, nylon 6, etc. A cellulose resin such as a phthalamide, a polyimide or a triethyl fluorenyl cellulose, a fluororesin such as a polyurethane or a polytetrafluoroethylene, a polymer of a vinyl compound such as polyvinyl chloride, or a polyacrylic acid or a poly Acrylate, polyacrylonitrile, addition compound of vinyl compound, polymethacrylic acid, polymethacrylate, polyvinylidene chloride, etc. a vinyl compound polymer, a vinylidene fluoride/trifluoroethylene copolymer, a vinyl compound such as an ethylene/vinyl acetate copolymer or a copolymer of a fluorine compound, a polyether such as polyethylene oxide, or an epoxy resin. Polyvinyl alcohol, polyvinyl butyral, and the like.

A preferred method for containing a specific colored material of the present invention in a resin as a base includes the following methods: (1) a method of kneading a resin with a specific colored material and heat molding; and (2) dispersing in an organic solvent, A method of forming a film by a casting method by dissolving a resin, a monomer which is a raw material of a resin, and a specific colored material, and further polymerizing a monomer when the monomer is used. When the resin is kneaded with a specific colored material, a masterbatch method may be employed in which colored particles obtained by kneading a resin with a specific colored material are prepared in advance, and the colored particles are kneaded with a resin.

In the case of the method of the above (1), a method of adding the specific colored material of the present invention to a powder or granule of a resin, heating to 150 ° C to 350 ° C to dissolve, and further kneading as needed Then, (i) a method of forming a sheet by molding; (ii) a method of forming a film by an extruder; (iii) producing a monolith film by an extruder, and the monolith film is at 30 ° C to 120 A method of forming a film of a desired thickness by stretching uniaxially, biaxially stretching at a temperature of ° C or by appropriately combining the two to 2 to 5 times. Further, an additive which is usually used for resin molding such as a plasticizer may be added during kneading.

The processing conditions at the time of film formation are preferably selected under the optimum conditions depending on the type of the specific colored material, the type of the resin, and the like.

The content of a specific colored material is based on the absorption coefficient of a specific colored material. The thickness of the fabricated optical substrate, the absorption intensity of the target, and the transmission characteristics of the target. Although the transmittance differs depending on the mass of the resin, it is usually 1 ppm to 20% by weight, preferably 1 ppm to 10% by weight, particularly preferably 1 ppm to 5% by weight.

The optical substrate of the present invention has a base material as a support, and has a colored material layer containing a specific colored material of the present invention on the base (hereinafter, the colored material layer is also referred to as a "specific colored material layer"). In the case of the aspect, it is not necessary to use a wider range of basal bodies in terms of the aspect in which the specific colored material of the present invention is contained on the basal body. Further, the thickness of the specific colored material layer is preferably 100 μm or less, preferably 10 μm or less, and particularly preferably 5 μm or less. The lower limit of the thickness is preferably 0.1 μm.

The material constituting such a base body is, for example, a resin, glass, or the like, and is not particularly limited as long as it has transparency of a light transmittance of 40% or more at a wavelength of 400 nm to 700 nm. Specific examples of the resin include polybenzonitrile, polysulfone (PSF), polyether sulfone (PES), polyethylene terephthalate (PET), and polymethylene. Polymethyl methacrylate (PMMA), polycarbonate (PC), polyether ether ketone (PEEK), polypropylene (PP), triacetyl cellulose, TAC) and so on. In particular, acrylic acid resins such as polyethylene terephthalate (PET), triethylenesulfonyl cellulose (TAC), and polymethyl methacrylate (PMMA), and polycarbonate resins have high transparency and mechanical properties. Strength is therefore preferred.

As long as the thickness of the base body can maintain a certain degree of mechanical strength, there is no special Further, it is usually 20 μm to 10 mm, preferably 20 μm to 1 mm, and particularly preferably 20 μm to 200 μm.

<Specific colored material layer>

The specific colored material layer is preferably a colored resin layer containing a specific colored material and a resin as a binder.

The colored resin layer contains an adhesive, and a non-adhesive person. When the colored resin layer is adhesive, the colored resin layer can be used as a function of the adhesive layer.

The adhesive colored resin layer is preferably a composition containing a transparent adhesive as a component other than the specific colored material. The transparent adhesive may be any known one, and examples thereof include an acrylic adhesive, an anthrone adhesive, a urethane adhesive, a polyvinyl butyral (PVB), and an ethylene-acetic acid. A sheet-like or liquid adhesive such as ethylene vinyl acetate (EVA), polyvinyl ether, saturated amorphous polyester or melamine resin.

On the other hand, in the case of a non-adhesive colored resin layer, a colored resin composition containing a specific colored material and a resin used as a general binder is used.

Examples of the resin include an aliphatic ester-based resin, an acrylic resin, a melamine-based resin, a urethane resin, an aromatic ester resin, a polycarbonate resin, an aliphatic polyolefin resin, an aromatic polyolefin resin, and a poly A vinyl resin, a polyvinyl alcohol resin, a polyvinyl-based modified resin (polyvinyl alcohol (PVA), EVA, etc.) or a resin monomer of the copolymerized resin.

A solution obtained by dissolving a colored resin composition in a solvent or a coating liquid as a dispersion liquid is prepared, and the coating liquid is applied onto a base body and dried to form a colored resin layer.

Examples of the solvent include a halogen system, an alcohol system, a ketone system, an ester system, an aliphatic hydrocarbon system, an aromatic hydrocarbon system, an ether solvent, or a solvent mixture system.

The total solid content of the coating liquid forming the colored resin layer is usually suitably from 5% by mass to 90% by mass, more preferably from 10% by mass to 50% by mass.

The content of the specific colored material is usually suitably from 0.01% by mass to 50% by mass, preferably from 0.1% by mass to 10% by mass based on the total solid content of the colored resin layer.

The content of the resin is preferably 10% by mass or more, and preferably 30% by mass or more based on the total solid content of the colored resin layer. The upper limit is set to a range that is different from the specific colored material.

The other method of forming the colored resin layer is also preferably a method in which, for example, a coating method such as a bar coater, a knife coater, a spin coater, a reverse coater, a die coater, or a spray is used, The curable resin composition of the specific colored material of the present invention is applied onto a base body, dried to form a colored curable resin layer, and the colored curable resin layer is cured by, for example, exposure or heating to obtain a colored Resin layer.

As the curable resin composition containing the specific colored material of the present invention, a known curable composition containing a polymerizable compound, a polymerization initiator, a resin as a binder, and an optional solvent may be used.

The content of the resin is preferably from 10% by mass to 50% by mass based on the content of the resin. Contains a polymeric compound.

The thickness of the colored resin layer formed on the base body is suitably 0.5 μm to 10 μm, particularly preferably 1 μm to 5 μm, particularly preferably 1 μm to 3 μm.

The content of the specific colored material contained in the colored resin layer is usually 10 ppm to 30% by weight, preferably 10 ppm to 20% by weight, particularly preferably 10 ppm to 10% by weight based on the total mass of the colored resin layer.

In the present invention, it is preferable to use an optical substrate having a specific coloring material layer on the base, and the specific coloring material layer is preferably a colored photosensitive resin layer obtained by applying and drying the colored photosensitive resin composition. The colored photosensitive resin layer is exposed and cured to obtain a layer.

A component other than the specific colored material in the colored photosensitive resin composition contains a polymerizable compound and a photopolymerization initiator. It is especially preferable to contain a binder such as an alkali-soluble resin, and various additives as needed.

(polymerizable compound)

The colored photosensitive resin composition of the present invention preferably contains at least one polymerizable compound. The polymerizable compound is, for example, a polymerizable compound having at least one ethylenically unsaturated double bond, and can be selected from components constituting a known composition, and the paragraph number [0010] of JP-A-2006-23696 is exemplified. The component described in paragraph number [0020] or the component described in paragraph number [0027] to paragraph number [0053] of JP-A-2006-64921.

Further, a urethane addition polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group is also suitable, as disclosed in Japanese Patent Laid-Open No. 51-37193. The urethane acrylates described in Japanese Patent Application Laid-Open No. Hei. No. Hei. No. 2-26765, Japanese Patent Publication No. Hei 2-16765, or Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. Sho 56 A urethane compound having an oxirane skeleton described in Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 is also preferred.

Other examples include the polyester acrylates described in each of the publications of Japanese Patent Publication No. Sho-49-64183, Japanese Patent Publication No. SHO-49-43191, and Japanese Patent Publication No. Sho 52-30490. A polyfunctional acrylate or methacrylate such as an epoxy acrylate obtained by reacting an epoxy resin with (meth)acrylic acid. Further, it can be introduced as a photocurable monomer and an oligomer in the Japanese Association of Associations, Vol. 20, No. 7, page 300 to page 308 (1984).

Specific examples thereof include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris((meth)propene).醯oxyethyl)isocyanurate, pentaerythritol tetra(meth)acrylate ethylene oxide (EO) modified body, dipentaerythritol hexa(meth)acrylate EO modified body, and the like; Commercially available products include: NK Ester A-TMMT, NK Ester A-TMM-3, NK Oligo UA-32P, NK Oligo UA-7200 ( The above is manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Aronix M-305, Aronix M-306, Aronix M-309, Aronix M- 450, Aronix M-402, TO-1382 (above manufactured by East Asia Synthetic Co., Ltd.), V#802 (Manufactured by Osaka Organic Chemical Industry Co., Ltd.), Kayarad (Kayarad) D-330, Kayarad D-320, Kayarad D-310, Kayarad DPHA (above manufactured by Nippon Kayaku Co., Ltd.), etc. As a preferred example.

These polymerizable compounds may be used singly or in combination of two or more.

The content of the polymerizable compound (the total content in the case of two or more kinds) of the solid content of the coloring photosensitive resin composition is preferably 10% by mass to 80% by mass, more preferably 15% by mass to 75% by mass. , particularly preferably from 20% by mass to 60% by mass.

(photopolymerization initiator)

The colored photosensitive resin composition of the present invention preferably contains at least one photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

The photopolymerization initiator is a compound which initiates light by exposure light and promotes polymerization of a polymerizable compound. It is preferred to induce a polymerization of a polymerizable compound by inducing an actinic ray having a wavelength of 300 nm or more. Further, a photopolymerization initiator which does not directly induce actinic rays having a wavelength of 300 nm or more may be preferably used in combination with a sensitizer.

Specific examples thereof include an oxime ester compound, an organic halogenated compound, an oxadiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxide, an azo compound, a coumarin compound, and a stack. Nitriding , metallocene compound, hexaarylbiimidazole compound, organoboric acid compound, disulfonic acid compound, phosphonium salt compound, mercaptophosphine (oxide), benzophenone compound, acetophenone compound and derivatives thereof and the like.

Among these compounds, a benzophenone compound, an oxime ester compound, and a hexaarylbiimidazole compound are preferable in terms of sensitivity.

Examples of the benzophenone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, and 4-methoxybenzophenone. 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid Or its tetramethyl ester, 4,4'-bis(dialkylamino)benzophenone (for example: 4,4'-bis(dimethylamino)benzophenone, 4,4'- Bis(dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino)benzophenone) , 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethyl The aminoamino acetophenone or the like is preferably 4,4'-bis(diethylamino)benzophenone from the viewpoint of sensitivity.

The oxime ester compound can be used, for example, in Japanese Patent Laid-Open Publication No. 2000-80068, Japanese Patent Laid-Open Publication No. 2001-233842, Japanese Patent Publication No. 2004-534797, International Publication No. 2005/080337, International Publication No. 2006/ Publication No. 018973, Japanese Patent Laid-Open No. 2007-210991, Japanese Patent Laid-Open No. 2007-231000, Japanese Patent Laid-Open No. Hei No. 2007-269779, Japanese Patent Laid-Open No. 2009-191061, and International Publication No. 2009/131189 The compound described in the booklet.

Specific examples include 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)benzene 1,1,2-butanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-pentanedione, 2-(O- Benzyl hydrazino)-1-[4-(phenylthio)phenyl]-1,2-hexanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio) Phenyl]-1,2-heptanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 2-( O-benzylidene hydrazide)-1-[4-(methylphenylthio)phenyl]-1,2-butanedione, 2-(O-benzylidene fluorenyl)-1-[4- (ethylphenylthio)phenyl]-1,2-butanedione, 2-(O-benzylidene fluorenyl)-1-[4-(butylphenylthio)phenyl]-1,2 -butanedione, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1 -(O-acetylhydrazine)-1-[9-methyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1-(O-acetamidine) (肟)-1-[9-propyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1- [9-Ethyl-6-(2-ethylbenzylidenyl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl- 6-(2-butylbenzylidene)-9H-indazol-3-yl]ethanone, 2-(benzylideneoxyimino)-1-[4-(phenylthio)phenyl ]-1-octyl ketone, 2-(ethyloxyimino)-4-(4-chlorophenylthio)-1-[9-ethyl-6 -(2-Methylbenzylidene)-9H-indazol-3-yl]-1-butanone. However, it is not limited to these compounds.

In the present invention, the compound represented by the following formula (1) is also suitable as the quinone compound from the viewpoints of sensitivity, stability over time, and coloration upon post-heating.

In the above formula (1), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer from 0 to 5.

In the general formula (1), R is preferably a mercapto group in terms of high sensitivity, and specifically, an ethylidene group, a propenyl group, a benzamidine group or a tolylmethyl group is preferable.

In the general formula (1), in terms of improving the sensitivity and suppressing the coloring caused by heating over time, A is preferably an unsubstituted alkylene group or an alkyl group (for example, methyl group, ethyl group, Tert-butyl, dodecyl) substituted alkyl, alkyl substituted by alkenyl (eg vinyl, allyl), aryl (eg phenyl, p-tolyl, An alkylene group substituted with xylyl, cumenyl, naphthyl, anthracenyl, phenanthryl, styryl).

In the general formula (1), Ar is preferably a substituted or unsubstituted phenyl group in terms of improving sensitivity and suppressing coloring caused by heating over time. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the general formula (1), X is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, and may have a substituent in terms of solvent solubility and absorption efficiency in a long wavelength region. Alkenyl group, alkynyl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylthio group which may have a substituent, aryl thiooxy which may have a substituent An amine group which may have a substituent.

n in the formula (1) is preferably an integer of 1 to 2.

Specific examples of the organic halogenated compound include: The Bulletin of the Chemical Society of Japan, Bull Chem. Soc. Japan, No. 42, pp. 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. Sho 46-4605, Japanese Patent Laid-Open No. Sho-48-36281, Japanese Patent Laid-Open Publication No. SHO-55-32070, Japanese Patent Laid-Open Publication No. SHO-60-239736, Japanese Patent Laid-Open No. 61-169835, and Japanese Patent Laid-Open No. 61 Japanese Laid-Open Patent Publication No. SHO-62-58241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, and JP-A-63-298339 The compound described in "Journal of Heterocyclic Chemistry" 1 (Phase 3) (1970) of MP Hutt, and the like, in particular, an oxazole compound substituted with a trihalomethyl group, Triazine compound.

Examples of the hexaarylbiimidazole compound include, for example, various compounds described in the respective specifications, such as Japanese Patent Publication No. Hei. 6-29285, U.S. Patent No. 3,479,185, U.S. Patent No. 4,311,783, and U.S. Patent No. 4,622,286. Usable are: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl)-4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis(o-, p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-double (o-chlorophenyl)-4,4',5,5'-tetrakis(m-methoxyphenyl)biimidazole, 2,2'-bis(o-o-o-dichlorophenyl)-4,4 ',5,5'-Tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis ( o-Methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenyl Biimidazole and the like.

The photopolymerization initiator may be used alone or in combination of two or more. another In addition, in the case of using an initiator which does not have absorption at the exposure wavelength, it is necessary to use a sensitizer.

The total content of the photopolymerization initiator is preferably from 0.5% by mass to 30% by mass, more preferably from 2% by mass to 20% by mass, most preferably 5% by mass based on the total solid content of the colored photosensitive resin composition. ~18% by mass. If it is in this range, the sensitivity at the time of exposure is high, and the color image characteristics are also favorable.

(alkali soluble binder)

The alkali-soluble binder is not particularly limited as long as it has alkali solubility, and is preferably selected from the viewpoints of heat resistance, developability, and availability.

The alkali-soluble binder is preferably a linear organic high molecular polymer, and is soluble in an organic solvent, and can be developed by a weak alkali aqueous solution. Examples of such a linear organic polymer include a polymer having a carboxylic acid in a side chain, for example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Publication No. Sho 54-34327, and Japanese Patent Publication No. Sho 58-12577. A methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, and a methacrylic acid copolymer, which are described in each of Japanese Patent Laid-Open Publication No. Sho 59-53836, and Japanese Patent Laid-Open Publication No. 59-71048, A crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer or the like is also useful as an acidic cellulose derivative having a carboxylic acid in a side chain.

In addition to the polymer, the alkali-soluble binder in the present invention may be used, such as an acid anhydride added to a polymer having a hydroxyl group, or a polyhydroxystyrene resin, a polyoxyalkylene resin, or a poly( 2-hydroxyethyl (meth)acrylate), polyvinylpyrrolidone or polyethylene oxide, polyvinyl alcohol, and the like. In addition, linear organic high scores The subpolymer may also be a polymer obtained by copolymerizing a monomer having hydrophilicity. Examples of the examples include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, glycerol (meth)acrylate, (meth)acrylamide, and N-methylolpropene oxime. Amine, 2-stage alkyl acrylamide or 3-grade alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinyl pyrrolidone, N -vinyl caprolactam, vinyl imidazole, vinyl triazole, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid branched or linear propyl ester, (methyl) Acrylic acid branched or linear butyl ester, or phenoxy hydroxypropyl (meth) acrylate. In addition, a hydrophilic monomer may also be used: a tetrahydroindenyl group, a phosphoric acid group, a phosphate group, a 4-stage ammonium salt group, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid group, and a derived therefrom. a monomer such as a salt group or a morpholinoethyl group.

Further, in order to improve the crosslinking efficiency, the alkali-soluble binder may have a polymerizable group in the side chain, and for example, it may be used in the side chain to contain an allyl group, a (meth)acryl group, an allyloxyalkyl group, or the like. Polymers, etc. Examples of the polymer containing the polymerizable group include a commercially available Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (a COOH group-containing polyamine group). Polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.; Viscoat R-264, KS resist 106 (both by Osaka Organic Chemistry) Industrial (stock) manufacturing); Cyclomer P series, Placcel CF200 series (all manufactured by Daicel Chemical industries); Ebecryl 3800 (Daicel Cytec) Manufacturing) and so on. Further, in order to increase the strength of the hardened film, an alcohol-soluble nylon or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin may be used.

Among these various alkali-soluble binders, polyhydroxystyrene resin, polyoxyalkylene resin, acrylic resin, acrylamide resin, acrylic acid/acrylamide copolymerization are preferred from the viewpoint of heat resistance. The resin is preferably an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin from the viewpoint of developability control.

The acrylic resin preferably comprises copolymerization of a monomer selected from the group consisting of benzyl (meth)acrylate, (meth)acrylic acid, hydroxyethyl (meth)acrylate, (meth)acrylamide, and the like. , or the commercial product of the Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), KS Resist -106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P Series, Placcel CF200 series (manufactured by Daicel Chemical Industry Co., Ltd.).

The alkali-soluble binder preferably has a weight average molecular weight (polystyrene-converted value measured by Gel Permeation Chromatography (GPC) method) of 1000 to 2 × from the viewpoints of developability, liquid viscosity, and the like. The polymer of 10 ⁵ is more preferably a polymer of 2000 to 1 × 10 ⁵ , particularly preferably a polymer of 5000 to 5 × 10 ⁴ . They may be used alone or in combination of two or more.

(Organic solvents)

The colored photosensitive resin composition of the present invention may contain an organic solvent.

The organic solvent is basically not particularly limited as long as it satisfies the solubility of each component to be coherent or the coloring of the photosensitive resin composition, and is particularly preferable. It is selected in consideration of the solubility, coatability, and safety of the solid component.

Examples of the organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, and isopropyl butyrate. Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically, methoxy) Methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate, 2-oxopropane Acid alkyl esters, methyl 2-oxo-2-methylpropanoate, ethyl 2-oxo-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetamidine acetate Methyl ester, ethyl acetate ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

Further, examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and the like.

Examples of the ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.

Examples of the aromatic hydrocarbons include, for example, toluene, xylene, and the like.

The organic solvent is preferably mixed in two or more kinds from the viewpoints of the solubility of the components and the solubility of the coating layer in the case of containing an alkali-soluble binder. In this case, it is particularly preferred to comprise a methyl ester selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethylene glycol dimethyl ether. , butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, A mixed solution of two or more kinds of ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

The content of the organic solvent in the coloring photosensitive resin composition is preferably such that the total solid content concentration in the composition is from 5% by mass to 80% by mass, more preferably from 5% by mass to 60% by mass, particularly preferably It is an amount of 10% by mass to 60% by mass.

(sensitizer)

A sensitizer may be added to the colored photosensitive resin composition of the present invention. Typical sensitizers which can be used in the present invention include sensitizers disclosed in Crivello [JV Vrivello, Advances in Polymer Science, Adv. in Polymer Sci, Vol. 62, No. 1 (1984)]. Specific examples include: pyrene, perylene, acridine, thioxanthone, 2-chlorothioxanthone, benzoflavine, N -vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine Derivatives, etc. The sensitizer is preferably added in a proportion of 50% by mass to 200% by mass based on the photopolymerization initiator.

(chain transfer agent)

A chain transfer agent may also be added to the colored photosensitive resin composition of the present invention.

Examples of the chain transfer agent which can be used in the present invention include N,N-dialkylaminobenzoic acid alkyl esters such as N,N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, and 2 -mercaptobenzoxazole, 2-mercaptobenzimidazole, N-phenylmercaptobenzimidazole, 1,3,5-three a fluorenyl compound having a heterocyclic ring such as (3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and pentaerythritol tetrakis(3-indenyl) An aliphatic polyfunctional thiol compound such as butyrate) or 1,4-bis(3-mercaptobutoxy)butane.

The chain transfer agent may be used singly or in combination of two or more.

From the viewpoint of reducing sensitivity unevenness, the amount of the chain transfer agent added is preferably in the range of 0.01% by mass to 15% by mass, more preferably 0.1% by mass to 10% by mass based on the total solid content of the composition of the present invention. %, particularly preferably from 0.5% by mass to 5% by mass.

(polymerization inhibitor)

The colored photosensitive resin composition of the present invention may contain a polymerization inhibitor.

The term "polymerization inhibitor" refers to a substance that performs hydrogen supply (or hydrogen donation) and energy supply to a polymerization starting species such as a radical generated in a colored photosensitive resin composition by light or heat. In combination with (or energy imparting), electron donating (or electron donating), etc., the polymerization starting species are deactivated, and the polymerization is inhibited from starting inadvertently. A polymerization inhibitor or the like described in Paragraph No. [0154] to Paragraph No. [0173] of JP-A-2007-334322 can be used.

Among these, the polymerization inhibitor is preferably p-methoxyphenol.

The content of the polymerization inhibitor in the colored photosensitive resin composition of the present invention is preferably 0.0001% by mass to 5% by mass, more preferably 0.001% by mass to 5% by mass, based on the total mass of the polymerizable compound. 0.001% by mass to 1% by mass.

(surfactant)

The colored photosensitive resin composition of the present invention may contain a surfactant.

The surfactant can be an anionic, cationic, nonionic, or two Any of the preferred surfactants, preferably a surfactant, is a nonionic surfactant. Specifically, a nonionic surfactant described in Paragraph No. [0058] of JP-A-2009-098616 is preferable, and among them, a fluorine-based surfactant is preferable.

Other surfactants which can be used in the present invention are, for example, commercially available products, namely: Megafac F142D, Megafac F172, Megafac F173, Megafac F176, and Megafa ( Megafac) F177, Megafac F183, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781, Megafac ) F781-F, Megafac R30, Megafac R08, Megafac F-472SF, Megafac BL20, Megafac R-61, Megafac R -90 (made by DiCai (DIC)), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431, Novec FC-4430 (made by Sumitomo 3M (share)), Asahi Guard AG7105, Asahi Guard AG7000, Asahi Guard AG950, Asa Asahi Guard AG7600, Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Shaflon (Surflon) S-145, Surflon S-382, Shafu Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Shafu Surflon SC-106 Manufacture of nitrocellulose (Eftop), Eftop EF351, Eftop 352, Eftop 801, Eftop 802 (Mitsubishi Materials) Electronic Chemicals), Ftergent 250 (manufactured by Neos), etc.

Further, as a surfactant, a copolymer comprising a structural unit A represented by the following formula (1) and a constituent unit B, and a tetrahydrofuran as a solvent, by gel permeation chromatography, is exemplified. The polystyrene-equivalent weight average molecular weight (Mw) measured is 1,000 or more and 10,000 or less.

In the formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R ⁴ represents a hydrogen atom or a carbon number of 1 or more and 4 In the following alkyl group, L represents an alkylene group having 3 or more and 6 or less carbon atoms, p and q are weight percentages indicating a polymerization ratio, p is a numerical value of 10% by mass or more and 80% by mass or less, and q is 20% by mass or more. 90% by mass or less, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less.

The L is preferably a branched alkyl group represented by the following formula (2). R ⁵ in the formula (2) represents an alkyl group having 1 or more carbon atoms and 4 or less carbon atoms, and preferably has a carbon number of 1 or more and 3 or less in terms of compatibility and wettability to a surface to be coated. The alkyl group is more preferably an alkyl group having 2 or 3 carbon atoms. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

The weight average molecular weight (Mw) of the copolymer is preferably 1,500 or more and 5,000 or less.

These surfactants may be used alone or in combination of two or more. The amount of the surfactant added to the colored photosensitive resin composition of the present invention is preferably from 0.01% by mass to 2.0% by mass, particularly preferably from 0.02% by mass to 1.0% by mass, based on the solid content. When it is this range, coatability and the uniformity of a cured film become favorable.

(close contact improver)

The colored photosensitive resin composition of the present invention may contain a adhesion improving agent.

The adhesion improving agent is a compound which improves the adhesion between the inorganic substance and the cured film which are, for example, glass, ruthenium, iridium oxide, or tantalum nitride, gold, copper, aluminum, or the like. Specific examples thereof include a decane coupling agent and a thiol compound. The decane coupling agent as the adhesion improving agent is not particularly limited as long as it is interfacially modified, and a known compound can be used.

The decane coupling agent is preferably a decane coupling agent described in Paragraph No. [0048] of JP-A-2009-98616, wherein γ-glycidoxypropyltrialkoxydecane or γ-methyl is more preferable. Propylene methoxypropyl trialkoxy decane. These compounds may be used alone or in combination of two or more.

The content of the adhesion improving agent in the colored photosensitive resin composition of the present invention is preferably from 0.1% by mass to 20% by mass, and more preferably from 0.2% by mass to 5% by mass based on the total solid content.

(crosslinking agent)

In the colored photosensitive resin composition of the present invention, a crosslinking agent may be used in a complementary manner, and the hardness of the colored cured film obtained by curing the colored photosensitive resin composition may be further improved.

The crosslinking agent is not particularly limited as long as it is a crosslinking agent which can be cured by a crosslinking reaction, and examples thereof include (a) an epoxy resin; and (b) a selected from a methylol group and an alkoxy group. a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent of a methyl group and a decyloxymethyl group; (c) selected from a methylol group, an alkoxy group A phenol compound, a naphthol compound or a hydroxy hydrazine compound substituted with at least one substituent in the methoxymethyl group. Among them, a polyfunctional epoxy resin is preferred.

For details of specific examples of the crosslinking agent, etc., the description of paragraph number [0134] to paragraph number [0147] of JP-A-2004-295116 can be referred to.

(other additives)

In the colored photosensitive resin composition of the present invention, it may be blended as needed Various additives thereof include a filler, a polymer compound other than the above, an ultraviolet absorber, an antioxidant, a coagulation preventing agent, and the like. The additives described in Paragraph No. [0155] to Paragraph No. [0156] of JP-A-2004-295116 may be mentioned.

The light-stable photosensitive resin composition of the present invention may contain the light stabilizer described in Paragraph No. [0078] of JP-A-2004-295116, and the thermal polymerization inhibitor described in Paragraph No. [0081] of the above-mentioned publication. .

<Method for Preparing Colored Photosensitive Resin Composition>

The preparation state of the colored photosensitive resin composition of the present invention is not particularly limited, and for example, each component described above, such as a specific colored material, a polymerizable compound, a photopolymerization initiator, and the like may be optionally used. Mix to prepare.

Further, when the colored photosensitive resin composition is prepared, the components contained in the colored photosensitive resin composition may be formulated in total, or the components may be dissolved. Disperse in a solvent and then mix them one by one. In addition, the order of input or the working conditions at the time of preparation are not particularly restricted. For example, all ingredients can be dissolved at the same time. The composition is prepared by dispersing in a solvent, and if necessary, the components may be appropriately prepared into two or more kinds of solutions. The dispersions were mixed to prepare a composition when used (at the time of coating).

Further, in the preparation of the colored photosensitive resin composition of the present invention, it is preferred to mix the components and filter them by a filter for the purpose of removing foreign matter or reducing defects. The filter can be used without any particular limitation in the filter used in the filtration use or the like. Specifically, for example, a fluororesin such as polytetrafluoroethylene (PTFE), nylon-6, nylon-6, 6, etc. may be used. A filter of a polyamide resin such as polyethylene, polypropylene or polypropylene (including a high-density, ultra-high molecular weight resin). Among these filter materials, a nylon-like resin such as nylon-6, nylon-6, 6, or polypropylene (including high-density polypropylene) is preferable.

The pore diameter of the filter is suitably from about 0.01 μm to about 7.0 μm, preferably from about 0.01 μm to about 2.5 μm, and more preferably from about 0.01 μm to about 2.0 μm. By setting it as the range, the fine foreign matter which inhibits the preparation of the uniform coloring photosensitive resin composition can be reliably removed in the subsequent step, and a uniform and smooth colored photosensitive resin composition can be formed.

When using filters, different filters can be combined. In this case, the filtration using the first filter may be performed only once or twice or more. Further, the filters having different pore sizes in the above range may be combined, and the first filter may be a first filter, including a plurality of filters. The aperture referred to here can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, from Pall Corporation, Advantec Toyo Co., Ltd., and Japan's Entegris Co., Ltd. (formerly Japan) Choose from various filters available from Mykrolis Co., Ltd. or Kitz Micro Filter Co., Ltd.

As the second filter, a filter formed of the same material or the like as the first filter can be used.

Further, for example, the filtration by the first filter may be performed only on the pigment dispersion, or the other components may be mixed in the pigment dispersion to form a colored photosensitive resin composition, and then the second filtration may be performed.

The optical substrate of the present invention has optical characteristics of light having a wavelength corresponding to 580 nm or more and 610 nm or less of an intermediate color of red (R) and green (G) contained in light from a light source in a display device. Therefore, by the optical substrate of the present invention disposed on the optical path of the color filter from the light source in the display device, the color purity of the displayed color image is improved.

Hereinafter, a display device in which the optical substrate of the present invention is incorporated will be described.

<display device>

A display device according to the present invention includes a color filter, a light source, and an optical substrate disposed on an optical path from the light source to the color filter by arranging a plurality of colored layers.

As the light source, for example, an edge light type using a light guide plate or a light source of a direct type is used. The light source is configured, for example, by including the following light source. Namely: Cold Cathode Fluorescent Lamp (CCFL), or Flat Fluorescent Lamp (FFL). In addition, a light emitting diode (LED), an electroluminescence (EL), or the like.

Further, in the form in which the quantum dot backlight is used for the blue LED light source, it is more preferable to obtain an effect of suppressing the decrease in luminance and expanding the color reproduction range. The quantum dot has a characteristic that, for example, a semiconductor material (CdS/ZnS) is formed into a crystal having a size of several nanometers, and has optical mechanical properties, absorbs electrons or photons, and emits a prescribed crystal size with high efficiency. The wavelength of light (ultraviolet (UV), visible light, far infrared). The quantum dots are used for red and green photoluminescent materials, combined with blue LED light sources for LCD backlighting Source, thereby increasing the range of color reproduction.

Further, in addition to the above, the light source may be provided with a reflection plate for diffusing the light returned from the liquid crystal display panel side and using it again as display light (recycling).

Preferably, a diffuser plate is disposed between the light source and the color filter. The diffusing plate has a function of diffusing the light of the light source to keep the brightness in the in-plane direction uniform.

The color filter is composed of at least three regions including a red region in which only one pixel transmits red (R), a green region that transmits only green (G), and a blue region that transmits only blue (B). For example, in the case of a color filter of 1768 × 1029 pixels, the pixel is arranged in a close arrangement of 1768 in the lateral direction and 1029 in the vertical direction.

For example, in the case of a liquid crystal display device, the display device includes a liquid crystal display panel and a backlight unit, and the light source is included in the backlight unit, and the color filter is included in the liquid crystal display panel, and the light from the light source included in the backlight unit It is guided to the liquid crystal display panel, and light passing through the liquid crystal display panel is observed as an image on the display panel.

In the present invention, the optical substrate of the present invention is disposed on the optical path of the light from the light source reaching the color filter. Thereby, light of a wavelength of 580 nm or more and 610 nm or less corresponding to an intermediate color of red (R) and green (G) contained in the light emitted from the light source is absorbed by the optical substrate. Therefore, the light reaching the color filter does not substantially include the light having a wavelength of 580 nm or more and 610 nm or less, and thus the color purity of the image displayed on the liquid crystal display panel is improved.

Therefore, the optical substrate can be disposed at any position as long as the light emitted from the light source reaches the color filter as long as it passes through the position of the optical substrate of the present invention.

The particularly preferable arrangement position of the optical substrate of the present invention includes, for example, a liquid crystal display panel between a liquid crystal display panel and a backlight unit in a liquid crystal display device, between a light source and a diffusion plate in a backlight unit, and a diffusion plate in a backlight unit. Side surface, etc.

In addition, the definition of the display device or the details of each display device is described in, for example, "Electronic display device (sasaki Sasaki, Industrial Research Association (share) issued in 1990)", "Display device (Ibuki Shunzhang, Industrial Book ( Shares) issued in 1989) and so on. In addition, the liquid crystal display device is described in, for example, "Next-Generation Liquid Crystal Display Technology (Editor Uchida Natsuo, Industrial Research Association, Ltd., 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited, and can be applied to, for example, a plurality of types of liquid crystal display devices described in the "Next Liquid Crystal Display Technology".

A liquid crystal display device of a thin film transistor (TFT) type is described, for example, in "Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., 1996)". Further, the optical substrate of the present invention can also be applied to a viewing angle expansion method such as a horizontal electric field driving method such as In Plane Switching (IPS) or a pixel division method such as Multi-Domain Vertical Alignment (MVA). Liquid crystal display device, or Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optically Compensated Splay (OCS), fringe field Fringe Field Switching (FFS) and Reflective Optically Compensated Bend (R-OCB) Wait.

The liquid crystal display device includes a plurality of members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film. These components are described, for example, in '94 Liquid Crystal Display Peripherals, Chemical Markets (Shima Kotaro, CMC (Shares) 1994), and 2003 Liquid Crystal Related Markets and Future Outlook (Vol. 2) , Fuji Chimera Research Institute (shares), issued in 2003).

The backlight is described in "Secondary Imagery Dissemination meeting Digest (SID meeting Digest)", 1380 (2005) (A. Konno et al.), or monthly display, December 2005. From the 18th to the 24th (Island Kangyu), the monthly display of the December 2005 issue, page 25 to page 30 (Yumu Longming).

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples as long as the scope of the invention is not exceeded. In addition, "parts" and "%" are quality standards unless otherwise stated.

<Manufacture of resist solution>

Each component shown below was blended in the following ratio, and stirred by a stirrer until each component was completely dissolved, and a resist solution was obtained.

<Production of red pixels>

75 parts of propylene glycol monomethyl ether acetate, 17 parts of red pigment: PR254, dispersant (made by Lubrizol Co., Ltd., Solsperse 5500), 8 parts, using a mixer After stirring for 3 hours, a mill base having a solid concentration of 25% was prepared. To the paste, 600 parts of 0.5 mmφ zirconia beads were used, and a dispersion treatment was carried out by using a bead mill at a peripheral speed of 10 m/s and a residence time of 3 hours to obtain a dispersed ink of P.R. 254.

Further, a color paste was prepared in the same composition as the dispersion ink of the PR254 except that the pigment was changed to PR177, and the dispersion treatment was carried out for 2 hours under the same dispersion conditions to obtain a dispersion ink of PR177. .

The two kinds of dispersion inks obtained in the above manner were mixed in such a manner that the mass ratio of PR254:PR177 was 48:52, and 25 parts of the obtained mixed dispersion ink was mixed with 17.5 parts of the resist solution, and stirred. A solvent (propylene glycol monomethyl ether acetate) was added so that the final solid content concentration became 18%, and a red resist composition was obtained.

The obtained red resist composition was applied to a glass substrate of 10 cm × 10 cm (Corning 1737 by Corning Co., Ltd.) by a spin coater so that the dry film thickness was 2.0 μm. On, and dry. The entire surface of the substrate was irradiated with ultraviolet rays of 100 mJ/cm ² , developed with an alkali developing solution, and post-baked in an oven at 230 ° C for 30 minutes to prepare a red pixel sample for measurement.

<Production of green pixels>

A color paste was prepared in the same manner as in the preparation method of the dispersion ink of the PR254 except that the pigment was changed to PG58, and the dispersion treatment was carried out for 1 hour using the same dispersion conditions to obtain a dispersion ink of PG58. .

Further, a color paste was prepared in the same composition as that of the dispersed ink of P.R. 254 except that the pigment was changed to P.Y. 150, and the dispersion treatment was carried out for 2 hours under the same dispersion conditions to obtain a dispersed ink of P.Y.

The two kinds of dispersion inks obtained in the above manner were mixed in such a manner that the mass ratio of PG58:PY150 was 87:23, and 25 parts of the obtained mixed ink was mixed with 12.8 parts of the resist solution, and stirred. A solvent (propylene glycol monomethyl ether acetate) was added so that the final solid content concentration became 18% by weight to obtain a green resist composition.

The obtained green resist composition was applied to a glass substrate of 10 cm × 10 cm (Corning Co., Ltd., "Corning 1737") by a spin coater so that the dry film thickness was 2.0 μm. On, and dry. The whole surface of the substrate was irradiated with ultraviolet rays of 100 mJ/cm ² , developed with an alkali developing solution, and post-baked in an oven at 230 ° C for 30 minutes to prepare a green pixel sample for measurement.

<Production of blue pixels>

A color paste was prepared in the same composition as the dispersed ink of PR254 except that the pigment was changed to PB15:6, and the dispersion treatment was carried out for 1 hour using the same dispersion conditions to obtain a dispersion ink of PB15:6. .

Further, a color paste was prepared in the same composition as that of the dispersed ink of P.R. 254 except that the pigment was changed to P.V.23, and the dispersion treatment was carried out for 2 hours under the same dispersion conditions to obtain a dispersed ink of P.V.23.

The two dispersion inks obtained in the manner described above were mixed in such a manner that the mass ratio of PB15:6 and PV23 was the former: the ratio of the latter was 44:55, and the obtained mixed ink was 25 parts with the anti- 31.7 parts of the etchant solution was mixed and stirred, and a solvent (propylene glycol monomethyl ether acetate) was added so that the final solid content concentration was 18 weight%, and the blue resist composition was obtained.

The obtained blue resist composition was applied to a 10 cm × 10 cm glass substrate (Corning 1737, manufactured by Corning Co., Ltd.) by a spin coater so that the dried film thickness was 2.0 μm. ), and dry. The entire surface of the substrate was irradiated with ultraviolet rays of 100 mJ/cm ² , developed with an alkali developing solution, and post-baked in an oven at 230 ° C for 30 minutes to prepare a blue pixel sample for measurement.

(Example 1) Preparation of an optical substrate comprising the exemplified compound (C-16)

The exemplified compound (C-16) was added as a specific colored material to the resist solution so as to be 1.2% with respect to the solid content of the resist solution, and was applied to the resist solution by a die coater. The polyethylene terephthalate film (manufactured by Teijin Co., Ltd., thickness: 35 μm) was dried, irradiated with ultraviolet rays of 100 mJ/cm ² , and then dried by hot air to prepare the optical substrate 1 of the present invention.

(Example 2) Preparation of an optical substrate comprising the exemplified compound (C-20)

The optical substrate 2 of the present invention is produced in the same manner as the preparation of the optical substrate 1, except that the exemplified compound (C-20) is used instead of the exemplified compound (C-16).

(Example 3) Preparation of an optical substrate comprising the exemplified compound (C-21)

The optical substrate 3 of the present invention was produced in the same manner as the preparation of the optical substrate 1, except that the exemplified compound (C-21) was used instead of the exemplified compound (C-16).

(Example 4) Preparation of optical substrate comprising the exemplified compound (A-10)

The optical substrate 4 of the present invention is produced in the same manner as the preparation of the optical substrate 1, except that the exemplified compound (A-16) is used instead of the exemplified compound (C-16).

(Example 5) Preparation of optical substrate comprising the exemplified compound (II-2)

The optical substrate 5 of the present invention is produced in the same manner as the preparation of the optical substrate 1, except that the J-association of the exemplified compound (II-2) is used instead of the exemplified compound (C-16).

(Example 6) Preparation of optical substrate comprising the exemplified compound (III-29)

The optical substrate 6 of the present invention is produced in the same manner as the preparation of the optical substrate 1, except that the exemplified compound (III-16) is used instead of the exemplified compound (C-16).

(Comparative Example 1) Preparation of Optical Substrate Containing Tetraazaporphyrin Compound

The optical substrate C1 of the comparative example was produced in the same manner as the preparation of the optical substrate 1, except that TAP-18 (Yamada Chemical Co., Ltd.) as a porphyrazine compound was used instead of the exemplified compound (C-16). .

(Comparative Example 2) Preparation of Optical Substrate Containing Tetraazaporphyrin Compound

The optical substrate C2 of the comparative example was produced in the same manner as the preparation of the optical substrate 1, except that TAP-2 (Yamada Chemical Co., Ltd.) as a porphyrazine compound was used instead of the exemplified compound (C-16). .

The spectral absorption characteristics of the optical base material 1 to the optical base material 6, the optical base material C1, and the optical base material C2 produced as described above were measured by a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation). The spectral transmittance spectrum of each optical substrate is shown in FIG. 1 in the spectral transmittance spectrum of the optical substrate 1 to the optical substrate 4, and the optical substrate 5, the optical substrate 6, the optical substrate C1, and the optical base are shown. The spectral transmittance spectrum of the material C2 is shown in Fig. 2. The numbers on the curves in Fig. 1 and Fig. 2 correspond to the numbers of the optical substrates.

(Examples 7 to 10, and Comparative Examples 3 to 5)

The LED-B+Y fluorescent backlight is illuminated at high frequency via an inverter ("HIU-742A" manufactured by Harison Toshiba Lighting Co., Ltd.). The "BM-5" manufactured by Topcon Corporation was used to measure the luminescence spectrum of the backlight. The measurement result (the spectral contrast luminance spectrum) is shown as a curve LED-BL in FIG.

Then, the red pixel sample, the green pixel sample, and the blue pixel sample are respectively attached to a backlight that is illuminated in a high frequency in the same manner as described above, and the light luminance measuring device is used. "BM5A" manufactured by Topcon Corporation to measure the respective chromaticity and spectral characteristics. The measurement results are as follows.

. Red pixel: x=0.640, y=0.326

. Green pixel: x=0.299, y=0.613

. Blue pixel: x=0.153, y=0.047

An optical substrate selected from the optical substrate 1 to the optical substrate 6, the comparative example C1, and the comparative example C2 of the present invention is attached to the backlight, and the red pixel sample is attached thereto, The green pixel sample and the blue pixel sample were measured for their respective chromaticities and brightness by a lightness measuring device ("BM5A" manufactured by Topcon Corporation). The results are shown in FIGS. 3 and 4. Further, in the correspondence shown in the graphs in FIG. 3 and FIG. 4, the numbers described after the * marks correspond to the numbers of the attached optical substrates.

In the actual display element, the data is red monochrome, green monochrome, and blue monochrome in the liquid crystal display element in which the backlight and the color filter are combined, except that the brightness is about 1/3. The state of light emission is equivalent, and the color reproduction range of the liquid crystal display element (National Television System Committee (NTSC) ratio) is calculated based on this.

The results are shown in Table 1.

As shown in the results of Table 1, the backlight confirmed color reproduction ratio of any of the optical substrate 1 to the optical substrate 6 to which the present invention was attached was improved. In particular, it is found that the maximum absorption wavelength is 580 nm or more and 610 nm or less as compared with the backlight of the optical substrate C1 and the optical substrate C2 which are comparative examples of the porphyrazine coloring matter (TAP2 or TAP18). The optical substrate 1 to the optical substrate 6 of the colored material not only maintain good brightness but also have high color reproduction rate. The reason for this is that the absorption spectrum of the porphyrazine coloring matter of the colored material used in the optical base material C1 and the optical base material C2 is wide in the vicinity of the wavelength range of 580 nm or more and 610 nm or less, and therefore absorbs the original desired transmission. In contrast, the color material used in the optical substrate 1 to the optical substrate 6 has a sharp absorption spectrum (half-value width narrow) at a wavelength of 580 nm or more and 610 nm or less. Light that was originally intended to be transmitted Less absorption.

Claims (9)

An optical substrate disposed in a display device including a color filter and a light source configured by arranging a plurality of color-colored layers in a two-dimensional direction, from the light source to the color filter In the optical path, the optical substrate contains a J-association compound selected from the group consisting of a metal-defect compound represented by the following formula (I), a cyanine dye represented by the following formula (II), and the following At least one colored material in the group consisting of the cyanine dye represented by the formula (III), and having a maximum absorption wavelength of 580 nm or more and 610 nm or less. (In the formula (I), R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent substituent; and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic ring. And R ⁸ and R ⁹ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amine group; a metal atom or a metal compound; X ³ and X ⁴ each independently represent NR ^a (R ^a represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an aryl sulfonate) a mercapto group, an oxygen atom, or a sulfur atom; Y ¹ and Y ² each independently represent NR ^b (R ^b represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an anthracenyl group, an alkylsulfonyl group) Or an arylsulfonyl group, an oxygen atom, or a sulfur atom; X ⁵ represents a group bondable to Ma; a represents 0, 1 or 2; and R ⁸ and Y ¹ may be bonded to each other to form a 5-member, Ring of 6 or 7 members, R ⁹ and Y ² can be bonded to each other to form a ring of 5, 6 or 7 members) (In the formula (II), Z ¹ and Z ² each independently represent a group of non-metal atoms necessary for forming a nitrogen-containing heterocyclic ring of 5 or 6 members of the condensable ring; R ¹⁰ and R ¹¹ respectively Independently represents an aliphatic group; L ¹ represents a methine chain containing 1, 3 or 5 methine groups; X' ^- represents an anion; and b, c and d each independently represent 0 or 1) (In the formula (III), R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an aryl group having 6 to 8 carbon atoms; U represents N or CH; W and Z each independently represent a group of atoms necessary for forming an aromatic ring; L represents a methine chain containing 3, 5 or 7 methine groups; X ^- represents Counter ion). The optical substrate according to claim 1, which comprises at least one colored material selected from the group consisting of the metal-defective compounds represented by the above formula (I) as the colored material. The optical substrate according to claim 2, wherein in the general formula (I), R ² and R ⁵ represent a heteroaryl group. The optical substrate according to claim 3, wherein the heteroaryl group is represented by the following formula (Ia), (In the formula (Ia), HetAr ¹ represents a heteroaryl ring). The optical substrate according to claim 2, wherein in the formula (I), R ³ and R ⁴ each independently represent an alkyl group or an aryl group, and Y ¹ and Y ² represent NH, X ³ And X ⁴ represents an oxygen atom, R ⁸ and R ⁹ represent an alkyl group, and Ma represents a metal atom. The optical substrate according to claim 1, comprising a layer formed of the at least one colored material, a polymerizable compound having an ethylenically unsaturated group, and light. Polymerization initiator. A display device comprising: a color filter formed by arranging a multi-colored coloring layer; a light source; and the optical substrate according to any one of claims 1 to 6 The optical substrate is disposed on an optical path from the light source to the color filter. The display device according to claim 7, wherein the optical substrate is also a diffusion film. The display device according to claim 7, wherein the optical substrate is also an adhesive layer.