JP2018163284A - Green photosensitive coloring composition for organic el display device, color filter, and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter that can attain a high brightness and a high purity at the same time in an organic EL display device using a white light emission organic EL element as a light source, and to provide a coloring component for a color filter excellent in the resistance to chemicals, and a color filter using the coloring composition.SOLUTION: The above object is achieved by inclusion of a green photosensitive coloring composition containing a phthalocyanine pigment expressed by a general formula (1), C.I. pigment yellow 185, and a specific photopolymerization initiator.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a green photosensitive coloring composition for an organic EL display device, a color filter, and a color display device which are preferably used in a color display device using a white color-emitting organic EL (electroluminescence). White means a broad concept including pseudo white.

Examples of color display devices using color filters include (i) a backlight as a light source, a liquid crystal as an optical shutter, and a combination of color filters having color adjustment functions (color conversion function, color separation function, color correction function, etc.) And (ii) a synthetic white organic EL light source, and an organic EL display device comprising a combination of color filters having a color adjustment function (color conversion function, color separation function, color correction function, etc.).

  Currently, liquid crystal displays (i) are the mainstream for flat panel displays. Due to the advantages of low power consumption and space saving, there are various types of monitors such as personal computer monitors, mobile phone displays, notebook personal computers, and personal digital assistants. In recent years, it has been used for liquid crystal televisions instead of conventional CRT televisions. For LCD TV applications, color reproducibility is important. The color reproducibility of the color liquid crystal display device is determined by the color of light emitted from the red, green, and blue filter segments, and the chromaticity points of the respective filter segments are (xR, yR), (xG, yG), When (xB, yB), the standard three primary colors, red, evaluated by the area of the triangle surrounded by these three points on the xy chromaticity diagram and defined by the US National Television System Committee (NTSC) (0.67, 0.33), ratio to the area surrounded by green (0.21, 0.71), blue (0.14, 0.08) (unit:%, hereinafter abbreviated as NTSC ratio) Expressed. This value is 40 to 100% for a general notebook computer, 50 to 100% for a monitor for a personal computer, and 70% to 100% for a liquid crystal television.

  As the backlight in the liquid crystal display device of (i), a cold cathode tube type backlight, a two-wavelength peak pseudo-white backlight and a three-wavelength peak backlight using a light emitting diode or an organic EL element using an inorganic material. and so on. In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The VA mode, the IPS mode, etc., and the type using a TN (twisted nematic) mode type liquid crystal is the mainstream. However, these liquid crystal display devices have a problem that energy is wasted because the backlight unit continues to emit the same light as white display even in black display.

  On the other hand, as a synthetic white light source of the organic EL display device of (ii), there are a light source having a two-wavelength peak, a light source having a three-wavelength peak, and a light source having many peaks in the visible light region, and an organic EL that emits light in each color. Synthetic white light is obtained by mixing or layering materials.

Since the organic EL display device can directly turn on / off the light source of the pixel by a TFT (thin film transistor) or the like, it is possible to perform black display by turning off the light emission of the designated pixel. Therefore, the deflecting plate used in the liquid crystal display device is not required in the light emitting device, and it is not necessary to control the liquid crystal body. For this reason, the amount of transmitted light in the display device increases, and energy consumption can be greatly reduced by turning off the light emitting device in black display. In addition, it is possible to reproduce true dark black, and the contrast ratio can be increased. As an organic EL color display device in which the problems in the liquid crystal display device are solved, for example, a product such as “XEL-1” manufactured by SONY is already on the market. (For example, see Patent Document 1)

  However, a light emitting device using such an organic EL element has a light emission spectrum different from that of a conventionally used light source. For example, a conventional light source has a peak in the vicinity of 420 to 430 nm, but a light source using an organic EL element has no peak in the vicinity of 420 to 430 nm due to the characteristics of the material, and has a peak in the vicinity of 460 nm. In addition, the emission spectrum of the light source using the organic EL element has a broad peak as compared with the conventional light source, and therefore, even after passing the peak around 460 nm, the conventional light source reaches about 500 nm. The spectrum is higher. For these reasons, currently used color filters cannot be used as they are in display devices using light sources using organic EL elements. For this reason, it is necessary to select and develop a color filter material that can be used for a light source using an organic EL element and has an optimum hue and transmittance characteristics.

  An organic EL display device having such a light source is also required to have a high NTSC ratio, as in a liquid crystal display device. In order to increase the NTSC ratio, it is necessary to increase the color purity of each filter segment. However, if the color purity is increased, the light use efficiency (represented by the brightness Y value) of the light source is decreased. There is a problem that increases.

  In order to improve the color reproduction characteristics of the color filter, it is necessary to increase the content of the colorant in the photosensitive coloring composition or to increase the film thickness. In the method of increasing the content of the colorant, the development characteristics, pattern shape, and alignment film solvent N-methyl-pyrrolidone (NMP) are deteriorated due to a decrease in the resin and photopolymerizable compound as the curing material. Problems such as deterioration of chemical resistance occur. Further, in the method of increasing the film thickness, the exposure light does not reach the bottom of the film, and a significant curing problem such as a decrease in chemical resistance is likely to occur due to a defective pattern shape or the presence of an uncured part. Furthermore, since there is an increasing demand for thinner color display devices and there is a tendency to reduce the film thickness, in a photosensitive coloring composition containing a colorant at a high concentration, the pigment has a high coloring power. There is a demand for improved dyes, developability, improved shape, and improved chemical resistance.

  Regarding the coloring composition for the green color filter segment, it is common to use various phthalocyanine compounds, and in particular, there have been many proposals for color filters for color filters using copper phthalocyanine compounds and zinc phthalocyanine compounds. Yes. In order to achieve high brightness with the phthalocyanine compound, it is necessary to precisely control the absorption wavelength of the phthalocyanine compound itself and the absorption wavelength / absorbance derived from the aggregate formed at the time of coating. , A method of changing the central metal species, and a method of introducing a functional group into the phthalocyanine ring.

For example, Patent Document 2 proposes a color filter composition using a halogenated phthalocyanine compound substituted with at least four halogen atoms.

Further, in Patent Document 3, as a green pigment, a copper halide phthalocyanine pigment and a central metal are selected from the group consisting of Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Zn, Ge, and Sn. There has been proposed a color filter composition comprising a green colorant comprising at least one kind of halogenated dissimilar metal phthalocyanine pigment.

  Patent Document 4 discloses a technique in which an aluminum phthalocyanine pigment is used as a main pigment, high brightness is obtained with high chromaticity even with a relatively small content, and both color density and color purity are achieved.

  As the aluminum phthalocyanine pigment, in addition to the monomer aluminum phthalocyanine pigment described in Patent Document 4, in Patent Document 5, bis (phthalocyanylalumino) tetraphenyl obtained by dimerizing an aluminum phthalocyanine pigment with diphenylchlorosilane is used. Bis (phthalocyanylaluminum) phenylphosphonate pigments dimerized with disiloxane pigments or phenylphosphonic acid are disclosed.

  Patent Document 6 improves NMP resistance by using a thermoplastic resin and an epoxy compound in addition to the aluminum phthalocyanine pigment.

  However, in the pigment composition containing these aluminum phthalocyanine compounds, the lightness, coloring power and NMP resistance are insufficient in the photosensitive coloring composition containing the colorant at a high concentration.

Japanese Patent Laid-Open No. 2005-10091 JP 2002-131521 A JP 2002-250812 A JP 2004-333817 A Japanese Unexamined Patent Publication No. 57-90058 JP 2006-075837 A

  An object of the present invention is to provide a color filter that can satisfy two characteristics of high brightness and high purity in an organic EL display device using a white light-emitting organic EL element as a light source. Furthermore, it aims at providing the coloring composition for color filters excellent also in chemical resistance, and a color filter using the same.

As a result of intensive studies to solve the above problems, the present inventors have found that a phthalocyanine pigment represented by the following general formula (1), C.I. I. It has been found that the above-mentioned problems can be solved by including a green coloring composition containing CI Pigment Yellow 185 and a specific photopolymerization initiator.

General formula (1)

(In the formula, X represents a halogen atom, and n represents an integer of 1 to 16. However, the average value of the number of substitutions of the halogen atom represented by X is 1 to 15, and the halogen distribution width is And Y represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ , wherein R ₁ and R ₂ are each independently selected. In addition, a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent or an aryloxy which may have a substituent R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. R ₄ represents a hydroxyl group, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Represents a heterocyclic group which may have a reel group or a substituent.)

That is, the present invention is a photosensitive coloring composition for an organic EL display device comprising a colorant (A), a binder resin, a photopolymerizable monomer (B) and a photopolymerizable initiator (C), Agent (A) is a phthalocyanine pigment represented by the following general formula (1); I. And a photopolymerizable initiator (C) containing an oxime ester-based compound (C1).

General formula (1)

(In the formula, X represents a halogen atom, and n represents an integer of 1 to 16. However, the average value of the number of substitutions of the halogen atom represented by X is 1 to 15, and the halogen distribution width is And Y represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ , wherein R ₁ and R ₂ are each independently selected. In addition, a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent or an aryloxy which may have a substituent R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. R ₄ represents a hydroxyl group, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Represents a heterocyclic group which may have a reel group or a substituent.)

The present invention also relates to the green photosensitive coloring composition for an organic EL display device, wherein the phthalocyanine pigment represented by the general formula (1) is a phthalocyanine pigment represented by the general formula (2).

General formula (2)

(In the formula, X ₁ represents a halogen atom, and n represents an integer of ₁ to 16. However, the average value of the number of substitutions of the halogen atom represented by X ₁ is 1 or more and less than 6, The distribution width is not less than 2. Y represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ , where R ₁ and R ₂ are Each independently has a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent or a substituent. R ₃ represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent or a substituent. .R ₄ where represents a heterocyclic group which may have a represents a hydroxyl group, an optionally substituted alkyl group, which may have a substituent Have a have an aryl group or a substituted group represents a heterocyclic group.)

  In the present invention, the content of the colorant (A) is 40% by weight or more in 100% by weight of the total solid content of the green photosensitive coloring composition. Relates to the composition.

  Further, the present invention relates to the green photosensitive coloring composition for organic EL display device, wherein the photopolymerizable monomer (B) of the present invention contains a polyfunctional urethane acrylate (B1).

Furthermore, in the color filter for an organic EL display device comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, at least one green filter segment is green sensitive for the organic EL display device. The present invention relates to a color filter for an organic EL display device formed of a coloring composition.

The present invention also relates to an organic EL display device comprising the color filter for an organic EL display device and a white organic EL light source.

The white organic EL light source has peak wavelengths (λ ₁ ) and (λ ₂ ) at which the emission intensity becomes maximum in at least the wavelength range of 430 nm to 485 nm and the wavelength range of 560 nm to 620 nm, and the emission intensity I at the wavelength λ ₁ . _The organic EL display device having an emission spectrum in which a ratio (I ₂ / I ₁ ) of emission intensity I ₂ at ₁ and wavelength λ ₂ is 0.4 or more and 0.9 or less.

  By the green photosensitive coloring composition for organic EL display devices of the present invention, a color filter for organic EL display devices that can satisfy high brightness and high coloring power can be obtained. Furthermore, a coloring composition with good chemical resistance can be obtained by a combination with a specific material.

It is an example of the emission spectrum of a white organic EL light source (EL-1)

Hereinafter, the present invention will be described in detail.
In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly described, Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. It shall represent.
Further, “CI” in this specification means a color index (CI).

First, the green photosensitive coloring composition for organic EL display devices of the present invention will be described.
The green photosensitive coloring composition of the present invention contains a phthalocyanine pigment represented by the general formula (1), a binder resin, a photopolymerizable monomer, and a photopolymerization initiator, and is particularly white organic EL. It is a green photosensitive coloring composition preferably used for a color filter of a color display device having a light source. First, the colorant used in the green photosensitive coloring composition, the binder resin, the photopolymerizable monomer, the photopolymerization initiator, and other components such as a dispersion aid, an antioxidant, and a solvent that are used as necessary. explain.

<Colorant>
The photosensitive green colorant composition for organic EL of the present invention is characterized by containing a phthalocyanine pigment represented by the general formula (1) and PY185.
By containing the general formula (1) and PY185, a color filter having high brightness and excellent coloring power can be obtained.
(Phthalocyanine pigment represented by the general formula (1))
The colorant of the photosensitive green colorant composition for organic EL of the present invention contains a phthalocyanine pigment represented by the following general formula (1).

General formula (1)

(In the formula, X represents a halogen atom, and n represents an integer of 1 to 16. However, the average value of the number of substitutions of the halogen atom represented by X is 1 to 15, and the halogen distribution width is And Y represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ , wherein R ₁ and R ₂ are each independently selected. In addition, a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent or an aryloxy which may have a substituent R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. R ₄ represents a hydroxyl group, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Represents a heterocyclic group which may have a reel group or a substituent.)

  Here, examples of the “halogen” include fluorine, bromine, chlorine and iodine, with bromine and chlorine being preferred. Two or more kinds of halogen atoms may be used in combination as long as they are within the range of the average value of the number of substitutions and the distribution width. In particular, it is preferable to use bromine and chlorine in combination.

  In the phthalocyanine pigment represented by the general formula (1), the average value of the number of substitution of the halogen atom represented by X is 1 to 15, and 2 to 12 is preferable from the viewpoint of hue and fastness. Moreover, the halogen distribution width is 2 or more, and 4-9 are preferable. When the halogen distribution width is 4 or more, the association between the phthalocyanine molecules is remarkably easily suppressed, which greatly contributes to the increase in the particle size due to the association between the molecules, and the suppression of the low contrast, and the transmittance. It became clear that it improved.

Here, the “halogen distribution width” is the distribution of the number of halogens substituted for the phthalocyanine pigment represented by the general formula (1). In the mass spectrum obtained by mass spectrometry, the halogen distribution width calculates the signal intensity (each peak value) of the molecular ion peak corresponding to each component, and the value (total peak value) obtained by integrating each peak value, The number of peaks having a ratio of each peak value to 1% or more with respect to the total peak value was counted as a halogen distribution width.

The alkyl group in R ₁ to R _4, a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, isobutyl group, tert- butyl group, neopentyl group, hexyl group n-, n-octyl group, stearyl group , A straight-chain or branched alkyl group such as 2-ethylhexyl group, and an alkyl group having 1 to 6 carbon atoms is preferable.
Examples of the substituent of the alkyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkoxyl groups such as methoxy group, aryl groups such as phenyl group and tolyl group, and nitro groups. Further, there may be a plurality of substituents. Accordingly, examples of the alkyl group having a substituent include, for example, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, and 2-butoxy. Ethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl Groups and the like.

Examples of the aryl group in R _{1 to} R ₄ include monocyclic aromatic hydrocarbon groups such as a phenyl group and a p-tolyl group, and condensed aromatic hydrocarbon groups such as a naphthyl group and an anthryl group. A hydrocarbon group is preferred. Moreover, a C6-C12 aryl group is preferable.
Examples of the substituent of the aryl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkoxyl groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Therefore, as the aryl group having a substituent, for example, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-dimethylaminophenyl group, Examples include 2-methyl-4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group and the like.

Examples of the alkoxyl group in R ₁ and R ₂ include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2,3-dimethyl-3- Examples thereof include linear or branched alkoxyl groups such as a pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, and an alkoxyl group having 1 to 6 carbon atoms is preferable.
Examples of the substituent of the alkoxyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, aryl groups such as alkoxyl groups, phenyl groups and tolyl groups, and nitro groups. Further, there may be a plurality of substituents. Therefore, examples of the alkoxyl group having a substituent include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, and a 2,2- Examples include ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

As the aryloxy group in R ₁ and R _2, an aryloxy group composed of a monocyclic aromatic hydrocarbon group such as a phenoxy group or a p-methylphenoxy group, or a condensed aromatic hydrocarbon such as a naphthaloxy group or an anthryloxy group An aryloxy group comprising a group, and an aryloxy group comprising a monocyclic aromatic hydrocarbon group is preferred. Moreover, a C6-C12 aryloxy group is preferable.
Examples of the substituent of the aryloxy group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Therefore, as the aryloxy group having a substituent, for example, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group, etc. Can be mentioned.

Examples of the cycloalkyl group in R ₃ include a monocyclic aliphatic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a 2,5-dimethylcyclopentyl group, a 4-tert-butylcyclohexyl group, a bornyl group, an adamantyl group, and the like. A condensed aliphatic hydrocarbon group is mentioned. Moreover, a C5-C12 cycloalkyl group is preferable.
Examples of the substituent of the cycloalkyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, hydroxyl groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Examples of the cycloalkyl group having a substituent include a 2,5-dichlorocyclopentyl group and a 4-hydroxycyclohexyl group.

Examples of the heterocyclic group in R ₃ and R ₄ include aliphatic heterocyclic groups such as pyridyl group, pyrazyl group, piperidino group, pyranyl group, morpholino group, acridinyl group, and aromatic heterocyclic groups. Moreover, a C4-C12 heterocyclic group is preferable and a C5-C13 heterocyclic group is preferable.
Examples of the substituent of the heterocyclic group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, hydroxyl groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Examples of the heterocyclic group having a substituent include a 3-methylpyridyl group, an N-methylpiperidyl group, and an N-methylpyrrolyl group.

As the phthalocyanine compound represented by the general formula (1), at least one of R ₁ and R ₂ has an aryl group or a substituent which may have a substituent from the viewpoint of dispersibility and color characteristics. May be an aryloxy group, R ₁ and R ₂ are both aryl groups or aryloxy groups, and R ₁ and R ₂ are both phenyl groups or phenoxy groups. More preferably. R ₃ and R ₄ are preferably an aryl group which may have a substituent or a heterocyclic group which may have a substituent.

  In the present invention, the phthalocyanine compound represented by the general formula (1) is represented by [AlPc (Y)] Xn (4 ≦ n ≦ 16) (where Pc is a phthalocyanine ring, X is a halogen atom, and n is 4 to 16). Are represented by [AlPc (Y)] Brn (4 ≦ n ≦ 16), [AlPc (Y)] Cln (4 ≦ n) as representative examples of the general formula (1). ≦ 16), [AlPc (Y)] In (4 ≦ n ≦ 16), [AlPc (Y)] Fn (4 ≦ n ≦ 16), and the like, but the present invention is not limited to these. Absent. Further, cyclized isomers of the exemplified compounds are also included as preferred examples of the present invention.

  Typical examples of Y in the general formula (1) include the structures shown below (* represents the bonding position of the substituent with Al in the general formula (1)). It is not limited to. Further, cyclized isomers of the exemplified compounds are also included as preferred examples of the present invention.

Among the phthalocyanine pigments represented by the general formula (1), the phthalocyanine pigment represented by the general formula (2) is preferable from the viewpoint of achieving both high brightness and high coloration.

(Phthalocyanine pigment represented by formula (2))

General formula (2)

(In the formula, X ₁ represents a halogen atom, and n represents an integer of ₁ to 16. However, the average value of the number of substitutions of the halogen atom represented by X ₁ is 1 or more and less than 6, The distribution width is not less than 2. Y represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ , where R ₁ and R ₂ are Each independently has a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent or a substituent. R ₃ represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent or a substituent. .R ₄ where represents a heterocyclic group which may have a represents a hydroxyl group, an optionally substituted alkyl group, which may have a substituent Have a have an aryl group or a substituted group represents a heterocyclic group.)

  Here, examples of the “halogen” include fluorine, bromine, chlorine and iodine, with bromine and chlorine being preferred. Two or more kinds of halogen atoms may be used in combination as long as they are within the range of the average value of the number of substitutions and the distribution width. In particular, it is preferable to use bromine and chlorine in combination.

In the phthalocyanine pigment represented by the general formula (2), the average value of the number of substitutions of the halogen atom represented by X ₁ is 1 to less than 6, and preferably 1 to 4 from the viewpoint of hue and fastness. The halogen distribution width is 2 or more, and preferably 4 or more and 10 or less. When the halogen distribution width is 4 or more and 10 or less, the association between the phthalocyanine molecules is remarkably suppressed, greatly contributing to the suppression of the increase in the particle size and the decrease in the contrast due to the association between the molecules, and the desired characteristics. Can be obtained.

Here, the “halogen distribution width” is the distribution of the number of halogens substituted for the phthalocyanine pigment represented by the general formula (2). In the mass spectrum obtained by mass spectrometry, the halogen distribution width calculates the signal intensity (each peak value) of the molecular ion peak corresponding to each component, and the value (total peak value) obtained by integrating each peak value, The number of peaks having a ratio of each peak value to 1% or more with respect to the total peak value was counted as a halogen distribution width.

  In addition, Y of the phthalocyanine pigment represented by the general formula (2) is the same as Y of the phthalocyanine pigment represented by the general formula (1).

(CI Pigment Yellow 185)
The green photosensitive coloring composition for a color filter of the present invention can be used for C.I. to satisfy high brightness and high coloring power at a certain chromaticity. I. Pigment Yellow 185 is contained.

In addition, as a colorant that can be used in combination, a green pigment or a yellow pigment can be used in combination.

(Green pigment)
A green pigment can also be added to the colorant of the present invention for the purpose of adjusting the hue. Examples of the green pigment include C.I. I. And green pigments such as CI Pigment Green 7, 10, 36, 37, 58, and 62.

The green pigment to be added is C.I. from the viewpoint of brightness and coloring power. I. Pigment Green 7 and 58 are preferable.

(Yellow pigment)
In order to further adjust the chromaticity, the colored composition of the present invention may contain a yellow pigment as long as the effects of the present invention are not impaired.

As the yellow pigment to be added, organic or inorganic pigments can be used alone or in admixture of two or more kinds, pigments having high color development and high heat resistance, particularly pigments having high heat decomposition resistance are preferred. Usually, an organic pigment is used. As the organic pigment, commercially available ones can be used, and natural pigments and inorganic pigments can be used in combination according to the desired hue of the filter segment.

Below, the specific example of the yellow organic pigment which can be used for the said coloring composition is shown. Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 182,187,188,192,193,194,196,198,199,213,214,231 can be used. In particular, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, examples of the yellow pigment include C.I. I. It is preferably at least one selected from CI Pigment Yellow 138, 139, 150, and 231.

  The content of the pigment in the green photosensitive coloring composition for an organic EL display device of the present invention is such that the content of the phthalocyanine green pigment represented by the general formula (1) is 15 to 15% in the total amount of the pigment (100% by weight). 85% by weight, C.I. I. It is preferable that the content of Pigment Yellow 185 is 15 to 85% by weight. Further, from the viewpoint of achieving both high brightness and coloring power at a certain chromaticity, the content of the phthalocyanine green pigment represented by the general formula (1) is 20 to 60% by weight, C.I. I. The pigment yellow 185 content is more preferably 10 to 40% by weight.

The content of the colorant (A) in the green photosensitive coloring composition for organic EL display devices of the present invention is 40% by weight or more in 100% by weight of the total solid content of the green photosensitive coloring composition. Is preferable from the viewpoint of coloring power, and more preferably 40 to 50% by weight. When the amount is 50% by weight or less, the pattern shape by the photolithography method is improved.
In addition, solid content of the photosensitive coloring composition shows the component except volatile components, such as a solvent.

(Miniaturization of colorant)
The pigment used in the present invention can be used after being refined. A phthalocyanine pigment represented by the general formula (1); I. Pigment Yellow 185 is also preferably used after being refined, but the refinement method is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation can be used, as exemplified in the present invention. In addition, a salt milling process by a kneader method, which is a kind of wet grinding, can be performed.
By making these colorants finer, they can be suitably used as a green photosensitive coloring composition for organic EL display devices.

The primary particle size of the refined pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm.
The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is approximated to a cube having the obtained particle diameter to obtain an average volume, and the length of one side of the cube having this average volume is determined as the average primary The particle size.

  Salt milling is a process of heating a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent using a kneader such as a kneader, trimix, two-roll mill, three-roll mill, ball mill, attritor or sand mill. Then, after mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Dispersing aid>
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter having a high spectral transmittance can be obtained.

(Dye derivative)
Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine. For example, those described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. These may be used alone or in combination of two or more.

  The blending amount of the pigment derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more with respect to 100 parts by mass of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 40 parts by mass or less, and most preferably 35 parts by mass or less with respect to 100 parts by mass of the colorant.

(Resin type dispersant)
The resin-type dispersant has a pigment-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to stabilize dispersion in the colorant carrier. It works. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

The following is mentioned as a commercially available resin-type dispersing agent.
Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181 manufactured by Big Chemie Japan 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, Or Lactimon, Lactimon-WS or Bykumen etc.
SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, manufactured by Nippon Lubrizol 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc.
EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by BASF 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc.
Ajinomoto Fine Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824, etc.

(Surfactant)
Examples of the surfactant include the following.
Sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate Anionic surfactants such as triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester;
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate;
Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts;
Amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines.
These can be used alone or in admixture of two or more, but are not necessarily limited thereto.

When a resin-type dispersant and / or a surfactant is added, these blending amounts are preferably 0.1 to 55 parts by weight, more preferably 100 parts by weight, respectively, from the viewpoint of the effect on dispersion. Is 0.1 to 45 parts by mass.
As one embodiment, the colorant may be independently dispersed prior to the dispersion treatment in a colorant carrier such as a binder resin. That is, after preparing a pigment dispersion by a pigment dispersion treatment, it may be used as a colorant.

<Binder resin>
The binder resin disperses, dyes, or penetrates the colorant, and examples thereof include a thermoplastic resin. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the colorant is fixed, heat resistance is improved, and fading (deterioration of spectral characteristics) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used as a photosensitive coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and The balance of the aromatic group is important for the dispersibility, penetrability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin is preferably used in an amount of 20 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 1000 parts by weight or less.

  Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group.
Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

  Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an unsaturated ethylenic monomer having a hydroxyl group is used, and a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

  Examples of unsaturated ethylenic monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

[Thermosetting compound]
In the present invention, a thermosetting compound may be further contained in combination with the thermoplastic resin which is a binder resin.

  Examples of the thermosetting compound include epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins, Examples include urea compounds and / or resins, phenol compounds and / or resins, but the present invention is not limited thereto.

<Photopolymerizable monomer (B)>
The green photosensitive coloring composition for organic EL display devices of the present invention contains a photopolymerizable monomer (B).
The photopolymerizable monomer (B) includes a monomer or oligomer that is cured by ultraviolet rays or heat to produce a transparent resin.
Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

The content of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability. .

When the content of the colorant in the photosensitive coloring composition is high, the chemical resistance of the coating film may be deteriorated because the amount of the coating film crosslinking component is reduced. Among them, the polyfunctional urethane acrylate (B1) is high in chemicals. It is preferable from the viewpoint of imparting resistance.

(Photopolymerizable monomer (B1))

There is no restriction | limiting in the structure of polyfunctional urethane acrylate (B1), polyfunctional urethane acrylate obtained by making polyfunctional isocyanate react with (meth) acrylate which has a hydroxyl group, polyfunctional isocyanate is made to react with alcohol, and it has a hydroxyl group further The polyfunctional urethane acrylate etc. which are obtained by making (meth) acrylate react are mentioned.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide modified penta (meth) acrylate, dipentaerythritol propylene oxide modified penta (meth) acrylate, dipentaerythritol caprolactone modified penta (meth) acrylate, glycerol acrylate Methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, containing epoxy groups The reaction product of compound and the carboxy (meth) acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

  Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

Moreover, although there is no restriction | limiting in the structure of alcohol, when a polyhydric alcohol is used, since the crosslinking degree of a cured coating film becomes high and coating-film resistance goes up, it is preferable. Examples of the polyhydric alcohol include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, and pentaerythritol.

The photopolymerizable monomer (B1) that can be used in the green photosensitive coloring composition for an organic EL display device color filter of the present invention includes a (meth) acrylate having a hydroxyl group in addition to the polyfunctional urethane acrylate described above. When reacting polyfunctional isocyanate, reacting polyfunctional isocyanate with alcohol, and further reacting with (meth) acrylate having a hydroxyl group, other components having double bond groups not obtained as polyfunctional urethane acrylate It may be included as a monomer.

  A commercially available polyfunctional acrylate can also be used for the photomonomer (B1) of the present invention. Specifically, KAYARAD UX-3204, KAYARAD UX-4101, KAYARAD UX-6100, KAYARAD UX-6101, KAYARAD UX-7101, KAYARAD UX-8101, KAYARAD UX-0937, X KAYARAD DPHA-40H, KAYARAD UX-5005, and Aronix M-1100, Aronix M-1200 manufactured by Toa Gosei Co., Ltd., and U-6LPA, UA-1100H, UA-160TM, UA-122P manufactured by Shin-Nakamura Chemical Co., Ltd. UA-7100, UA-W2A, KSM-4I, KUA-6I, KUA-9N, KUA-10H, etc. manufactured by KSM Co., Ltd. can be preferably used.

<Photopolymerization initiator (C)>
In the colored composition of the present invention, the composition is cured by ultraviolet irradiation, and a photopolymerization initiator (C) is added to form a filter segment by photolithography, and a solvent development type or alkali development type photosensitivity is added. It can be prepared in the form of a colored composition.

(Oxime ester compound (C1))
The green photosensitive coloring composition for organic EL display devices of the present invention is characterized by containing an oxime ester compound (C1) as a photopolymerization initiator.
When the oxime ester compound (C1) absorbs ultraviolet rays, the N—O bond of the oxime is cleaved to generate an iminyl radical and an alkyloxy radical. Since these radicals are further decomposed to generate radicals with high activity, a pattern can be formed with a small exposure amount. When the concentration of the colorant in the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the curing degree of the coating film may be low. The More preferably, when it has a carbazole group, it can be set as the composition excellent in the brightness and color purity. Particularly preferred is an oxime ester photopolymerization initiator represented by the general formula (3).

(Oxime ester photopolymerization initiator represented by the general formula (3))
General formula (3)

In general formula (3),
Y ¹ is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group An alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group,
Y ² is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group , An alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group.
Z is a direct bond or a -CO- group,
Y ³ is a monovalent organic group including a carbazole group which may have a substituent, a Ph-S-Ph- group (Ph represents a phenyl group or a phenylene group which may have a substituent). Etc.

Examples of the alkenyl group which may have a substituent in Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkenyl group having 1 to 18 carbon atoms, and these include a plurality of carbon atoms in the structure. -It may have a carbon double bond, and specific examples include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group. 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1 , 3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group and the like, but are not limited thereto.

The alkyl group which may have a substituent for Y ¹ is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms and optionally 1 Examples include a linear, branched, monocyclic or condensed polycyclic alkyl group interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include —CH ₂ —O—CH ₃ , —CH _2. —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1) To 8), — (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH ₂ —. _{CH 3 -, - CH 2 -CH-} (OCH 3) but ₂ and the like, but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- include the following, but are not limited thereto. Is not to be done.

The alkyloxy group which may have a substituent for Y ¹ is a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. Examples include linear, branched, monocyclic or condensed polycyclic alkyloxy groups optionally interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms include methyloxy group, ethyloxy group, propyloxy group, butyloxy group, pentyloxy group, hexyloxy Group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyl Oxy group, tert-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boroni Group, 4-decyl cyclohexyl although group and the like, but is not limited thereto. Specific examples of the linear or branched alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , _{-O-CH 2 -CH 2 -O-} CH 2 -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n -CH ₃ (wherein n is 1 to _{8), - O- (CH 2} -CH 2 -CH 2 -O) m -CH 3 ( here m is 5 1), - O-CH _{2 -CH (CH 3) -O-} CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include the following. It is not limited.

Examples of the aryl group that may have a substituent in Y ¹ include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms, and specific examples thereof include a phenyl group, a 1-naphthyl group, and 2-naphthyl. Group, 1-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group Group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p -Cumenyl group, p-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromopheny Group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group, etc., but are not limited thereto. It is not something.

Examples of the aryloxy group which may have a substituent for Y ¹ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms, and specific examples include a phenoxy group, a 1-naphthyloxy group, 2- Naphtyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group , 9-fluorenyloxy group and the like, but are not limited thereto.

Examples of the heterocyclic group which may have a substituent for Y ¹ include aromatic or aliphatic heterocyclic groups having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl Group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquino Lyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, Imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-coumarinyl of the group and the like, but is not limited thereto.

Examples of the heterocyclic oxy group that may have a substituent for Y ¹ include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyl. Examples thereof include, but are not limited to, a ruoxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, and a 9-acridinyloxy group.

Examples of the alkylsulfanyl group which may have a substituent in Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms. Specific examples include a methylthio group. , Ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like, but are not limited thereto.

Examples of the arylsulfanyl group which may have a substituent in Y ¹ include a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, 2- Examples thereof include, but are not limited to, a naphthylthio group, a 9-anthrylthio group, and a 9-phenanthrylthio group.

The alkylsulfinyl group which may have a substituent in Y ¹ is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, Butylsulfinyl group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methyloxymethylsulfinyl group, etc. Although it is mentioned, it is not limited to these.

The arylsulfinyl group which may have a substituent in Y ¹ is preferably an arylsulfinyl group having 6 to 30 carbon atoms, and specific examples thereof include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methyloxyphenylsulfinyl group, 2-butyloxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methyloxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4- Examples thereof include, but are not limited to, a phenylsulfanylphenylsulfinyl group and a 4-dimethylaminophenylsulfinyl group.

The alkylsulfonyl group which may have a substituent in Y ¹ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, Butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methyloxymethylsulfonyl group, etc. Although it is mentioned, it is not limited to these.

The arylsulfonyl group which may have a substituent for Y ¹ is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specific examples include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methyloxyphenylsulfonyl group, 2-butyloxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methyloxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfo Examples thereof include, but are not limited to, a nyl group and a 4-dimethylaminophenylsulfonyl group.

Examples of the acyl group which may have a substituent for Y ¹ include a hydrogen atom or a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, A carbonyl group substituted by an alkyloxy group having 2 to 20 carbon atoms, a carbonyl group to which a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms is bonded, or a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms. Examples include a carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms including a substituted carbonyl group, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom is bonded. Specific examples include formyl Group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl Group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, cinnamoyl group benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyl Oxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-an Thrylcarbonyl group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-dimethylaminopheny Oxycarbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthrylyloxycarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, Although an isonicotinoyl group etc. can be mentioned, it is not limited to these.

Examples of the acyloxy group which may have a substituent in Y ¹ include an acyloxy group having 2 to 20 carbon atoms, and specific examples include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, and a pentanoyloxy group. Group, trifluoromethylcarbonyloxy group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

Examples of the amino group which may have a substituent in Y ¹ include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, and a dibenzylamino group. Can be mentioned.

  Here, as the alkylamino group, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group , Octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentyl Amino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantami Group, and the like, but not limited thereto.

  Dialkylamino groups include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, Examples include, but are not limited to, piperazino groups.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- A biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, and the like are exemplified, but the invention is not limited thereto.

  Examples of the diarylamino group include, but are not limited to, a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like are exemplified, but not limited thereto.

Examples of the phosphinoyl group which may have a substituent in Y ¹ include phosphinoyl groups having 2 to 50 carbon atoms, and specific examples thereof include dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group. Group, diphenylphosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group, etc. Is not to be done.

Examples of the carbamoyl group which may have a substituent for Y ¹ include carbamoyl groups having 1 to 30 carbon atoms, and specific examples thereof include an N-methylcarbamoyl group, an N-ethylcarbamoyl group, and an N-propylcarbamoyl group. N-butylcarbamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group Group, N-2-chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanoph Enylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl Group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group, and the like, but are not limited thereto.

Examples of the sulfamoyl group which may have a substituent in Y ¹ include a sulfamoyl group having 0 to 30 carbon atoms, and specific examples thereof include a sulfamoyl group, an N-alkylsulfamoyl group, and an N-arylsulfamoyl group. Group, N, N-dialkylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like. It is not limited to.

Y ² may have a substituent, an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, As the arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, and amino group, the aforementioned alkenyl group that may have a substituent in R1, an alkyl group that may have a substituent, and a substituent An alkyloxy group that may have, an aryl group that may have a substituent, an aryloxy group that may have a substituent, a heterocyclic group that may have a substituent, and a substituent A good heterocyclic oxy group, an alkylsulfanyl group which may have a substituent, an arylsulfanyl group which may have a substituent, a substituent An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and a substituent. It is synonymous with the acyloxy group which may be sufficient, and the amino group which may have a substituent.

Examples of these substituents for Y ¹ and Y ² include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group and p-tolyloxy. Aryloxy groups such as methoxycarbonyl groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups , Acyl groups such as methacryloyl group, methoxalyl group, alkylsulfanyl groups such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino , Alkylamino groups such as cyclohexylamino group, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, methyl group, ethyl group, tert- Alkyl groups such as butyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclooctadecyl, phenyl, p-tolyl, xylyl, cumenyl, naphthyl Group, anthryl group, aryl group such as phenanthryl group, heterocyclic group such as furyl group, thienyl group, etc., hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, Amino group, nitro group, cyano group, tri Examples thereof include a fluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammoniumum group, a dimethylsulfoniumyl group, and a triphenylphenacylphosphoniumyl group.
One or more of these substituents may be present, or one or more of these substituents may be present, and the hydrogen atom of these substituents may be further substituted with another substituent.

  Among these, the oxime ester photopolymerization initiator represented by the following general formula (4) or (5) is excellent in sensitivity and is preferable.

[Oxime ester photopolymerization initiator represented by formula (4)]
General formula (4)

The general formula (4) corresponds to the case where Z in the general formula (3) is a —CO— group and Y ³ is a Ph—S—Ph— group, and Y ⁴ to Y ^{6 each} represents a hydrogen atom or a substituent. An alkyl group or an aryl group which may be contained is preferable.

Furthermore the aryl group which may have a substituent as Y ^1, alkyl group having 1 to 20 carbon atoms that may have a substituent as Y ² is preferably a hydrogen atom as Y ⁴ to Y ⁶ .

The alkyl group that may have a substituent or the aryl group that may have a substituent in Y ^{4 to} Y ⁶ has the same meaning as the alkyl group or aryl group in Y ¹ and Y ² .

The alkyl group which may have a substituent or the substituent of the aryl group which may have a substituent has the same meaning as the substituent in Y ¹ and Y ² .

Y ² is preferably an alkyl group having 1 to 20 carbon atoms that may have a substituent, and the substituent is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, A cycloalkyl group such as a cyclooctadecyl group;

Specific examples of the oxime ester photopolymerization initiator represented by the general formula (4) include a photopolymerization initiator represented by the following chemical formula (4-1) or (4-2).

[Oxime ester photopolymerization initiator represented by general formula (5)]
General formula (5)

The general formula (5) corresponds to the case where Y ³ in the general formula (3) is a monovalent organic group including a carbazole group which may have a substituent, and Y ⁷ to Y ¹⁴ are Y ¹ and Y It is synonymous with the substituent in ² .

Further, the alkyl group having 1 to 20 carbon atoms which may have a substituent as Y ¹ may have an alkyl group having 1 to 20 carbon atoms which may have a substituent as Y ² or a substituent. A good aryl group is preferably a hydrogen atom as Y ^{7 to} Y ¹⁴ , an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.

  When Z in the general formula (5) is a direct bond, an oxime ester photopolymerization initiator represented by the following general formula (5a) is preferable.

"Oxime ester photopolymerization initiator represented by formula (5a)"
General formula (5a)

The general formula (5a) corresponds to the case where Z in the general formula (5) is a direct bond and Y ³ is a monovalent organic group including a carbazole group which may have a substituent. Y < ⁷ > -Y < ¹⁰ > and Y < ¹² > -Y < ¹³ > are hydrogen atoms.
Y ¹¹ is preferably a Y ¹⁵ —CO— group or a nitro group. Y ¹⁵ is synonymous with the substituent in Y ¹ and Y ² and is preferably an aryl group which may have a substituent. The Y ¹⁵ —CO— group is preferably an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, or a methoxalyl group, which may further have a substituent. More preferred is a benzoyl group or nitro group which may have a substituent. Y ¹⁴ is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.

Moreover, as a substituent in the benzoyl group which may have a substituent, a C1-C20 alkyl group or an alkyloxy group is preferable. Further, the alkyl group is preferably a methyl group or an ethyl group, and among the alkyloxy groups, a linear or branched chain having 2 to 18 carbon atoms and optionally interrupted by one or more —O— Monocyclic or condensed polycyclic alkyloxy groups are preferred, linear, branched, monocyclic or condensed polycyclic having 2 to 18 carbon atoms in Y ¹ and optionally interrupted by one or more —O— Synonymous with alkyloxy group.

Y ² is preferably an alkyl group having 1 to 20 carbon atoms that may have a substituent, and the substituent is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, A cycloalkyl group such as a cyclooctadecyl group; Further, an aryl group which may have a substituent is preferable, and as the substituent, an alkyl group having 1 to 20 carbon atoms which may further have a substituent, a methoxy group, an ethoxy group, or a tert-butoxy group Etc. are preferred.

Specific examples of the oxime ester photopolymerization initiator represented by the general formula (5a) include photopolymerization initiators represented by the following chemical formulas (5a-1) to (5a-4).

"Oxime ester photopolymerization initiator represented by general formula (5b)"
When Z in the general formula (5) is a -CO- group, an oxime ester photopolymerization initiator represented by the following general formula (5b) is preferable.

General formula (5b)

The general formula (5b) corresponds to the case where Z in the general formula (5) is a —CO— group and Y ³ is a monovalent organic group including a carbazole group which may have a substituent. Is an oxime ester photopolymerization initiator.
Y ^{7 to} Y ¹³ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and Y ¹⁴ may have a substituent. A good aryl group is preferred.
As the substituent of the aryl group which may have a substituent, an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group and a methoxalyl group is preferable, and a benzoyl group is more preferable.

Specific examples of the oxime ester photopolymerization initiator represented by the general formula (5b) include photopolymerization initiators represented by the following chemical formulas (5b-1) to (5b-4).

  Commercially available products of these oxime ester compounds (C1) include 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IRGACURE OXE-01) from BASF. ), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02) is commercially available. In addition to these, oximes described in JP2007-210991A, JP2009-179619A, JP2010-037223A, JP2010-215575A, JP2011-020998A, and the like. It is also possible to use an ester photopolymerization initiator.

  The content of the oxime ester compound (C1) is preferably 2 to 50 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 2 to 30 parts by weight from the viewpoint of photocurability and developability. preferable. When the amount is less than 2 parts by weight, the adhesion of the formed pattern to the substrate is deteriorated, and when it exceeds 50 parts by weight, a problem may occur in developability and the brightness may be lowered after heat treatment at 230 ° C.

(Other photopolymerization initiators)
In the photosensitive coloring composition of the present invention, other photopolymerization initiators can be used in combination with the oxime ester photopolymerization initiator (C1).
Other photopolymerization initiators in the present invention include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, phosphine compounds, quinone compounds, borate compounds, carbazole compounds, imidazole compounds. A photopolymerization initiator (C2) such as a compound and a titanocene compound, and a sensitizer (C3).

  Specific examples of the photopolymerization initiator (C2) include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methyl Acetophenone such as phenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Compounds: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Benzoin compounds such as tereline or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 Benzophenone compounds such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4- Thioxanthone compounds such as diethyl thioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, -(P-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4, 6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl)- s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2, Triazine compounds such as 4-trichloromethyl- (4′-methoxystyryl) -6-triazine; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds Compounds; or titanocene compounds and the like.

  As the sensitizer (C3), chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives Anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin Conductor, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphylline derivative, annulene derivative, spiropyran derivative, Spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler ketone derivatives, biimidazole derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrene Quinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, or 4,4′-tetra (t-butyl Peroxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone, and the like.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  These photopolymerization initiators (C2) or other photopolymerization initiators such as the sensitizer (C3) may be used alone or in combination of two or more at any ratio as required. it can.

  Among other photopolymerization initiators, the patterning property is improved. Therefore, in the photopolymerization initiator (C2), an acetophenone compound, a phosphine compound, and an imidazole compound, and in the sensitizer (C3), a thioxanthone derivative, It is preferable to use Michler's ketone derivative, carbazole derivative or the like.

  In the case of containing other photopolymerization initiator, the content is 0.1% in 100% by weight of the photopolymerization initiator (C) contained in the photosensitive coloring composition from the viewpoint of photocurability and resolution. % To 90% by weight, more preferably 10% to 90% by weight.

  In the photosensitive coloring composition of the present invention, the weight ratio of the photopolymerization initiator (C) to the photopolymerizable monomer (B) (photopolymerization initiator) (C) / (photopolymerizable monomer) (B )) Is preferably from 0.01 to 3.00, more preferably from 0.04 to 2.50, since both photocurability and resolution can be achieved.

<Antioxidant>
The photosensitive coloring composition for color filters of this invention can contain antioxidant (G). Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the photosensitive coloring composition for color filters from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. The transmittance can be increased. In particular, when the colorant concentration of the photosensitive coloring composition is high, the amount of coating crosslinking component decreases, so the use of a highly sensitive crosslinking component and the increase in the amount of photopolymerization initiator are taken into account. This phenomenon is seen.
Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. In addition, the antioxidant used in the present invention preferably does not contain a halogen atom.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2′-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4′-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2′-thio -Bis- (6-tert-butyl-4-methylphenol), 2,5-di-tert-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-tert-butyl-4-hydroxy Phenyl) -propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1- Methyl-cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-) Hydrocinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di ( , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy)- Benzene, phosphorous acid ethyl bis (2,4-di-tert- butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol, 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3- (Dodecylthio) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2- Hydroxy-4-octadecyloxybenzophenone, 2,2′dihydroxy-4-methoxybenzophenone, 2,2′dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2- Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone and the like can be mentioned. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by mass in 100% by mass of the solid content of the coloring composition because the spectral characteristics and sensitivity are good.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the coloring composition for a color filter of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent is preferably used in an amount of 0.003 to 0.5% by weight in 100% by weight of the total weight of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivatives bicyclic amidine compounds and salts thereof (eg imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl) -4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example tri Phenylphosphine ), Guanamine compounds (for example, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino) -S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) Can do. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

<Storage stabilizer>
Examples of the storage stabilizer include organic acids such as lactic acid and oxalic acid and methyl ether thereof, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

<Adhesion improver>
Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (Aminoethyl) γ-aminopropylto Ethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include silane coupling agents such as aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

<Multifunctional thiol>
The coloring composition of the present invention may contain a compound having two or more thiol (SH) groups as the polyfunctional thiol.
By using a polyfunctional thiol together with a photopolymerization initiator, a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation, so the resulting colored composition is highly sensitive. It becomes. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable. Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibuty Amino) -4,6-dimercapto--s- triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tris thiopropionate, pentaerythritol tetrakis thiopropionate.

These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types.
The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the colorant. If the polyfunctional thiol content is less than 0.05 parts by weight, the effect of the chain transfer agent is small. .

<Organic solvent>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and permeated in the coloring agent carrier, and is applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to make it easy to form, it is preferable to contain an organic solvent. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl- 1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, N, N-dimethyl Acetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl Benzene, n-propyl acetate, o-xylene, o-diethylbenzene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol Monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl Ether, ethylene glycol Monoethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, di Propylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol mono Chill ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol Monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, vinegar Propyl, dibasic acid esters and the like.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a desired colored film having a uniform thickness. Is preferred.

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. Coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Method for producing photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, the colorant is first mixed in a dye carrier such as a binder resin and / or a solvent, preferably together with a dispersion aid, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal type. A finely dispersed pigment dispersion is produced using various dispersing means such as a sand mill, a vertical sand mill, an annular bead mill, or an attritor, and an antioxidant, a photopolymerization initiator, and photopolymerization are produced in the pigment dispersion. The photosensitive monomer and, if necessary, a solvent, other pigment dispersants, additives and the like can be mixed to prepare a solvent developing type or alkali developing type photosensitive coloring composition.

<Color filter>
The color filter for organic EL display devices of the present invention will be described.
The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and at least one green filter segment is composed of the green photosensitive coloring composition of the present invention. It is preferable.
Moreover, the red photosensitive coloring composition which forms a red filter segment can be produced similarly to the above-mentioned green photosensitive coloring composition by replacing with a red pigment or dye. The same applies to the blue coloring composition forming the blue filter segment.

  The red filter segment can be formed using a normal red photosensitive coloring composition. Examples of the red photosensitive coloring composition include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276, etc. can be used. Among these, azo pigments, diketopyrrolopyrrole-based, anthraquinone-based, quinophthalone-based, isoindoline-based, perinone-based, perylene-based, and benzimidazolone-based pigments are exemplified from the viewpoint of brightness and coloring power. Specifically, C.I. I. Pigment Red 176, 177, 179, 242, 254, and 269 are preferable.

A yellow pigment or dye can be used in combination with the red photosensitive coloring composition for color adjustment.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, 231 and the like. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment yellow 138, 139, 150, 185, 231.

  The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a colorant carrier. Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 or the like is used. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment Blue 15: 6. Moreover, the aluminum phthalocyanine pigment etc. which are described in Unexamined-Japanese-Patent No. 2004-333817, patent 4893859 etc. can also be used, It is not limited to these in particular.

  In addition, C.I. I. Purple pigments such as CI Pigment Violet 23, C.I. I. A metal lake pigment of a rhodamine dye such as CI Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5 can be used in combination. Further, a basic dye or a salt forming compound of an acidic dye that exhibits blue or purple can be used.

The filter segment has peak wavelengths (λ ₁ ) and (λ ₂ ) at which the emission intensity is maximized in the wavelength range of 430 nm to 485 nm and the wavelength range of 560 nm to 620 nm, and the emission intensity I1 at the wavelength λ ₁ . the ratio of the emission intensity I2 at the wavelength λ ₂ (I2 / I1) is, in the case of using a white organic EL light source having a spectral characteristic is 0.4 to 0.9, in each of colors, specific chromaticity characteristics Is preferable because color reproducibility as a color display device is improved.

  The ratio (I2 / I1) of the emission intensity I2 of such an emission spectrum is 0.4 or more and 0.9 or less, preferably 0.5 or more and 0.8 or less, more preferably 0.5 or more and 0.7 or less. And by satisfy | filling a specific chromaticity characteristic in either conditions in these ranges, the quality requested | required as a color filter for organic EL display apparatuses, such as NTSC ratio, can be achieved.

The color filter for an organic EL display device of the present invention has peak wavelengths (λ ₁ ) and (λ ₂ ) at which the emission intensity is maximized in a wavelength range of 430 nm to 485 nm and a wavelength range of 560 nm to 620 nm. If the ratio of the emission intensity I2 of the light emitting intensity I1 and the wavelength lambda ₂ in ₁ (I2 / I1) is, using white organic EL light source having a spectral characteristic is 0.4 to 0.9, XYZ colored film When the chromaticity coordinates in the color system are (xR, yR), (xG, yG), and (xB, yB), the area of the triangle surrounded by these three points is red (0.67, 0. 33) If the area is 75% or more with respect to the area surrounded by green (0.21, 0.71) and blue (0.14, 0.08), color reproducibility as a color display device is enhanced. preferable.

  As the substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

<Color filter manufacturing method>
The color filter of the present invention can be produced by using a coloring composition by a printing method or a photolithography method.

  Formation of a colored film by a printing method can be performed by simply repeating printing and drying of a colored composition prepared as a printing ink, so that the color filter manufacturing method is low cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When forming a colored film by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for manufacturing a color filter by using a transparent conductive film formed on a substrate and forming a colored film on the transparent conductive film by electrodeposition of colloidal particles. . The transfer method is a method in which a colored film is formed in advance on the surface of a peelable transfer base sheet, and this colored film is transferred to a desired substrate.

If the black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast of the display panel can be further increased. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the panel can be increased and the luminance can be improved.
On the color filter of the present invention, an overcoat film or a transparent conductive film is formed as necessary.

<Organic EL display device>
The organic EL display device according to the present invention includes a phthalocyanine pigment represented by the general formula (1), C.I. I. A color filter formed of a green photosensitive coloring composition containing Pigment Yellow 185, a binder resin, a photopolymerizable monomer (B), and a photopolymerization initiator (C); and a white light-emitting organic EL device (hereinafter referred to as organic). It is preferable that the display device has an EL element) as a light source.

(Organic EL element (white light-emitting organic EL element))
The organic EL element used in the present invention has peak wavelengths (λ ₁ ) and (λ ₂ ) at which the emission intensity is maximized in at least a wavelength range of 430 nm to 485 nm and a wavelength range of 560 nm to 620 nm, and a wavelength of λ the ratio of the emission intensity _{I 2} in the light-emitting intensity _{I 1} and the wavelength lambda ₂ in _{1 (I} 2 / _{I 1)} is preferably has an emission spectrum is 0.4 to 0.9, 0.5 More preferably, it is 0.8 or less. Most preferably, it is 0.5 or more and 0.7 or less.
It is preferable that the emission intensity I2 ratio (I2 / I1) has an emission spectrum of 0.4 or more and 0.9 or less because high brightness and wide color reproducibility can be obtained.

Furthermore, it is preferable that the light emission intensity has a maximum value or a shoulder in the wavelength range of 530 nm to 650 nm.
The wavelength range of 430 nm to 485 nm is preferable when the color display device including the color filter displays blue with good color reproducibility. More preferably, it is the range of 430 nm-475 nm.
By using the organic EL element satisfying these configurations and the color filter, a color display device having a wide color reproduction region and high brightness can be obtained.

  An organic EL element is comprised from the element which formed the organic layer of one layer or a multilayer between the anode and the cathode. Here, the single-layer organic EL element refers to an element composed of only a light emitting layer between an anode and a cathode, while the multilayer organic EL element refers to a hole or a hole in the light emitting layer in addition to the light emitting layer. Hole injection layer, hole transport layer, hole blocking layer, electron injection for the purpose of facilitating electron injection and smooth recombination of holes and electrons in the light emitting layer It refers to a laminate of layers. Therefore, typical element configurations of the multilayer organic EL element include (1) anode / hole injection layer / light emitting layer / cathode, and (2) anode / hole injection layer / hole transport layer / light emitting layer / cathode. (3) Anode / hole injection layer / light emitting layer / electron injection layer / cathode, (4) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode, (5) Anode / positive Hole injection layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (6) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (7) Examples include an anode / light emitting layer / hole blocking layer / electron injection layer / cathode, and (8) an element configuration laminated in a multilayer structure such as anode / light emitting layer / electron injection layer / cathode. However, the organic EL element used in the present invention is not limited to these.

  Moreover, each organic layer mentioned above may be formed by the layer structure of 2 or more layers, respectively, and several layers may be laminated | stacked repeatedly. As such an example, an element configuration called “multi-photon emission” in which a part of the multilayer organic EL element is multilayered has been proposed in recent years for the purpose of improving light extraction efficiency. For example, in an organic EL device composed of a glass substrate / anode / hole transport layer / electron transporting light emitting layer / electron injection layer / charge generating layer / light emitting unit / cathode, the charge generating layer and the light emitting unit There is a method of laminating a plurality of portions.

  First, materials that can be used for each of these layers are specifically exemplified. However, materials that can be used in the present invention are not limited to these.

As a material that can be used for the hole injection layer, a phthalocyanine-based compound is effective, and copper phthalocyanine (abbreviation: CuPc), vanadyl phthalocyanine (abbreviation: VOPc), or the like can be used. There are also materials obtained by chemically doping conductive polymer compounds, such as polyethylenedioxythiophene (abbreviation: PEDOT) doped with polystyrene sulfonic acid (abbreviation: PSS), polyaniline (abbreviation: PANI), or the like. You can also. Further, thin films of inorganic semiconductors such as molybdenum oxide (abbreviation: MoO _x ), vanadium oxide (abbreviation: VO _x ), nickel oxide (abbreviation: NiO _x ), and inorganic insulation such as aluminum oxide (abbreviation: Al ₂ O ₃ ) An ultra-thin body film is also effective. In addition, 4,4 ′, 4 ″ -tris (N, N-diphenyl-amino) -triphenylamine (abbreviation: TDATA), 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N -Phenyl-amino] -triphenylamine (abbreviation: MTDATA), N, N'-bis (3-methylphenyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine (abbreviation) : TPD), 4,4′-bis [N- (1-naphthyl) -N-phenyl-amino] -biphenyl (abbreviation: α-NTPD), 4,4′-bis [N- (4- (N, Aromatic amine compounds such as (N-di-m-tolyl) amino) phenyl-N-phenylamino] biphenyl (abbreviation: DNTPD) can also be used. Further, a substance showing acceptability with respect to these aromatic amine compounds may be added to the aromatic amine compound, specifically, 2,3,5,6-tetrafluoro-7 which is an acceptor for VOPc. , 7,8,8-tetracyanoquinodimethane (abbreviation: F4-TCNQ), or α-NPD to which acceptor MoO _x is added may be used.

  As a material that can be used for the hole transport layer, an aromatic amine compound is preferable, and TDATA, MTDATA, TPD, α-NPD, DNTPD, and the like described for the hole injection material can be used.

  Examples of the electron transport material that can be used for the electron transport layer include tris (8-quinolinolato) aluminum (abbreviation: Alq3), tris (4-methyl-8-quinolinolato) aluminum (abbreviation: Almq3), bis (10-hydroxybenzo). [H] -quinolinato) beryllium (abbreviation: BeBq2), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (abbreviation: BAlq), bis [2- (2-hydroxyphenyl) benzoxazola And metal complexes such as zinc (substantially: Zn (BOX) 2) and bis [2- (2-hydroxyphenyl) benzothiazolate] zinc (substantially: Zn (BTZ) 2). In addition to metal complexes, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis [5- Oxadiazole derivatives such as (p-tert-butylphenyl) -1,3,4-oxadiazol-2-yl] benzene (abbreviation: OXD-7), 3- (4-tert-butylphenyl) -4 -Phenyl-5- (4-biphenylyl) -1,2,4-triazole (abbreviation: TAZ), 3- (4-tert-butylphenyl) -4- (4-ethylphenyl) -5- (4-biphenylyl) ) -1,2,4-triazole (abbreviation: p-EtTA Z) and other triazole derivatives, 2,2 ′, 2 ″-(1,3,5-benzenetriyl) tris [1-phenyl-1H-benz Imidazole] (abbreviated Imidazole derivatives such as TPBI), bathophenanthroline (abbreviation: can be used phenanthroline derivatives such as BCP): BPhen), bathocuproine (abbreviation.

Materials that can be used for the electron injection layer include Alq3, Almq3, BeBq2, BAlq, Zn (BOX) ₂ , Zn (BTZ) ₂ , PBD, OXD-7, TAZ, p-EtTAZ, TPBI, Electron transport materials such as BPhen and BCP can be used. In addition, an ultra-thin film of an insulator such as an alkali metal halide such as LiF or CsF, an alkaline earth halide such as CaF ₂ , or an alkali metal oxide such as Li ₂ O is often used. In addition, alkali metal complexes such as lithium acetylacetonate (abbreviation: Li (acac)) and 8-quinolinolato-lithium (abbreviation: Liq) are also effective. Further, a substance exhibiting a donor property with respect to these electron injection materials may be added to the electron injection material, and alkali metals, alkaline earth metals, rare earth metals, and the like can be used as donors. Specifically, a material obtained by adding lithium as a donor to BCP or a material obtained by adding lithium as a donor to Alq ₃ can be used.

  Furthermore, a hole blocking material that can prevent holes from passing through the light emitting layer from reaching the electron injection layer and form a layer having excellent thin film formability is used for the hole blocking layer. Examples of such hole blocking materials include aluminum complex compounds such as bis (8-hydroxyquinolinato) (4-phenylphenolato) aluminum, and bis (2-methyl-8-hydroxyquinolina). -To) (4-phenylphenolato) gallium complex compounds such as gallium, nitrogen-containing condensed aromatic compounds such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (abbreviation: BCP) Can be mentioned.

  Although there is no restriction | limiting in particular as a light emitting layer which obtains white light emission, For example, the following can be used. That is, the energy level of each layer of the organic EL laminated structure is defined and light is emitted using tunnel injection (European Patent No. 0390551). Similarly, a white light-emitting element is an example of an element using tunnel injection. What is described (JP-A-3-230584), a light-emitting layer having a two-layer structure (JP-A-2-220390 and JP-A-2-216790), and a plurality of light-emitting layers A layered material composed of materials having different emission wavelengths (Japanese Patent Laid-Open No. 4-51491), a blue light emitter (fluorescent peak 380 to 480 nm) and a green light emitter (480 to 580 nm), Further, a red phosphor is included (Japanese Patent Laid-Open No. 6-207170), the blue light emitting layer contains a blue fluorescent dye, and the green light emitting layer is a red fluorescent dye. It has contained area, such as construction of those (JP-A-7-142169) and the like further containing a green phosphor.

  Further, as the light emitting material used in the present invention, a material known as a conventional light emitting material may be used. Examples of compounds suitably used for blue, green, orange to red light emission are shown below. However, the light emitting material is not limited to those specifically exemplified below.

  Blue light emission can be obtained by using perylene, 2,5,8,11-tetra-t-butylperylene (abbreviation: TBP), 9,10-diphenylanthracene derivative, or the like as a guest material, for example. Further, styrylarylene derivatives such as 4,4′-bis (2,2-diphenylvinyl) biphenyl (abbreviation: DPVBi), 9,10-di-2-naphthylanthracene (abbreviation: DNA), 9,10-bis It can also be obtained from an anthracene derivative such as (2-naphthyl) -2-tert-butylanthracene (abbreviation: t-BuDNA). A polymer such as poly (9,9-dioctylfluorene) may also be used.

  Further preferred specific examples are shown in Table 1.

Green light is emitted from coumarin dyes such as coumarin 30 and coumarin 6, bis [2- (2,4-difluorophenyl) pyridinato] picolinatoiridium (abbreviation: FIrpic), bis (2-phenylpyridinato) acetyl. It can be obtained by using acetonatoiridium (abbreviation: Ir (ppy) (acac)) or the like as a guest material. In addition, metal complexes such as tris (8-hydroxyquinoline) aluminum (abbreviation: Alq ₃ ), BAlq, Zn (BTZ), bis (2-methyl-8-quinolinolato) chlorogallium (abbreviation: Ga (mq) ₂ Cl) Can also be obtained from A polymer such as poly (p-phenylene vinylene) may also be used.

Further preferred specific examples are shown in Table 2.

  Light emission from orange to red is caused by rubrene, 4- (dicyanomethylene) -2- [p- (dimethylamino) styryl] -6-methyl-4H-pyran (abbreviation: DCM1), 4- (dicyanomethylene) -2- Methyl-6- (9-julolidyl) ethynyl-4H-pyran (abbreviation: DCM2), 4- (dicyanomethylene) -2,6-bis [p- (dimethylamino) styryl] -4H-pyran (abbreviation: BisDCM) Bis [2- (2-thienyl) pyridinato] acetylacetonatoiridium (abbreviation: Ir (thp) 2 (acac)), bis (2-phenylquinolinato) acetylacetonatoiridium (abbreviation: Ir (pq) (acac) )) Etc. as a guest material. It can also be obtained from a metal complex such as bis (8-quinolinolato) zinc (abbreviation: Znq2) or bis [2-cinnamoyl-8-quinolinolato] zinc (abbreviation: Znsq2). A polymer such as poly (2,5-dialkoxy-1,4-phenylenevinylene) may be used.

  Further preferred specific examples are shown in Table 3.

Furthermore, the material used for the anode of the organic EL element used in the present invention is preferably a material having a work function (4 eV or more) metal, alloy, electrically conductive compound or a mixture thereof as an electrode substance. Specific examples of such an electrode substance include metals such as Au, and conductive materials such as CuI, ITO, SNO ₂ , and ZNO. In order to form this anode, a thin film can be formed from these electrode materials by a method such as vapor deposition or sputtering. The anode desirably has such a characteristic that when light emitted from the light emitting layer is extracted from the anode, the transmittance of the anode for light emission is greater than 10%. The sheet resistance of the anode is preferably several hundred Ω / cm ² or less. Further, although the film thickness of the anode depends on the material, it is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm.

The material used for the cathode of the organic EL device used in the present invention is a material having a work function (4 eV or less) metal, alloy, electrically conductive compound and a mixture thereof as an electrode substance. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / silver alloy, aluminum / aluminum oxide, aluminum / lithium alloy, indium, and rare earth metals. This cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Here, when light emitted from the light-emitting layer is extracted from the cathode, the transmittance of the cathode for light emission is preferably greater than 10%. Further, the sheet resistance as the cathode is preferably several hundred Ω / cm ² or less, and the film thickness is usually 10 nm to 1 μm, preferably 50 to 200 Nm.

  Regarding the method for producing the organic EL device used in the present invention, an anode, a light emitting layer, a hole injection layer as necessary, and an electron injection layer as necessary are formed by the above materials and methods, and finally a cathode is formed. What is necessary is just to form. Moreover, an organic EL element can also be produced from the cathode to the anode in the reverse order.

  This organic EL element is manufactured on a translucent substrate. This translucent substrate is a substrate that supports the organic EL element, and for the translucency, it is desirable that the transmittance of light in the visible region of 400 to 700 nm is 50% or more, preferably 90% or more, Further, it is preferable to use a smooth substrate.

  These substrates have mechanical and thermal strengths and are not particularly limited as long as they are transparent. For example, glass plates, synthetic resin plates and the like are preferably used. Examples of the glass plate include plates made of soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, and the like. Examples of the synthetic resin plate include plates such as polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyether sulfide resin, and polysulfone resin.

  As a method for forming each layer of the organic EL element used in the present invention, a dry film forming method such as vacuum deposition, electron beam beam irradiation, sputtering, plasma, ion plating, or spin coating, dipping, flow coating, inkjet A wet film-forming method such as a method, a method of vapor-depositing a light emitter on a donor film, JP-A-2002-534882, and S. T.A. Lee, et al. , Proceedings of SID'02, p. LITI (Laser Induced Thermal Imaging) method described in 784 (2002), printing (offset printing, flexographic printing, gravure printing, screen printing), inkjet, and the like can also be applied.

  The organic layer is particularly preferably a molecular deposited film. Here, the molecular deposited film is a thin film formed by deposition from a material compound in a gas phase state or a film formed by solidifying from a material compound in a solution state or a liquid phase state. Can be classified from a thin film (accumulated film) formed by the LB method according to a difference in an agglomerated structure and a higher-order structure and a functional difference resulting therefrom. Also, as disclosed in JP-A-57-51781, a binder such as a resin and a material compound are dissolved in a solvent to form a solution, and then this is thinned by a spin coat method or the like. Also, an organic layer can be formed. The film thickness of each layer is not particularly limited, but if the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. Conversely, if the film thickness is too thin, the pinhole is used. Or the like, and even when an electric field is applied, it is difficult to obtain sufficient light emission luminance. Accordingly, the thickness of each layer is suitably in the range of 1 nm to 1 μm, but more preferably in the range of 10 nm to 0.2 μm.

  Further, in order to improve the stability of the organic EL element against temperature, humidity, atmosphere, etc., a protective layer may be provided on the surface of the element, or the entire element may be covered or sealed with a resin or the like. In particular, when the entire element is covered or sealed, a photocurable resin that is cured by light is preferably used.

  The current applied to the organic EL element used in the present invention is usually a direct current, but a pulse current or an alternating current may be used. The current value and the voltage value are not particularly limited as long as they are within the range that does not destroy the element. However, considering the power consumption and life of the element, it is desirable to efficiently emit light with as little electrical energy as possible.

  The driving method of the organic EL element used in the present invention can be driven not only by the passive matrix method but also by the active matrix method. Further, the method for extracting light from the organic EL device of the present invention is applicable not only to the method of bottom emission for extracting light from the anode side but also to the method of top emission for extracting light from the cathode side. These methods and techniques are described in Shinji Kido, “All about organic EL”, published by Nihon Jitsugyo Shuppansha (published in 2003).

  The main method of the full color method of the organic EL element used in the present invention is a color filter method. The color filter method uses a white light emitting organic EL element to extract light of three primary colors through a color filter. In addition to these three primary colors, a part of white light is extracted as it is and used for light emission. In addition, the luminous efficiency of the entire device can be increased.

  Furthermore, the organic EL element used in the present invention may adopt a microcavity structure. This is because the organic EL device has a structure in which the light emitting layer is sandwiched between the anode and the cathode, and the emitted light causes multiple interference between the anode and the cathode, but the reflectance and transmission of the anode and the cathode This is a technology that actively uses the multiple interference effect and controls the emission wavelength extracted from the device by appropriately selecting the optical characteristics such as the rate and the film thickness of the organic layer sandwiched between them. . Thereby, it is also possible to improve the emission chromaticity. For the mechanism of this multiple interference effect, see J.A. Yamada et al., AM-LCD Digest of Technical Papers, OD-2, p. 77-80 (2002).

  As described above, an RGB color filter layer is produced in parallel with a glass substrate, and a light emitting layer (backlight) produced using the ITO electrode layer and the organic EL element is placed on the color filter layer. As a result, color display is possible, and a color display device is obtained. At this time, a color display device having a high contrast ratio can be realized by controlling the current flow during light emission by the TFT.

<Example of manufacturing organic EL element>
The production example of the organic EL element used as a white light source is specifically shown below. In the production examples of organic EL elements, all the mixing ratios are weight ratios unless otherwise specified. Vapor deposition (vacuum deposition) was performed in a vacuum of 10 ⁻⁶ Torr and under conditions without temperature control such as substrate heating and cooling. In the evaluation of the light emission characteristics of the element, the characteristics of an organic EL element having an electrode area of 2 mm × 2 mm were measured.

(Manufacture of organic EL element 1 (EL-1))
After the cleaned glass plate with the ITO electrode was treated with oxygen plasma for about 1 minute, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) was vacuum deposited, A hole injection layer having a thickness of 150 nm was obtained. On the hole injection layer, the compound (R-2) and the compound (R-3) shown in Table 3 were further co-deposited at a composition ratio of 100: 0.5 to form a first light emitting layer having a thickness of 20 nm. Formed. Furthermore, the compound (B-3) and the compound (B-4) shown in Table 1 were co-evaporated at a composition ratio of 100: 2 to form a second light emitting layer having a thickness of 40 nm. On this light emitting layer, tris (8-hydroxyquinoline) aluminum complex is further vacuum-deposited to form a third light emitting layer with a film thickness of 30 nm. The complex was vacuum-deposited to form an electron injection layer having a thickness of 20 nm, and 1 nm of lithium fluoride and then 300 nm of aluminum were deposited thereon to form an electrode, whereby an organic EL device 1 was obtained.

Furthermore, in order to protect this organic EL element from the surrounding environment, it was hermetically sealed in a dry glow box filled with pure nitrogen. This device produced white light emission with a direct current voltage of 5 V and an emission luminance of 950 (cd / m ² ), a maximum emission luminance of 55000 (cd / m ² ), and an emission efficiency of 3.9 (lm / W). FIG. 1 shows an emission spectrum of the obtained EL device (EL-1).

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

  The weight average molecular weight (Mw) of the resin and the pigment evaluation method are as follows.

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin was measured using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, TSK-GEL SUPER HZM-N connected in series as a column, and THF as a solvent. The molecular weight in terms of polystyrene.
(Evaluation of pigment)
(Identification of phthalocyanine)
The identification of phthalocyanine is the agreement between the molecular ion peak of the mass spectrum obtained using a time-of-flight mass spectrometer (autoflex III (TOF-MS), Bruker Daltonics) and the mass number obtained by calculation, and The ratio of carbon, hydrogen and nitrogen obtained using an elemental analyzer (2400CHN elemental analyzer, manufactured by Perkin Elmer) was matched with the theoretical value.

(Average number of halogen atom substitutions)
The average value of the number of halogen atoms substituted is analyzed by ion chromatography (ICS-2000 ion chromatography, manufactured by DIONEX) of a liquid in which the pigment is burned by the oxygen combustion flask method and the combustion product is absorbed in water. Then, the amount of halogen was quantified and obtained by converting to the average value of the number of halogen atom substitutions.

(Halogen distribution width in pigment)
The halogen distribution width is the signal intensity of each molecular ion peak corresponding to each component (each peak value) in a mass spectrum obtained using a time-of-flight mass spectrometer (autoflex III (TOF-MS), manufactured by Bruker Daltonics). ) And a value obtained by integrating each peak value (total peak value), and the number of peaks having a ratio of each peak value to 1% or more with respect to the total peak value was counted as a halogen distribution width.

(Volume average primary particle size (MV))
The volume average primary particle size (MV) was obtained by a transmission electron microscope (TEM) “H-7650” manufactured by Hitachi High-Technologies Corporation and the following calculation formula. First, colorant particles were photographed by TEM. In the obtained image, 100 arbitrary pigments or colorant particles were selected, and the average value of the minor axis diameter and major axis diameter of the primary particles was defined as the particle diameter (d) of the colorant particles. Next, each pigment or colorant was regarded as a sphere having the previously determined particle diameter (d), and the volume (V) of each particle was determined. This operation was performed for 100 pigment or colorant particles, and the calculation was performed using the following formula (1).

Formula (1)
MV = Σ (V · d) / Σ (V)

  First, the binder resin solution, the colorant, the pigment dispersant solution, and the method for producing the pigment dispersion used in Examples and Comparative Examples will be described.

<Binder-resin solution>
(Preparation of binder resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, cooling tube, nitrogen gas introduction tube, dropping tube and stirring device was charged with 196 parts of propylene glycol monomethyl ether acetate, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen After that, from the dropping tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) ) A mixture of 20.7 parts and 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Ether ether was added to prepare a binder resin solution 1. The weight average molecular weight (Mw) was 26000.

(Preparation of binder resin solution 2)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, cooling tube, nitrogen gas introduction tube, dropping tube and stirring device was charged with 207 parts of propylene glycol monomethyl ether acetate, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen Then, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2, 2 A mixture of 1.33 parts of '-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Ether ether was added to prepare a binder resin solution 2. The weight average molecular weight (Mw) was 18000.

<Preparation of resin-type dispersant solution>
(Resin Dispersant Solution 1)
EFKA4300 manufactured by BASF, which is a commercially available resin type dispersant, and propylene glycol monomethyl ether acetate were mixed to prepare a solution having a nonvolatile content of 40% by mass, and a resin type dispersant solution 1 was obtained.
(Resin Dispersant Solution 2)
A commercially available resin type dispersant LPN2116 manufactured by BYK and propylene glycol monomethyl ether acetate were mixed to prepare a solution having a nonvolatile content of 40% by mass, and a resin type dispersant solution 1 was obtained.

<Method for producing colorant>
(Production of phthalocyanine pigment (P-1))
In a reaction vessel, 1250 parts of n-amyl alcohol and 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were mixed and stirred. To this, 266 parts of DBU (1,8-Diazabicclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine (P-1).
Elemental analysis was performed on the obtained chloroaluminum phthalocyanine. As a result, the calculated value (C) 66.85%, (H) 2.80%, and (N) 19.49% were compared with the actually measured value (C) 66. 7%, (H) 3.0%, (N) 19.2%, and identified as the target compound.

(Production of phthalocyanine pigment (P-2))
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine (P-1) was slowly added to 1200 parts of concentrated sulfuric acid at room temperature. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water and dried to obtain 92 parts of hydroxyaluminum phthalocyanine (P-2).

(Production of phthalocyanine pigment (CP-1))
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine (P-1) was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 40 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added, followed by stirring at 25 ° C. for 6 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3 ° C., and the resulting precipitate was treated in the order of filtration, water washing, 1% sodium hydroxide aqueous solution washing and water washing, followed by drying to obtain 125 parts of phthalocyanine. A pigment (CP-1) was obtained.
When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (CP-1), it was an average of 1.8, and a peak corresponding to the same molecular weight was also confirmed from the mass spectrum, and identified as the target compound. did. The halogen distribution width was 3.

(Production of phthalocyanine pigment (CP-2))
(CP-1) except that 40 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) were changed to 80 parts of N-bromosuccinimide (NBS) in the production of the phthalocyanine pigment (CP-1). In the same manner, 143 parts of a phthalocyanine pigment (CP-2) was produced. Table 4 shows the average value of the number of halogen atom substitutions represented by X and the halogen distribution width.

(Production of phthalocyanine pigments (CP-3, CP-4))
In the production of the phthalocyanine pigment (CP-1), except that the amount of DBDMH was changed to the conditions described in Table 4, 143 parts of phthalocyanine pigment (CP-3, CP, -4) was obtained. Table 4 shows the average value of the number of halogen atom substitutions represented by X and the halogen distribution width.

(Production of phthalocyanine pigment (CP-5))
In a reaction vessel, 406 parts of aluminum chloride, 94 parts of sodium chloride and 10 parts of ferric chloride were heated and melted, and 100 parts of chloroaluminum phthalocyanine (P-1) was further added at 140 ° C. The temperature was raised to 160 ° C. and 20 parts of chlorine was blown. The above reaction solution is poured into 5000 parts of water, treated in the order of filtration, hot water washing, 1% hydrochloric acid aqueous solution washing, warm water washing, 1% sodium hydroxide aqueous solution washing, hot water washing, and then dried and crude chlorination. 160 parts of aluminum phthalocyanine were obtained.
The obtained crude chlorinated aluminum phthalocyanine was dissolved in 1200 parts of concentrated sulfuric acid and stirred at 50 ° C. for 3 hours. Next, the solution was poured into 7200 parts of water with stirring, heated to 70 ° C., filtered, washed with warm water, washed with 1% aqueous sodium hydroxide, washed with warm water, dried, and 152 parts of phthalocyanine pigment (CP-5). ) Table 4 shows the average value of the number of halogen atom substitutions represented by X and the halogen distribution width.

(Production of phthalocyanine pigments (CP-6, CP-7))
In the production of the phthalocyanine pigment (CP-5), 168 parts of phthalocyanine pigments (CP-6, CP, respectively) were obtained in the same manner as (CP-5) except that the amount of chlorine was changed to the conditions described in Table 2. -7) was obtained. Table 4 shows the average value of the number of halogen atom substitutions represented by X and the halogen distribution width.

(Production of phthalocyanine pigment (CP-8))
In the production of the phthalocyanine pigment (CP-1), 40 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) are replaced with 45 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) and N- 141 parts of phthalocyanine pigment (CP-8) were obtained in the same manner as (CP-1) except that the amount was changed to 45 parts of chlorosuccinimide (NCS). Table 4 shows the average value of the number of halogen atom substitutions represented by X and the halogen distribution width.

(Production of phthalocyanine pigment (CP-9))
In the production of the phthalocyanine pigment (CP-1), 40 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) were changed to 120 parts of 1,3-diiodo-5,5-dimethylhydantoin (DIDMH). Otherwise, 135 parts of a phthalocyanine pigment (CP-9) was obtained in the same manner as (CP-1). Table 4 shows the average value of the number of halogen atom substitutions represented by X and the halogen distribution width.

  The structural formulas of the phthalocyanine pigments (CP-1) to (CP-9) are shown below. In the structural formula, the number of halogen atoms bonded to the phthalocyanine ring is an average value of the number of halogen atoms substituted.

(Production of phthalocyanine pigment (CP-10))
To the reaction vessel, 500 parts of concentrated sulfuric acid, 50 parts of hydroxyaluminum phthalocyanine (P-2) and 99.1 parts of N-bromosuccinimide (NBS) were added and stirred, and reacted at 20 ° C. for 3 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added and stirred at 80 ° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water, and dried to obtain a phthalocyanine pigment (CP-10). Table 5 shows the yield, the yield, the average value of the number of substitution of halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment (CP-11))
In the production of the phthalocyanine pigment (CP-10), 50 parts of hydroxyaluminum phthalocyanine (P-2) is added to 50 parts of chloroaluminum phthalocyanine (P-1) and 99.1 parts of NBS is 1,3-dibromo-5,5- A phthalocyanine compound (CP-11) was obtained in the same manner as (CP-10) except that 104.4 parts of dimethylhydantoin (DBDMH) was changed from 3 hours to 4 hours. Table 5 shows the yield, the yield, the average value of the number of substitution of halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment (CP-12))
In the production of the phthalocyanine pigment (CP-11), the phthalocyanine compound (CP-12) was prepared in the same manner as (CP-11) except that the amount of DBDMH and the reaction time were changed to the conditions described in Table 6, respectively. Obtained. Table 5 shows the yield, the yield, the average value of the number of substitution of halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment (CP-13))
In a reaction vessel, 203 parts of aluminum bromide, 47 parts of sodium bromide and 5 parts of ferric bromide were heated and melted, and 50 parts of chloroaluminum phthalocyanine (P-2) was added at 140 ° C. The temperature was raised to 160 ° C., and the reaction was carried out at 160 ° C. for 6 hours while blowing 173.7 parts of bromine. The above reaction mixture was poured into 2500 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. The residue was washed with 1% hydrochloric acid aqueous solution, warm water, 1% sodium hydroxide aqueous solution and warm water in this order, and then dried to obtain 98 parts of brominated aluminum phthalocyanine. The obtained crude brominated aluminum phthalocyanine was dissolved in 980 parts of concentrated sulfuric acid and stirred at 50 ° C. for 3 hours. Thereafter, the sulfuric acid solution was poured into 9800 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration, washed with water, and dried. Next, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added to the beaker, and the mixture was stirred at 80 ° C. for 1 hour. Thereafter, the mixture was collected by filtration, washed with water, and dried to obtain a phthalocyanine pigment (CP-13). Table 5 shows the yield, the yield, the average value of the number of substitution of halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigments (CP-14, CP-15))
In the production of the phthalocyanine pigment (CP-13), except that the amount of bromine and the reaction time were changed to the conditions described in Table 4, respectively, in the same manner as (CP-13), the phthalocyanine pigment (CP-14, CP-15) was obtained. Table 5 shows the yield, the yield, the average value of the number of substitution of halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment (CP-16))
(CP-10) except that 99.1 parts of NBS was changed to 74.4 parts of N-chlorosuccinimide (NCS) and the reaction time was changed from 3 hours to 4 hours in the production of the phthalocyanine pigment (CP-10). Similarly, a phthalocyanine pigment (CP-16) was obtained. Table 5 shows the yield, the yield, the average value of the number of substitution of halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment (CP-17))
To the reaction vessel, 250 parts of aluminum chloride, 60 parts of sodium chloride and 2.25 parts of iodine were added and stirred at 150 ° C. for 30 minutes. Thereto was added 50 parts of hydroxyaluminum phthalocyanine (P-2), and the mixture was stirred at 155 ° C. for 30 minutes to be dissolved. Further, 58.5 parts of trichloroisocyanuric acid was added and stirred at 190 ° C. for 5 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added and stirred at 80 ° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water, and dried to obtain a phthalocyanine pigment (CP-17). Table 5 shows the yield, the yield, the average value of the number of substitution of halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigments (CP-18 to CP-21))
In the production of the phthalocyanine pigment (CP-17), except that the amount of trichloroisocyanuric acid and the reaction time were changed to the conditions described in Table 4, respectively, the same as for (CP-17), respectively, the phthalocyanine pigment (CP- 18 to CP-21) were obtained. Table 5 shows the yield, the yield, the average value of the number of substitution of halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment (CP-22))
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine (P-1) was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 45.0 parts of trichloroisocyanuric acid was gradually added, followed by stirring at 25 ° C. for 3 hours. Thereafter, 210.0 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added, followed by stirring at 25 ° C. for 5 hours. Subsequently, this sulfuric acid solution is poured into 9000 parts of cold water at 3 ° C., and the formed precipitate is treated in the order of filtration, water washing, 1% sodium hydroxide aqueous solution washing and water washing, followed by drying, 165.7 parts. Phthalocyanine pigment (CP-22) was obtained. Table 5 shows the yield, the yield, the average value of the number of substitution of halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment (CP-23))
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine (P-1) was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 125.0 parts of trichloroisocyanuric acid was gradually added, followed by stirring at 25 ° C. for 3 hours. Thereafter, 155.0 parts of 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) was gradually added, and the mixture was stirred at 25 ° C. for 5 hours. Subsequently, the sulfuric acid solution was poured into 9000 parts of cold water at 3 ° C., and the formed precipitate was treated in the order of filtration, water washing, 1% sodium hydroxide aqueous solution washing and water washing, and then dried to 157.1 parts. Phthalocyanine pigment (CP-23) was obtained. Table 5 shows the yield, the yield, the average value of the number of substitution of halogen atoms represented by X, and the halogen distribution width.

(Production of phthalocyanine pigment (CP-24))
In a reaction vessel, 100 parts of chloroaluminum phthalocyanine (P-1) was added to 1500 parts of concentrated sulfuric acid in an ice bath. Thereafter, 45.0 parts of trichloroisocyanuric acid was gradually added, followed by stirring at 25 ° C. for 3 hours. Thereafter, 205.0 parts of 1,3-diiodo-5,5-dimethylhydantoin (DIDMH) was gradually added, followed by stirring at 25 ° C. for 5 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3 ° C., and the produced precipitate was treated in the order of filtration, water washing, 1% sodium hydroxide aqueous solution washing and water washing, and dried to obtain 145.3 parts. Phthalocyanine pigment (CP-24) was obtained. Table 5 shows the yield, the yield, the average value of the number of substitution of halogen atoms represented by X, and the halogen distribution width.

  The structural formulas of the obtained phthalocyanine pigments (CP-10 to CP-24) are shown below. However, in the structural formula, the number of halogen atoms bonded to the phthalocyanine ring is an average value of the number of halogen atoms substituted.

(Production of phthalocyanine pigment (PCY-1))
To the reaction vessel, 1000 parts of 1-methyl-2-pyrrolidinone, 100 parts of phthalocyanine pigment (CP-1) and 40 parts of diphenylphosphinic acid were added. After reacting at 85 ° C. for 3 hours, this solution was poured into 5000 parts of water. The reaction product was filtered, washed with 12000 parts of water, and dried overnight at 60 ° C. under reduced pressure to obtain 124 parts of a phthalocyanine pigment (PCY-1).
When the number of bromine substitutions was calculated for the obtained phthalocyanine pigment (PCY-1), it was 1.7 on average, and a peak corresponding to the same molecular weight was confirmed from the mass spectrum, and the target compound was identified. did. The halogen distribution width was 3.

(Production of phthalocyanine pigments (PCY-2 to CP-19))
In the production of the phthalocyanine pigment (PCY-1), the same operations as in (PCY-1) were carried out except that the raw material phthalocyanine pigment and acidic compound were changed to the conditions described in Table 6, respectively. PCY-2 to PCY-19) were obtained. Table 7 shows the average value of the number of substitutions of halogen atoms represented by X and the halogen distribution width.

Hereinafter, structural formulas of the phthalocyanine pigments (PCY-1 to PCY-19) are shown. In the structural formula, the number of halogen atoms bonded to the phthalocyanine ring is an average value of the number of halogen atoms substituted.

(Production of phthalocyanine pigment (PCY-20))
To the reaction vessel, 500 parts of N-methylpyrrolidone, 50 parts of phthalocyanine pigment (CP-10) and 18.2 parts of diphenyl phosphate were added, heated to 90 ° C., and reacted for 8 hours. After cooling this to room temperature, this reaction solution was poured into 4000 parts of water. The product was filtered, washed with methanol, and dried to obtain a phthalocyanine pigment (PCY-20). Table 9 shows the yield, yield, average value of the number of substitutions of halogen atoms represented by X, and halogen distribution width.

(Production of phthalocyanine pigments (PCY-21 to PCY-42))
In the production of the phthalocyanine pigment (PCY-20), the same operations as in (PCY-20) were performed except that the raw material phthalocyanine pigment and acidic compound were changed to the conditions described in Table 8, respectively. PCY-21 to PCY-42) were obtained. Table 9 shows the yield, yield, average value of the number of substitutions of halogen atoms represented by X, and halogen distribution width.

  The structural formula of the obtained phthalocyanine pigment (PCY-20 to PCY-42) is shown below. However, in the structural formula, the number of halogen atoms bonded to the phthalocyanine ring is an average value of the number of halogen atoms substituted.

<Method for producing green pigment dispersion>
(Preparation of green pigment dispersion DG-1)
After uniformly stirring and mixing the mixture having the following composition, it was dispersed for 5 hours with an Eiger mill (Eiger Japan's “Mini Model M-250 MKII”) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A red colorant body DG-1 was produced.
Phthalocyanine pigment (PCY-1): 11.0 parts Binder resin solution 1: 17.5 parts Resin-type dispersant solution 1: 5.0 parts ("EFKA4300" manufactured by BASF)
Propylene glycol monomethyl ether acetate (PGMAc): 65.0 parts

(Preparation of green pigment dispersions DG-2 to DG-42)
Green pigment dispersions DG-2 to DG-42 were prepared in the same manner as DG-1, except that the phthalocyanine pigment was changed as shown in Tables 10 and 11.

(Yellow fine pigment (PY-1))
C. I. 100 parts of Pigment Yellow 185 (PY185) (“Pariogen Yellow D1155” manufactured by BASF), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. . The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 95 parts of yellow A colorant (PY-1) was obtained. The average primary particle size was 42.3 nm.

(Yellow pigment dispersion (DY-1))
(Preparation of yellow pigment dispersion DY-1)
After uniformly stirring and mixing the mixture having the following composition, it was dispersed for 5 hours with an Eiger mill (Eiger Japan's “Mini Model M-250 MKII”) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A red colorant body DG-1 was produced.
Yellow refined pigment (PY-1): 21.5 parts Binder resin solution 1: 17.0 parts Resin-type dispersant solution 1: 5.5 parts ("EFKA4300" manufactured by BASF)
Propylene glycol monomethyl ether acetate (PGMAc): 66.5 parts

<Pigment production method>
(Yellow fine pigment (PY-2))
C. I. 100 parts of Pigment Yellow 139 (PY139) ("Irgafore Yellow 2R-CF" manufactured by BASF), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C for 6 hours. Kneaded. The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 95 parts of yellow A colorant (PY-2) was obtained. The average primary particle size was 42.3 nm.

(Yellow fine pigment (PY-3))
Using compound (1) as a raw material, compound (2) was obtained according to the synthesis method described in JP-A-2008-81566.

(Compound (1))

(Compound (2))

To 300 parts of methyl benzoate, 100 parts of compound (2), 108 parts of tetrachlorophthalic anhydride and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. The formation of the compound (3) and the disappearance of the starting compound (2) were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was added to 3510 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 120 parts of compound (3). As a result of mass spectrometry by TOF-MS, it was identified as compound (3).

(Compound (3))

  Subsequently, 100 parts of the obtained compound (3), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow refined pigment (PY-3) were obtained.

(Yellow fine pigment (PY-4))
Compound (3) was converted to C.I. I. 98 parts of a yellow colorant (PY-4) was obtained in the same manner as the yellow fine pigment (PY-3) except that the pigment yellow 138 was changed to "Pariol yellow K0961HD" manufactured by BASF. The average primary particle size was 35.5 nm.

(Green fine pigment (PG-1))
Phthalocyanine green pigment C.I. I. Pigment Green 7 (PG7) (“Rionol Green YS-07” manufactured by Toyocolor Co., Ltd.) 200 parts, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 120 ° C. Kneaded for 4 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. And 490 parts of a green colorant (PG-1) was obtained. The average primary particle size was 50.2 nm.

(Green fine pigment (PG-2))
Phthalocyanine green pigment C.I. I. Pigment Green 7 (PG7) is C.I. I. 97 parts of a green colorant (PG-2) was obtained in the same manner as the green fine pigment (PG-1) except that it was changed to CI Pigment Green 58 (“FASTOGEN GreenA110” manufactured by DIC). The average primary particle size was 28.2 nm.

(Green fine pigment (PG-3))
In a reaction vessel, 1000 parts of methanol, 100 parts of phthalocyanine pigment (P-2) and 49.5 parts of diphenyl phosphate were added, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of an aluminum phthalocyanine pigment represented by the general formula (6).
100 parts of the obtained aluminum phthalocyanine pigment represented by the general formula (6), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. did. The kneaded product is poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a whole day and night. A fine pigment (PG-3) was obtained. The average primary particle size was 31.2 nm.

General formula (6)

(Green fine pigment (PG-4))
In a reaction vessel, add 1000 parts of methanol and 100 parts of aluminum phthalocyanine pigment represented by phthalocyanine pigment (P-2) and 43.2 parts of diphenylphosphinic acid to 1000 parts of methanol, heat to 40 ° C., and react for 8 hours. It was. After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain 112 parts of an aluminum phthalocyanine pigment represented by the general formula (7).
The resulting aluminum phthalocyanine pigment represented by the general formula (7) was subjected to a salt milling process similar to that for the blue colorant (PB-1) to obtain a green fine pigment (PG-4). The average primary particle size was 29.5 nm.

General formula (7)

(Preparation of yellow pigment dispersion DY-2)
After uniformly stirring and mixing the mixture having the following composition, it was dispersed for 5 hours with an Eiger mill (Eiger Japan's “Mini Model M-250 MKII”) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A red colorant body DG-1 was produced.
Yellow refined pigment (PY-2): 11.0 parts Binder resin solution 1: 21.5 parts Resin-type dispersant solution 1: 1.0 part (“EFKA4300” manufactured by BASF)
Propylene glycol monomethyl ether acetate (PGMEA): 66.5 parts

(Preparation of yellow pigment dispersion DY-3, 4 and green pigment dispersion DG43-46)
A yellow pigment dispersion DY-3,4 and a green pigment dispersion DG43-46 were prepared in the same manner as the yellow pigment dispersion DY-2 except that the composition was changed to the composition shown in Table 12.

(Photopolymerizable monomer (B1-1))
A five-neck reaction vessel with an internal volume of 1 liter is charged with 623 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Aronix M-400 (manufactured by Toagosei Co., Ltd.)) and 44 g of hexamethylene diisocyanate at 60 ° C. It was made to react for 8 hours and the product containing polyfunctional urethane acrylate (1) was obtained. The proportion of the polyfunctional urethane acrylate (1) in the product was 45% by weight, and a photopolymerizable monomer (B1-1) in which the remainder was occupied by another photopolymerizable monomer was obtained.
In addition, it was confirmed by IR analysis that no isocyanate group was present in the reaction product.

(Photopolymerizable monomer (B1-2))
A five-neck reaction vessel with an internal volume of 1 liter was charged with 600 g of trimethylolpropane hexamethylene diisocyanate adduct (Coronate HL (manufactured by Tosoh Corporation)) and 950 g of pentaerythritol triacrylate, and reacted at 60 ° C. for 8 hours. A product containing a functional urethane acrylate (2) was obtained. The proportion of the polyfunctional urethane acrylate (2) in the product was 80% by weight, and a photopolymerizable monomer (B1-2) in which the remainder was occupied by another photopolymerizable monomer was obtained.
In addition, it was confirmed by IR analysis that no isocyanate group was present in the reaction product.

<Green photosensitive coloring composition for organic EL color filter>
[Example 1]
(Green photosensitive coloring composition (RG-1))
A mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain a green photosensitive coloring composition (RG-1).

Green pigment dispersion (DG-1) 27.2 parts (PCY-1)
Yellow pigment dispersion (DY-1) 36.5 parts (PY185)
Binder resin solution 2 4.5 parts Photopolymerizable monomer 1.5 parts ("Aronix M-402" manufactured by Toagosei Co., Ltd.)
Oxime ester-based compound 1.9 parts (“ADEKA CRUISE NCI831” manufactured by ADEKA)
57.3 parts propylene glycol monomethyl ether acetate (PGMAc)

[Examples 2 to 66, Comparative Examples 1 to 10]
Green photosensitive coloring compositions RG-2 to 76 were prepared in the same manner as the green photosensitive coloring composition RG-1, except that the compositions shown in Table 13-15 were changed.

Abbreviations in Tables 13 to 15 are described below.
Photopolymerizable monomer [B]: Dipentaerythritol hexaacrylate / pentaacrylate mixture (“Aronix M402” manufactured by Toagosei Co., Ltd.)

(Oxime ester compound [C1])
・ Oxime ester compound (C1-1):
("ADEKA CRUISE NCI-831" manufactured by ADEKA)
Oxime ester photopolymerization initiator (C1-2): ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)
("IRGACURE OXE 02" manufactured by BASF)
Oxime ester photopolymerization initiator (C1-3): a compound having the structure of the following chemical formula (4)

Chemical formula (4)

Oxime ester photoinitiator (C1-4): Compound chemical formula (5) having the structure of the following chemical formula (5)

(Other photopolymerization initiators)
2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one ("IRGACURE 907" manufactured by BASF)
(Sensitizer)
2,4-diethylthioxanthone (“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
PGMAc; propylene glycol monomethyl ether acetate

<Evaluation of green photosensitive coloring composition for organic EL display device>
Using the obtained photosensitive coloring composition, a green filter segment was formed, and brightness, coloring power, and chemical resistance were evaluated by the following methods. The results are shown in Tables 16-18.

<Formation of green filter segment>
The green photosensitive coloring composition (RG-1 to RG-78) was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and then dried at 70 ° C. for 20 minutes. Using a high-pressure mercury lamp, UV exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. Subsequently, after heating and cooling at 230 ° C. for 20 minutes, the coated substrate was obtained. The alkali developer was 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant (“Perex NBL” manufactured by Kao Corporation), and 90% by weight of water. The thing which consists of was used.

[Brightness evaluation]
The lightness Y of the obtained coating film base was measured using an organic EL element (EL-1) as a light source. The prepared coated substrate was subjected to heat treatment at 230 ° C., and an organic EL element (EL-1) was used as a light source so as to meet chromaticity of x = 0.210 and y = 0.700. The brightness (Y) of the obtained green filter segment was measured using an organic EL element (EL-1) as a light source. The evaluation criteria are as follows.
◎: 36.0 or more: Extremely good for practical use ○: 33.0 or more and less than 36.0: Good △: 30.0 or more and less than 33.0: Practical use ×: Less than 30.0: Unpreferable for practical use

[Evaluation of coloring power]
First, a coating film substrate was formed by the same method as the brightness evaluation. When the hue of the obtained green filter segment is x = 0.210 and y = 0.700 when the organic EL element (EL-1) is used as a light source, the film thickness of the green filter segment is measured. The coloring power was evaluated. In the measurement, a stylus type step gauge (DeVACaK8 manufactured by ULVAC) was used. The evaluation criteria are as follows.
A: 1.5 μm or more and less than 2.5 μm: Extremely good ○: 2.5 μm or more and less than 3.0 μm: Good Δ: 3.0 μm or more and less than 3.5 μm: Practical use ×: 3.5 μm or more: Impractical use

[Evaluation of chemical resistance]
<NMP resistance test evaluation 1>
For the stripe pattern formed for evaluating the lightness and coloring power, the chromaticity ([L * (1), a * (1), b * (1) when the organic EL element (EL-1) is used as the light source]. )]) Was measured. Furthermore, the substrate on which the stripe pattern is formed is immersed in NMP for 15 minutes, washed with water, dried, and then the chromaticity with a C light source ([L * (2), a * (2), b * (2)]) The color difference ΔE * ab was determined by the following calculation formula and evaluated in the following four stages.

ΔE * ab = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )

A: ΔE * ab is less than 1.0
○: ΔE * ab is 1.0 or more and less than 1.5
Δ: ΔE * ab is 1.5 or more and less than 3.0 ×: ΔE * ab is 3.0 or more

<NMP resistance test evaluation 2>
The board | substrate with which the stripe pattern formed for the said brightness and coloring power evaluation was formed was immersed in NMP for 15 minutes, and after water washing and drying, the external appearance of the green pixel was observed with the following method.
The surface of 50 pixels was observed using a metal microscope “BX60” (manufactured by Olympus System) with 25 μm × 100 μm as one pixel. The magnification was 500 times, and the number of pixels in which cracks occurred due to reflection was counted. Evaluation was performed in the following four stages.

◎: No cracking of 50 pixels ○: Number of cracking pixels 1 or more, less than 10 Δ: Number of cracking pixels 10 or more, less than 30 ×: Number of cracking pixels 30 or more

As shown in Examples 1-46 in Tables 16 to 18, phthalocyanine pigments represented by the general formula (1) and C.I. I. The photosensitive coloring composition containing Pigment Yellow 185 and the oxime ester compound [C1] has a colorant content of 40% by weight or more based on the total solid weight of the photosensitive coloring composition for color filter However, it showed good results in lightness, coloring power and chemical resistance.
Further, as shown in Example 1-22, the phthalocyanine pigment represented by the general formula (2) and C.I. I. The photosensitive coloring composition containing Pigment Yellow 185 and the oxime ester compound [C1] also showed good results in coloring power.
Further, as shown in Examples 47 to 58, even when the content of the colorant was 45% by weight or more based on the weight of the total solid content of the photosensitive coloring composition for color filter, good results were obtained in coloring power. .
Furthermore, as shown in Examples 59-66, when the content of the colorant is 45% by weight or more based on the total solid content of the photosensitive coloring composition for color filter, the polyfunctional urethane acrylate (B1) is added. When contained, the chemical resistance was even better.

On the other hand, as in Comparative Example 1, C.I. I. When CI Pigment Green 7 was used, brightness and NMP resistance evaluations 1 and 2 were inferior to those of the present invention.
Further, as in Comparative Example 2, C.I. I. When CI Pigment Green 58 was used, coloring power and NMP resistance evaluations 1 and 2 were inferior to those of the present invention.
Further, when the phthalocyanine pigments of Comparative Examples 3 and 4 were used, NMP resistance evaluations 1 and 2 were inferior to those of the present invention in addition to one of brightness and coloring power.
Even when a green pigment dispersion or a yellow pigment dispersion was combined as in Comparative Examples 5 and 6, the coloring power and NMP resistance evaluations 1 and 2 were inferior to those of the present invention.
Moreover, when it combined with photoinitiators other than an oxime ester type compound (C1) like the comparative example 7, NMP tolerance evaluation 1, 2 was inferior to this invention.
Further, as shown in Comparative Examples 8 to 10, a phthalocyanine pigment represented by the general formula (1), which is a feature of the present invention, and C.I. I. Even combinations of pigments other than CI Pigment Yellow 185 were not able to satisfy all the characteristics of brightness, tinting strength and NMP resistance test as in the present invention.

<Production of color filter>
First, the red photosensitive coloring composition and the blue photosensitive coloring composition used for preparation of a color filter were produced.

<Pigment production method>
(Red refined pigment (PR-1))
C. I. Pigment Red 269 (PR269) (Clariant “Toner Magenta F8B”) 100 parts, sodium chloride 1200 parts and diethylene glycol 120 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours. And salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a refined naphthol azo pigment (PR-1) were obtained. The average primary particle size was 37 nm.

(Blue refined pigment (PB-1))
C. I. 100 parts of Pigment Blue 15: 6 (PB15: 6) (“Rionol Blue ES” manufactured by Toyocolor Co., Ltd.), 800 parts of crushed salt, and 100 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho), 70 The mixture was kneaded for 12 hours. The mixture was poured into 3000 parts of warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 98 parts of blue A colorant (PB-1) was obtained. The average primary particle size was 28.3 nm.

(Purple refined pigment (PV-1))
C. I. 120 parts of Pigment Violet 23 (PV23) (“Fast Violet RL” manufactured by Clariant), 1600 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. The mixture was poured into 5000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 118 parts of purple A colorant (PV-1) was obtained. The average primary particle size was 26.4 nm.

(Red pigment dispersion (DR-1))
(Preparation of red pigment dispersion (DR-1))
After uniformly stirring and mixing the mixture having the following composition, it was dispersed for 5 hours with an Eiger mill (Eiger Japan's “Mini Model M-250 MKII”) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A red colorant body DG-1 was produced.
Red fine pigment (PR-1): 21.5 parts Binder resin solution 1: 17.0 parts Resin type dispersant solution 1: 5.5 parts ("EFKA4300" manufactured by BASF)
Propylene glycol monomethyl ether acetate (PGMAc): 66.5 parts

(Preparation of blue pigment dispersion (DB-1) and purple pigment dispersion (DV-1))
A blue pigment dispersion (DB-1) and a purple pigment dispersion (DV-1) were prepared in the same manner as the red pigment dispersion (DR-1) except that the composition was changed to the composition shown in Table 19.

(Preparation of red photosensitive coloring composition (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a red photosensitive coloring composition (RR-1).

Pigment dispersion (DR-1): 30.2 parts (PR269)
Pigment dispersion (DY-2): 8.4 parts (PY139)
Binder resin solution 2: 15.2 parts Photopolymerizable monomer: 0.7 parts (“Aronix M402” manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator: 0.3 part ("IRGACURE OXE-02" manufactured by BASF)
Solvent: 44.2 parts (propylene glycol monomethyl ether acetate (PGMAc))

(Preparation of blue photosensitive coloring composition (RB-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (RB-1).
Pigment dispersion (DB-1): 10.4 parts (PB15: 6)
Pigment dispersion (DV-1): 6.1 parts (PV23)
Binder resin solution 2: 24.2 parts Photopolymerizable monomer: 0.7 parts ("Aronix M402" manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator: 0.3 part ("IRGACURE OXE-02" manufactured by BASF)
Solvent: 44.2 parts (propylene glycol monomethyl ether acetate (PGMAc))

<Preparation of color filter for organic EL display device>
The green filter segment formed by the same method as the green filter segment of Example 1 using the green photosensitive coloring composition (RG-1), the organic EL element (EL-1) as the light source, and the red filter segment is The photosensitive green coloring composition (RR-1) is used so that the chromaticity of x = 0.670 and y = 0.330 is met, and the blue filter segment is the photosensitive blue coloring composition (RB-1). Was applied to meet the chromaticity of x = 0.140 and y = 0.080, and a color filter was prepared.

  By using the green photosensitive coloring composition (RG-1) of the present invention, it is possible to increase the brightness of the color filter and to use it suitably.

As described above, by using the green photosensitive coloring composition (RG-1) of the present invention, the color filter has high brightness and good chemical resistance. Therefore, even when used in an organic EL display, an organic EL device is used. It was possible to use it suitably without damaging it.

Claims (7)

A photosensitive coloring composition for an organic EL display device comprising a colorant (A), a binder resin, a photopolymerizable monomer (B) and a photopolymerizable initiator (C), wherein the colorant (A) is A phthalocyanine pigment represented by the following general formula (1); I. Pigment Yellow 185, and the photopolymerizable initiator (C) contains an oxime ester compound (C1), a green photosensitive coloring composition for an organic EL display device.

General formula (1)

(In the formula, X represents a halogen atom, and n represents an integer of 1 to 16. However, the average value of the number of substitutions of the halogen atom represented by X is 1 to 15, and the halogen distribution width is And Y represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ , wherein R ₁ and R ₂ are each independently selected. In addition, a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent or an aryloxy which may have a substituent R ₃ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. R ₄ represents a hydroxyl group, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Represents a heterocyclic group which may have a reel group or a substituent.) The green photosensitive coloring composition for organic EL display devices according to claim 1, wherein the phthalocyanine pigment represented by the general formula (1) is a phthalocyanine pigment represented by the general formula (2).

General formula (2)


(In the formula, X ₁ represents a halogen atom, and n represents an integer of ₁ to 16. However, the average value of the number of substitutions of the halogen atom represented by X ₁ is 1 or more and less than 6, The distribution width is not less than 2. Y represents —OP (═O) R ₁ R ₂ , —OC (═O) R ₃ , —OS (═O) ₂ R ₄ , where R ₁ and R ₂ are Each independently has a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent or a substituent. R ₃ represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent or a substituent. .R ₄ representing a heterocyclic group which may have a can have a hydroxyl group, an optionally substituted alkyl group, a substituent Have an aryl group or a substituted group represents a heterocyclic group.)   The green photosensitive property for an organic EL display device according to claim 1 or 2, wherein the content of the colorant (A) is 40% by weight or more in 100% by weight of the total solid content of the green photosensitive coloring composition. Coloring composition.   The green photosensitive coloring composition for organic EL display devices according to any one of claims 1 to 3, wherein the photopolymerizable monomer (B) contains a polyfunctional urethane acrylate (B1). 5. The organic EL display device color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one green filter segment is the organic EL according to claim 1. A color filter for an organic EL display device, which is formed from a green photosensitive coloring composition for a display device. An organic EL display device comprising the color filter for an organic EL display device according to claim 5 and a white organic EL light source. The white organic EL light source has peak wavelengths (λ ₁ ) and (λ ₂ ) at which the emission intensity becomes maximum in at least the wavelength range of 430 nm to 485 nm and the wavelength range of 560 nm to 620 nm, and the emission intensity I at the wavelength λ ₁ . 7. The organic EL display device according to claim 6, wherein the organic EL display device has an emission spectrum in which a ratio (I ₂ / I ₁ ) of emission intensity I ₂ at ₁ and wavelength λ ₂ is 0.4 or more and 0.9 or less.