JP5593632B2 - Blue coloring composition for color filter, color filter, and color display device - Google Patents

Description

  The present invention relates to a blue coloring composition for a color filter, a color filter, and a color display device formed by combining a color filter and a light source. More specifically, the present invention is used for a color filter preferably used in a color display device using a white light-emitting organic EL (electroluminescence) element (hereinafter sometimes referred to as “OLED”), and for forming the color filter. The present invention relates to a blue coloring composition, and a color display device including the color filter and an OLED. White means a broad concept including pseudo white.

  As an image display device using a color filter, for example, (A) 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 (B) a synthetic white organic EL light source, and an organic EL display device comprising a combination of color filters having a color adjustment function (such as a color conversion function, a color separation function, and a color correction function).

  As a backlight in the liquid crystal display device of (A), 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.

  As the synthetic white light source of the organic EL display device of (B), there are a light source having a two-wavelength peak, a light source having a three-wavelength peak, and a light source having a number of peaks in the visible light region. Synthetic white light is obtained by mixing or layering.

  For backlights other than OLEDs, the emission line spectrum has been designed from the viewpoints of display performance as a liquid crystal display device, matching with color filters, and durability of the backlight. There is a difference in specific spectrum and structure between a conventional backlight and an OLED used as a backlight or a white light source. (For example, see Non-Patent Documents 1 and 2)

  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, a 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, in the light emitting device using such an OLED, as described above, the light emission spectrum and the light emission spectrum of a conventionally used light source are different. For example, a conventional light source has a peak in the vicinity of 420 to 430 nm, but an OLED light source 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. Moreover, since the emission spectrum of the OLED light source has a broader peak as compared with the conventional light source, the spectrum is higher than that of the conventional light source up to around 500 nm even after passing the peak around 460 nm. ing. For these reasons, currently used color filters cannot be used as they are in display devices using OLED light sources. For this reason, it is necessary to select and develop a color filter material that can be used for an OLED light source and that has optimum hue and transmittance characteristics.

  Conventionally, phthalocyanine pigments that are generally excellent in resistance and color tone are often used for coloring compositions used to form blue filter segments. As this phthalocyanine pigment, those having various central metals such as copper, zinc, nickel, cobalt, and aluminum are known. Among them, copper phthalocyanine is widely used because it has the clearest color tone, but other metal phthalocyanines such as metal-free phthalocyanine, zinc phthalocyanine, and cobalt phthalocyanine other than copper phthalocyanine have been put into practical use. In addition, phthalocyanine pigments have different crystal types such as α-type, β-type, δ-type, and ε-type, and each has excellent properties such as clearness and high coloring power. Yes. In conventional color filters, these copper phthalocyanine pigments are dioxazine pigments C.I. I. In combination with Pigment Violet 23, etc., high brightness and a wide color display area can be achieved in a display device such as a liquid crystal display device using a cold cathode tube type backlight as a backlight. It was.

On the other hand, it has also been conventionally used for a color filter to use a colorant in combination with a pigment and a dye, and it has been proposed to use a copper phthalocyanine pigment, an oil-soluble dye, a dispersible dye, and a basic dye as a blue filter segment. ing. (For example, see Patent Documents 2 and 3)
It has also been proposed to use a xanthene dye as the color filter pixel, and furthermore, a color filter having excellent heat resistance can be obtained by using acid rhodamine (CI Acid Red 52) together with a polyimide resin or a photosensitive acrylic resin. It is known that (For example, see Patent Document 4)

  In recent years, color display devices using organic EL elements have attracted attention due to their excellent display performance. However, in a configuration in which a light emitting layer is formed for each display color (red, green, blue), these organic EL light emitting layers are: Usually formed by RGB coating, the structure of the element is complicated, and mask alignment at the time of element creation is difficult. When manufacturing is complicated, the cost increases, and it is difficult to achieve high precision and a large screen. As a configuration for solving these problems, a configuration in which a light emitting layer is a white light emitting layer and a desired light emission color is obtained by a color filter has been proposed (see Patent Documents 5, 6, and 7).

Japanese Patent Laid-Open No. 2005-10091 Japanese Patent Laid-Open No. 11-242109 JP 2001-124915 A JP-A-6-59114 JP 2004-47469 A JP 2008-518400 A Japanese Patent Application Laid-Open No. 07-220871

T. T. et al. K. Hatwar et al. , IMID '07 DIGEST 15-1 Osamu Akahoshi “Development of Organic Electronics” Information Organization 2007/09/27

  The present invention has been made in view of such a situation, and in a color display device such as a liquid crystal display device or an organic EL display device using an OLED light emitting device (light source), a color capable of high brightness and a wide color reproduction region. Provided is a blue coloring composition for a color filter capable of forming a filter, and a color filter including a filter segment formed using the same, and further, an OLED light emitting device (light source) equipped with the color filter and the light emitting device An object of the present invention is to provide a color display device using the above.

  As a result of intensive studies to solve the above problems, the present inventors combined a xanthene dye with a copper phthalocyanine blue pigment that has been conventionally used as a colorant for a blue coloring composition for a color filter. In the case where the OLED light emitting device is used as a backlight, it has been found that high brightness and a wide color reproduction region are possible, and the present invention has been made based on this finding.

  That is, this invention relates to the blue coloring composition for color filters in which a coloring agent consists of a copper phthalocyanine blue pigment and a xanthene dye.

  The present invention also relates to a blue coloring composition for a color filter, wherein the xanthene dye is a rhodamine dye.

  Further, in the present invention, a salt-forming compound of an organic sulfonic acid and a dye in which the rhodamine-based dye is at least one selected from rhodamine-based basic dyes, rhodamine-based oil-soluble dyes, and rhodamine-based basic dyes It is related with the blue coloring composition for color filters which is.

  In the present invention, the rhodamine basic dye is C.I. I. Basic Red 1, C.I. I. Basic Red 1: 1 or C.I. I. Basic violet 10, rhodamine-based oil-soluble dye is C.I. I. The present invention relates to a blue coloring composition for color filters which is Solvent Red 49.

  In the present invention, the copper phthalocyanine blue pigment is C.I. I. Pigment blue 15: 6 and C.I. I. It is related with the blue coloring composition for color filters which is at least 1 sort (s) chosen from CI pigment blue 15: 1.

  Moreover, this invention relates to the blue coloring composition for color filters characterized by including transparent resin further.

  Moreover, this invention relates to the blue coloring composition for color filters which further contains a monomer and / or a polymerization initiator.

  The present invention is also a color filter having at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein at least one of the blue filter segments includes the blue coloring composition. It relates to a color filter.

  In the present invention, the green filter segment is at least C.I. I. Pigment green 36 and C.I. I. Pigment Green 58 and at least one selected from C.I. I. The present invention relates to a color filter including CI Pigment Yellow 185.

  According to the present invention, the red filter segment is at least C.I. I. Pigment Red 177 and C.I. I. The present invention relates to a color filter including CI Pigment Red 254.

  The present invention also relates to a color filter for a light emitting device having a white light emitting organic EL element as a light source.

  The present invention also relates to a color display device comprising the color filter described above and a light emitting device having a white light emitting organic EL element as a light source.

  In the present invention, by combining a white light-emitting organic EL light source and a color filter formed of a blue coloring composition using at least a copper phthalocyanine blue pigment and a xanthene dye as a colorant, high brightness, a wide color display area, A color display device having a high contrast ratio can be obtained.

It is an example of the emission spectrum of a white light emission organic electroluminescent light source. It is an example of the emission spectrum of another white light emission organic EL light source.

Hereinafter, the present invention will be described in detail.
[First form of blue coloring composition for color filter of the present invention (blue colorant paste for color filter or blue coloring ink form)]
The first form of the blue coloring composition for a color filter of the present invention is a blue coloring composition for a color filter comprising a coloring agent dispersion containing a coloring agent, a transparent resin, and a solvent. A blue coloring composition for a color filter comprising at least a copper phthalocyanine blue pigment and a xanthene dye. The blue colored composition of the first form is a blue colored composition (colored resist) for color filter or a blue colored composition for forming color filter (colored ink composition) of the third form of the present invention described later. Blue color composition (colored ink composition) that can be used as a colorant component (colorant paste) and that itself forms a blue filter segment of a color filter by selecting viscosity, materials used, and production method ) Can also be used. Hereinafter, other components such as a colorant, a transparent resin, a solvent, a dispersibility improver used as necessary, and a dispersion aid used in the blue coloring composition for a color filter according to the first embodiment of the present invention will be sequentially described. .

[Colorant]
As a colorant of the blue coloring composition, at least a copper phthalocyanine blue pigment and a xanthene dye are used. First, examples of the copper phthalocyanine blue pigment include C.I. represented by the following general formula (1). I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, and the like. Among them, copper phthalocyanine blue pigments having ε-type and α-type structures are preferable. Such preferred pigments are specifically C.I. I. Pigment blue 15: 6 and C.I. I. Pigment Blue 15: 1.

General formula (1)

As the xanthene dyes, the following five forms of dyes can be used. Of the xanthene dyes, rhodamine dyes are preferably used. That is, rhodamine dyes are used in the following forms (a) to (e).
A) Basic dyes of xanthene dyes b) Oil-soluble dyes of xanthene dyes c) Salt-forming compounds of xanthene basic dyes with organic sulfonic acids and aromatic hydroxycarboxylic acids d) Acid dyes of xanthene dyes Salt Forming Compound of Xanthene Acid Dye and Quaternary Ammonium These forms include, among others, basic dyes of rhodamine dyes, salt forming compounds of rhodamine basic dyes and organic sulfonic acids and aromatic hydroxycarboxylic acids. It is preferable to use it.

  The rhodamine dye contains an amino group of a xanthene dye and exhibits a unique bright red color. However, in spite of having a unique color tone, the light resistance and heat resistance are very poor like general dyes, and the characteristics are as follows for use in an image display device using a color filter that requires high reliability. Not enough. Therefore, in order to improve the drawbacks of these dyes, it is preferable to make the dyes base, chlorinated, oil-soluble, or modified with a resin.

  The basic dye of the xanthene dye will be described. Among the xanthene-based basic dyes, rhodamine-based basic dyes are preferable. Rhodamine 6G, rhodamine 6GCP (both are CI Basic Red 1), rhodamine G (CI Basic Red 8), rhodamine B (C I. Basic violet 10) and the like.

 Next, an oil-soluble dye of a xanthene dye will be described. As the xanthene-based oil-soluble dye, a rhodamine-based oil-soluble dye is particularly preferable, and examples thereof include rhodamine B base (CI Solvent Red 49).

  Xanthene-based dye basic dyes and oil-soluble dyes are preferably mixed with resins having acid groups such as carboxyl groups, rosin esters, and rosin-modified maleic acid resins (also synonymous with rosin-modified fumaric acid resins) to improve resistance. Is. The acid values of these acid group-containing resins, rosin esters, and rosin-modified maleic resins are preferably 20 to 200. (Method of JIS K-0070)

Next, a salt-forming compound of xanthene basic dye and organic sulfonic acid will be described. The xanthene-based basic dye and the organic sulfonic acid can be reacted with each other by dissolving them in an aqueous solution or an alcohol solution to obtain a salt-forming compound.
As the organic sulfonic acid, a sulfonated product of naphthalene, a sulfonated product of naphthol, or the like can be used.
For example, after a xanthene basic dye (preferably a rhodamine basic dye) is dissolved in water, a sulfonated product of naphthalene and / or a naphthol sulfonated product is added, and the chlorination treatment can be performed while stirring. That's fine. Here, an amino group (—NHC ₂ H ₅ ) portion in a xanthene basic dye and a sulfonate group (—SO ₃ H) portion of a sulfonated product of naphthalenes and / or a sulfonated product of naphthols are combined. A salt compound is obtained.
Here sulfonated sulfonated and / or naphthols of naphthalenes before performing the salt formation process, is dissolved in an alkaline solution such as sodium hydroxide, also be used in the form of sodium sulfonate (-SO ₃ Na) it can. In the present invention, a sulfonic acid group (—SO ₃ H) and a functional group (—SO ₃ Na) which is sodium sulfonate are also synonymous.

The sulfonated product of naphthalene is a general term for a compound in which a sulfonic acid group is bonded to a carbon atom of naphthalene, and the sulfonated product of a naphthol is a general term for a compound in which a sulfonic acid group is bonded to a carbon atom of naphthol.
Examples of the sulfonated products of naphthalenes include naphthalene monosulfonic acid having one sulfonic acid group bonded thereto, naphthalene disulfonic acid having two bonded groups, and naphthalene trisulfonic acid having three bonded groups.
Specifically, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, 1,3-naphthalenedisulfonic acid, 1,5-naphthalenedisulfonic acid, 1,6-naphthalenedisulfonic acid, 1,7-naphthalenedisulfonic acid, 2 1,6-naphthalene disulfonic acid, 2,7-naphthalene disulfonic acid, 1,3,5-naphthalene trisulfonic acid, 1,3,6-naphthalene trisulfonic acid, 1,3,7-naphthalene trisulfonic acid, etc. .
The sulfonated product of naphthalenes includes naphthylamine sulfonic acid in addition to the above-mentioned naphthalene sulfonic acid. There are naphthylamine monosulfonic acid with one sulfonic acid group bonded, naphthylamine disulfonic acid with two bonded naphthylamine trisulfonic acids, and naphthylamine trisulfonic acid with three bonded sulfonic acid groups.
Specifically, 1,4-naphthylamine sulfonic acid (naphthoic acid), 1,5-naphthylamine sulfonic acid (Lorentzic acid), 1,6-naphthylamine sulfonic acid (6-clebic acid), 1,7-naphthylamine sulfonic acid (7-clebic acid), 1,8-naphthylaminesulfonic acid (peric acid), 2,1-naphthylaminesulfonic acid (tobias acid), 2,5-naphthylaminesulfonic acid, 2,6-naphthylaminesulfonic acid (brenamic acid) 1,3,6-naphthylamine disulfonic acid (Freundic acid), 1,3,7-naphthylamine disulfonic acid, 2,3,6-naphthylamine disulfonic acid (amino R acid), 2,4,6-naphthylamine disulfonic acid ( C acid), 2,5,7-naphthylamine disulfonic acid (amino J acid), 2,6,8-naphthyla Njisuruhon acid (amino G acid), 1,3,6,8-naphthylamine trisulfonic acid (Koch acid) and the like.

  The sulfonated products of naphthols include naphthol monosulfonic acid having one sulfonic acid group bonded thereto, naphthol disulfonic acid having two bonded sulfonic groups, and naphthol trisulfonic acid having three bonded naphthol groups. Specifically, 1-naphthol-2-sulfonic acid, 1-naphthol-4-sulfonic acid (NW acid), 1-naphthol-5-sulfonic acid (L acid), 1-naphthol-8-sulfonic acid, 2 -Naphthol-1-sulfonic acid, 2-naphthol-6-sulfonic acid (Shafer acid), 2-naphthol-8-sulfonic acid (croseiic acid), 1-naphthol-2,4-disulfonic acid, 1-naphthol-3 , 6-Disulfonic acid, 1-naphthol-3,8-disulfonic acid (ε acid), 2-naphthol-3,6-disulfonic acid (R acid), 2-naphthol-3,8-disulfonic acid, 2-naphthol -6,8-disulfonic acid (G acid), 1-naphthol-2,4,7-trisulfonic acid, 1-naphthol-3,6,8-trisulfonic acid (oxycofolic acid), 2-naphthol-3, , And the like 8- trisulfonate.

Of these, naphthalene disulfonic acid and naphthol disulfonic acid having two sulfonic acid groups bonded thereto are preferable. Of these, 1,5-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acid, 2-naphthol-3,6-disulfonic acid, and 2-naphthol-3,8-disulfonic acid are preferable.
Further, a salt-forming compound comprising rhodamine 6G (CI Basic Red 1) and naphthalenedisulfonic acid, and a salt-forming compound comprising rhodamine 6G (CI Basic Red 1) and naphthol disulfonic acid are preferred dyes. .

  When a disulfonated product of naphthalene or a disulfonated product of naphthol is reacted with a xanthene basic dye to form a colorant of the present invention, 1 mol of disulfonated product reacts with 2 mol of xanthene dye to form a salt. This is preferable because the charge component is neutralized and the pigment component has an amount twice the molar ratio of the counter ion component, so that the coloring of the dye as a colorant is not impaired. That is, it is preferable to use an organic sulfonic acid having at least two sulfonic acid groups.

A salt-forming compound of a xanthene basic dye, an organic sulfonic acid, or an aromatic hydroxycarboxylic acid can be synthesized by a conventionally known method.
For example, after the xanthene dye is dissolved in water, a chlorination treatment may be performed while adding a sulfonated product of naphthalenes and / or a sulfonated product of naphthols and stirring them. Here, a salt-forming compound in which the amino group (—NHC ₂ H ₅ ) portion in the xanthene dye is bonded to the sulfonated product of naphthalene and / or the sulfonated group (—SO ₃ H) of the sulfonated product of naphthols. Is obtained.
Here sulfonated sulfonated and / or naphthols of naphthalenes before performing the salt formation process, is dissolved in an alkaline solution such as sodium hydroxide, also be used in the form of sodium sulfonate (-SO ₃ Na) it can. In the present invention, a sulfonic acid group (—SO ₃ H) and a functional group (—SO ₃ Na) which is sodium sulfonate are also synonymous.

Further, a salt-forming compound can be obtained using an aromatic hydroxycarboxylic acid in the same manner as the organic sulfonic acid described above. Among them, 3,5-di-tert-butylsalicylic acid, 3-hydroxy-2-naphthoic acid, and 3-phenylsalicylic acid are preferably used as the aromatic hydroxycarboxylic acid. When an aromatic hydroxycarboxylic acid is used, a salt-forming compound is obtained in which the amino group (—NHC ₂ H ₅ ) part of the xanthene dye and the carboxylic acid (—COOH) part of the aromatic hydroxycarboxylic acid are combined. . Further, the hydroxyl group (—OH) remains irrespective of the salt formation reaction.

  Acid dyes of xanthene dyes include Food Red 3 (CI Acid Red 51), Acid Rhodamine B (CI Acid Red 52), Eosin G (CI Acid Red 87), Acid Phloxine PB (C.I. Acid Red 92), Rose Bengal B (C.I. Acid Red 94), Acid Rhodamine G, C.I. I. Acid Violet 9 etc. can be used. Of these, acid rhodamine B (CI acid red 52) and eosin G (CI acid red 87) are preferably used.

As a salt-forming compound of a xanthene acid dye and a quaternary ammonium compound, it can be synthesized by a conventionally known method.
For example, after dissolving a xanthene acid dye in water, a quaternary ammonium compound may be added and subjected to chlorination treatment with stirring. Here, a salt-forming compound in which the sulfonic acid group (—SO ₃ H) moiety in the xanthene acid dye and the ammonium group (NH 4+) moiety of the quaternary ammonium compound are obtained is obtained.
As the quaternary ammonium compound, triethylbenzyl chloride or the like is preferably used.
Furthermore, a salt-forming compound comprising acid rhodamine B (CI acid red 52) and triethylbenzyl chloride, and a salt-forming compound comprising eosin G (CI acid red 87) and triethylbenzyl chloride are preferred salt forming compounds. It is a dye.

  The xanthene dye used in the present invention has a transmittance of 90% or more in the region of 650 nm in the transmission spectrum, a transmittance of 75% or more in the region of 600 nm, a transmittance of 5% or less in the region of 500 to 550 nm, 400 nm. In this region, the transmittance is preferably 70% or more. More preferably, the transmittance is 95% or more in the region of 650 nm, the transmittance is 80% or more in the region of 600 nm, the transmittance is 10% or less in the region of 500 to 550 nm, and the transmittance is 75% in the region of 400 nm. That's it.

  The use ratio of the copper phthalocyanine blue pigment and the xanthene dye is preferably 20 to 150 parts by weight of the xanthene dye with respect to 100 parts by weight of the copper phthalocyanine blue pigment.

 As a colorant for the blue coloring composition of the present invention, in addition to the above copper phthalocyanine blue pigment and xanthene dye, as a complementary color, a metal phthalocyanine pigment other than copper such as zinc phthalocyanine pigment, aluminum phthalocyanine pigment, nickel phthalocyanine pigment, triaryl Blue pigments such as methane pigments and anthraquinone pigments can be used. Further, purple pigments such as anthraquinone pigments, triarylmethane pigments, azo pigments, oxazine pigments, and quinacridone pigments can be used. The addition amount of these complementary colorants is preferably 20 parts by weight or less with respect to the entire colorant (100 parts by weight) of the blue coloring composition.

[Transparent resin]
The transparent resin used in the blue coloring composition of the present invention 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 transparent resin may be any of a thermoplastic resin, a thermosetting resin, and a photocurable resin, and can be used in an amount of 30 to 500% by weight based on the total weight of the colorant. If it is less than 30% by weight, the film formability and various resistances are insufficient, and if it exceeds 500% by weight, the colorant concentration is low and color characteristics cannot be expressed.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  When the coloring composition is used in the form of an alkali developing type colored resist, it is preferable to use an alkali-soluble resin having an acidic group such as a (meth) acrylic acid copolymer resin (alkali-soluble acrylic resin). In order to disperse the colorant preferably, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 30,000 to 80,000. 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.

  In the present invention, the resin molecular weight distribution (weight average molecular weight (Mw), number average molecular weight (Mn)) is a GPC equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corp., HLC-8120GPC). And measured using THF as a developing solvent.

  Measurement is performed under the above conditions, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used in calculating the molecular weight of the sample. Furthermore, it calculates by converting into polyethylene by the conversion formula derived from the Mark-Houwink viscosity formula.

  As the photocurable resin, a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group has a reactive substituent such as an isocyanate group, an aldehyde group, an epoxy group, or a carboxyl group (meta ) A resin obtained by reacting an acrylic compound or cinnamic acid to introduce a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

〔solvent〕
The coloring composition according to the first aspect of the present invention is applied so that the coloring agent is sufficiently dispersed in the coloring agent carrier, and the dry film thickness is 0.2 to 5 μm on a substrate such as a glass substrate. When forming the filter segment, a solvent is contained in order to facilitate the formation of the coating film.

  Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 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, m-dichlorobenzene N, N-dimethylacetamide, N, N-dimethylformamide, n-butylal N-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, 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 Ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl 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, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene Recall monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl 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 Tons, methylcyclohexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, but dibasic acid ester and the like, not necessarily limited thereto. These solvents are used alone or in combination. When the colored composition according to the first form is used as a colorant paste such as the colored composition of the third form, the solvent is an amount of 800 to 4000% by weight based on the total weight of the colorant. It is preferable to use in.

[Dye derivative]
In the coloring composition for a color filter of the present invention, a dye derivative can be used for the purpose of improving the dispersibility of the copper phthalocyanine pigment. A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Such organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more. When a pigment derivative is used, the blending amount is preferably 0.001 to 40% by weight based on the total amount of the colorant, and more preferably 0.1 to 30% by weight from the viewpoint of dispersibility, heat resistance and light resistance. In view of the above, it is most preferably 0.5 to 25% by weight. If the blending amount of the pigment derivative is less than 0.001% by weight relative to the total amount of the colorant, the dispersibility may be deteriorated, and if it exceeds 40% by weight, the heat resistance and light resistance may be deteriorated.

In addition, the colorant of the present invention comprises a copper phthalocyanine blue pigment and a xanthene dye, whereby the dye component in the colorant works to improve the dispersibility of the copper phthalocyanine blue pigment.
Among them, a salt-forming compound of a xanthene dye is a preferable material because it has an effect of improving the dispersibility of the pigment and is excellent in heat resistance and light resistance.

[Dispersion aid]
When dispersing the pigment and the xanthene dye in the colorant carrier, a dispersion aid such as a resin-type pigment dispersant can be appropriately used. The dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a coloring composition obtained by dispersing the pigment in the colorant carrier using the dispersion aid is used. In this case, a color filter having a high spectral transmittance can be obtained.

  Resin-type pigment dispersants have a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the colorant carrier, and adsorb to the pigment to stabilize the dispersion of the pigment into the colorant carrier. It works to do. Specific examples of resin-type pigment 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 alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more. The compounding amount of the resin-type pigment dispersant is preferably 0.001 to 40% by weight based on the total amount of the colorant, more preferably 0.1 to 35% by weight from the viewpoint of dispersibility, heat resistance and light resistance. From the viewpoint, it is most preferably 0.5 to 30% by weight. If the blending amount of the pigment derivative is less than 0.001% by weight relative to the total amount of the colorant, the dispersibility may be deteriorated, and if it exceeds 40% by weight, the heat resistance and light resistance may be deteriorated.

(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 colored composition 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 content is preferably 0.003 to 0.5% by weight based on the total weight (100% by 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, a hardening | curing agent, a hardening accelerator, etc. may be included 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.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative 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- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 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 be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01 to 15 weight% is preferable with respect to the thermosetting resin whole quantity.

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

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of the colorant.

  Examples of the silane coupling agent 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-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane. The silane coupling agent 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.

[Method for producing colored composition according to first embodiment]
The colored composition according to the first aspect of the present invention can be obtained by treating a colorant, a transparent resin, a solvent, and other components such as a pigment derivative and a dispersion aid as necessary with a wet pulverizer. Examples of the wet pulverizer used in the present invention include an attritor, sand mill, dyno mill, ball mill, super apex mill, spike mill, coball mill, diamond fine mill, DCP mill, and OB mill. Examples include media-type wet pulverizers such as Royder, Trigonal, Thrasher, Colloid Mill, Cavitron, Golator, Genus, and Claremix. The distribution method may be either circulation or path distribution. Furthermore, the coloring composition by the 1st form of this invention can also be manufactured by mixing the several coloring agent separately disperse | distributed finely.

[Removal of coarse particles]
The colored composition according to the first aspect of the present invention is a coarse particle of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove coarse particles and 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. In addition, the particle diameter here means the particle diameter measured by SEM.

[Second Form (Chip Form) of Blue Coloring Composition for Color Filter of the Present Invention]
The second form of the blue coloring composition for a color filter of the present invention is a coloring composition in the form of a chip containing a coloring agent and a thermoplastic resin. The coloring agent includes at least a copper phthalocyanine blue pigment, xanthene. And a blue coloring composition for a color filter comprising a dye.

[Method for producing colored composition according to second embodiment]
The coloring composition according to the second aspect of the present invention comprises a coloring agent and a thermoplastic resin, and optionally other components such as a pigment derivative and a dispersion aid, a Henschel mixer, a cooler mixer, a nauter mixer, a drum mixer, After mixing using a tumbler or the like, it is manufactured by heating and kneading with a Banbury mixer, a kneader, a two-roll mill, a single-screw extruder, a twin-screw extruder, etc., cooling and pulverizing. The colorant chip thus produced is refined as necessary using various grinding devices such as a hammer mill, a turbo crusher, an air jet mill, etc., and the first form of the colorant paste and the blue color composition for forming the blue filter segment are used. It can be used as a colorant for objects (ink form).

[Third Form of Blue Coloring Composition for Color Filter of the Present Invention (for example, Colored Resist Form)]
A third form of the blue coloring composition for a color filter of the present invention is a coloring composition containing a coloring agent, a transparent resin, a solvent, a monomer and / or a polymerization initiator, and the coloring agent is at least A blue coloring composition for a color filter comprising a copper phthalocyanine blue pigment and a xanthene dye, and the coloring composition which is the first embodiment of the present invention itself forms a blue filter segment of a color filter. The blue coloring composition to be used further contains a monomer and / or a polymerization initiator as essential components. Therefore, except for the components other than the monomer and / or the polymerization initiator in the blue coloring composition for the color filter of the third form, and further, if necessary, the composition components used are: Basically, it is not particularly different from the components used in the blue coloring composition of the first form, which is itself used to form the blue filter segment of the color filter. For this reason, below, the monomer which is an arbitrary component, a polymerization initiator, and also the sensitizer used with these are demonstrated in a 1st form. In addition, when the blue coloring composition for color filters of the third form is formed using the blue coloring composition for color filters of the first form (colorant paste) as a colorant component, A blue coloring composition (colorant paste) for color filter in the form, a monomer, a polymerization initiator, and a transparent resin, a solvent, a leveling agent, a storage stabilizer, a silane coupling agent, etc. It is preferable to be formed from other components. The polymerization initiator of the present invention includes a photopolymerization initiator and a thermal polymerization initiator.

〔monomer〕
The monomer of the present invention includes a monomer or oligomer that is cured by ultraviolet rays or heat to produce a transparent resin, and these can be used alone or in combination of two or more. The blending amount of the monomer is preferably 5 to 400% by weight based on the total amount of the colorant, and more preferably 10 to 300% by weight from the viewpoint of photocurability and developability.

  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 Ether 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 monomers or oligomers that are cured by irradiation with active energy rays to form a transparent resin can be used alone or in admixture of two or more.

(Photopolymerization initiator)
In the colored composition for color filter in the third aspect of the present invention, a photopolymerization initiator is added as necessary in order to cure the composition by irradiation with ultraviolet rays and form a filter segment by a photolithographic method. Is done. Note that a photopolymerization initiator is also used when a photocurable resin is used as the transparent resin in the first embodiment. The blending amount when using the photopolymerization initiator is preferably 5 to 200% by weight based on the total amount of the colorant, and 10 to 150% by weight from the viewpoint of photocurability and developability. More preferred.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpho Acetophenone photopolymerization initiators such as linopropan-1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, benzoylbenzoic acid Me , Benzophenone photopolymerization initiators such as 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthio Thioxanthone photopolymerization initiators such as xanthone and 2,4-diisopropylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (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-bi (Trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) Triazines such as -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine And photopolymerization initiators, borate photopolymerization initiators, carbazole photopolymerization initiators, and imidazole photopolymerization initiators. The said photoinitiator can be used individually or in mixture of 2 or more types.

[Sensitizer]
Moreover, a sensitizer may be used with the said photoinitiator as needed. As the sensitizer, any conventionally known sensitizer for the polymerization initiator can be used. Specifically, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, Examples of the compound include 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and 4,4′-diethylaminobenzophenone, but are not limited thereto. The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the photopolymerization initiator contained in the colored composition, and 5 to 50 from the viewpoint of photocurability and developability. More preferably, it is% by weight.

(Thermal polymerization initiator)
When a thermosetting resin is used as the transparent resin, a thermopolymerization initiator may be included as necessary. Examples of the thermal polymerization initiator include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne-3, 1,4- Bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5- Di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, tert-butylperisobutyrate, tert-butylper-sec-octoate, tert-butylperpivalate, cumylper Bareto and tert- butyl hydroperoxide diethyl acetate, other azo compounds such as azobisisobutyronitrile, dimethyl azoisobutyrate, and the like.

[Method for producing colored composition according to third embodiment]
The coloring composition according to the third aspect of the present invention uses a colorant, a transparent resin, a solvent, and, if necessary, a pigment derivative using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. It is prepared by finely dispersing, and can be obtained by adding and mixing the monomer and / or polymerization initiator and, if necessary, other components described above by known means. In the colored composition according to the third aspect of the present invention, as described above, the blue colored composition (colorant paste) of the first form may be used as a colorant, and such a method is preferable. It is an aspect. Further, several kinds of colorants are separately finely dispersed to prepare a colorant dispersion, which is mixed, and further, the monomer and / or the polymerization initiator and, if necessary, the above-mentioned other components are added by known means. It can also be produced by adding and mixing.

[Removal of coarse particles]
The colored composition according to the third aspect of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably 0.5 μm or more by means of centrifugation, a sintered filter, a membrane filter or the like. It is preferable to remove coarse particles and 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. In addition, the particle diameter here means the particle diameter measured by SEM.

[Color filter]
The color filter of the present invention is a color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the blue filter segment is at least a copper phthalocyanine blue pigment as a colorant. And xanthene dyes.

[Blue filter segment]
The blue filter segment of the color filter of the present invention is characterized by containing at least a copper phthalocyanine blue pigment and a xanthene dye as a colorant as described above. Such a blue filter segment can be formed using the blue coloring composition for color filters of the present invention described above. As a formation method, any one of publicly known or well-known methods for forming a conventional color filter segment, such as a printing method, an ink jet method, and a photolithography method, may be employed depending on the composition of the blue coloring composition. .

  Xanthene dyes have high transmittance in the vicinity of 450 to 480 nm and strong light absorption in the vicinity of 500 to 550 nm in terms of their transmittance characteristics, so that light in this region can be cut efficiently. is there. Conventionally, in a display device using a cold cathode tube type backlight as a light source, a dioxazine pigment has been used as a colorant together with a copper phthalocyanine blue pigment in a blue coloring composition for forming a blue filter segment. Dioxazine pigments do not have sufficient ability to cut light in the range of 500 to 550 nm. Therefore, blue color for OLED light sources using blue coloring compositions for color filters using conventional copper phthalocyanine blue pigments and dioxazine pigments. In order to form the filter segment, it is necessary to increase the thickness of the color filter in order to cut light in the region of 500 to 550 nm existing in the OLED light source. A conventional light source such as a cold-cathode tube type backlight has a peak at around 425 nm and is not affected by the thickening of the film, but an OLED light source has a light emission peak at around 460 nm, and dioxazine pigments are around 460 nm. Also has a light absorption greater than the 500-550 nm region. For this reason, the transmittance near the peak near 460 nm also decreases due to the increase in thickness, and as a result, the brightness of the color filter decreases.

On the other hand, by combining a xanthene dye with a copper phthalocyanine blue pigment, in a display device using an OLED light source, a color having lightness and a color display region far superior to those of conventional color filter coloring compositions. It became possible to obtain a filter. In order to reproduce a color at a relatively high density near a standard area such as sRGB or NTSC in the CIE chromaticity coordinates, this is aimed at a wide color display area from the characteristics of the emission line spectrum of the OLED light source. The filter segment needs to have an optimal hue. In order to reproduce the color in the vicinity of the standard region, a certain amount of copper phthalocyanine blue pigment having high coloring power and high brightness is required. However, xanthene dye is 150 parts by weight with respect to 100 parts by weight of copper phthalocyanine blue pigment. If it is more, high brightness is exhibited, but a wide color display area cannot be achieved. On the other hand, if the xanthene dye is less than 20 parts by weight based on 100 parts by weight of the copper phthalocyanine blue pigment, a wide color display area can be achieved, but high brightness cannot be achieved.
The copper phthalocyanine blue pigment used as the colorant of the present invention has a transmittance of 80% or more in the 450 nm region in the transmission spectrum, a transmittance of 70% or more in the 500 nm region, and a transmittance in the 550 to 600 nm region. What is 30% or less is preferable.

  As described above, the OLED light source has characteristics that are greatly different in the emission spectrum compared to the conventional light source for liquid crystal display devices. Therefore, in the display device using the OLED light source, in order to achieve a high brightness and a wide color display region, the present inventors have repeatedly studied, and as described above, as a blue filter segment, a copper phthalocyanine blue pigment and a xanthene series are used. By using a blue coloring composition for a color filter made of a dye, the conventional problem can be solved.

[Green filter segment]
The green filter segment of the color filter of the present invention contains a green pigment as a colorant. Examples of the green pigment include C.I. I. Pigment green 7, 10, 36, 37, 58 and the like.

  Moreover, a yellow pigment may be used in combination with the green filter segment as a colorant. 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, 185, 187, 188, 193, 194, 198, 199, 213, 214 and the like.

In the present invention, in order to realize a high brightness and a wide color display area in consideration of optimization with the OLED light source, the green filter segment is at least C.I. I. Pigment green 36 and / or C.I. I. Pigment green 58, C.I. I. Pigment Yellow 185 is preferably included. The reason why the combination of these pigments is preferable in the green filter segment is that the high coloring power of each pigment is effective in developing a wide color display region. Further, as a feature of the OLED light source, there is a weak light source emission line at a place where the sensitivity of the color matching function Y is highest near 525 to 550 nm. Therefore, it is required to be a green filter segment having a considerably strong yellowish transmissive region. For this reason, it is necessary to combine pigments with strong coloring power. I. Pigment Yellow 185 is preferably used. Further, for green pigments, C.I. I. Pigment green 36 and / or C.I. I. Pigment Green 58 is preferably used. Further, by using these pigments, the transmission region of the green filter segment is shifted to the long wavelength side, so that high brightness can be obtained.

  The content of the green pigment and the yellow pigment is preferably 40 to 95 wt% for the green pigment and 5 to 60 wt% for the yellow pigment, more preferably green, based on the total weight of the pigment (100 wt%). The pigment is 50 to 90% by weight, and the yellow pigment is 10 to 50% by weight. If the blending amount of the yellow pigment is less than the above range, the brightness will not be sufficiently increased due to the spectral characteristics of the pigment, and conversely if it exceeds the above range, the yellowness will be strong due to the spectral characteristics of the pigment, and the target chromaticity The deviation will be large.

  In order to form the green filter segment of the color filter of the present invention, a green pigment and a yellow pigment as described above are used, for example, a transparent resin component, a solvent, and further, if necessary, a monomer, a polymerization initiator, and other blue coloring composition. Using the same material as used for forming, a green colored composition is manufactured by the same method as the blue colored composition, and using this green colored composition, the same method as the formation of the blue filter segment is performed. A green filter segment may be formed.

[Red filter segment]
The red filter segment of the color filter of the present invention contains a red pigment as a colorant. Examples of red pigments include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 279, and the like.

  Further, in the red filter segment of the color filter of the present invention, in addition to the red pigment, C.I. I. Pigment Orange 43, 71, 73, etc. and / or 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, 185, 187, 188, 193, 194, 198, 199, 213, 214, etc., may be used in combination.

  In the present invention, in order for the red filter segment to realize high brightness and a wide color display area in consideration of optimization with the OLED light source, the above-described C.I. I. Pigment Red 177 and C.I. I. And CI Pigment Red 254.

  For example, C.I. I. Pigment red 254 or C.I. I. When only CI Pigment Red 177 is used alone, it is difficult to achieve both high brightness and a wide color display area because of the relationship with the organic EL light source. This is because the OLED light source has a peak in the vicinity of 580 to 600 nm, and the emission line gradually weakens as the wavelength increases, so that C.I. I. When CI Pigment Red 177 is used alone, a wide color reproduction region can be obtained, but the brightness is low. Conversely, C. which is a relatively yellowish pigment. I. This is because when the pigment red 254 is used alone, the brightness is high, but the color reproduction region is slightly narrowed.

The pigment content is C.I. based on the total weight of the pigment (100% by weight). I. Pigment Red 254 is 30 to 75% by weight, C.I. I. CI Pigment Red 177 is preferably 20 to 60% by weight, and the yellow pigment is preferably 0 to 30% by weight, and more preferably C.I. I. Pigment red 254 is 35 to 65% by weight, C.I. I. Pigment Red 177 is 30 to 50% by weight, and yellow pigment is 0 to 25% by weight. C. I. When the content of Pigment Red 254 is less than 30% by weight, sufficient brightness cannot be obtained, and when it exceeds 75% by weight, the color reproduction region becomes narrow. In addition, C.I. I. Even when the content of Pigment Red 177 is less than 20% by weight, the color reproduction region becomes narrow, and when it exceeds 60% by weight, sufficient brightness cannot be obtained. On the other hand, when the content of the yellow pigment exceeds 30% by weight, the color reproducibility is deteriorated because the hue is excessively shifted to yellow.

  In order to form the red filter segment of the color filter of the present invention, the red pigment as described above and, if necessary, an orange pigment or a yellow pigment, for example, a transparent resin component, a solvent, and further, if necessary, a monomer or a polymerization initiator, In addition, a red colored composition is produced by the same method as the production of the blue colored composition using the same material as that used for forming the blue colored composition, and this red colored composition is used to produce a blue filter segment. What is necessary is just to form a red filter segment by the method similar to formation.

[Manufacture of color filters]
Below, the manufacturing method of the color filter using the coloring composition of this invention is demonstrated.
The color filter of the present invention includes a filter segment on a substrate, and can include, for example, a black matrix and red, green, and blue filter segments. The said filter segment can be formed on a board | substrate by apply | coating the coloring composition of this invention by a spin coat system or a die coat system, for example. At this time, each segment can be formed using a photolithography technique using a colored composition containing a monomer, a photopolymerization initiator, and the like. Each segment can also be formed by a printing method. As a printing method at this time, a conventional well-known printing method or an inkjet method can be used.

  As a substrate of the color filter, a substrate having a high transmittance for visible light, for example, a glass plate such as soda lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, polycarbonate, polymethyl methacrylate, polyethylene A resin plate such as terephthalate is used.

  When forming a filter segment, when using a photocurable coloring composition (coloring resist) containing a monomer, a photopolymerization initiator, etc., the coloring composition film is developed after exposure. As the developer, a known alkali developer conventionally used for developing a photosensitive resin, for example, an aqueous solution of sodium carbonate, sodium hydroxide or the like, or an organic alkali such as dimethylbenzylamine, triethanolamine or the like is used. Can do. Moreover, an antifoamer and surfactant can also be added to a developing solution. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  In order to increase the UV exposure sensitivity, after coating and drying the colored composition, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

[Organic EL device]
Next, the organic EL element used in the present invention will be described.
As an organic EL element, it is preferable that the light source has a light emission characteristic having one or more maximum values within a wavelength range of 400 nm to 700 nm, and has a maximum value of emission intensity within a wavelength range of 430 nm to 485 nm. 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 organic EL display device including the color filter displays blue with good color reproducibility. More preferably, it is the range of 430 nm-475 nm.

  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- ( Aromatic amine compounds such as N, 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.

As an electron transport material that can be used for the electron transport layer, tris (8-quinolinolato) aluminum (abbreviation: Alq ₃ ), tris (4-methyl-8-quinolinolato) aluminum (abbreviation: Almq ₃ ), bis (10− Hydroxybenzo [h] -quinolinato) beryllium (abbreviation: BeBq ₂ ), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (abbreviation: BAlq), bis [2- (2-hydroxyphenyl) And metal complexes such as benzoxazolate] zinc (abbreviation: Zn (BOX) ₂ ), bis [2- (2-hydroxyphenyl) benzothiazolate] zinc (abbreviation: 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] (abbreviation: Imidazole derivatives such as PBI), bathophenanthroline (abbreviation: can be used phenanthroline derivatives such as BCP): BPhen), bathocuproine (abbreviation.

Materials that can be used for the electron injection layer include Alq ₃ , Almq ₃ , BeBq ₂ , BAlq, Zn (BOX) ₂ , Zn (BTZ) ₂ , PBD, OXD-7, TA described above.
Electron transport materials such as Z, p-EtTAZ, TPBI, 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. Tris (8-hydroxyquinoline) aluminum (abbreviation: Alq ₃ ), BAlq, Zn (BTZ), bis (
It can also be obtained from a metal complex such as 2-methyl-8-quinolinolato) chlorogallium (substantially: Ga (mq) ₂ Cl). 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 device of 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. T. et al. 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 with respect to temperature, humidity, atmosphere and the like, 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).

  Examples of the main method of full-color organic EL device used in the present invention include a three-color coating method, a color conversion method, and a color filter method. In the three-color coating method, an evaporation method using a shadow mask, an ink jet method, and a printing method can be used. Also, Japanese translations of PCT publication No. 2002-534882 and S.A. T. T. et al. Lee, et al. , Proceedings of SID'02, p. 784 (2002) can also be used. The laser thermal transfer method (also referred to as Laser Induced Thermal Imaging, LITI method) can also be used. In the color conversion method, a blue light emitting layer is used to convert green and red having a longer wavelength than blue through a color conversion (CCM) layer in which fluorescent dyes are dispersed. The color filter method is a method of extracting light of three primary colors through a color filter for liquid crystal using a white light emitting organic EL element. In addition to these three primary colors, a part of white light is directly extracted and used for light emission. Thus, 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. that time. A color display device having a high contrast ratio can be realized by controlling the flow of current during light emission using TFTs.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the following, “parts” means “parts by weight” unless otherwise specified.

First, the preparation of acrylic resin solutions used in Examples and Comparative Examples will be described.
(Preparation of acrylic resin solution)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate (PGMAC) was added to prepare an acrylic resin solution.
Here, the polymerization average molecular weight (Mw) of the acrylic resin was measured by using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. The weight average molecular weight (Mw) in terms of polystyrene.

[Preparation of Coloring Composition for Color Filter (Colorant Dispersion)]
(1) The colorant dispersion used for the blue coloring composition (resist) for color filters was prepared by the following procedure.
(Blue colorant dispersion 1: colored composition according to the first aspect of the present invention)
Blue pigment (Lionol Blue ES CI Pigment Blue 15: 6 manufactured by Toyo Ink Manufacturing Co., Ltd.) 11.0 parts, acrylic resin solution 40 parts, propylene glycol monomethyl ether acetate (PGMAC) 48.0 parts, resin-type dispersant ( EFKA4300) After 1.0 part of the mixture was stirred and mixed uniformly, it was dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. A blue colorant dispersion 1 was prepared by filtration through a 0.0 μm filter.

(Blue colorant dispersions 2-3, red colorant dispersions 1-6, purple colorant dispersion 1: colored composition according to the first embodiment of the present invention)
The blue colorant dispersions 2 to 3 and the red colorant dispersion 1 used for the blue coloring composition (resist) are the same as the preparation of the blue colorant dispersion 1 except that the colorants shown in Table 4 are used. -6, Purple colorant dispersion 1 was prepared.

(2) The colorant dispersion used for the red coloring composition for color filters (resist) was prepared by the following procedure.
(Red colorant dispersion 7-8, yellow colorant dispersion 1)
The red colorant dispersions 7 to 8 and the yellow colorant dispersion 1 used for the red color composition (resist) were prepared in the same manner as in the preparation of the blue colorant dispersion 1 except that the pigments shown in Table 5 were used. Produced.

(3) The colorant dispersion used for the green coloring composition for color filters (resist) was prepared by the following procedure.
(Green colorant dispersion 1, Yellow colorant dispersion 2)
Using the pigments shown in Table 6, green colorant dispersion 1 and yellow colorant dispersion 2 used for the green coloring composition (resist) were prepared.

[Preparation of Colored Composition for Color Filter (Colored Resist)]
(1) A blue colored composition (colored resist) for color filters (hereinafter sometimes referred to as “blue resist”) was prepared by the following procedure.
(Blue resist 1: coloring composition according to the third aspect of the present invention)
When the blue coloring composition (coloring resist) is applied to the substrate, the blue colorant dispersion 1 and the red colorant dispersion 1 are mixed so that x = 0.150 and y = 0.060. After that, 60.0 parts of a colorant dispersion, 1.2 parts of a photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan), dipentaerythritol pentaacrylate and hexaacrylate (“Aronix M400” manufactured by Toagosei Co., Ltd.) 4 2 parts, 0.4 parts of sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.), 11.0 parts of acrylic resin solution, and 23.2 parts of propylene glycol monomethyl ether acetate (PGMAC) The mixture was stirred and mixed, and filtered through a 1.0 μm filter to prepare a blue resist 1.

(Blue resists 2 to 9: coloring composition according to the third aspect of the present invention)
Blue resists 2 to 9 were prepared in the same manner as the blue resist 1 except that the combination of colorant dispersions shown in Table 7 was used.

(2) A red colored composition (colored resist) for color filters (hereinafter sometimes referred to as “red resist”) was prepared by the following procedure.
(Red resist)
When the red coloring composition (coloring resist) is applied to the substrate, the red dispersion 7, the red colorant dispersion 8, and the yellow colorant are mixed so that x = 0.640 and y = 0.330. After mixing dispersion 1, 60.0 parts of colorant dispersion, 1.2 parts of a photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan), dipentaerythritol pentaacrylate and hexaacrylate (manufactured by Toagosei Co., Ltd.) Aronix M400 ") 4.2 parts, sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts, acrylic resin solution 11.0 parts, propylene glycol monomethyl ether acetate (PGMAC) 23.2 parts The mixture was stirred and mixed so as to be uniform, and filtered through a 1.0 μm filter to prepare a red resist.

(2) A green colored composition for color filter (colored resist) (hereinafter sometimes referred to as “green resist”) was prepared by the following procedure.
(Green resist)
When the green coloring composition (coloring resist) is applied to the substrate, the green coloring agent dispersion 1 and the yellow coloring agent dispersion 2 are mixed so that x = 0.300 and y = 0.600. After that, 60.0 parts of a colorant dispersion, 1.2 parts of a photopolymerization initiator (“Irgacure 907” manufactured by Ciba Japan), dipentaerythritol pentaacrylate and hexaacrylate (“Aronix M400” manufactured by Toagosei Co., Ltd.) 4 2 parts, 0.4 parts of sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.), 11.0 parts of acrylic resin solution, and 23.2 parts of propylene glycol monomethyl ether acetate (PGMAC) The mixture was stirred and mixed, and filtered through a 1.0 μm filter to produce a green resist.

Next, the organic EL light source used in the present invention will be described. In the following examples, all 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.

(Organic EL (OLED) light source 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 compounds (R-1) and (R-3) shown in Table 3 are co-evaporated at a composition ratio of 100: 0.5 to form a first light emitting layer having a thickness of 10 nm. Further, the compound (B-1) 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 20 nm. On this light emitting layer, the following compound (A) is further vacuum-deposited to form an electron injection layer with a film thickness of 35 nm. On top of that, lithium fluoride is first deposited to 1 nm and then aluminum is deposited to 200 nm to form an electrode. Thus, an organic EL device was obtained.

Compound (A):

Furthermore, in order to protect this organic EL element from the surrounding environment, it was hermetically sealed in a dry gyro box filled with pure nitrogen. This device produced white light emission with a direct current voltage of 5 V and an emission luminance of 720 (cd / m ² ), a maximum emission luminance of 49000 (cd / m ² ), and an emission efficiency of 2.6 (lm / W). FIG. 1 shows an emission spectrum of the obtained white organic EL light source 1.

(Organic EL (OLED) light source 2)
4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) is vacuum-deposited on a glass plate with an ITO electrode treated in the same manner as the organic EL light source 1 to obtain a film thickness. A 50 nm hole injection layer was obtained. On this hole injection layer, the compound (R-2) and the compound (R-3) in Table 3 were vacuum-deposited at a composition ratio of 100: 1 to form a first light emitting layer having a thickness of 20 nm, Further, the compound (B-2) 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. A tris (8-hydroxyquinoline) aluminum complex is further vacuum-deposited on the light emitting layer to form a third light emitting layer having a thickness of 30 nm. Lithium fluoride was co-evaporated at a composition ratio of 100: 1 to form an electron injection layer having a thickness of 30 nm, and finally MgAg was evaporated to 200 nm to form an electrode to obtain an organic EL device.

Furthermore, in order to protect this organic EL element from the surrounding environment, it was hermetically sealed in a dry gyro box filled with pure nitrogen. This device obtained white light emission with a direct current voltage of 5 V and a light emission luminance of 1500 (cd / m ² ), a maximum light emission luminance of 65000 (cd / m ² ), and a light emission efficiency of 3.1 (lm / W). FIG. 2 shows an emission spectrum of the obtained white organic EL light source 2.

[Example 1]
The red resist obtained above was applied to a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 0.7 mm using a spin coater so that x = 0.640 and y = 0.330. After drying, striped pattern exposure was performed with an exposure device with an integrated light amount of 150 mJ, and development was performed with an alkaline developer for 90 seconds to form a striped red filter segment. The alkali developer was 0.15% by weight of sodium carbonate, 0.05% by weight of sodium hydrogen carbonate, 0.1% by weight of an anionic surfactant (“PERILEX NBL” manufactured by Kao) and 99.7% of water. Consists of% by weight. The coated substrate was heated and allowed to cool, and then the green resist was coated to a thickness such that x = 0.300 and y = 0.600 in the same manner as the red resist. After drying, a striped pattern adjacent to the red filter segment was exposed with an exposure machine and developed with an alkaline developer for 90 seconds to form a striped green filter segment.

  Further, in the same manner as the red resist, the blue resist 1 was applied to a film thickness such that x = 0.150 and y = 0.060. After drying, striped pattern exposure was performed with an exposure machine and development was performed with an alkaline developer for 90 seconds to form striped blue filter segments adjacent to the red and green filter segments.

  The shape of each color filter segment was good, and the resist resolution was also good. Finally, the obtained color filter is heated in an oven at 230 ° C. for 30 minutes to completely react with the remaining polymerizable functional groups, whereby three colors of red, green, and blue are formed on the transparent substrate. A color filter having a stripe-shaped filter segment was obtained. The chromaticity of the obtained coating film was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.).

  An ITO electrode layer and an organic EL light source 1 were respectively mounted on the RGB color filter layers produced side by side on a glass substrate or the like as described above, to produce a color display device. Thereafter, the light source was emitted to display a color image, and the brightness of the blue filter segment was measured with a microspectrophotometer. The results are shown in Table 8.

[Examples 2-9, Comparative Examples 1-2]
In the same manner as in Example 1, except that the blue resists 2 to 9 are used instead of the blue resist 1 or the combination of the blue resist and the organic EL light source is set as shown in Table 8, Examples 2 to 2 are used. 9 and Comparative Examples 1-2 were produced. In the same manner as in Example 1, the brightness of the blue filter segment portion was measured with a microspectrophotometer. The results are shown in Table 8.

  When Examples 1 to 8 and Comparative Example 1 are compared, high lightness is obtained in a resist containing a xanthene dye, as compared with a resist containing a dioxazine pigment that has been conventionally suitably used. Further, from Example 9 and Comparative Example 2, even when the organic EL light source 2 having a bright line different from that of the organic EL light source 1 is used, higher brightness is obtained when the xanthene dye is used. From this, when using an OLED light source, it can be said that the coloring composition for color filters containing a copper phthalocyanine blue pigment and a xanthene dye is excellent.

Claims (6)

A blue coloring composition for a color filter comprising a copper phthalocyanine blue pigment and a xanthene dye,
The xanthene dye is a basic dye of a xanthene dye, an oil-soluble dye of a xanthene dye, a salt-forming compound of a xanthene basic dye and an organic sulfonic acid or an aromatic hydroxycarboxylic acid, and a xanthene acid dye and a fourth dye. Ri der one selected from the group consisting of salt-forming compounds of the grade ammonium,
Xanthene dyes, color filter blue coloring composition, wherein the rhodamine dye or eosin dyes der Rukoto.   The blue coloring composition for a color filter according to claim 1, wherein the copper phthalocyanine blue pigment is a copper phthalocyanine blue pigment having an ε-type or α-type structure.   The blue coloring composition for a color filter according to claim 1 or 2, further comprising a monomer and / or a polymerization initiator.   A color filter having at least one red filter segment, at least one green filter segment and at least one blue filter segment, wherein at least one of the blue filter segments comprises the blue coloring composition according to any one of claims 1 to 3. A color filter characterized by that.   The color filter according to claim 4, wherein the color filter is for a light emitting device having a white light emitting organic EL element as a light source. A color display device comprising: the color filter according to claim 5; and a light emitting device having a white light emitting organic EL element as a light source.

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