JP2010018788A - Ink for inkjet, color filter and method for producing the same, and liquid crystal display and image display device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet ink capable of forming a color pixel giving a good hue, forming a color filter excellent in light-fastness, heat resistance and chemical resistance, producing a color filter excellent in light-fastness, heat resistance and chemical resistance, and excellent in discharge stability, and to provide the color filter excellent in characteristics such as light-fastness, heat resistance, and a method for producing the color filter. <P>SOLUTION: There is provided the ink for inkjet at least comprising a dipyrromethene-based boron complex compound represented by general formula (I) (wherein R<SP>1</SP>to R<SP>6</SP>are each independently hydrogen or a substituent; R<SP>7</SP>is hydrogen, halogen, alkyl, aryl or heterocyclic group; and X<SP>1</SP>and Y<SP>1</SP>are each independently halogen, alkoxy, aryloxy, hydroxyl, alkylthio, arylthio or heterocyclic thio). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an inkjet ink, a color filter, a method for producing the same, and a liquid crystal display and an image display device using the same.

  In recent years, with the development of personal computers, particularly large-screen liquid crystal televisions, the demand for liquid crystal displays (LCD), especially color liquid crystal displays, has been increasing. However, since color liquid crystal displays are expensive, there is an increasing demand for cost reduction. In particular, there is a high demand for cost reduction for color filters with high specific gravity. Such a color filter usually includes a coloring pattern of three primary colors of red (R), green (G), and blue (B). In a liquid crystal display provided with this color filter, the liquid crystal operates as a shutter by turning on and off the electrodes corresponding to the R, G, and B pixels, and the R, G, and B pixels are illuminated with light. Passes and color display is performed.

  As a conventional method for producing a color filter, for example, a dyeing method may be mentioned. In this dyeing method, first, a water-soluble polymer material, which is a dyeing material, is formed on a glass substrate, patterned into a desired shape by a photolithography process, and then the obtained pattern is immersed in a dyeing bath. To obtain a colored pattern. By repeating this three times, R, G, and B color filter layers are formed.

  Another method is a pigment dispersion method. In this method, a photosensitive resin layer in which a pigment is dispersed is first formed on a substrate, and this is patterned to obtain a monochromatic pattern. Further, by repeating this process three times, R, G, and B color filter layers are formed.

  However, in any method, in order to color three colors of R, G, and B, it is necessary to repeat the same process three times, which causes a problem that the cost is high, and the yield decreases because the same process is repeated. There is a problem of doing. As a method of manufacturing a color filter that solves these problems, a method of forming a colored layer (color pixel) by spraying colored ink by an inkjet method has been proposed (Patent Documents 1 and 2).

The ink jet method is a recording method in which characters and images are obtained by ejecting and adhering ink droplets directly from a very fine nozzle to a recording member. The ink jet method has an advantage that a color filter having a large area can be manufactured with high productivity by moving the ink jet head sequentially, and has low noise and good operability.
Ink-jet inks using pigments are used in the production of color filters by such an ink-jet method. As an inkjet ink using such a pigment, for example, a binder component, a pigment, and an inkjet ink for a color filter containing a solvent having a boiling point of 180 ° C. to 260 ° C. and a vapor pressure at room temperature of 0.5 mmHg or less. Has been proposed (Patent Document 3).

  When an ink jet ink using such a pigment is used for the production of a color filter, the produced color filter is excellent in light resistance and heat resistance, but on the other hand, a decrease in contrast due to scattering by pigment particles, Problems such as increased haze arise. Further, nozzle clogging due to ink pigment aggregation frequently occurs, which is not preferable from the viewpoint of ejection stability. Furthermore, because of the aggregated pigment, the recovery function of the ink discharge state by the discharge recovery operation such as wiping and purging also deteriorates. In addition, at the time of wiping, the nozzle surface may be rubbed by the agglomerated pigment, and the ink ejection direction may be bent.

On the other hand, in the case of an ink using a dye, an improvement in optical properties such as color filter contrast and haze is expected. Also, the ejection stability is generally high, and it is expected that the ink ejection state can be easily recovered by wiping or purging even when there is nozzle clogging accompanying an increase in ink viscosity. However, the fastness such as light resistance and heat resistance of the color pixels is still insufficient and not always satisfactory in practical use.
For this reason, there has been a problem that it is difficult to cope with recent high-brightness backlights.
Moreover, the above-mentioned characteristics such as optical characteristics change due to the high temperature during the deposition of ITO (indium tin oxide), which is often used as an electrode for FPD (flat panel display) such as a liquid crystal display (LCD). was there.

  For example, for blue inks, inks using violet dyes are known, but as described above, the level of light resistance, heat resistance, chemical resistance, etc. of color pixels is not sufficient, and further improvements are made. Was desired.

JP 59-75205 A JP 2004-339332 A JP 2002-201387 A

  The present invention has been made in view of the above circumstances, and the object thereof is to exhibit a good hue and to form a color pixel excellent in light resistance, heat resistance, and chemical resistance. An ink jet ink excellent in optical properties such as haze and having excellent light resistance, heat resistance, and chemical resistance, and excellent in ejection stability, and the above-mentioned ink jet ink obtained by such ink jet ink Color filters with excellent optical characteristics, light resistance, heat resistance, chemical resistance, etc., and color filters with such characteristics that can be manufactured stably and without increasing costs It is an object of the present invention to provide a manufacturing method and a liquid crystal display and an image display device with high contrast and high saturation that can be used for a high-brightness backlight.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by the following <1> to <24> configurations.

<1> An inkjet ink containing at least a dipyrromethene-based boron complex compound represented by the general formula (I) described later.
<2> In general formula (I) described later, at least one of R ¹ and R ⁶ represents an amino group, a carbonamido group, a ureido group, an alkoxycarbonylamino group, or an imide group, and R ² and R ^5. <1>, wherein at least one of these represents a cyano group or a structural formula (i) described later.
<3> The inkjet ink according to <1> or <2>, further comprising a tetraazaporphyrin-based cyan dye represented by the general formula (A) described later.
<4> The inkjet according to <3>, wherein the tetraazaporphyrin-based cyan dye represented by the general formula (A) described later is a phthalocyanine-based dye represented by the general formula (B) described later. For ink.
<5> The inkjet ink according to any one of <1> to <4>, further comprising a cyan dye represented by the general formula (C) described later.
<6> The inkjet ink according to any one of <1> to <5>, further containing a polymerizable monomer.
<7> The inkjet ink according to <6>, wherein the polymerizable group of the polymerizable monomer is any one selected from the group consisting of an epoxy group, an acryloyloxy group, and a methacryloyloxy group.
<8> The inkjet ink according to any one of <1> to <7>, further containing a binder resin.
<9> The ink-jet ink according to any one of <1> to <8>, further containing a surfactant.
<10> The inkjet ink according to any one of <1> to <9>, wherein the viscosity at the time of ejection is 2 to 30 mPa · s.
<11> The inkjet ink according to any one of <1> to <10>, wherein the surface tension at 25 ° C. is 20 to 40 mN / m.
<12> A color pixel of a color filter is formed by applying ink-jet ink droplets according to any one of <1> to <11> to a recess defined by a partition formed on a substrate by an ink-jet method. A method of manufacturing a color filter including a pixel forming step.
<13> The pixel forming step includes a drawing step of applying the ink to the recess as a droplet by the inkjet method, and a curing step of forming the color pixel by curing the ink applied to the recess. The manufacturing method of the color filter as described in <12> which has.
<14> The curing step includes an irradiation step of irradiating the remaining ink with active energy rays and / or a heating step of heating the remaining ink after removing the solvent contained in the ink to form the remaining ink. <13> The method for producing a color filter according to <13>, wherein the color pixel is formed by polymerizing the remaining ink in the irradiation step and / or the heating step.
<15> The drawing step is performed by discharging droplets of the inkjet ink from an ejection nozzle of an inkjet head and applying the droplets to the concave portion of the substrate.
Further, before the drawing step, an inspection step for inspecting the discharge state of the discharge nozzle of the inkjet head;
A pre-processing step of performing an ink ejection operation for ejection nozzles that fall outside the predetermined prescribed range outside the drawing area by the inkjet head when the ejection state inspection result is outside the prescribed prescribed range;
After this pre-processing step, the process returns to the inspection step, and the discharge state is inspected again, and when it is within the predetermined prescribed range, drawing of the color pixel is started by the drawing step <13> or <14 The manufacturing method of the color filter as described in>.
<16> The drawing step is performed by discharging the ink-jet ink droplets from a discharge nozzle of an ink-jet head and applying the droplets to the concave portion of the substrate.
Further, before the drawing step, an inspection step for inspecting the discharge state of the discharge nozzle of the inkjet head;
When there is a non-ejection nozzle in the inkjet head by the inspection in the inspection step, the ejection by the head pressure is applied to a part or all of the plurality of ejection nozzles of the inkjet head including the non-ejection nozzle. A pretreatment step of performing part or all of ink purging of the nozzle, ink suction from the ejection nozzle, and wiping of the nozzle surface of the inkjet head;
After this pre-processing step, the process returns to the inspection step, and the discharge state is inspected again, and when it is within the predetermined prescribed range, drawing of the color pixel is started by the drawing step <13> or <14 The manufacturing method of the color filter as described in>.
<17> Further, a collection step of collecting the ink ejected by the ink ejection operation in the pretreatment step, the ink purged by the ink purge, and the ink sucked by the ink suction,
A storage process for storing the recovered ink collected;
An evaluation process for evaluating ink characteristics including the concentration of recovered ink stored;
The color according to <15> or <16>, further comprising a re-adjusting step of re-adjusting the recovered ink as the ink-jet ink for forming the color pixel based on the evaluation result of the evaluated recovered ink. A method for manufacturing a filter.
<18> Furthermore, a first storage step for storing high-density ink in a high-density ink storage tank and dilution ink in a dilution-ink storage tank in advance;
Supplying the high concentration ink from the high concentration ink storage tank, and supplying the dilution ink from the dilution ink storage tank;
A liquid preparation step of preparing liquid preparation ink as the ink-jet ink for preparing the color pixel by preparing the supplied high-concentration ink and the supplied dilution ink;
A second storage step of storing the prepared ink prepared as the inkjet ink in a prepared ink storage tank;
The method for producing a color filter according to any one of <12> to <17>, wherein in the drawing step, the liquid preparation ink stored in the liquid preparation ink storage tank is supplied as the inkjet ink.
<19> The method for producing a color filter according to any one of <12> to <18>, wherein the dilution ink is a solvent.
<20> A color filter manufactured by the method for manufacturing a color filter according to any one of <12> to <19>.
<21> A color filter produced by an inkjet method using the inkjet ink according to any one of <1> to <11>.
<22> A color filter comprising color pixels formed using the inkjet ink according to any one of <1> to <11>.
<23> A liquid crystal display including the color filter according to any one of <20> to <22>.
<24> An image display device comprising the color filter according to any one of <20> to <22>.

  According to the present invention, it is possible to form an image exhibiting a good hue and excellent in light resistance, heat resistance, and chemical resistance, in particular, excellent optical properties such as contrast and haze, and light resistance and heat resistance. Ink-jet inks that can produce color filters with excellent chemical resistance and excellent discharge stability, the above-mentioned optical characteristics, light resistance, heat resistance, chemical resistance, etc. obtained with such ink-jet inks Color filter with excellent characteristics, a color filter manufacturing method that can stably manufacture a color filter with such characteristics without causing an increase in cost, and high contrast that can be applied to a high-brightness backlight A high-saturation liquid crystal display and an image display device can be provided.

It is a flowchart which shows the manufacturing process in one Embodiment of the manufacturing method of the color filter of this invention. (A)-(f) is typical sectional drawing of the board | substrate and color filter shown in order of the manufacturing process from the board | substrate to a color filter, respectively in the manufacturing method of the color filter of this invention. It is a perspective view which shows a part of one Embodiment of the inkjet drawing apparatus used for implementing the drawing process of the manufacturing method of the color filter of this invention. FIG. 4 is a partial cross-sectional view of the ink jet drawing apparatus shown in FIG. 3. It is a schematic diagram which shows schematic structure of one Embodiment of the ink circulation system in the inkjet drawing apparatus shown in FIG. It is a flowchart which shows the flow of one Embodiment of the drawing method implemented in the inkjet drawing apparatus shown in FIG. (A)-(c) is a schematic diagram which shows the pixel arrangement | sequence of the color filter drawn by the inkjet drawing apparatus shown in FIG. 3, respectively. It is a schematic diagram which shows schematic structure of other embodiment of the ink circulation system applied to the inkjet drawing apparatus shown in FIG. (A)-(d) is a model which respectively shows one Example of the nozzle arrangement of the inkjet head of the inkjet drawing apparatus shown in FIG. 3, and the dot formation of the pixel of the color filter drawn by the inkjet head with the nozzle arrangement FIG. It is a figure which shows the wavelength spectrum distribution of the light inject | emitted from the cold cathode tube light source used in contrast measurement.

Hereinafter, the inkjet ink of the present invention, the dipyrromethene-based boron complex compound that can be used in the ink, its tautomer, a color filter, and a method for producing the color filter will be described in detail.
≪Inkjet ink≫
The ink-jet ink of the present invention is characterized by containing at least one dipyrromethene-based boron complex compound represented by the following general formula (I) (hereinafter, appropriately referred to as “specific boron complex compound”).

In the general formula ^(I), the R 1 to R ⁶ each independently represent a hydrogen atom or a substituent, ^{R 7} represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, X ¹ and Y ¹ each independently represents a halogen atom, an alkoxy group, an aryloxy group, a hydroxyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group.

In general formula (I), the substituents in R ^{1 to} R ⁶ are, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably having 1 to 48 carbon atoms, and more preferably a carbon atom). A linear, branched or cyclic alkyl group of 1 to 24, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl , Cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as vinyl, allyl, 3-butene -1-yl), an aryl group (preferably an aryl having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms). Groups such as phenyl and naphthyl), heterocyclic groups (preferably having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), silyl group (preferably having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms) For example, trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group, alkoxy group (preferably having 1 to 48 carbon atoms, more preferably carbon number) 1 to 24 alkoxy groups such as methoxy, ethoxy, 1-butoxy, 2-butoxy, iso Roxy, t-butoxy, dodecyloxy, cycloalkyloxy groups, for example, cyclopentyloxy, cyclohexyloxy), aryloxy groups (preferably C6-C48, more preferably C6-C24 aryloxy groups, For example, a phenoxy, 1-naphthoxy), a heterocyclic oxy group (preferably a C1-C32, more preferably a C1-C18 heterocyclic oxy group, such as 1-phenyltetrazol-5-oxy, 2- Tetrahydropyranyloxy), silyloxy groups (preferably silyloxy groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), acyloxy groups (Preferably 2 to 48 carbon atoms, more preferably Is an acyloxy group having 2 to 24 carbon atoms, such as acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably having 2 to 48 carbon atoms, more preferably having 2 to 24 carbon atoms). Group, for example, ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy group, for example, cyclohexyloxycarbonyloxy, aryloxycarbonyloxy group (preferably having 7 to 32 carbon atoms, more preferably having carbon number) A 7-24 aryloxycarbonyloxy group such as phenoxycarbonyloxy), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N Dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), a sulfamoyloxy group (preferably having 1 to 32 carbon atoms, more preferably having 1 to 24 carbon atoms) A sulfamoyloxy group, for example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), an alkylsulfonyloxy group (preferably having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms). Alkylsulfonyloxy group, for example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy),

An arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as phenylsulfonyloxy), an acyl group (preferably having 1 to 48 carbon atoms, more preferably carbon An acyl group having 1 to 24, for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably an alkoxy having 2 to 24 carbon atoms) A carbonyl group, for example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl, a group represented by the following structural formula (i)),

An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, such as phenoxycarbonyl), a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably a carbon number). 1 to 24 carbamoyl groups such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methyl-N -Phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), an amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as amino, methylamino, N, N-dibutylamino, Tetradecylamino, 2-ethylhexylamino, Rohexylamino), anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as anilino, N-methylanilino), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, and more). Preferably it is a C1-C18 heterocyclic amino group, for example, 4-pyridylamino), a carbonamido group (preferably a C2-C48, more preferably a C2-C24 carbonamido group, for example, acetamide Benzamide, tetradecanamide, pivaloylamide, cyclohexaneamide), a ureido group (preferably a ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido, N, N-dimethylureido, N-phenyl). Ureido) and imide groups (preferably having 36 or less carbon atoms, more preferably 24 or less carbon atoms). An imide group such as N-succinimide and N-phthalimide), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonylamino, Ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino), aryloxycarbonylamino group (preferably 7-32 carbon atoms, more preferably 7-24 carbon atoms aryloxycarbonylamino group) For example, phenoxycarbonylamino), sulfonamide groups (preferably C1-C48, more preferably C1-C24 sulfonamide groups such as methanesulfonamide, butanesulfonamide, benzenes). Sulfone amide, hexadecane sulfonamide, cyclohexane sulfonamide), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfuramide). Moylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, phenylazo, 3-pyrazolylazo),

An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, for example, methylthio, ethylthio, octylthio, cyclohexylthio), an arylthio group (preferably having 6 to 48 carbon atoms, more preferably An arylthio group having 6 to 24 carbon atoms, such as phenylthio, and a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, such as 2-benzothiazoli Ruthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably an alkylsulfinyl group having 1 to 24 carbon atoms, for example, dodecanesulfinyl group), an arylsulfinyl group ( Preferably it has 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms. An arylsulfonyl group (for example, phenylsulfinyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, Isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfonyl, 1-naphthylsulfonyl), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as sulfamoyl, N, N-dipropylsulfa , N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, phosphonyl group (preferably having 1 to 32 carbon atoms, more preferably carbon A phosphonyl group having 1 to 24 carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), phosphinoylamino group (preferably having 1 to 32 carbon atoms, more preferably phosphino having 1 to 24 carbon atoms) An ylamino group includes, for example, diethoxyphosphinoylamino, dioctyloxyphosphinoylamino), or a combination thereof.

When the substituent of R ¹ to R ⁶ is a group capable of being further substituted may have a substituent explained in R ¹ to R ^6, and when two or more substituents These substituents may be the same or different.

R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and / or R ⁵ and R ⁶ are each independently bonded to each other to form a 5-membered, 6-membered, or 7-membered saturated ring, or A saturated ring may be formed. 5-membered to be formed, 6-membered, and 7-membered rings, in the case of further substitutable groups may be substituted with substituents described above R ¹ to R ^6, 2 or more When substituted with a substituent, these substituents may be the same or different.

R ⁷ in the general formula (I) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and the halogen atom, alkyl group, or aryl group described above for the substituents R ^{1 to} R ^6. And the same group as the heterocyclic group, and the preferred range thereof is also the same.
When the alkyl group, aryl group, and heterocyclic group of R ⁷ are further substitutable groups, they may be substituted with the substituents described for the substituents of R ^{1 to} R ⁶ above. When substituted with the above substituents, these substituents may be the same or different.

X ¹ and Y ¹ in the general formula (I) each independently represent a halogen atom, an alkoxy group, an aryloxy group, a hydroxyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group. Preferred ranges of these halogen atoms, alkoxy groups, aryloxy groups, hydroxyl groups, alkylthio groups, arylthio groups, and heterocyclic thio groups are the same as those described for R ^{1 to} R ⁶ above.

When X ¹ and Y ¹ in the general formula (I) is a substitutable group may be substituted with a group described in the substituent of the R ¹ to R ^6, 2 or more substituents In the case where the substituent is substituted, the substituents may be the same or different.

Next, the preferable range of the compound represented by the general formula (I) will be described.
In general formula (I), R ¹ and R ⁶ are preferably each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy Group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfone Represents an amide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, and R ² and R ⁵ each independently represent a hydrogen atom, a halogen atom, Alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxyl Group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group, Represents an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, or a group represented by the above structural formula (i), wherein R ³ and R ⁴ each independently represents a hydrogen atom; , Halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, anilino group , Carbonamido group, ureido group, imide group, al It represents alkoxycarbonylamino group, a sulfonamido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a phosphinoylamino group, R ⁷ is a hydrogen atom, It represents a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, X ^1, and Y ¹ represents a fluorine atom, an alkoxy group, an aryloxy group.

More preferably, in the general formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, Amino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, azo group, alkylsulfonyl group, arylsulfonyl group, or phosphinoylamino group R ² and R ⁵ are each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, nitro group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, Alkylsulfonyl group, arylsulfonyl group, or sulfamoy Or a group represented by the above structural formula (i), wherein R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, Represents an alkoxycarbonyl group, a carbamoyl group, a carbonamido group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group , R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and X ¹ and Y ¹ represent a fluorine atom, an alkoxy group, or an aryloxy group.

Particularly preferably, in general formula (I), at least one of R ¹ and R ⁶ represents an amino group, a carbonamido group, a ureido group, an alkoxycarbonylamino group, or an imide group, and other than R ¹ and R ⁶ One of them is a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, heterocyclic amino group, carbonamido group, ureido group, imide Group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, an azo group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, and at least one of R ² and R ⁵ is a cyano group , or a group represented by the structural formula, another of R ² and R ⁵ are alkyl groups, alkenyl , Aryl group, heterocyclic group, cyano group, nitro group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group, or the above structural formula (i R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and X ¹ and Y ¹ represent a fluorine atom, an alkoxy group, or an aryloxy group. .

Most preferably, in the general formula (I), at least one of R ¹ and R ⁶ represents an amino group, another of R ¹ and R ⁶ are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group , Heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group represents an azo group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, at least one of R ² and R ⁵ is represented by a cyano group, or a group represented by the above structural formula, R ² , and another one of R ⁵ is an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acyl group, an alkoxycarbonyl Boniru group, an aryloxycarbonyl group, a carbamoyl group, an imido group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, or a group represented by the structural formula (i), R ⁷ is a methyl group or a hydrogen atom X ¹ and Y ¹ represent a fluorine atom.

In general formula (I), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and / or R ⁵ and R ⁶ are independently bonded to each other and have no substituent. In the case of forming a 5-membered, 6-membered, or 7-membered saturated ring or an unsaturated ring, examples of the 5-membered, 6-membered, or 7-membered saturated or unsaturated ring having no substituent include pyrrole Ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine ring, pyrazine ring, pyridazine ring, and the like. Preferably, a benzene ring and a pyridine ring are mentioned.
Also, if having a substituent, examples of the substituent, for example, the include substituents described in R ¹ to R ^6, the same preferred substituent as R ¹ to R ^6.
In addition, the compound represented by general formula (I) may be a tautomer.

The molar extinction coefficient of the specific boron complex compound in the present invention is preferably as high as possible from the viewpoint of film thickness. The maximum absorption wavelength λmax is preferably 520 nm to 570 nm, more preferably 530 nm to 570 nm, from the viewpoint of improving color purity. The maximum absorption wavelength and the molar extinction coefficient are measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation).
The melting point of the specific boron complex compound in the present invention is preferably not too high from the viewpoint of solubility.
The dipyrromethene complex, which is a specific boron complex compound used in the present invention, is 1) sharp in absorption compared with pyrazoloazole-based azomethine dyes, and the absorption at 450 nm, which is an essential requirement for blue color filters, is small (transmittance is low). High) Color purity is high. 2) The pyrazoloazole azomethine dye has an extinction coefficient of 60000, whereas the dipyrromethene complex has an extinction coefficient of 130,000 and a high extinction coefficient (high color value). 3) The dipyrromethene complex has high heat resistance and is robust. 4) The dipyrromethene boron complex alone has high light resistance and is robust.

  Next, specific boron complex compounds in the present invention (Exemplary compounds Ia-1 to Ia-19, Ib-1 to Ib-13, Ic-1 to Ic-17, II-1 to II-17, III-1 to III Specific examples of (-15, IIIa-1 to IIIa-47, IV-1 to IV-20) are shown below, but the present invention is not limited thereto.

The boron complex compounds represented by the above general formula (I) are disclosed in U.S. Pat. Nos. 4,774,339, 5,433,896, JP-A-2001-240761, 2002-155052, and JP 3614586. No., Aust. J. et al. Chem, 1965, 11, 1835-1845, J. Am. H. Boger et al, Heteroatom Chemistry, Vol. 1, No. 1 5,389 (1990) and the like.
Below, the synthesis example of exemplary compound (Ia-1, Ib-1, Ic-6, III-4) mentioned above is explained in full detail.

-Synthesis Example 1
(Synthesis of Exemplified Compound Ia-1)
Synthesized according to Reaction Scheme A below.

(Synthesis of Intermediate 1)
N-methylpyrrolidone (NMP) was added to 96.2 g (1.04 mol) of 300 ml of chloroacetone and stirred at 15 to 20 ° C. To this solution, 175 g (0.945 mol) of phthalimide potassium was added in several portions so that the temperature of the reaction solution was kept at 30 ° C. or lower. After completion of the addition, the reaction was completed by stirring at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into 3000 ml of water with stirring to precipitate crystals. The crystals were filtered, washed with water and dried. 163 g (yield: 84.9%) of intermediate 1 was obtained.

(Synthesis of Intermediate 2)
400 ml of toluene was added to 56.2 g (0.66 mol) of cyanoacetic acid and 136 g (0.6 mol) of 2,6-di-tert-butyl-4-methylcyclohexanol, followed by stirring at room temperature. To this solution, 53.5 ml of pyridine was added dropwise. Subsequently, 125 ml (0.132 mol) of acetic anhydride was added dropwise so as to keep the temperature of the reaction solution at 30 ° C. or lower. After completion of the dropwise addition, the reaction was completed by stirring at room temperature for 4 hours. This reaction solution was slowly added to an aqueous solution consisting of 110 g of sodium bicarbonate and 2000 ml of water. Subsequently, 1200 ml of ethyl acetate was added and extracted. The ethyl acetate solution was washed with water and then dried over anhydrous magnesium sulfate. The ethyl acetate solution was concentrated under reduced pressure, 400 ml of methanol was added to the residue, and the mixture was stirred to precipitate crystals. Further, 100 ml of water was added dropwise and stirred at room temperature for 1 hour. The crystals were filtered, washed with a mixed solution of methanol / water = 4/1, and dried. 137 g (yield: 77.8%) of intermediate 2 was obtained.

(Synthesis of Intermediate 3)
To 102 g (0.5 mol) of Intermediate 1 obtained by the above method and 147 g (0.5 mol) of Intermediate 2 were added 500 ml of ethanol, and the mixture was cooled to 5 ° C. to 10 ° C. and stirred. To this dispersion, 201 ml of SM-28 (sodium methoxide 28% methanol solution) was added dropwise. The temperature of the reaction solution was kept at 10 ° C. or lower. After completion of the dropwise addition, the mixture was returned to room temperature and stirred for 30 minutes, and then 20 ml of water was added and stirred for 4 hours while heating under reflux. After completion of the reaction, the reaction solution was cooled to room temperature, and 750 ml of water was added dropwise to precipitate crystals. The crystals were filtered, washed with water and dried. The crystals were dispersed in 1000 ml of n-hexane, washed by stirring, filtered and dried. 143 g (yield: 82.2%) of intermediate 3 was obtained.

(Synthesis of Intermediate 4)
50 ml of acetic acid was added to 14.0 g (0.04 mol) of Intermediate 3 obtained by the above method and stirred at room temperature. To this solution, 3.3 g (0.022 mol) of triethyl orthoformate was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 12 hours. The precipitated crystals were filtered, washed with acetonitrile and dried. 9.5 g (yield: 67.2%) of intermediate 4 was obtained.
The molar absorption coefficient (ε) was 65400 at the maximum absorption wavelength (λmax = 531.7 nm) in an ethyl acetate solution. The melting point was 236-238 ° C.

(Synthesis of Exemplified Compound Ia-1)
To intermediate 4 (7.07 g, 0.01 mlo) obtained by the above method, 100 ml of dehydrated tetrahydrofuran was added and stirred at room temperature. To this solution, 1.8 g of 1,8-diazabicyclo [5.4.0] undecene (DBU) was added and stirred at room temperature, and then 32 ml of a trifluoroborane diethyl ether solution having a concentration of 46 to 49 wt% was added dropwise. The reaction solution was stirred at room temperature for 1 hour, and then heated to reflux and stirred for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and slowly poured into 1500 ml of 3% sodium bicarbonate water while stirring. Subsequently, 500 ml of ethyl acetate was added and extracted. The ethyl acetate solution was washed with saturated brine and then dried over anhydrous magnesium sulfate. The ethyl acetate solution was concentrated under reduced pressure. The residue was separated and purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 2/1), crystals were precipitated from acetonitrile, filtered and dried. Illustrative compound Ia-1, 4.2 g (yield: 55.6%) was obtained. The maximum absorption wavelength of the visible part in ethyl acetate was 561.4 nm, and the extinction coefficient was 163300.

The ¹ H-NMR data of the obtained exemplary compound (Ia-1) is shown below.
¹ HNMR (CDCl ₃ ): 6.94 (s, 1H), 6.80 to 6.45 (br, 4H), 6.00 (s, 2H), 2.48 (s, 6H), 1.75 To 1.63 (br, 4H), 1.60 to 1.45 (br, 4H), 1.35 to 1.15 (m, 6H), 1.02 (d, 6H), 0.88 (s , 36H)

-Synthesis Example 2-
(Synthesis of Exemplified Compound Ib-1)
Synthesis was performed according to the same method as in Synthesis Example 1.
In an ethyl acetate solution of Exemplified Compound Ib-1, λamx = 583.5 nm, and the extinction coefficient was 169500.

-Synthesis Example 3-
(Synthesis of Exemplified Compound 1c-6)
Synthesis was performed according to the same method as in Synthesis Example 1.
In an ethyl acetate solution of Exemplified Compound Ic-6, λamx = 588.1 nm, and the extinction coefficient was 163000.

(Synthesis of Exemplified Compound III-4)
Synthesized according to Reaction Scheme B below.

(Synthesis of Intermediate 7)
100 ml of dehydrated dimethylformamide (DMF) was cooled to 5 ° C. and stirred. To this solution, 14.0 ml of phosphorus oxychloride was added dropwise. After completion of dropping, the mixture was stirred at 5 ° C to 10 ° C for 30 minutes. Intermediate 6, 32.2 g (0.1 mol) synthesized according to the method described in JP-A No. 2000-63353 was added to this solution in several portions. The reaction temperature was kept at 5-10 ° C. After completion of the addition, the mixture was returned to room temperature and stirred for 1 hour. After completion of the reaction, the reaction solution was poured into 1000 ml of water while stirring, and then adjusted to a pH of 7 to 8 using a 2N aqueous sodium hydroxide solution. After stirring this solution at room temperature for 1 hour, the precipitated crystals were filtered, washed with water, and dried. 30.7 g (yield: 87.6%) of Intermediate 7 was obtained.

(Synthesis of Intermediate 9)
30 ml of acetic acid was added to Intermediate 7 and 7.0 g (0.02 mol) obtained by the above method and Intermediate 8 and 8.2 g (0.02 mol) synthesized according to the same method as Synthesis Example 1 and stirred at room temperature. did. Next, 2 ml of trifluoroacetic acid was added to this solution and stirred at room temperature for 5 hours. After completion of the reaction, 20 ml of acetonitrile was added to the reaction solution and stirred. The precipitated crystals were filtered, washed with acetonitrile and dried. 12.3 g (yield: 82.7%) of intermediate 9 was obtained.

(Synthesis of Exemplified Compound III-4)
60 ml of dehydrated tetrahydrofuran was added to 7.43 g (0.01 mol) of the intermediate 9 obtained by the above method, and the mixture was stirred at room temperature. To this solution was added 2.3 g of DBU. Next, 15 ml of a 46% -49 wt% trifluoroborane diethyl ether solution was added dropwise. After completion of the dropwise addition, the mixture was heated and refluxed for 3 hours. After completion of the reaction, it was poured into 600 ml of water with stirring. Next, the mixture was neutralized with sodium bicarbonate and extracted by adding 500 ml of ethyl acetate. The ethyl acetate solution was washed with water and then dried over anhydrous magnesium sulfate. The ethyl acetate solution was concentrated under reduced pressure, and the residue was separated and purified by column chromatography (eluent: n-hexane / ethyl acetate = 2/1). 2-Propanol was added to precipitate crystals, and then filtered and dried. 5.32 g (yield: 67.3%) of Exemplary Compound III-4 was obtained. Λmax = 525.6 nm in ethyl acetate solution and ε = 79700.

The ¹ H-NMR data of the obtained exemplary compound (III-4) is shown below.
¹ HNMR (CDCl ₃ ):
8.15 to 8.00 (br, 1H), 7.6 to 7.2 (m, 9H), 6.62 (s, 1H), 6.45 to 6.30 (br, 1H), 5. 90 (s, 1H), 4.05 (t, 2H), 3.07 (s, 3H), 2.36 (s, 3H), 1.35 to 1.13 (m, 6H), 1.07 ~ 0.96 (m, 2H), 0.82 (s, 18H), 0.73 (d, 3H), 0.50 to 0.30 (m, 2H)

  In addition, it can synthesize | combine by the method similar to the above also about other exemplary compounds other than the exemplary compound Ia-1, Ib-1, Ic-6, and III-4 mentioned above.

  In the inkjet ink of the present invention, each of the specific boron complex compounds may be used alone or in combination of two or more.

  The content of the specific boron complex compound in the inkjet ink of the present invention varies depending on the molecular weight and molar absorption coefficient, but is preferably 0.5 to 80% by mass with respect to the total solid content component of the inkjet ink. 0.5-60 mass% is more preferable, and 0.5-50 mass% is the most preferable.

<Tetraazaporphyrin-based cyan dye represented by formula (A)>
The inkjet ink of the present invention uses a tetraazaporphyrin-based cyan dye represented by the following general formula (A) (hereinafter, referred to as “specific dye-A” as appropriate) in addition to the specific boron complex compound. Therefore, it is excellent in color purity, excellent in fastness, and a color filter can be produced by using an inkjet ink and an inkjet method. In particular, a color filter including color pixels formed using an inkjet ink can be manufactured, and can be suitably used for a liquid crystal display and an image display device using the color filter.

In General Formula (A), M ¹ represents a metal atom or a metal compound, and Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently an atom selected from a carbon atom, a nitrogen atom, and a hydrogen atom. The atomic group which forms the 6-membered ring comprised by these is represented.
The metal atom or metal compound may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, Or a bivalent metal chloride is contained.

M ¹ in the general formula (A) is, for example, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, and the like, and AlCl, InCl, FeCl. , TiCl ₂ , SnCl ₂ , SiCl ₂ , GeCl ₂ and other metal chlorides, TiO, VO and other metal oxides, and Si (OH) _{2 and} other metal hydroxides.
Z ¹ in the general formula ^{(A), Z 2, Z} 3, and Z ⁴ are each independently, a carbon atom, a nitrogen atom, and in order to form a 6-membered ring composed of atoms selected from hydrogen atoms Represents the necessary atomic group. The 6-membered ring may be a saturated ring or an unsaturated ring, and may be unsubstituted or have a substituent. Furthermore, other 5-membered or 6-membered rings may be condensed. The 6-membered ring includes a benzene ring, a cyclohexane ring, a pyridine ring, a pyrimidine ring, a pyrazine ring and the like.

  In the present invention, the maximum absorption wavelength λmax of the specific dye-A is preferably 580 nm to 700 nm, and more preferably 600 nm to 680 nm, from the viewpoint of improving color purity. In addition, the maximum absorption wavelength was measured similarly to the specific boron complex compound.

<Phthalocyanine dye represented by the following general formula (B)>
Among the tetraazaporphyrin dyes represented by the general formula (A), a phthalocyanine dye represented by the following general formula (B) (hereinafter referred to as “specific dye-B” as appropriate) is particularly preferable.

In General Formula (B), R ^{101 to} R ¹¹⁶ each independently represent a hydrogen atom or a substituent, and M ² represents a metal atom or a metal compound.

In the general formula (B), M ² is the same as the examples of M ¹ in the compound represented by the above formula (A), and also the same preferred embodiment thereof.
In General Formula (B), R ^{101 to} R ¹¹⁶ each independently represent a hydrogen atom or a substituent, and the substituent represented by R ^{101 to} R ¹¹⁶ is R ¹ in General Formula (I) described above. to R ⁶ have the same meanings as illustrative of substituents represented by the same also its preferred embodiments. When the substituents R ^{101 to} R ¹¹⁶ of the compound represented by the general formula (B) are further substitutable groups, they may be substituted with the substituents described in the above R ^{1 to} R ⁶ , When substituted with two or more substituents, these substituents may be the same or different.

In addition, as one of preferred embodiments of the substituents represented by R ^{101 to} R ¹¹⁶ , “* -S (═O) _m- (L) _n- (A) _p ” (hereinafter referred to as substituent A) The group represented by these is mentioned. A represents a hydrogen atom or a substituent each independently, and the definition of this substituent is synonymous with the substituent represented by R < ¹⁰¹ > -R < ¹¹⁶ >. * Indicates the bonding position with the benzene ring. In addition, it is preferable that at least one of R ^{101 to} R ¹¹⁶ is the substituent A, and it is preferable that 1 to 4 is the substituent A. It is also preferred that there is one substituent A for each benzene ring group in general formula (B). When a plurality of substituents A are included, they may be the same or different.

  m independently represents 1 or 2, and m is preferably 2. Each n independently represents 0 or 1, and n is preferably 1. p represents the integer of 1-5 each independently, the case where it is 1-3 is preferable, and the case where it is 1 is more preferable.

L represents an aliphatic or aromatic linking group, and a plurality of L may be the same or different. The aliphatic linking group represented by L may be unsubstituted or substituted, and is preferably an aliphatic group having 1 to 20 carbon atoms in total, and an aliphatic group having 1 to 15 carbon atoms in total. More preferred. For example, a methylene group, ethylene group, propylene group, butylene group and the like can be mentioned.
The aromatic linking group represented by L may be unsubstituted or substituted, and is preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having 6 to 16 carbon atoms. preferable. For example, a phenylene group, a naphthylene group, etc. are mentioned, The most preferable is a phenylene group.
When n is 0, A and S (sulfur atom) are directly bonded.

  In terms of the effects of the present invention, A is a halogen atom, an aliphatic group (such as an alkyl group), a cyano group, a carboxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a hydroxy group, an aliphatic group. Oxy group, carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio Group, arylthio group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, aliphatic sulfonylcarbamoyl group, arylsulfonylcarbamoyl group, aliphatic carbonylsulfamoyl group, arylcarbonylsulfamoyl group, aliphatic sulfonylsulfamoyl group Ant Le acylsulfamoyl group, an imido group, is preferably a sulfo group or a group having a combination thereof.

In the present invention, a plurality of A in the molecule may be the same or different, and in the plurality of A, at least one A is —OY, —COOY, —SO ₃ Y, —CON (Y ) CO-, CON (Y) SO 2 - or preferably has a _-SO 2 N (Y) CO-.
The _{-OY, -COOY, -SO 3 Y,} -CON (Y) CO-, CON (Y) SO 2 - or _-SO 2 N (Y) CO- may be attached to the linking group L, It may be directly bonded to —S (═O) _m — without using the linking group L. When it is directly bonded to —S (═O) _m — without the linking group L, R ¹ is preferably —OY, and directly bonded to the tetraazaporphyrin ring together with —S (═O) _m —. constituting a -SO ₃ Y to (m = 2) is preferred.

  Y represents a hydrogen atom, a metal atom or a conjugate acid. Examples of the metal atom represented by Y include Li, Na, K, Mg, and Ca. Li, Na, and K are preferable. Examples of the base that forms the conjugate acid represented by Y include tertiary amines (for example, triethylamine, tripropylamine, tributylamine, diisopropylethylamine, N-methylpiperidine, 4-methylmorpholine), and guanidines (for example, guanidine). N, N-diphenylguanidine, 1,3-di-o-tolylguanidine), pyridines (for example, pyridine, 2-methylpyridine) and the like. Among these, triethylamine, tripropylamine, tributylamine, N, N-diphenylguanidine, and 1,3-di-o-tolylguanidine are preferable.

Hereinafter, examples (T-1 to T141) of the substituents R ^{101 to} R ¹¹⁶ of the specific dye-B are shown. However, the present invention is not limited to these. In the following examples, T-87, T-89, T-94, T-95, T-96, T-97, T-98, T-125, T-126, T-127 are preferable. , T-128, T-129, T-140, and T-141.

Next, a preferable range of the phthalocyanine dye represented by the general formula (B) will be described.
The phthalocyanine dyes represented by the general formula (B) are (R ¹⁰¹ and R ¹⁰⁴ ), (R ¹⁰⁵ and R ¹⁰⁸ ), and (R ¹⁰⁹ and R ¹¹² ) as α-substituents (α-substituents). , And (R ¹¹³ and R ¹¹⁶ ) have a substituent in at least one pair, or as β-substituents (β-substituents) (R ¹⁰² and R ¹⁰³ ), (R ¹⁰⁶ and R ¹⁰⁷ ) , (R ¹¹⁰ and R ¹¹¹ ), and (R ¹¹⁴ and R ¹¹⁵ ) have a substituent in at least one pair, or as substituents at the α-position and β-position, (R ¹⁰¹ and R ¹⁰³ And / or R ¹⁰² and R ¹⁰⁴ ), (R ¹⁰⁵ and R ¹⁰⁷ and / or R ¹⁰⁶ and R ¹⁰⁸ ), (R ¹⁰⁹ and R ¹¹¹ and / or R ¹¹⁰ and R ¹¹² ), and (R ¹¹³ and R ¹¹⁵ and / or R Among the combinations of ¹⁴ and R ^116), preferably it has at least one pair substituent.
Here, examples of the substituent represented by R ^{101 to} R ¹¹⁶ include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, and an alkoxy group. Group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acyl group , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, sulfamoy Examples include amino group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, phosphonyl group, and phosphinoylamino group. . Examples of M ² include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, TiO, and VO.

Preferred range of the phthalocyanine dye represented by the general formula (B), alpha substituents (disubstitutions) as ^{(R 101} or ^{R 104), (R 105} or ^{R 108), (R 109} or ^{R 112)} , And (R ¹¹³ or R ¹¹⁶ ) have a substituent, or β-substitution (mono-substitution) (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and (R ¹¹⁴ or R ¹¹⁵ ).
Examples of the substituent represented by R ¹⁰¹ to R ^116, halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy Group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, ureido group, imide group, alkoxy Carbonylamino group, aryloxycarbonylamino group, sulfonamido group, sulfamoylamino group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, Rufamoiru group, a sulfo group, and a phosphinoylamino group. Examples of M ² include Zn, Pd, Cu, Ni, Co, TiO, and VO.

As a more preferable range of the phthalocyanine dye represented by the general formula (B), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) having a substituent in at least three of them, or (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and ( R ¹¹⁴ or R ¹¹⁵ ) is a compound having a substituent in at least three of them.
Here, examples of the substituent represented by R ^{101 to} R ¹¹⁶ include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, and an aryl group. Oxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, sulfo group Examples include a famoylamino group, an azo group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, and a sulfo group. Examples of M ² include Zn, Pd, Cu, Ni, Co, and VO.

As a more preferable range of the phthalocyanine dye represented by the general formula (B), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) having the same substituent in at least three of them, or (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ) as β substituents, And (R ¹¹⁴ or R ¹¹⁵ ) are compounds having the same substituent in at least three of them.
Here, examples of the substituent represented by R ^{101 to} R ¹¹⁶ include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, a cyano group, an alkoxy group, an aryloxy group, and a heterocyclic oxy group. Groups, acyl groups, alkoxycarbonyl groups, carbamoyl groups, carbonamido groups, ureido groups, imide groups, sulfonamido groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, sulfamoyl groups, sulfo groups. . Examples of M ² include Zn, Pd, Cu, Ni, Co, and VO.

As a particularly preferable range of the phthalocyanine dye represented by the general formula (B), (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) having substituents on at least three of them, or (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and (R ¹¹⁴ or R ¹¹⁵ ) has a substituent in at least three, and the substituents are all the same compound.
Here, examples of the substituent represented by R ^{101 to} R ¹¹⁶ include a halogen atom, an alkyl group, a heterocyclic group, a carboxyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkoxycarbonyl group, A carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a sulfo group can be mentioned. Examples of M ² include Zn, Pd, Cu, Ni, Co, and VO.

The most preferred range of the phthalocyanine dye represented by the general formula (B), as α substituents ^{(R 101} or ^{R 104), (R 105} or ^{R 108), (R 109} or ^{R 112),} and (R ¹¹³ or having at least three substituents of ^{R 116),} as β substituents ^{(R 102} or ^{R 103), (R 106} or ^{R 107), (R 110} or ^{R 111),} and ^{(R 114} or R ¹¹⁵ ) have a substituent, and all of the substituents are the same compound, and the substituents represented by R ^{101 to} R ¹¹⁶ include a halogen atom, an alkyl group, and a heterocyclic ring. Group, carboxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group Group, a sulfamoyl group, or a sulfo group. Examples of M ² include Zn, Cu, Co, and VO.

  Specific examples (example compounds CA-1 to CA-46, CB-1) of tetraazaporphyrin dyes represented by the general formula (A) (including phthalocyanine dyes represented by the general formula (B)) are shown below. CB-46, CC-1 to CC-10, CK-1 to CK-19, CE-1 to CE-46, CF-1 to CF-46, CG-1 to CG-46, CI-1 to CI -46, and CH-1 to CH-46). However, the present invention is not limited to these.

-Synthesis example-
Next, a synthesis example of the dye represented by the general formula (A) or (B) will be described in detail with reference to the following scheme D by taking the synthesis of the exemplified compound CI-29 as an example.

(Synthesis of Intermediate A)
Sodium carbonate (16.5 g, 0.156 mol) was added to a mixture of 3-nitrophthalonitrile (25 g, 0.144 mol), DMSO (200 ml) and 3-mercaptopropanesulfonic acid sodium salt (32 g, 0.18 mol). The mixture was heated to 60 ° C. and stirred for 3 hours. The reaction mixture was poured into 10% brine (300 g), and the precipitated solid was collected by filtration and washed with an isopropanol / water (3/1) mixture. Water (200 ml), acetic acid (3 ml) and Na ₂ WO ₄ (2 g) were added to the obtained solid, and 31% hydrogen peroxide solution (50 ml) was added, followed by heating and stirring at 60 ° C. After stirring for 4 hours, the reaction mixture was poured into isopropanol (500 ml), and the precipitated solid was collected by filtration and washed with an isopropanol / water (3/1) mixture. The solid obtained here was dried to obtain 24 g of intermediate A (yield from 3-nitrophthalonitrile 49%).

(Synthesis of Intermediate B)
200 ml of acetonitrile was added to 67.3 g (0.2 mol) of Intermediate A, and the mixture was heated to 70 ° C. to 75 ° C. and stirred. To this dispersion, 37 ml of phosphorus oxychloride was added dropwise. After completion of the dropwise addition, stirring was performed at 70 to 75 ° C. for 4 hours to complete the reaction. After completion of the reaction, the reaction solution was cooled to room temperature and poured into 2000 ml of water with stirring to precipitate crystals. The crystals were filtered and washed with water, and then dispersed in 300 ml of 2-propanol. The dispersion was stirred for 1 hour, then filtered and dried. 63.0 g (yield: 94,5%) of intermediate B was obtained.

(Synthesis of Intermediate C)
250 ml of acetonitrile was added to 50.0 g (0.15 mol) of the intermediate B obtained by the above method, and the mixture was cooled to 5 ° C. and stirred. To this solution, 31.0 g of 3-ethoxypropylamine was added dropwise. After completion of the dropwise addition, the mixture was returned to room temperature and stirred for 2 hours to complete the reaction. The reaction solution was poured into 1500 ml of water while stirring to precipitate crystals. The crystals were filtered and washed with water, and then dispersed in 500 ml of 2-propanol. The mixture was stirred at room temperature for 2 hours, filtered and dried. 52.6 g of intermediate C was obtained (yield: 87.7%).

(Synthesis of CI-29)
Intermediate C obtained by the above method, 7.9 g (0.02 mol), o-phthalonitrile 1.28 g (0.01 mol), intermediate A 3.36 g (0.01 mol), diethylene glycol 30 ml, 2-methoxy 100 ml of propanol was added and the mixture was heated to 100 ° C. and stirred. To this solution was added 3.87 g ammonium benzoate and 1.26 g copper acetate. After completion of the addition, stirring was performed at 95 ° C to 100 ° C for 6 hours to complete the reaction. The reaction solution was cooled to room temperature, 60 ml of methanol was added, and 75 ml of hydrochloric acid was poured into an aqueous solution diluted with 800 ml of water while stirring. The precipitated crystals were filtered, washed with water and dried. The crystals were dissolved in 250 ml of methanol by heating and filtered to remove insoluble matters. The filtrate was concentrated under reduced pressure, and 250 ml of ethyl acetate was added to the residue and stirred. The dispersed crystals were filtered and dried. 24.7g (yield: 92.9%) of exemplary compound CI-29 was obtained. The maximum absorption wavelength and molar extinction coefficient of CI-29 in chloroform were λmax = 665.6 nm and ε = 84600, respectively.

  When the maximum absorption wavelength (λmax) and molar extinction coefficient (ε) of the obtained dye were measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation), the maximum absorption wavelength λmax, molar extinction coefficient (Ε) were 623.4 nm and 47000, respectively.

  In addition, it can synthesize | combine by the method similar to the above about other exemplary compounds other than the pigment | dye CI-29 mentioned above.

  In the present invention, the maximum absorption wavelength λmax of the specific dye-B is preferably 580 nm to 700 nm, and more preferably 600 nm to 680 nm, from the viewpoint of improving color purity. The maximum absorption wavelength was measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation).

<Pyrroazole azomethine dye represented by formula (C)>
In the present invention, in addition to the specific dye-A and the specific dye-B, a pyrroloazole azomethine dye represented by the following general formula (C) (hereinafter, referred to as “specific dye-C” as appropriate) is preferable. Ink-jet ink cured products having excellent color purity, particularly high transmittance of 450 nm or less, and color filters using the cured products can be obtained. The color filter can be suitably used for a liquid crystal display, an image display display and the like.

In formula (C), R ^{50 to} R ⁵⁵ each independently represent a hydrogen atom or a substituent, and R ⁵⁶ and R ⁵⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or hetero Represents a cyclic group, and Za and Zb each independently represent -N = or -C ( ^R58 ) =. R ⁵⁸ represents a hydrogen atom or a substituent. R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁷ , R ⁵⁴ and R ⁵⁵ , R ⁵⁵ and R ⁵⁶ , and / or R ⁵⁶ and R ⁵⁷ are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. It may be formed.

The substituents of R ^{50 to} R ^{55 in} the general formula (C) have the same meanings as the groups described for the substituents of R ^{1 to} R ^{6 in} the general formula (I), and their preferred ranges are also the same.
When the substituents of R ^{50 to} R ^{55 in} the general formula (C) are further substitutable groups, they may be substituted with the groups described for the substituents of R ^{1 to} R ⁶ above. When substituted with the above substituents, these substituents may be the same or different.
R ⁵⁶ and R ^{57 in} formula (C) each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Preferred ranges of the alkyl group, alkenyl group, aryl group, and heterocyclic group are the same as the alkyl group, alkenyl group, aryl group, and heterocyclic group described in R ^{1 to} R ⁶ in the general formula (I). is there.
The alkyl group, alkenyl group, aryl group, and heterocyclic group of R ⁵⁶ and R ^{57 in} the general formula (C) may be further substituted with the substituents described in the above R ^{1 to} R ^6. When it is substituted with more than one substituent, these substituents may be the same or different.

Za and Zb in the general formula (C) each independently represent -N = or -C ( ^R58 ) =. R ⁵⁸ represents a hydrogen atom or a substituent. Substituents R ⁵⁸ are the same as the substituents described in the above Formula (I), and also the preferred ranges thereof. When the substituent of R ⁵⁸ is a further substitutable group, it may have the substituent described in the above general formula (I) and may be substituted with two or more substituents. These substituents may be the same or different.

The dyes represented by the general formula (C) are bonded to each other and R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁷ , R ⁵⁴ and R ⁵⁵ , R ⁵⁵ and R ⁵⁶ , and / or R ⁵⁶ and R ⁵⁷ are bonded to each other. , 6 or 7 membered rings may be formed.

The specific dye-C is preferably such that R ⁵⁰ and R ⁵¹ are selected from the substituents described in R ^{1 to} R ⁶ above, and the Hammett substituent constant σp value of the substituent represented by R ⁵⁰ and R ⁵¹ is This represents a substituent having a total sum of 0.7 or more, and R ⁵⁹ is represented by a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

  Hammett's law was established in 1935 by L. P. This is an empirical rule proposed by Hammett and is described in a general book. For example, J. et al. A. Dean, “Lange's and book of Chemistry”, 12th edition, 1979 (McGrew-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). However, even if each substituent is limited or specified by Hammett's substituent constant σp value in the present invention, it is not limited to only a substituent having a known value that can be found in the above-mentioned booklet, but Hammett's rule Substituents whose values fall within the range when measured based on As for the “Hammett substituent constant σp value” in the present invention, the σp value is used as a scale indicating the electronic effect of a substituent even for a substituent that is not a benzene derivative, regardless of the substitution position.

  Examples of the electron withdrawing group having a Hammett substituent constant σp value of 0.3 or more include, for example, an acyl group (preferably an acyl group having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, such as acetyl and pivaloyl). , 2-ethylhexyl, benzoyl, cyclohexanoyl), acyloxy group (preferably an acyloxy group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, acetoxy, pivaloyloxy), carbamoyl group (preferably carbon number) 1 to 24, more preferably a carbamoyl group having 1 to 18 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N-ethylcarbamoyl, Nt-butylcarbamoyl, N-cyclohexylcarbamoyl, N-phenylcarbamoyl, N, N-diethylcarbamoyl, N, N-diisopropylcarbamo , N-ethyl-N-phenylcarbamoyl), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, isopropyloxycarbonyl, Cyclohexylcarbonyl), aryloxycarbonyl groups (preferably aryloxycarbonyl groups having 7 to 24 carbon atoms, more preferably 7 to 18 carbon atoms, such as phenoxycarbonyl), cyano groups, nitro groups, alkylsulfinyl groups (preferably An alkylsulfinyl group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, such as methylsulfinyl, ethylsulfinyl, butylsulfinyl, 2-ethylhexylsulfinyl, cyclopentylsulfinyl), aryl A sulfinyl group (preferably an arylsulfinyl group having 6 to 24 carbon atoms, more preferably an arylsulfinyl group having 6 to 18 carbon atoms, such as phenylsulfinyl or p-toluenesulfinyl), an alkylsulfonyl group (preferably having 1 to 24 carbon atoms, more preferably Is an alkylsulfonyl group having 1 to 18 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclohexylsulfonyl), arylsulfonyl group (preferably having 6 to 24 carbon atoms, more preferably arylsulfonyl having 6 to 18 carbon atoms) A group such as phenylsulfonyl, naphthylsulfonyl), a sulfamoyl group (preferably a sulfamoyl group having 24 or less carbon atoms, more preferably 18 or less carbon atoms, such as N-ethylsulfamoyl, N, N-dipropylsulfa Moyle N-ethyl-N-phenylsulfamoyl, N-phenylsulfamoyl, N-cyclohexylsulfamoyl), halogenated alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms) An alkyl group such as trifluoromethyl or pentafluoropropyl), a halogenated alkoxy group (preferably a halogenated alkoxy group having 1 to 24 carbon atoms, more preferably a halogenated alkoxy group having 1 to 18 carbon atoms, for example, trifluoromethoxy), halogen Aryloxy group (preferably a halogenated aryloxy group having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, such as pentafluorophenyloxy), a heterocyclic group (preferably having 1 to 24 carbon atoms, and more Preferably it is a C1-C12 heterocyclic group, for example, 2-benzoxazoyl, 2-ben Thiazolyl, 1-phenyl-2-benzimidazolyl, 5-chloro-1-tetrazolyl, 1-pyrrolyl) and the like.

  Specific examples (CD-1 to CD-46) of the compound represented by the general formula (C) are shown below, but the present invention is not limited thereto.

  Synthesis of the compound represented by the general formula (C) is described in paragraphs [0070] to [0072] of JP-A-5-177959, paragraphs [0041] to [0054] of JP-A-2003-96326, It can be synthesized by the method described in paragraph numbers [0043] to [0056] of 2003-96327.

  In the present invention, the maximum absorption wavelength λmax of the specific dye-C is preferably 580 nm to 700 nm, more preferably 600 nm to 680 nm, from the viewpoint of improving color purity. The maximum absorption wavelength and molar extinction coefficient were measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation).

The content of the specific dye-A, the specific dye-B, and / or the specific dye-C varies depending on the molar extinction coefficient, the required spectral characteristics, the film thickness, and the like, but the ink jet according to the present invention. It is preferably 1% by mass to 80% by mass and more preferably 10% by mass to 70% by mass with respect to the total solid content of the ink.
These colorants may be contained alone in the inkjet ink of the present invention, or two or more kinds may be used in combination.

  The inkjet ink of the present invention and the color filter using the inkjet ink include triarylmethane-based colorants having an absorption maximum at 550 nm to 650 nm, such as C.I. Acid Blue 7 (C.I. Acid Blue 7), C.I. Acid Blue 83 (C.I. Acid Blue 83), C.I. Acid Blue 90 (C.I. Acid Blue 90), C.I. Blue 38 (CI Solvent Blue 38), CI Acid Violet 17 (CI Acid Violet 17), CI Acid Violet 49 (CI Acid Violet 49), CI Eye Acid 49・ Green 3 (C.I. Aci d Green3) or the like can be used.

  Furthermore, a xanthene dye having an absorption maximum at 500 nm to 600 nm, such as C.I. Acid Red 289, can be used.

  The content of the triarylmethane-based colorant can be used within a range not impairing the effects of the present invention, and is 0.5% by mass to 50% by mass with respect to the total solid content of the inkjet ink of the present invention. It is preferable.

In order to produce a blue filter array, it is preferable to use a mixture of the specific boron complex compound and at least one of the specific dye-A, the specific dye-B, and the specific dye-C.
At this time, each mixing ratio varies depending on each molar extinction coefficient, required spectral characteristics, film thickness, etc., but in general, the content ratio (total content of the specific boron complex compound): (above The total content of the specific dye-A, the specific dye-B, and the specific dye-C) = 20: 1 to 1:20. Preferably it is the range of 10: 1 to 1:10, More preferably, it is used in the range of 4: 1 to 1: 1.

<Solvent>
The ink-jet ink of the present invention preferably contains a solvent. The solvent is basically not particularly limited as long as the solubility of each component and the boiling point of the solvent described later are satisfied, but it is preferably selected in consideration of the solubility, coating property, and safety of the binder described later. Specific examples of the solvent include esters such as amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, oxy Butyl acetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate, ethyl 3-oxypropionate, for example, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc .; methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxypropionic acid pro 2-oxypropionic acid alkyl esters, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2 -Methyl oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc .; methyl pyruvate, pyruvate Ethyl, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like; ethers such as diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoe Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones, For example, cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as xylene; dicyclohexylmethylamine and the like are preferable. These may be used alone or in combination of two or more.

  The content of the solvent in the inkjet ink of the present invention is preferably 30 to 90% by mass, and more preferably 50 to 90% by mass. When the amount is 30% by mass or more, the amount of ink ejected in one pixel is maintained, and the wetting and spreading of the ink in the pixel is good. Further, when it is 90% by mass or less, the amount of components other than the solvent for forming a functional film (for example, a pixel or the like) in the ink can be kept at a predetermined amount or more. As a result, when forming a color filter, the required amount of ink per pixel does not increase too much. For example, when ink is applied to the concave portion partitioned by the partition wall by the ink jet method, the ink overflows from the concave portion. And the occurrence of color mixing with adjacent pixels can be suppressed.

  The ink-jet ink of the present invention preferably contains a solvent having a high boiling point among the above-mentioned solvents from the viewpoints of ink discharge performance with respect to the nozzle and wettability with respect to the substrate. Since the solvent having a low boiling point evaporates quickly even on the ink jet head, it easily causes an increase in the viscosity of the ink on the head, precipitation of solids, and the like, and is often accompanied by a deterioration in dischargeability. Also, when the ink lands on the substrate surface and spreads on the substrate surface, the viscosity of the ink increases due to the evaporation of the solvent at the edge of the wet spread, and the phenomenon of pinning (PINING) causes the wetting and spreading. It may be suppressed.

  The boiling point of the solvent used in the present invention is not limited as long as it is in a suitable range used for inkjet inks, but is preferably 130 to 260 ° C. from the viewpoint of ejection stability (continuous ejection and ejection after pause). If it is lower than 130 ° C., it is not preferable in terms of uniformity of the shape of the pixels in the surface. A temperature higher than 260 ° C. is not preferable in terms of solvent removal by pre-baking. In addition, the boiling point of a solvent means the boiling point under the pressure of 1 atm, and can be known from a physical property value table such as a compound dictionary (Chapman & Hall). These may be used alone or in combination of two or more.

  In addition, when the ink-jet ink described above does not contain a polymerizable monomer, which will be described later, the thickness of the remaining ink (color pixel) obtained by removing the solvent contained in the ink is reduced, so that the substrate is used for the purpose of preventing color mixing. The height of the partition formed on the top can be reduced, which is preferable from the viewpoint of cost and productivity.

<Polymerizable monomer>
The inkjet ink of the present invention may contain a polymerizable monomer. Addition of the polymerizable monomer improves the adhesion between the ink droplet and the substrate. In addition, it can be expected to improve the dispersion uniformity of the above-described dipyrromethene-based boron complex compound in the ink and to improve the fastness such as weather resistance and heat resistance. Although there is no restriction | limiting in particular as this polymerizable monomer, One or more types selected from a (meth) acrylic-type monomer, an epoxy-type monomer, and an oxetanyl-type monomer at the point with many variations of various substituents and easy acquisition. It is preferable to contain.

  As the polymerizable monomer, a monomer having two or more polymerizable groups (hereinafter also referred to as “bifunctional or higher functional monomer”) is preferable. The polymerizable monomer is not particularly limited as long as it can be polymerized by active energy rays and / or heat, but it has three or more polymerizable groups from the viewpoint of film strength and solvent resistance. (Hereinafter also referred to as “tri- or higher functional monomer”) is more preferable.

  Although there is no restriction | limiting in particular as a kind of polymeric group mentioned above, As above-mentioned, an acryloyloxy group, a methacryloyloxy group, an epoxy group, and an oxetanyl group are especially preferable. Specific examples of the polymerizable monomer include an epoxy group-containing monomer described in paragraph numbers [0061] to [0065] of JP-A No. 2001-350012, and a paragraph number [0016] of JP-A No. 2002-371216. Acrylate monomer and methacrylate monomer, paragraph numbers [0021] to [0084] of JP-A No. 2001-220526, JP-A No. 2001-310937, JP-A No. 2003-341217 and paragraph No. of JP-A No. 2004-91556 Examples include oxetanyl group-containing monomers described in [0022] to [0058], and monomers described in CMC Publishing “Market Prospects for Reactive Monomers”.

  Examples of the epoxy group-containing monomer that is an epoxy monomer include bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, Naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, Dicyclopentadienephenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene Glycol type epoxy resins, glycidyl ester epoxy resins, glycidyl amine type epoxy resin, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin.

  More specifically, bisphenol A type epoxy resins such as trade name Epicoat 828 (manufactured by Yuka Shell Epoxy), bisphenol F type epoxy resins such as trade name YDF-175S (manufactured by Tohto Kasei Co., Ltd.), trade name YDB-715 Brominated bisphenol A type epoxy resins (made by Toto Kasei Co., Ltd.), bisphenol S type epoxy resins such as trade name EPICLON EXA1514 (Dainippon Ink Chemical Co., Ltd.), trade name YDC-1312 (made by Toto Kasei Co., Ltd.), etc. Hydroquinone type epoxy resin, Naphthalene type epoxy resin such as trade name EPICLON EXA4032 (manufactured by Dainippon Ink & Chemicals), Biphenyl type epoxy resin such as trade name Epicoat YX4000H (manufactured by Yuka Shell Epoxy), Trade name Epicoat 157S70 (oil) Shell Epoxy ) Phenol novolac epoxy resin such as bisphenol A type epoxy resin, trade name Epicoat 154 (manufactured by Yuka Shell Epoxy), trade name YDPN-638 (manufactured by Tohto Kasei Co., Ltd.), trade name YDCN-701 Cresol novolac type epoxy resin such as Kasei Co., Ltd., dicyclopentadiene phenol type epoxy resin such as EPICLON HP-7200 (produced by Dainippon Ink and Chemicals), Epicoat 1032H60 (produced by Yuka Shell Epoxy), etc. Trishydroxyphenylmethane type epoxy resin, trifunctional epoxy resin such as trade name VG3101M80 (manufactured by Mitsui Chemicals), tetraphenylolethane type epoxy resin such as trade name Epicoat 1031S (manufactured by Yuka Shell Epoxy), trade name Denako Tetrafunctional epoxy resin such as EX-411 (manufactured by Nagase Kasei Kogyo Co., Ltd.), hydrogenated bisphenol A type epoxy resin such as trade name ST-3000 (manufactured by Tohto Kasei Co., Ltd.) ), Glycidyl ester type epoxy resins such as trade name YH-434 (manufactured by Toto Kasei Co., Ltd.), glyoxal type epoxy resins such as trade name YDG-414 (manufactured by Tohto Kasei Co., Ltd.), and brand name Epolide GT Examples include alicyclic polyfunctional epoxy compounds such as -401 (manufactured by Daicel Chemical Industries), and heterocyclic epoxy resins such as triglycidyl isocyanate (TGIC). Further, if necessary, a trade name Neotote E (manufactured by Toto Kasei Co., Ltd.) can be mixed as an epoxy reactive diluent.

  In addition, acrylate monomers and methacrylate monomers that are (meth) acrylic monomers include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate. Polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexa Ethylene oxide and propylene oxide are added to acrylate or methacrylate such as diol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, and polyfunctional alcohols such as glycerin and trimethylolethane. Trimethylolpropane PO (propylene oxide) modified tri (meth) acrylate, trimethylolpropane EO (ethylene oxide) modified tri (meth) acrylate, caprolactone modified dipentaerythritol hexaacrylate obtained by adding (meth) acrylate after addition, Urethane acrylates described in JP-B-48-41708, JP-B-50-6034, and JP-A-51-37193, Polyfunctional compounds such as polyester acrylates described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490, and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid Acrylates and methacrylates, and mixtures thereof. Furthermore, the Japan Adhesion Association magazine Vol. 20, no. 7, pages 300 to 308 include those introduced as photocurable monomers and oligomers. It is preferable to adjust the viscosity by appropriately combining a monofunctional monomer, a bifunctional monomer, a trifunctional or higher polyfunctional monomer, and an oligomer. When a monofunctional monomer or a bifunctional monomer is used in combination, the viscosity of the ink decreases, and the effect of preventing nozzle clogging can be obtained. The viscosity at 25 ° C. is used to supplement the strength of the film or provide adhesion to the substrate. A high-viscosity polyfunctional monomer having a viscosity of 700 mPa · s or more, a highly polar monomer such as urethane acrylate, an oligomer, or the like may be used in a small amount.

  As the oxetanyl group-containing monomer that is an oxetanyl-based monomer, compounds described in paragraph numbers [0021] to [0084] of JP-A No. 2003-341217 can be suitably used. Furthermore, the compounds described in JP-A-2004-91556, paragraphs [0022] to [0058] can also be used.

  The content of the polymerizable monomer described above is preferably 30 to 80% by mass, and more preferably 40 to 80% by mass in the solid content of the inkjet ink. If the amount of the monomer used is within the above range, the polymerization of the pixel portion is sufficient, so that scratches due to insufficient film strength of the pixel portion are less likely to occur or cracks occur when applying a transparent conductive film. And reticulation are less likely to occur, the solvent resistance when providing the alignment film is improved, and the voltage holding ratio is not lowered. Here, the solid content of the inkjet ink for specifying the blending ratio includes all components except for the solvent, and liquid polymerizable monomers and the like are also included in the solid content.

<Binder resin>
The ink jet ink of the present invention may contain a binder resin for the purpose of adjusting the viscosity and adjusting the ink hardness. As the binder resin, a binder resin that is simply dried and solidified such that it is composed only of a resin having no polymerization reactivity may be used. However, in order to impart sufficient strength, durability, and adhesion to the coating film, a binder resin that can cure the pixel by a polymerization reaction after forming a pixel pattern on the substrate by an inkjet method is used. Preferably, it can be polymerized and cured, such as a photo-curable binder resin that can be polymerized and cured by visible light, ultraviolet light, electron beam, etc., or a thermosetting binder resin that can be polymerized and cured by heating. Binder resin can be used.

  The total addition amount of the binder resin is not particularly limited as long as the effect of the present invention is achieved. The binder resin may be used by being dissolved in a solvent, or may be used by being dispersed in a solvent. When used by dispersing in a solvent, the average particle size of the binder resin to be dispersed is preferably 1.0 μm or less, and more preferably 0.1 μm or less. When the average particle size is 1.0 μm or less, clogging at the head, and transparency and smoothness of the film can be prevented from being lowered. In addition, the binder resin may increase the viscosity of the ink-jet ink, and it is preferable not to use it essentially.

  Examples of binder resins that are not polymerized by themselves include epoxy resins, diallyl phthalate resins, silicone resins, phenol resins, unsaturated polyester resins, polyimide resins, polyurethane resins, melamine resins, urea resins, ionomer resins, and ethylene ethyl. Acrylate resin, acrylonitrile acrylate styrene copolymer resin, acrylonitrile styrene resin, acrylonitrile chlorinated polyethylene styrene copolymer resin, ethylene vinyl acetate resin, ethylene vinyl alcohol copolymer resin, acrylonitrile butadiene styrene copolymer resin, vinyl chloride resin, chlorinated polyethylene resin, Polyvinylidene chloride resin, cellulose acetate resin, fluororesin, polyoxymethylene resin, polyamide resin, polyarylate resin, thermoplastic polyurethane Elastomer, polyether ether ketone resin, polyether sulfone resin, polyethylene, polypropylene, polycarbonate resin, polystyrene, polystyrene maleic acid copolymer resin, polystyrene acrylic acid copolymer resin, polyphenylene ether resin, polyphenylene sulfide resin, polybutadiene resin, polybutylene terephthalate Resins, acrylic resins, methacrylic resins, methylpentene resins, polylactic acid, polybutylene succinate resins, butyral resins, formal resins, polyvinyl alcohol, polyvinylpyrrolidone, ethyl cellulose, carboxymethyl cellulose, gelatin, and copolymer resins thereof Can do. These can be appropriately selected in consideration of the film strength, viscosity, residual viscosity of the inkjet ink, pigment dispersion stability, thermal stability, non-coloring property, water resistance, and chemical resistance.

(1) Photocurable binder resin In the photocurable resin (photocurable binder resin) that can be polymerized and cured by light such as ultraviolet rays and electron beams, the shape stability of the applied colored composition droplets and A polymer having a relatively large molecular weight can be included for the purpose of imparting adhesion to the substrate. Here, the relatively large molecular weight means that the molecular weight is larger than that of the so-called monomer or oligomer, and a weight average molecular weight of 10,000 or more can be used as a guide. In addition, a polymer having no polymerization reactivity as described above may be further used.

  The photo-curable binder resin is an oligomer formed by introducing a polymerizable functional group into a non-polymerizable binder molecule or a polymer having a molecular weight higher than that of the oligomer, and undergoes a polymerization reaction upon receiving light irradiation. Or what induces a polymerization reaction by the effect | action of other components, such as a photoinitiator activated by receiving light irradiation, can be used. Various ethylenic double bond-containing compounds themselves have polymerization reactivity and can be used as photocurable binder resins. Conventionally, a prepolymer blended in a UV curable resin composition used in various fields such as inks, paints, and adhesives can be used as a polymer having a relatively high molecular weight in the present invention. Conventionally known prepolymers include radical polymerization type prepolymers, cationic polymerization type prepolymers, thiol / ene addition type prepolymers, and any of them may be used.

  Among these, radical polymerization type prepolymers are most easily available on the market, such as ester acrylates, ether acrylates, urethane acrylates, epoxy acrylates, amino resin acrylates, acrylic resin acrylates, unsaturated polyesters. Examples can be given.

  In the present invention, the molecular weight of the ethylenic double bond-containing compound that is used as a polymer that itself has polymerization reactivity so that the viscosity of the inkjet ink is too high to adversely affect the ejection properties from the ejection head. The weight average molecular weight is preferably 100,000 or less.

(2) Thermosetting binder resin As the thermosetting binder resin, a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is usually used, and the thermosetting reaction can be further promoted. A catalyst may be added. An epoxy group is preferably used as the thermosetting functional group. In addition, a polymer having no polymerization reactivity as described above may be further used.

  As a compound having two or more thermosetting functional groups in one molecule, an epoxy compound having two or more epoxy groups in one molecule is usually used. An epoxy compound having two or more epoxy groups in one molecule is an epoxy compound having two or more, preferably 2 to 50, more preferably 2 to 20 epoxy groups in one molecule (referred to as an epoxy resin). Is included). The epoxy group only needs to have a structure having an oxirane ring structure, and examples thereof include a glycidyl group, an oxyethylene group, and an epoxycyclohexyl group. Examples of the epoxy compound include known polyvalent epoxy compounds that can be cured by carboxylic acid. Examples of such an epoxy compound include “Epoxy resin handbook” edited by Masaki Shinbo, published by Nikkan Kogyo Shimbun (Showa 62). Are widely disclosed, and these can be used.

  As an epoxy compound, in order to give solvent resistance and heat resistance to the cured film, a polymer having a relatively large molecular weight and the crosslinking density of the cured film are increased, or the inkjet discharge performance is improved by lowering the viscosity. Therefore, it is preferable to use a compound having a relatively low molecular weight in combination.

  As an epoxy compound which is a polymer having a relatively large molecular weight (hereinafter sometimes referred to as “binder epoxy compound”), at least one of structural units represented by the following general formula (11) and the following general formula ( A polymer composed of at least one of the structural units represented by 12) and having two or more glycidyl groups can be used.

  As an epoxy compound which is a polymer having a relatively large molecular weight (hereinafter sometimes referred to as “binder epoxy compound”), at least one of structural units represented by the following general formula (11) and the following general formula ( A polymer composed of at least one of the structural units represented by 12) and having two or more glycidyl groups can be used.

In General Formula (11), R ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² is a hydrocarbon group having 1 to 12 carbon atoms. Moreover, R < ³ > in General formula (12) is a hydrogen atom or a C1-C10 alkyl group.

  The structural unit represented by the general formula (11) can be derived from a monomer represented by the following general formula (13).

During the above-mentioned general formula (13), ^{R 1} and ^{R 2} have the same meanings as ^{R 1} and ^{R 2} in the general formula (11) described above.

By using the monomer represented by the general formula (13) as at least one of the constituent units of the binder epoxy compound, the functional film (for example, colored pixels) formed by the ink-jet ink of the present invention has good hardness. And transparency can be imparted. In the general formula (13), R ² is a hydrocarbon group having 1 to 12 carbon atoms, and may be any of a linear aliphatic, alicyclic, and aromatic hydrocarbon group, and an additional structure. For example, it may contain a double bond, a side chain of a hydrocarbon group, a side chain of a spiro ring, an intra-ring bridged hydrocarbon group, and the like.

  Specific examples of the monomer represented by the general formula (13) include methyl (meth) acrylate, ethyl (meth) acrylate, i-propyl (meth) acrylate, n-propyl (meth) acrylate, i-butyl ( (Meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) Examples include acrylate, para-t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and phenyl (meth) acrylate.

In the general formula (13) described above, R ¹ is preferably a hydrogen atom or a methyl group, and R ² is preferably an alkyl group having 1 to 12 carbon atoms. Among them, a methyl group and a cyclohexyl group are particularly preferable. . Preferable examples of the monomer represented by the general formula (13) include methyl methacrylate (MMA) and cyclohexyl methacrylate (CHMA).

The structural unit represented by the above general formula (12) in the polymer is derived from a monomer represented by the following general formula (14). In the following general formula (14), ^{R 3} has the same meaning as ^{R 3} in the general formula (12).

The monomer represented by the general formula (14) can be used, for example, for introducing an epoxy group (epoxy reaction point) into the polymer. In the above-described general formula (14), preferred as R ³ is a hydrogen atom or a methyl group. Specific examples of the monomer represented by the general formula (14) include glycidyl (meth) acrylate, and glycidyl methacrylate (GMA) is particularly preferable.

  The polymer may be a random copolymer or a block copolymer. In addition, this polymer has a main chain structure other than the above general formula (11) or the above general formula (12) as long as the performance required for each detail of the color filter, such as hardness and transparency, can be ensured. Units may be included. Specific examples of such a monomer include acrylonitrile and styrene.

The content of the structural unit represented by the general formula (11) and the structural unit represented by the general formula (12) in the binder epoxy compound described above is the structure represented by the general formula (11). Charged mass ratio of the monomer for deriving the unit and the monomer for deriving the structural unit represented by the general formula (12) (monomer for deriving the general formula (11): deriving the general formula (12) Monomer), it is preferably within the range of 10:90 to 90:10.
When the proportion of the structural unit represented by the general formula (11) is 90:10 or less, the curing reaction point ratio can be increased and the crosslinking density can be further increased. Moreover, when the quantity of the structural unit of General formula (12) is said ratio 10:90 or less, the ratio of a bulky skeleton can be increased and hardening shrinkage can be suppressed.

The weight average molecular weight of the binder epoxy compound is preferably 3,000 or more, particularly 4,000 or more, when expressed in terms of polystyrene-equivalent weight average molecular weight. When the weight average molecular weight of the binder epoxy compound is 3,000 or more, physical properties such as strength and solvent resistance required for pixels as details of the color filter are improved.
Furthermore, the weight average molecular weight of the binder epoxy compound is preferably 20,000 or less, and particularly preferably 15,000 or less, when expressed in terms of polystyrene-equivalent weight average molecular weight. When the molecular weight is 20,000 or less, an increase in viscosity can be suppressed, and the stability of the ejection amount when ejecting from the ejection head and the straightness in the ejection direction are improved. In addition, the long-term storage stability is improved.

  As the binder epoxy compound, it is particularly preferable to use a glycidyl methacrylate (GMA) / methyl methacrylate (MMA) copolymer having a polystyrene-reduced weight average molecular weight (Mw) in the above range. The GMA / MMA copolymer may contain other monomer components as long as the object of the present invention can be achieved.

<Polymerization initiator>
In the inkjet ink of the present invention, a polymerization initiator may be used in combination for the purpose of promoting the polymerization reaction of the polymerizable monomer and the binder resin. The polymerization initiator can be selected according to the type of polymerizable monomer and binder used in the ink jet ink and the polymerization route.

(1) Polymerization initiator suitable for acrylate (methacrylate) monomer and photo-curable binder resin As a polymerization initiator suitable for acrylate monomer, methacrylate monomer and photo-curable binder resin, the polymerization reaction is carried out by active energy rays. For the photopolymerization initiator, a photopolymerization initiator is used. When the polymerization reaction is performed by heat, a thermal polymerization initiator is used. As a photopolymerization initiator, at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl-substituted coumarin compounds, lophine dimers, benzophenone compounds, acetophenone compounds And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds, and the like.

  Examples of the active halogen compound that is the halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloromethyl, and the like. -5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxy) Styryl) -1,3,4-oxadiazole, and the like.

  Examples of the active halogen compound that is the halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (naphtho-) described in JP-A-53-133428. 1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound.

  Other specific examples include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl)- 1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1- p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1) Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2 -Methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis- Trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1- Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- ( 6-methoxy-naphtho 2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4 7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine,

2- (6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloro Methyl-s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethyla) Nophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p- N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl)- s-triazine, 4- [p-N- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) ) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophen Le] -2,6-di (trichloromethyl) -s-triazine,

4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N- Di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [ o-Fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloro) Ethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN , N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine,

4- [m-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN- Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 (O-FLUORO -p-N-chloroethyl aminophenyl) -2,6-di (trichloromethyl) -s-triazine, and the like.

  In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123, etc.) manufactured by Midori Chemical, manufactured by PANCHIM T series (for example, T-OMS, T-BMP, TR, T-B, etc.), Irgacure series (for example, Irgacure 369, Irgacure 784, Irgacure 651, Irgacure 184) manufactured by Ciba Specialty Chemicals Co., Ltd. Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261, etc.), Darocure series (eg Darocure 1173 etc.),

4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2-benzyl-2-dimethylamino-4- Morpholinobyrophenone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4 , 5-Diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer , 2-(p-methyl) -4,5-diphenyl imidazolyl dimer, benzoin isopropyl ether, are also useful, such as.

  A sensitizer and a light stabilizer can be used in combination with the photopolymerization initiator. Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9. Anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (Dimethylamino) phenyl-p-methyls Tinuvine 1130, 400, etc. Is mentioned.

  In addition to the above, it is preferable to add a thermal polymerization inhibitor. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4, 4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like are useful.

  Further, examples of the photopolymerization initiator include those described in JP-A-2006-28455, paragraphs [0079] to [0088], and preferred specific examples include 2-trichloromethyl-5-styryl-1,3. , 4-oxadiazole and 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethylamino) -3′-bromophenyl] -s-triazine.

  As the thermal polymerization initiator, generally known organic peroxide compounds and azo compounds can be used. In addition to the thermal polymerization initiator, a curing catalyst such as imidazole can also be used. An organic peroxide compound and an azo compound can be used in combination of two or more in addition to the single use. Here, the organic peroxide is a derivative of hydrogen peroxide (H—O—O—H) and refers to an organic compound having —O—O— bond in the molecule.

  When classified by chemical structure, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates and the like can be mentioned. Specifically, 3,3 ′, 4,4′-tetrakis (t-butylperoxycarbonyl) benzophenone, benzoyl peroxide, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxybenzoate, di-t-butylperoxybenzoate, di-t-butylperoxyisophthalate, t -Butyl peroxyacetate, t-hexyl peroxybenzoate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t- Butyl peroxy-2-ethylhexyl monocarbonate, 2,5-bis (m- Louis peroxy) hexane, 2,5-dimethyl-2,5-bis (benzoyl peroxy) hexane, t-hexyl peroxy isopropyl monocarbonate,

t-butylperoxyisobutyrate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, t-butylperoxy-2-ethylhexanoate, t-butylperoxymaleic acid, cyclohexanone peroxide, methylacetoacetate peroxide, methylhexanone peroxide, acetylacetone peroxide Oxide, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis ( -Butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, diisopropylbenzene hydroperoxide, 1, 1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide and the like are preferable, such as 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane. Peroxyketal compounds, diacyl peroxide compounds such as benzoyl peroxide, and peroxyester compounds such as t-butyl peroxybenzoate are preferred.

  Examples of the azo compounds described above include compounds described in paragraphs [0021] to [0023] of JP-A-5-5014. Among these compounds, a compound that has a decomposition temperature that is somewhat high and is stable at room temperature, is a compound that decomposes when heated to generate radicals and serves as a polymerization initiator. Among organic peroxide compounds or azo compounds (thermal polymerization initiators), those having a relatively high half-life temperature (preferably 50 ° C. or higher, more preferably 80 ° C. or higher) are used. The viscosity can be suitably configured without changing with time, and examples thereof include azobis (cyclohexane-1-carbonitrile) and the like as a preferable thermal polymerization initiator.

  The content of the photopolymerization initiator and / or thermal polymerization initiator suitable for the acrylate monomer, methacrylate monomer, and photocurable binder resin is preferably 0.01 to 50 mass% with respect to the solid mass of the ink-jet ink. More preferably, it is 1-30 mass%. These polymerization initiators can be used alone or in combination of two or more.

(2) Polymerization Initiator Suitable for Oxetanyl Group-Containing Monomer or Binder Resin Suitable polymerization initiators for the oxetanyl group-containing monomer or binder resin include compounds that generate an acid. The compound capable of generating an acid means a compound capable of generating an acid by light or heat after the ink jet ink is discharged, and it is Bronsted by the action of light and / or heat in the ink droplet of the ink jet after discharge. Any compound that generates an acid or a Lewis acid can be used.

  Acids to be generated include carboxylic acid, sulfonic acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, sulfuric acid, sulfuric acid monoester, sulfinic acid, hydrochloric acid, nitric acid, boric acid, trifluoroboric acid, boron complex, antimony derivative And hexafluorophosphoric acid.

  Among them, as an acid that can effectively cure the above-mentioned oxetanyl group-containing monomer (oxetane compound) by light and / or heat, hydrochloric acid, sulfonic acid, or an acid having a boron atom or a phosphorus atom is generated. It is preferable to generate an acid having a phosphorus atom.

  Specific compounds (photopolymerization initiators) that generate such acids include, for example, organic halogenated compounds, oxydiazole compounds, organic borate compounds, disulfone compounds, oxime ester compounds, and onium salt compounds. It is done. Among these, onium hydrochloric acid generators such as iodonium salts or sulfonium salts are preferably used.

  Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Examined Patent Publication No. 46-4605, Japanese Unexamined Patent Publication No. 48-36281, Japanese Unexamined Patent Publication No. 55-3070, Japanese Unexamined Patent Publication No. 60-239736, Japanese Unexamined Patent Publication No. 61-169835, Japanese Unexamined Patent Publication No. 61-169837, Japanese Unexamined Patent Publication No. 62-58241. JP, 62-21401, JP 63-70243, 63-298339, M.M. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No. 3), (1970) ”, and in particular, oxazole compounds having a trihalomethyl group and s-triazine compounds.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, JP-A-2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”, etc. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, and organic boron oxosulfonium complexes, No. 175554, JP-A-6-17555 Organoboron iodonium complexes described in JP-A-9-188710, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, Specific examples include organoboron transition metal coordination complexes such as Kaihei 7-306527 and JP-A-7-292014.

  Examples of the disulfone compound include compounds described in JP-A Nos. 61-166544 and 2002-328465 (Japanese Patent Application No. 2001-132318).

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Compounds described in Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797, etc. Is mentioned.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Diazonium salts described in Bal et al, Polymer, 21, 423 (1980), ammonium salts described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069 , 055 and 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, Examples thereof include iodonium salts described in JP-A-2-150848 and JP-A-2-296514.

  The iodonium salt that can be preferably used in the present invention is a diaryl iodonium salt, and from the viewpoint of stability, it may be substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group. preferable. More preferably, the alkoxy group is preferably substituted by 3 or more, and most preferably 4 or more. Moreover, as another preferable diaryl iodonium salt form having good curability by light, at least one of the diaryls forms part of a chromophore having absorption at 300 nm or more. Alternatively, as a substituent, an iodonium salt having a functional group having absorption at 300 nm or more is preferable.

  Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability. It is preferably substituted. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids. Other preferred sulfonium salts are triarylsulfonium salts from the viewpoints of thermal decomposability, balance of stability, and photocurability when used in combination with sensitizers, such as halogen atoms and carboxy groups. It is preferable to have at least one electron-withdrawing group, more preferably 2 or more, and most preferably 3 or more.

  In addition, as another preferable form of the sulfonium salt, a sulfonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorbs at 300 nm or more can be given. As another preferred sulfonium salt, the triarylsulfonium salt forms part of a chromophore in which at least one of the triaryls has an absorption at 300 nm or more. Alternatively, as a substituent, a triarylsulfonium salt having a functional group having absorption at 300 nm or more is preferable.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  The content of the polymerization initiator suitable for the above-mentioned oxetanyl group-containing monomer or binder resin is preferably 0.01 to 50% by mass, more preferably 1 to 50% by mass with respect to the total solid content in the inkjet ink. 30% by mass. When the content is in the above-described range, a better sensitivity and a strong cured portion can be formed. Moreover, the said compound which generate | occur | produces an acid can be used 1 type or in mixture of 2 or more types.

<Curing agent>
The epoxy monomer (epoxy group-containing monomer) and the thermosetting binder resin can usually be combined with a curing agent. As the curing agent, the curing agent and the accelerator described in Chapter 3 of “Review Epoxy Resin Basics I” issued on November 19, 2003, published by the Epoxy Resin Technology Association, can be suitably used. Carboxylic anhydride or polyvalent carboxylic acid can be used.

  Specific examples of the polyvalent carboxylic acid anhydride include phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, dimethyltetrahydro anhydride Aliphatic or alicyclic dicarboxylic anhydrides such as phthalic acid, hymic anhydride, and nadic anhydride; fats such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride Polyhydric carboxylic acid dianhydrides; aromatic polycarboxylic anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride; ester groups such as ethylene glycol bistrimellitate and glycerin tris trimellitate Containing acid anhydrides, particularly preferably aromatic poly It may be mentioned carboxylic acid anhydrides. Moreover, the epoxy resin hardening | curing agent which consists of a commercially available carboxylic acid anhydride can also be used suitably.

  Specific examples of the polyvalent carboxylic acid used in the present invention include aliphatic polyvalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, and itaconic acid; hexahydrophthalic acid, Aliphatic polycarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, Aromatic polyvalent carboxylic acids such as 1,4,5,8-naphthalenetetracarboxylic acid and benzophenonetetracarboxylic acid can be mentioned, and aromatic polyvalent carboxylic acids can be mentioned preferably.

  Moreover, it is preferable to use vinyl ether block carboxylic acid for polyvalent carboxylic acid which can be used for this invention. Specific examples include vinyl ether block carboxylic acids described in “Review Epoxy Resin Basics I” P193-194, JP2003-66223A, JP2004-339332A published by the Epoxy Resin Technology Association. . By blocking the carboxylic acid with vinyl ether, the addition reaction (esterification reaction) of the carboxylic acid and the epoxy compound gradually proceeds at room temperature, and the color composition viscosity can be prevented from increasing with time. Moreover, the solubility to various solvents, epoxy monomers, and epoxy resins is improved, and a uniform composition can be made. This vinyl ether block carboxylic acid is preferably used in combination with a thermal latent catalyst described later. By using in combination with a heat latent catalyst, the deblocking reaction is promoted during heating, and there is little film beveling during heating, and a color filter with higher strength can be formed.

  These polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids can be used singly or in combination of two or more. The compounding quantity of the hardening | curing agent used for this invention is the range of 1-100 mass parts normally per 100 mass parts of components (monomer and resin) containing an epoxy group, Preferably it is 5-50 mass parts. By setting the blending amount of the curing agent to 1 part by mass or more, curability is improved and a tough pixel can be formed. Moreover, by making the compounding quantity of a hardening | curing agent into 100 mass parts or less, the adhesiveness with respect to the board | substrate of the formed pixel can be made favorable, and a uniform and smooth pixel can be formed.

<Thermal latent catalyst>
In the present invention, when an epoxy group-containing monomer and a thermosetting binder resin are used, a catalyst capable of accelerating the thermosetting reaction between acid and epoxy is added to improve the hardness and heat resistance of the ink. Also good. As such a catalyst, a thermal latent catalyst that exhibits activity during heat curing can be used.

  The heat-latent catalyst exhibits catalytic activity when heated, accelerates the curing reaction and gives good properties to the cured product, and is added as necessary. The thermal latent catalyst is preferably one that exhibits acid catalytic activity at a temperature of 60 ° C. or higher. As such, a compound obtained by neutralizing a protonic acid with a Lewis base, a compound obtained by neutralizing a Lewis acid with a Lewis base, Lewis Examples thereof include a mixture of an acid and a trialkyl phosphate, sulfonic acid esters, onium compounds, and the like, and various compounds described in JP-A-4-218561 can be used.

In particular,
(A) A compound obtained by neutralizing halogenocarboxylic acids, sulfonic acids, mono- and diesters of phosphoric acid with various amines such as ammonia, monomethylamine, triethylamine, pyridine, ethanolamine, or trialkylphosphine.
(B) A compound obtained by neutralizing a Lewis acid such as BF ₃ , FeCl ₃ , SnCl ₄ , AlCl ₃ , ZnCl ₂ with the aforementioned Lewis base.
(C) ester compounds of primary alcohol and secondary alcohol with methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid and the like.
(D) Primary alcohols, phosphoric acid monoester compounds of secondary alcohols, phosphoric acid diester compounds, and the like.

As the onium compound, an ammonium compound ^{[R 1 NR 2 R 3 R} 4] + X-, a sulfonium compound ^{[R 1 SR 2 R 3]} + X-, cited oxonium compound ^{[R 1 OR 2 R 3]} + X- , etc. be able to. R ^{1 to} R ⁴ represent an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or the like.

  The thermal latent catalyst is preferably a halogen-free acidic catalyst from the viewpoint of liquid crystal contamination. Specific examples of the halogen-free acidic catalyst include Nofure LC-1 and Nofure LC-2 (both trade names, manufactured by NOF Corporation).

<Surfactant>
A surfactant may be further used in the inkjet ink of the present invention. As examples of the surfactant, the surfactants disclosed in JP-A-7-216276, paragraph [0021], JP-A-2003-337424, and JP-A-11-133600 are preferable. As mentioned. The content of the surfactant is preferably 5% by mass or less based on the total amount of the ink.

  Examples of other additives include other additives described in paragraph numbers [0058] to [0071] of JP-A No. 2000-310706.

  In order to adjust the color tone of the inkjet ink of the present invention, other colorants may be used in combination with the dipyrromethene-based boron complex compound.

As content of each component of the inkjet ink of the present invention, the content of the dipyrromethene-based boron complex compound is preferably 1 to 20% by mass, more preferably 5 to 15% by mass with respect to the total amount of the ink. The content of is preferably 30 to 90% by mass, more preferably 50 to 85% by mass, the content of the polymerizable monomer is preferably 5 to 50% by mass, more preferably 7 to 30% by mass, and the surfactant is contained. The amount is preferably 5% by mass or less, and more preferably 0.1 to 5% by mass.
In addition, when the solid content concentration is 21% by mass or less in the total amount of ink, each ejection property (e.g., ejection stability after resting) described in Examples described later is further improved. In addition, solid content includes all the components except a solvent, and a liquid polymerizable monomer etc. are contained in solid content.

<Inkjet ink manufacturing method>
For the production of the inkjet ink of the present invention, a known inkjet ink production method can be applied. For example, after dissolving the dipyrromethene-based boron complex compound represented by the general formula (I) in a solvent, the ink jet ink is prepared by dissolving each component necessary for the ink jet ink (for example, a polymerizable monomer and a binder). can do.

  When preparing the monomer liquid, if the solubility of the material used in the solvent is low, the monomer liquid may be appropriately subjected to a treatment such as heating or ultrasonic treatment within a range that does not cause a polymerization reaction. Is possible.

  In the case where the dipyrromethene-based boron complex compound represented by the general formula (I) is dispersed in an aqueous medium, JP-A Nos. 11-286637, 2001-240763 (Japanese Patent Application No. 2000-78491), and JP-A-2001-262039 ( As described in Japanese Patent Application No. 2000-80259) and Japanese Patent Application Laid-Open No. 2001-247788 (Japanese Patent Application No. 2000-62370), colored fine particles containing a dipyrromethene-based boron complex compound represented by the general formula (I) and an oil-soluble polymer are aqueous. Or dispersed in a medium, as disclosed in JP-A-2001-262018 (Japanese Patent Application No. 2000-78454), JP-A-2001-240763 (Japanese Patent Application No. 2000-78491), JP-A-2001-335734 (Japanese Patent Application No. 2000-203856). A dipyrromethene-based boron complex compound represented by the general formula (I) dissolved in a high-boiling organic solvent It may be dispersed in the sexual medium. Specific methods in the case of dispersing the dipyrromethene-based boron complex compound represented by the general formula (I) in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additives, and the amounts used thereof are described in the above-mentioned patent documents. Those described in (1) can be preferably used. Alternatively, the dipyrromethene-based boron complex compound represented by the general formula (I) may be dispersed in a fine particle state as a solid. At the time of dispersion, a dispersant or a surfactant can be used.

  Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high-pressure emulsification dispersion method (high-pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000, and the like. In addition to the above-mentioned patent documents, JP-A-5-148436, 5-295212, 7-97541, 7-82515, 7-185858, Details are described in Japanese Laid-Open Patent Publication No. 11-286637 and Japanese Patent Application Laid-Open No. 2001-271003 (Japanese Patent Application No. 2000-87539), and can also be used for preparing the ink-jet ink of the present invention.

<Physical properties of ink-jet ink>
The physical property value of the inkjet ink of the present invention is not particularly limited as long as it can be ejected by an inkjet head, but the viscosity at the time of ejection is preferably 2 to 30 mPa · s from the viewpoint of stable ejection. 20 mPa · s is more preferable. Moreover, when discharging with an apparatus, it is preferable to maintain the temperature of an inkjet ink at the substantially constant temperature in the range of 20-80 degreeC. If the temperature of the device is set to a high temperature, the viscosity of the ink decreases and it becomes possible to eject ink with a higher viscosity.However, due to the increase in temperature, the ink is denatured by heat and a thermal polymerization reaction occurs in the head. In addition, the temperature of the apparatus is preferably in the range of 20 to 80 ° C. because the solvent easily evaporates on the surface of the nozzle that ejects ink and nozzle clogging easily occurs.

  The viscosity is measured by using a commonly used E-type viscometer (for example, an E-type viscometer (RE-80L) manufactured by Toki Sangyo Co., Ltd.) with the inkjet ink held at 25 ° C. Value.

  Further, the surface tension (static surface tension) at 25 ° C. of the inkjet ink is preferably 20 to 40 mN / m, preferably 20 to 35 mN / m in terms of improving wettability with respect to a non-permeable substrate and discharge stability. m is more preferable. Moreover, when discharging with an apparatus, it is preferable to maintain the temperature of the ink for inkjet in the range of 20-80 degreeC, and it is preferable to make the surface tension at that time into 20-40 mN / m. In order to keep the temperature of the inkjet ink constant with a predetermined accuracy, the ink temperature detecting means, the ink heating or cooling means, and the control means for controlling the heating or cooling according to the detected ink temperature are provided. Preferably it is. Alternatively, it is also preferable to have a means for reducing the influence on the ink physical property change by controlling the energy applied to the means for ejecting ink according to the ink temperature.

  The above-mentioned surface tension is measured by a Wilhelmy method using a commonly used surface tension meter (for example, Kyowa Interface Science Co., Ltd., surface tension meter FACE SURFACE TENSIOMETER CBVB-A3), 60% liquid temperature. It is a value measured by RH.

  In addition, in order to appropriately maintain the shape in which the ink-jet ink wets and spreads after landing on the substrate, it is preferable to maintain a predetermined liquid property of the ink-jet ink after landing on the substrate. For this purpose, it is preferable to keep the substrate and / or the vicinity of the substrate within a predetermined temperature range. Alternatively, it is also effective to reduce the influence of temperature change by increasing the heat capacity of the table that supports the substrate.

<Color filter and manufacturing method thereof>
Next, a color filter using the inkjet ink of the present invention and a manufacturing method thereof will be described in detail with reference to preferred embodiments shown in the drawings.
The color filter of the present invention is characterized by comprising color pixels formed by the ink jet method using the ink jet ink of the present invention, that is, manufactured by the ink jet method using the ink jet ink of the present invention. It is characterized by that. The color filter manufacturing method of the present invention includes a step of forming pixels by applying the inkjet ink of the present invention to a recess surrounded by a partition formed on a substrate by an inkjet method (hereinafter referred to as “pixel formation”). Process) ”. Preferably, the pixel forming step activates the drawing step of applying ink as droplets to the recesses defined by the partition walls on the substrate by an inkjet method, and at least one drawn pixel (ink in the recesses). A curing process including an irradiation process in which color pixels are formed by curing by irradiation with energy rays, and a heating process in which color pixels are formed by curing with heat after forming all the pixels of the desired hue (ink in the recesses). And can be configured by providing other processes such as a baking process as necessary.

FIG. 1 is a flowchart showing a manufacturing process in an embodiment of a method for manufacturing a color filter of the present invention. FIGS. 2A to 2F are diagrams showing how a color filter is changed from a substrate in the method for manufacturing a color filter of the present invention. It is typical sectional drawing of the board | substrate and color filter which are shown in order of the manufacturing process to reach.
As shown in FIGS. 1 and 2 (a) to 2 (f), the manufacturing method of the color filter 10 of the present invention is a partition wall forming step S102 in which a partition wall (bank) 14 serving as a black matrix (BM) is formed on a substrate 12. (See FIG. 2B), the liquid repellent treatment step S104 for imparting liquid repellency (ink repellency) to the partition wall 14, and the ink jet ink 18 of the present invention in the recess 16 between the adjacent partition walls 14. The color filter 10 is manufactured by forming a pixel forming step S106 (see FIGS. 2C to 2E) for forming the color pixel 20 by applying the method, and forming a protective film 22 that protects the formed color pixel 20. And a protective film forming step S108 (see FIG. 2F).

In addition, as described above, the pixel forming step S106 includes a drawing step S110 (see FIG. 2C) in which the ink 18 is ejected and applied as droplets to the recesses 16 between the partition walls 14 by the ink jet method. The applied ink 18 is dried to remove the solvent in the ink 18 to make the ink remaining portion 18a, and the pretreatment step S112 (see FIG. 2D) and the ink remaining portion 18a in the recess 16 on the substrate 12 are activated. There is a curing step S114 (see FIG. 2E) for forming the color pixel 20 by polymerizing and curing the ink remaining portion 18a by an irradiation step of irradiating energy rays and / or a heating step of heating the ink remaining portion 18a.
The partition 14 is formed on the substrate 12 in advance in the partition formation step S102 before the pixel formation step S106. Details of the partition formation step S102 of the partition 14 and the method for forming the partition 14 will be described later. First, the pixel formation step S106 will be described.

<Pixel formation process>
As shown in FIGS. 2C to 2E, in the pixel forming step S106, the ink-jet ink 18 of the present invention is ejected into the recesses 16 between the partition walls (color separation partitions) 14 in the drawing step S110. Then, the ink 18 applied in the curing step S114 is cured to form the pixels 20. The pixel 20 is a color pixel of red (R), green (G), blue (B), etc. constituting the color filter 10. Details of the ink jet method and the drawing step S110 used in the present invention will be described later. By using the ink-jet ink of the present invention, the color filter 10 having blue (B) color pixels can be manufactured. In addition, it does not specifically limit as the board | substrate 12 of a color filter, Resin plates, such as a glass plate and a polycarbonate, a polymethyl methacrylate, a polyethylene terephthalate, can be used.

  The color filter manufactured using the inkjet ink of the present invention is not only a single color filter, but also a red (R) color pixel composed of yellow (Y) and magenta (M), yellow (Y) and cyan. A three-color filter having a green (G) color pixel composed of (C), a blue (B) color pixel composed of magenta (M) and cyan (C), yellow (Y), magenta (M), and a color filter having 4 to 6 color pixels having cyan (C) color pixels.

  As the blue (B) ink-jet ink, an ink-jet ink containing a compound represented by the general formula (I) and a compound represented by the general formula (B) is preferably used. The red (R) inkjet ink, the yellow (Y) inkjet ink, and the green (G) inkjet ink are not particularly limited. For example, you may use what is described in Japanese Patent Application No. 2007-303595 application specification.

  As each of the coloring inks for forming the color filter having the above-described magenta (M) and other color pixels, publicly known ones can be used. For example, in the case of magenta color ink, aryl having phenols, naphthols, anilines, heterocycles such as pyrazine, open-chain active methylene compounds, etc. as coupling components (hereinafter referred to as coupler components) Heteryl azo dyes; for example, azomethine dyes having open-chain active methylene compounds as coupler components; anthrapyridone dyes (for example, No. 20 compound in Table 1 described in US 2004/0239739 A1, and WO 04/104108 pamphlet) And an ink containing the compound (13) described).

  Examples of yellow color inks include, for example, aryl or heteryl azo dyes having, as coupler components, phenols, naphthols, anilines, heterocyclic rings such as pyrazolone and pyridone, and open-chain active methylene compounds; Azomethine dyes having open-chain type active methylene compounds as examples; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dyes Examples of the seed include ink containing a quinophthalone dye, a nitro / nitroso dye, an acridine dye, an acridinone dye, and the like.

  Examples of cyan dyes include aryl or heteryl azo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethines having heterocycles, such as phenols, naphthols, pyrrolotriazole, etc., as coupler components Dyes; polymethine dyes such as cyanine dyes, oxonol dyes, merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes; phthalocyanine dyes; anthraquinone dyes; inks containing indigo / thioindigo dyes, etc. Can be mentioned.

  The shape of the color filter pattern is not particularly limited, and may be a general stripe shape, a lattice shape, or a delta array shape as a black matrix shape.

  In the present invention, as shown in FIG. 2C, after a droplet of ink 18 is applied to the recess 16 on the substrate 12 to form a layer of ink 18 in the drawing step S110, the layer shown in FIG. As shown in FIG. 2E, after the organic solvent contained in the ink 18 is dried and removed to form the ink remaining portion 18a in the pretreatment step S112, an active energy ray is applied to the ink remaining portion 18a as shown in FIG. The remaining ink 18a is polymerized by a curing step S114 including an irradiation step (hereinafter also referred to as a first curing step) and / or a heating step (hereinafter also referred to as a second curing step) for heating the ink remaining portion. 20 may be formed. In addition, when the temperature at which thermal polymerization of the remaining ink starts is T ° C., preheating (hereinafter also referred to as a preheating step) is performed at a temperature lower than T ° C. in the pretreatment step S112, and the ink is contained in the ink 18. After the organic solvent to be dried is forcibly dried to form the ink residue 18a, an irradiation step of irradiating the ink residue 18a with active energy rays and / or a heating step of heating the ink residue 18a at a temperature of T ° C. or higher. The remaining ink 18a may be polymerized and cured to form the pixel 20.

<First curing step>
A step of irradiating and curing an ink remaining portion (hereinafter referred to as uncured pixel ink) 18a in the recess 16 for forming pixels of at least one color formed in the drawing step S110 (first curing step). Can be provided. In the first curing step, the cured pixels 20 can be formed by curing the inks of the respective colors including red (R), green (G), and blue (B). Curing may be performed every time the uncured pixel ink 18a of one color is formed, or may be performed after the uncured pixel ink 18a of a plurality of colors or all colors is formed.

In the first curing step, when the ink in the concave portion 16 for each color or a plurality of colors, that is, the uncured pixel ink 18a is cured, the order of curing is not particularly limited, and may be any order.
The ink such as R, G, and B can be cured by performing an exposure process that promotes polymerization and curing using an energy source that emits an active energy ray in a wavelength region corresponding to the photosensitive wavelength of the ink. .

  Examples of the energy source include 400 to 200 nm ultraviolet light, far ultraviolet light, g-line, h-line, i-line, KrF excimer laser light, ArF excimer laser light, electron beam, X-ray, molecular beam, or ion beam. Those to which the above-mentioned polymerization initiator is sensitive can be appropriately selected and used. Specifically, a light source that emits actinic rays belonging to a wavelength region of 250 to 450 nm, preferably 365 ± 20 nm, for example, LD, LED (light emitting diode), fluorescent lamp, low pressure mercury lamp, high pressure mercury lamp, metal halide lamp, carbon arc lamp. , Xenon lamps, chemical lamps and the like. Preferred light sources include LEDs, high pressure mercury lamps, and metal halide lamps.

  The irradiation time of the active energy ray can be appropriately set according to the combination of the monomer and the polymerization initiator, and can be set to 1 to 30 seconds, for example.

<Second curing step>
In the method for producing a color filter of the present invention, a step of curing the uncured pixel ink 18a having a desired hue such as red (R), green (G), and blue (B) by heat (second curing step). Can be provided. As described above, by providing the first curing step and the second curing step, both the manufacturing efficiency of the color filter 10 and the display characteristics can be achieved. Moreover, you may make it harden | cure only by a 2nd hardening process.

  In the second curing step, an uncured pixel ink having partition walls and a desired hue is formed, and after the first curing step, further heat treatment (so-called baking treatment) is performed to cure by heat. be able to. That is, the substrate on which the partition wall and the pixel photopolymerized by light irradiation are formed can be heated by being put in an electric furnace, a dryer, or by being irradiated with an infrared lamp.

  The heating temperature and heating time at this time depend on the composition of the inkjet ink and the thickness of the pixel, but generally from about 120 ° C. to about 250 ° C. from the viewpoint of ensuring sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. It is preferable to heat at about 10 minutes to about 120 minutes.

  In the method for producing a color filter using the ink jet ink of the present invention, the pretreatment step is performed before the polymerization of the ink in the pixel forming recesses (uncured pixels) by active energy ray exposure and / or heat treatment. A preheating step may be provided as S112. The heating temperature in the preheating step is not particularly limited, but a temperature at which the polymerization of the uncured pixel ink does not occur is preferable when the temperature at which the thermal polymerization of the uncured pixel ink starts is T ° C. 50-100 degreeC is more preferable, and 60-90 degreeC is further more preferable. By including this preheating step, the evaporation of the organic solvent in the ink applied by the ink jet method is promoted, and the color filter can be efficiently produced, and the viscosity of the remaining ink is reduced by heat. Higher fluidity can be obtained, and a color filter having highly flat pixels can be obtained.

  The preheating step is effective not only for ink that is polymerized by heat in the pixel but also for ink that is polymerized by light as long as the remaining ink portion has fluidity as in the present invention. In the case of an ink that is polymerized by light, the temperature T at which the above-described ink starts thermal polymerization is the temperature at which a photopolymerization initiator or the like is decomposed by heat to initiate a polymerization reaction, or the monomer itself is decomposed by heat to cause polymerization reaction Means the temperature at which. Although there is no restriction | limiting in particular in the time of a preheating process, It is preferable to carry out for 1 to 5 minutes.

  The temperature T can be obtained as follows. Let T be the temperature at which the ink is heated, the polymerization of the ink is started by heating, and the gelation of the ink is observed. More specifically, T is the heating temperature when the increase in ink viscosity after heating is 5 mPa · s or more with respect to the ink viscosity before heating.

In the method for producing a color filter using the ink of the present invention, the pixel formation process from the drawing process S110 to the preheating process (S112) and the curing process (S114) including the first curing process and the second curing process. S106 is preferably performed within 24 hours, more preferably within 12 hours, and even more preferably within 6 hours. By performing pixel formation from the drawing step S110 to the final curing step (second curing step) S114 within 24 hours, the surface shape of the pixel can be improved.
In the color filter manufacturing method of the present invention, the pixel formation step S106, that is, the drawing step S110, the preheating step (S112), the first curing step, and the second curing step (S114) is performed for each color. Or may be performed for each of a plurality of colors, or drawing is performed for all colors in the drawing step S110, preheating in the preheating step (S112), and curing in the curing step S114 is performed for all colors. Also good. Further, when the pixel formation step S106 is performed for each color or a plurality of colors, the order of the colors of the pixels to be formed is not particularly limited, and any order of colors may be used.

<Partition forming process>
In the method for producing a color filter of the present invention, in the pixel forming step S106 described above, as shown in FIGS. A pixel 20 is formed by applying droplets of the inkjet ink 18 of the present invention by the method.
The partition 14 is not particularly limited, and a known partition may be used. Any partition may be used. When a color filter is manufactured, the partition 14 has a black matrix function and has a light blocking effect. It is preferable.
Therefore, in the example shown in FIG. 1, in the partition forming step S102, as shown in FIG. 2 (b), on the substrate 12 shown in FIG. A partition wall 14 is formed.

In addition, this partition 14 can be produced by the same known method using the same material as the known black matrix for color filter. For example, paragraph numbers [0108] to [0126] in Japanese Patent Application Laid-Open No. 2007-193090, paragraph numbers [0021] to [0074] in Japanese Patent Application Laid-Open No. 2005-3861, and paragraph numbers in Japanese Patent Application Laid-Open No. 2004-240039. [0012] to [0021] black matrix (so-called resin black matrix), paragraph numbers [0015] to [0020] of JP-A No. 2006-17980, paragraph number of JP-A No. 2006-10875 [ The inkjet black matrix described in [0009] to [0044]. Further, the partition wall 14 may have a two-layer structure including layers having a black matrix function and a partition function separately. For example, paragraph numbers [0054] to [0057] of JP 2004-361491 A, paragraph numbers [0067] to [0069] of JP 2004-295039 A, and paragraph numbers of JP 2006-86128 A. [0068]-[0069], [0103], [0109]-[0110] metal light-shielding film and resin-made, preferably liquid-repellent resin partition (bank) layer formed thereon A two-layer structure consisting of
In the method of the present invention, among the above-described known production methods, it is preferable to use a photosensitive resin transfer material from the viewpoint of cost reduction. The photosensitive resin transfer material is a material in which at least a light-shielding resin layer is provided on a temporary support, and the resin layer having a light-shielding property can be transferred to the substrate by pressure bonding to the substrate.

  The photosensitive resin transfer material is preferably formed using a photosensitive resin transfer material described in JP-A-5-72724, that is, an integral film. Examples of the constitution of the integral film include a temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer (in the present invention, the “photosensitive resin layer” refers to a resin that can be cured by light irradiation, Is also referred to as a “light-shielding resin layer”, and when it is colored in a desired color, it is also referred to as a “colored resin layer”) / protective film laminated in this order. Regarding the temporary support, the thermoplastic resin layer, the intermediate layer, the protective film, and the production method of the transfer material constituting the photosensitive resin transfer material, paragraph numbers [0023] to [0066] in JP-A-2005-3861 Examples described in paragraphs [0108] to [0126] of JP-A-2007-193090 are preferable.

Further, such a partition wall 14 may be subjected to an ink repellent treatment in order to prevent color mixing of ink jet ink.
Therefore, in the example shown in FIG. 1, after the partition formation step S102, in the liquid repellent treatment step S104, the partition 14 on the substrate 12 shown in FIG.
As such an ink repellent treatment, for example, the ink repellent treatment method described in paragraph numbers [0086] to [0087] of JP-A No. 2007-18784, specifically, (1) Ink Repellency (2) A method of newly providing an ink-repellent layer (for example, see JP-A-5-241011), (3) Plasma treatment A method of imparting ink repellency (for example, see JP-A No. 2002-62420), (4) a method of applying an ink-repellent material to the upper surface of the partition wall (for example, see JP-A No. 10-123500), and the like. In particular, (3) a method in which the partition formed on the substrate is subjected to an ink repellent treatment with plasma is preferable.

In addition to these, as an ink repellent treatment method applicable to the method of the present invention, an ink repellent treatment method described in paragraph No. [0058] of JP-A No. 2004-361491 (for example, JP-A-9-203803, (See Kaihei 9-230129 and JP-A-9-230127) and paragraph numbers [0074] to [0075], [0111] to [0118], and [0130] of JP-A-2006-86128. Ink repellent treatment methods and the like can be mentioned.
In the above-described example, the ink repellent process is performed on the partition wall 14 on the substrate 12, but the present invention is not limited to this, and the ink affinity process may be performed on the recess 16 on the substrate 12 at the same time.
In addition, when the partition 14 has ink repellency, the liquid repellent treatment step S104 is unnecessary, but in that case, the ink affinity treatment may be performed in the recess 16 on the substrate 12.

  As shown in FIG. 2E, after the partition wall 14 and the pixel 20 are formed on the substrate 12 and the color filter 10 is manufactured, as shown in FIG. An overcoat layer 22 can be formed as a protective layer so as to cover the entire surface of 20 and the partition wall 14. The overcoat layer 22 can protect the pixels 20 such as R, G, and B and the partition wall 14 and can flatten the surface. However, it is preferable not to provide from the point which the number of processes increases. The overcoat layer 22 can be configured using a resin (OC agent), and examples of the resin (OC agent) include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition. Among them, an acrylic resin composition is desirable because it is excellent in transparency in the visible light region, and the resin component of the ink for ink jet usually has an acrylic resin as a main component and has excellent adhesion. Examples of the overcoat layer include those described in paragraphs [0018] to [0028] of JP-A No. 2003-287618, and commercially available overcoat agents such as Optomer SS6699G manufactured by JSR.

  The color filter of the present invention may further have an indium tin oxide (ITO) layer as a transparent conductive film. Examples of the ITO layer forming method include in-line low-temperature sputtering method, in-line high-temperature sputtering method, batch-type low-temperature sputtering method, batch-type high-temperature sputtering method, vacuum deposition method, and plasma CVD method. In order to reduce damage, a low-temperature sputtering method is preferably used.

The color filter of the present invention is not particularly limited, for example, for use in liquid crystal displays, televisions, personal computers, liquid crystal projectors, game consoles, mobile terminals such as mobile phones, digital cameras, car navigation systems, and particularly color image display applications. Applicable to.
The color filter of the present invention can also be applied to image display devices such as electronic paper and organic EL element devices, particularly color image display devices.

Next, a drawing process of the method for producing a color filter of the present invention, an ink jet drawing method used therefor, an ink jet drawing apparatus for carrying out the same, and an ink jet head used therefor will be described.
FIG. 3 is a perspective view showing a part of an embodiment of an ink jet drawing apparatus used for carrying out the drawing step of the color filter manufacturing method of the present invention, and FIG. 4 is a diagram of the ink jet drawing apparatus shown in FIG. FIG. 5 is a partial cross-sectional view, and FIG. 5 is a schematic diagram showing a schematic configuration of an embodiment of an ink circulation system in the ink jet drawing apparatus shown in FIG.

  3 and 4, an ink jet drawing apparatus (hereinafter also simply referred to as a drawing apparatus) 30 includes a platen 32 on which the substrate 12 is placed and supported, and an ink jet head 34 that discharges color filter manufacturing ink onto the substrate 12. A carriage type head unit 36, a head moving mechanism 38 that moves the head unit 36 in the main scanning direction (direction indicated by arrow X in FIG. 3) on the substrate 12 supported on the platen 32, and the platen 32. A substrate transport mechanism 40 that transports the placed substrate 12 in a sub-scanning direction (direction indicated by arrow Y in FIGS. 3 and 4) substantially orthogonal to the main scanning direction (X direction), and an inkjet head 34 of the head unit 36. The substrate 12 is supplied to the platen 32 via the ink supply system 50 (see FIG. 5) for supplying ink to the substrate and the substrate transport mechanism 40. And a substrate supply means (not shown). The substrate supply unit may be any substrate supply unit as long as it can supply the substrate 12 to the substrate transfer mechanism 40 so that the substrate transfer mechanism 40 can transfer the substrate 12 to the platen 32. Alternatively, an automatic plate feeder that automatically supplies the substrate 12 to the platen 32 via the substrate transport mechanism 40 may be used.

  Here, the platen 32 has a flat plate shape, and is configured to place and support the substrate 12 supplied from the substrate supply means on the surface thereof. Here, it is preferable that an air suction hole is provided on the surface of the platen 32 to attract the substrate 12 during drawing by the head unit 36, that is, during drawing by the inkjet head 34 of the head unit 36. Thereby, the planarity of the substrate 12 can be properly maintained. Further, when the substrate transport mechanism 40 transports the substrate 12 in the sub-scanning direction (Y direction), it is preferable that the surface of the platen 32 has a small friction with the back surface of the substrate 12. The platen 32 is attached to a housing (not shown) of the drawing device 30.

The head unit 36 includes an inkjet head 34, is disposed to face the platen 32, and is supported by a head moving mechanism 38 described later so as to be movable in parallel with the surface of the platen 32. The head unit 36 is connected to an ink supply pipe 54 for supplying ink in the ink tank 52 (see FIG. 5) of the ink supply system 50 to the inkjet head 34.
The ink-jet head 34 ejects the ink-jet ink 18 for manufacturing the color filter of the present invention described above in accordance with the ink ejection signal of a predetermined color for forming the color filter, and the pixels (uncured pixels 18a) are formed on the substrate 12. ) Is drawn to form a cured pixel 20 (see FIGS. 2E and 2F). Here, the ejection signal is an ejection signal for ejecting droplets based on the image signal so that ink is selectively applied to a portion to be a pixel of the color filter.
As an inkjet head, various types of inkjet heads (ejection heads) such as a continuous type and an on-demand type piezo method, a thermal method, a solid method, and an electrostatic suction method can be used. It is preferable to use an ink jet head of this type, and it is particularly preferable to use an on-demand type piezo ink jet head. Further, the ejection units (nozzles) of the inkjet head are not limited to a single row arrangement, and may be arranged in a plurality of rows or in a staggered pattern. The arrangement of the nozzles of the inkjet head and the drawing method corresponding to the arrangement will be described later.

In the drawing device 30 shown in FIGS. 3 and 4, the R pixel of the color filter is formed using one color, for example, magenta ink, but two or more colors of the color filter, for example, three colors of RGB In order to form the pixels, the ink of different colors may be replaced by one drawing device 30 to sequentially form pixels of other colors, or each of the three drawing devices 30 using different color inks. Pixels of different colors may be formed, or the drawing apparatus 30 shown in FIGS. 3 and 4 may include two or more head units that can move in a two-dimensional direction.
In the illustrated example, the head unit 36 includes one type of inkjet head 34 that ejects one color of ink. However, the present invention is not limited to this, and two or more colors, for example, three colors or Two or more, for example, three or four types of ink jet heads 34 each ejecting four full-color inks may be provided. In this case, each of the three or four ink jet heads 34 is supplied with the respective ink supply system 50, that is, three or four ink supply systems for supplying three or four full-color inks, respectively. 50, and three or four ink supply pipes 54 are connected to the head unit 36 according to each of them.

  The head moving mechanism 38 scans and moves the head unit 36 in the main scanning direction (arrow X direction in FIG. 3). The head screw 36, the guide rail 43, the drive support portion 44, the support portion 45, and the like. Have The drive screw 42 and the guide rail 43 are separated from each other by a predetermined distance, and both can be used in parallel with the main scanning direction (X direction in FIG. 3) perpendicular to the conveyance direction (Y direction in FIG. 3) of the substrate 12. It is arranged so as to straddle the largest (longest in the main scanning direction) substrate 12 from the left end to the right end.

The drive screw 42 is composed of a ball screw (not shown) having a male screw portion that is screwed with a female screw portion (not shown) formed in the head unit 36, and moves the head unit 36 by rotating. The guide rail 43 is a guide that is inserted through a through-hole formed in the head unit 36 and guides the posture of the inkjet head 34 that moves by the rotation of the drive screw 42 so as not to change.
The drive support portion 44 is provided at one end portion of the drive screw 42 and the guide rail 43, and the support portion 45 is provided at the other end portion thereof, and supports the drive screw 42 in a state where the drive screw 42 can be rotated forward and backward. The guide rail 43 is supported so as not to move. The drive support unit 44 includes a drive source (not shown) such as a motor that drives the drive screw 42. The drive support unit 44 and the support unit 45 are both supported by the casing of the drawing apparatus 30 (not shown) described above.

  The head unit 36 is supported by a drive screw 42 and a guide rail 43 so as to be movable, and the drive support unit 44 rotates the drive screw 42 forward and backward so that the head unit 36 is guided by the guide rail 43 while being guided in the main scanning direction ( It is reciprocated (scanned) in the X direction). The head moving mechanism 38 may include a plurality of guide rails or other posture holding means in order to maintain the posture of the head unit 36. The head unit 36 is moved by the guide rail 43 while maintaining a predetermined posture in which the ink droplet discharge surface, that is, the ink droplet discharge surface of the inkjet head 34 faces the platen 32.

  Here, the moving mechanism of the head unit 36 is not limited to the head moving mechanism 38 described above, and various known head moving mechanisms can be used. For example, the drive screw is a rod-shaped member such as a guide rail, and guide wires are attached to both sides of the X-direction end of the inkjet head, and the guide wire in the moving direction is wound and moved along the guide rail. Can also be used. Moreover, you may make it move with a timing belt instead of a guide wire. In this case, a timing belt sprocket may be used instead of the wire reel. Further, a rack and pinion mechanism may be used. Moreover, it is good also as a self-propelled type. Further, a linear motor may be used.

The substrate transport mechanism 40 transports the substrate 12 placed on the platen 32 to the head unit 36 in the sub-scanning direction (Y direction). 1 which is arranged to extend in the main scanning direction (X direction) and is separated from the usable minimum (the length in the sub scanning direction is the shortest) by a distance slightly shorter than the length of the substrate 12, and is connected to a drive source (not shown). A pair of small restraints for each feed roller 46 disposed at positions sandwiching the pair of feed rollers 46 and both ends of the substrate 12 placed on each feed roller 46 in the main scanning (X) direction. The substrate 12 is sandwiched between the feed roller 46 and the suppression roller 48 and conveyed in the sub-scanning (Y) direction. The pair of feed rollers 46 is composed of two long drive rollers that are longer than the maximum length (longest in the main scan direction) of the substrate 12 in the main scan direction, and the drive shafts of the two drive rollers are They are coupled to each other and driven synchronously by synchronous driving means such as a driving belt. On the other hand, two holding rollers 48 are provided for each feed roller 46, a total of four driven rollers having a small width, and can be used from the positions of both ends of the longest substrate 12 in the usable main scanning direction. It is preferable that it is movable in the main scanning direction between the positions of both ends of the substrate 12 that is shortest in the main scanning direction, and can be appropriately adjusted to the positions of both ends of the substrate 12 to be used.
One feed roller 46 and two restraining rollers 48 are arranged with the transport path of the substrate 12 sandwiched vertically. The substrate 12 supplied from the automatic plate feeder is sandwiched between the feed roller 46 and the pressure roller 48 with a predetermined nip pressure, and the feed roller 46 is turned in a predetermined direction (not shown in FIG. 4) by a drive source (not shown). By rotating in the clockwise direction, the sheet is conveyed in the sub-scanning (Y) direction.

Here, when the substrate 12 is attracted to the surface of the platen 32 during the drawing by the head unit 36, the rotation of all the feed rollers 46 and the suppression rollers 48 is stopped, and the drawing by the head unit 36 is not performed. In the meantime, it is preferable that the feed roller 48 is rotationally driven by a drive source (not shown), and the substrate 12 sandwiched between the feed roller 48 is conveyed in the sub-scanning (Y) direction. That is, it is preferable that the substrate transport mechanism 40 intermittently sub-scans and transports the substrate 12. Both the feed roller 46 and the pressure roller 48 are rotatably supported by a housing of the drawing device 30 (not shown). The substrate transport mechanism 40 used in the present invention may be of any type as long as it can transport the substrate 12 in the sub-scanning direction, and all known sub-scan transport mechanisms can be applied.
In this way, the substrate transport mechanism 40 can move the head unit 36 relative to the substrate 12 in the sub-scanning direction by transporting the substrate 12 in the sub-scanning direction.

As described above, the head moving mechanism 38 and the substrate transport mechanism 40 can move the head unit 36 relative to the substrate 12 in the main scanning direction and the sub-scanning direction, and the inkjet head 34 of the head unit 36. The two-dimensional scanning (XY scanning) of the substrate 12 can be realized. In the present invention, the drive source of the head moving mechanism 38 and the substrate transport mechanism 40 is not particularly limited as long as drawing for manufacturing a color filter or the like can be accurately performed, but is preferably a step motor.
The head moving mechanism 38 moves the head unit 36 to a predetermined head retracted position when the inkjet head 34 is not used and to a predetermined maintenance position during maintenance. In addition, the predetermined head retracted position and the predetermined maintenance position are preferably a position off the substrate 12 on the platen 32 or a position off the platen 32, and more preferably, the predetermined head retracted position is The position on the platen 32 may be removed from the substrate 12, and the predetermined maintenance position may be a position removed from the platen 32.
In the illustrated example, the head unit 36 moves in the main scanning direction by the head moving mechanism 38 and the substrate transport mechanism 40 transports the substrate 12 in the sub-scanning direction. However, the present invention is not limited to this, and the substrate 12 is placed and fixed on a platen 32 as a support base, and the head unit 36 is moved by a head unit scanning means or the like. Two-dimensional scanning (XY scanning) with respect to the fixed substrate 12 may be performed by moving and scanning in the main scanning (X) direction and the sub-scanning (Y) direction.
The two-dimensional scanning of the substrate by the head unit 36 will be described in detail later together with the ink jet drawing method for manufacturing the color filter of the present invention.

FIG. 5 shows a schematic configuration of the ink supply system 50 in the ink jet drawing apparatus 30.
The ink supply system 50 includes an ink tank 52 that stores ink to be supplied to the inkjet head 34, an ink supply pipe 54 that connects the inkjet head 34 and the ink tank 52, and a filter 56 that is provided in the middle of the ink supply pipe 54. A cap 58 that covers the nozzle area of the inkjet head 34, a cleaning blade 60 that cleans the nozzle surface 34a of the inkjet head 34, a suction pump 62 that is connected to the cap 58 and sucks the nozzle of the inkjet head 34, and a suction pump A recovery tank 64 that recovers the ink sucked by 62, an ink recovery pipe 66 that connects the cap 58 and the recovery tank 64 via the suction pump 62, and an ink supply pipe 54 are provided to branch to the inkjet head 34. Nozzle pressure chamber (illustrated Having a head pressure pump 68 for the forced discharge and an ink refill system 70 for replenishing the ink in the ink tank 52 to not) under pressure.
The cap 58, the cleaning blade 60, the suction pump 62, and the head pressurization pump 68 constitute a maintenance system for the ink jet head 34, and the cap 58, the recovery tank 64, the ink recovery pipe 66, and an ink replenishment system 70 described later are recovered. The ink replenishment tube 82, the filter 84, and the density detector 86 constitute an ink recovery system.
Here, the ink supply system 50 includes not only a narrowly-defined supply system that supplies ink from the ink tank 52 to the inkjet head 34, but also a maintenance system, an ink recovery system, and an ink replenishment system 70 for the inkjet head 34.

The ink tank 52 is a main tank for supplying ink to the ink-jet head 34, and is for storing various inks including the ink-jet ink of the present invention for manufacturing the color filter described above. In the illustrated example, an ink replenishment system 70 is provided as a form of the ink tank 52. When the ink remaining amount in the ink tank 52 decreases, the ink replenishment system 70 through a replenishment port (not shown). Although a method of replenishing ink is employed, the present invention is not limited to this, and a cartridge method in which the ink tank 52 is replaced with the ink tank as an ink cartridge may be employed.
In the case of mass production of color filters, each color and each type is equipped with an inkjet head 34 and an ink supply system 50. When a large amount of ink is consumed, the ink replenishment method is suitable from the viewpoint of ink replacement and cost. However, when a small amount of ink is consumed and the ink type is changed according to the intended use, the cartridge system is suitable. In the case of this cartridge system, it is preferable that the ink type information is identified by a barcode or the like, and ejection control is performed according to the ink type.

As shown in FIG. 5, a filter 56 is provided in the middle of the ink supply pipe 54 that connects the ink tank 52 and the inkjet head 34 to remove foreign substances and bubbles. The mesh size of the filter 56 is preferably equal to or smaller than the nozzle diameter of the inkjet head 34 (generally, about 20 μm). Although details will be described later, the pressure chamber (not shown) of the nozzle of the ink jet head 34 is further provided in the middle of the ink supply pipe 54 when an ink ejection failure occurs in the ink jet head 34. A head pressurizing pump 68 is provided to forcibly pressurize and perform forced discharge. The ink supply pipe 54 is connected to the ink jet head 34, for example, a portion on the ink jet head 34 side of the head pressurizing pump 68 when the head unit 36 moves two-dimensionally (XY direction). In order to realize smooth movement, it is good to use a flexible tube.
Although not shown in FIG. 5, it is also preferable that a sub tank is provided in the vicinity of the inkjet head 34 or integrally with the inkjet head 34. The sub-tank has a function of improving a damper effect and refill that prevents fluctuations in the internal pressure of the head.

  The illustrated ink jet drawing apparatus 30 includes a cap 58, a cleaning blade 60, and the like for maintaining the ink jet head 34 in a proper discharge state in order to appropriately discharge ink from each nozzle of the ink jet head 34. A maintenance unit is provided. These maintenance units can be moved relative to the inkjet head 34 by a moving mechanism (not shown), and are moved from the predetermined retracted position below the inkjet head 34 in the maintenance position as necessary. In the case of the ink jet drawing apparatus 30 shown in FIG. 3, the retracting position of the maintenance unit and the maintenance position are both positions that are out of the substrate 12 on the platen 32, preferably positions that are out of the platen 32.

The cap 58 is attached so as to cover the nozzle region of the nozzle surface 34a of the inkjet head 34, and is provided as a means for preventing the nozzle from drying when the inkjet head 34 is not used or preventing the ink viscosity from increasing near the nozzle. . The cap 58 is used for inspection of the discharge state of nozzles (not shown) of the inkjet head 34 and / or preliminary discharge (hereinafter also referred to as dummy discharge) for eliminating discharge defects, and nozzles by the head pressure pump 68. In order to collect the ejected ink and forcibly ejecting the nozzle from the ink jet head 34 by the suction pump 62, the suction ink can be sucked by the suction pump 62 and sucked ink. In order to collect the ink, the ink jet head 34 is used so as to cover the nozzle surface 34a.
The cap 58 is displaced up and down relatively with respect to the inkjet head 34 by an elevator mechanism (not shown) at the maintenance position. The lifting mechanism is configured to cover the nozzle region of the nozzle surface 34 a with the cap 58 by raising the cap 58 to a predetermined ascending position when the power is off (OFF) or when waiting for drawing. .

The cleaning blade 60 is provided as a means for cleaning the nozzle surface 34a of the inkjet head 34, and is made of an elastic member such as rubber. At the maintenance position, the cleaning surface 60 is an ink ejection surface (nozzle surface) of the inkjet head 34 by a blade moving mechanism (not shown). 34a) is slidable. When ink droplets or foreign matter adheres to the nozzle surface 34a, the nozzle surface 34a is wiped by sliding the cleaning blade 60 on the nozzle surface 34a to clean the nozzle surface 34a.
The suction pump 62 is connected to the cap 58 by an ink recovery pipe 66. The suction pump 62 performs a suction operation by bringing the cap 58 into contact with the nozzle surface 34a of the ink jet head 34 when initial ink is loaded into each nozzle of the ink jet head 34 or when use is started after a long stoppage. Nozzle suction operation) is performed to suck out and remove the deteriorated ink that has been solidified due to an increase in viscosity. The suction pump 62 sends and recovers the deteriorated ink sucked and removed to the recovery tank 64.

Also, during printing or standby, when a specific nozzle is used less frequently and the ink viscosity in the vicinity of the nozzle increases, preliminary ejection toward the cap 58 is performed to discharge the ink that has deteriorated due to the increased viscosity. Is done. However, even if preliminary ejection is performed from each nozzle of the inkjet head 34, there may be a nozzle with ejection failure as a result of the inspection of the ejection state of each nozzle.
As described above, when the pre-discharge nozzle does not recover so that the discharge failure nozzle can be easily discharged, that is, when the discharge failure is not easily eliminated, for example, when air bubbles are mixed in the ink in the ink jet head 34 (pressure chamber). Even when the ink becomes highly viscous in the nozzle or solidifies to become deteriorated ink, the cap 58 is brought into contact with the ink jet head 34, and the suction pump 62 causes the ink in the pressure chamber (bubbles mixed) to flow. In addition, it is used to remove highly viscous or solidified deteriorated ink by suction (nozzle suction). Of course, in this case as well, the suction pump 62 sends and collects the air bubble mixed ink and the deteriorated ink removed by suction to the recovery tank 64.

The head pressurizing pump 68 is branched from the ink supply pipe 54 connected to the inkjet head 34. Similar to the suction pump 62 described above, the head pressurizing pump 68 is an ink jet printer that is used for initial ink loading or when the ejection failure is not easily eliminated even by preliminary ejection at the start of use after a long stoppage. This is to pressurize the pressure chambers of the nozzles of the head 34 and forcibly eject the ink containing the bubble mixed ink in the pressure chambers and the deteriorated ink in the nozzles from each nozzle (forced ejection is performed). Also in this case, the cap 58 is pressed against the ink jet head 34 and receives ink including bubble-mixed ink and deteriorated ink that is forcibly ejected by the head pressurizing pump 68, and passes through the suction pump 62 and the ink recovery pipe 66. The solution is sent to the collection tank 64 and collected.
Note that the suction pump 62 and the head pressurization pump 68 have the same function, so that only one of them may be provided, but both may be provided as in the illustrated example.

The collection tank 64 collects ink that has been preliminarily ejected, ink that has been suctioned and removed by the suction pump 62, ink that has deteriorated, ink that has been forcibly ejected by the head pressure pump 68, and ink that has deteriorated in the nozzles. And stored as recovered ink.
The collected ink collected and stored in the collection tank 64 may be discarded. However, as will be described later, the collected ink is sent to the ink replenishment system 70, and the ink concentration, electrical conductivity, etc. After ink characteristics are detected and evaluated, the ink tank 52 is preferably replenished based on the evaluation result after being reconditioned as reusable ink for the production of a color filter.

  By the way, if the ink jet head 34 is not ejected for a certain period of time, the ink solvent in the vicinity of the nozzles evaporates and the viscosity of the ink in the vicinity of the nozzles increases, and pressure generation means (not shown) for ejection driving. Ink will not be ejected from the nozzles even if is operated. Therefore, before this state is reached (within the viscosity range in which ink can be discharged by the operation of the pressure generating means), the pressure generating means is operated toward the cap 58 serving as an ink receiver, and the viscosity increases. “Preliminary ejection” for ejecting ink in the vicinity of the nozzles is performed. Also, after the dirt on the nozzle surface 34a is cleaned by a wiper such as a cleaning blade 60 provided as a means for cleaning the nozzle surface 34a, this wiper rubbing operation prevents foreign matter from entering the nozzle. Preliminary discharge is performed. Note that the preliminary discharge may be called “dummy discharge”, “empty discharge”, “purge”, “spitting”, or the like.

Further, if bubbles are mixed in the nozzles or pressure chambers of the ink jet head 34 or if the viscosity increase of the ink in the nozzles exceeds a certain level, the ink cannot be ejected by the preliminary ejection. And the head pressurizing operation by the head pressurizing pump 68 are performed.
That is, when air bubbles are mixed in the ink in the nozzle of the ink jet head 34 or the pressure chamber, or when the ink viscosity in the nozzle rises to a certain level or more, ink is ejected from the nozzle even if the pressure generating means is operated. become unable. In such a case, the cap 58 is brought into contact with the nozzle surface 34a of the ink-jet head 34, and the suction pump 62 sucks ink mixed with bubbles in the pressure chamber or thickened ink or solidified ink, or a head pressurizing pump. In 68, an operation of forcibly pressurizing the pressure chamber and forcibly discharging from the nozzle is performed.

However, since the above-described suction operation and forced ejection operation by pressurizing the head are performed on the entire ink in the pressure chamber, the amount of ink consumption is large. Therefore, when the increase in viscosity is small, it is preferable to perform preliminary discharge as much as possible. Needless to say, the cap 58 described with reference to FIG. 5 functions not only as a suction unit but also as a preliminary discharge ink receiver.
Further, it is preferable that the inside of the cap 58 is divided into a plurality of areas corresponding to the nozzle rows by a partition wall, and each of the partitioned areas can be selectively sucked by a selector or the like.

Next, as shown in FIG. 5, the ink replenishment system 70 detects the ink concentration in the ink refill tank 72, the dilution replenishment tank 74 that stores the diluted liquid, and the ink tank 52. Concent ink replenishment is received by receiving information on the density detection unit 76, the level detection unit 78 that detects the amount of ink stored in the ink tank 52, the detected density from the density detection unit 76, and the amount of ink storage from the level detection unit 78. And a replenishment control unit 80 for controlling the replenishment amount of the concentrate from the tank 72 and the replenishment amount of the diluent from the diluent replenishment tank 74.
In the ink replenishment system 70 shown in FIG. 5, the ink tank 52 and the collection tank 64 are connected by a collection ink supplement pipe 82. A filter 84 for removing deteriorated ink such as solidified ink contained in the collected ink collected in the collected tank 64 is provided in the middle of the collected ink supplementing pipe 82, and the ink tank 52 of the collected ink supplemented pipe 82 is provided. A density detector 86 is provided on the side close to. Here, the replenishment control unit 80 also receives information on the detected density of the recovered ink from the density detection unit 86, and in addition to the replenishment amount of the concentrated ink and the replenishment amount of the diluting liquid, the replenishment ink replenishment amount from the recovery tank 64 is set. Control.

The conc ink replenishment tank 72 is a tank that is filled with conc ink (high concentration ink), and includes a pump (not shown) that supplies the conc ink in the conc ink replenishment tank 72 to the ink tank 52. Ink ink is replenished to the ink tank 52 in accordance with an instruction from the replenishment control unit 80.
On the other hand, the dilution liquid replenishment tank 74 is a tank that is filled with a solvent used as an ink dilution liquid when replenishing ink, and has a pump that supplies the dilution liquid to the ink tank 52. The ink tank 52 is replenished with the diluent according to the instructions from the above.
Here, in the present invention, the density of the concentrated ink is not particularly limited as long as it is higher than the target density of the ink. That is, as the ink having a predetermined density for replenishment, an ink having a higher density than the target density of the ink may be used. Further, the dilution liquid is not particularly limited, and an ink having a lower concentration than the target concentration of the ink may be used. In other words, in the present invention, replenishment may be performed using a plurality of inks having different densities, including ink having a higher density than the target density of ink and ink having a lower density, as the concentrated ink and dilution liquid. Good.

The density detector 76 detects the density of the ink using an optical detector and supplies it to the replenishment controller 80.
For example, in the ink supply system 50 of the ink jet drawing apparatus 30, the ink supply tube 54 has a transmission part that is partially formed of a light-transmitting member such as glass, and the density detection unit 76 is emitted from the light emitting element. Measurement light is incident on the light transmission part, and the amount of transmitted light that has passed through the light transmission part is measured by the light receiving element. The density detection unit 76 has a look-up table (LUT) that is created in advance by experiments or the like and shows the relationship between the measurement result of transmitted light and the ink density. Using this LUT, the measurement result of the transmitted light is obtained. Obtain the ink density. Alternatively, instead of the LUT, the ink density may be obtained by an arithmetic expression using the measurement result of transmitted light as a parameter.
In the present invention, the ink density detection method and means in the density detection unit 76 are not limited to optical methods and means, and various methods and means can be used. The ink density may be obtained by detecting ink characteristics such as the electrical conductivity of the ink. In the present invention, such an optical density detection method and means can be preferably used in that the density of the ink can be detected directly and with high accuracy.

The level detection unit 78 is for detecting the ink level in the ink tank 52 (the ink level, that is, the amount of ink) and supplying it to the replenishment control unit 80. That is, in the illustrated example, the ink level in the ink supply system 50 is detected by detecting the ink level in the ink tank 52.
In the present invention, the ink level detection means and method are not particularly limited, and an electrical level detection means using an electrode rod or the like, a level detection means using a float, an ultrasonic level detection means, a capacitance type Various known means and methods such as a level detection means and a detection method using these means can be used. Further, instead of detecting the ink level, the ink amount in the ink tank 52 may be directly detected by measuring the ink weight in the ink tank or the like.

When the ink replenishment control unit 80 replenishes ink in the ink tank 52, information on the density of ink and recovered ink from the density detection units 76 and 86 and information on the amount of ink in the ink tank 52 from the level detection unit 78 are displayed. Receiving, the replenishment amount of the conk ink and the diluting liquid, or the replenishment amount of the recovered ink, the conk ink and the diluting liquid, and the replenishing amount of the conk ink to the conk ink replenishing tank 72 and the dilution liquid to the diluting liquid replenishing tank 74. The replenishment amount is for instructing the collection tank 64 for the replenishment amount of the collected ink.
In the recording apparatus 10 using the present invention, the timing of ink replenishment is not particularly limited, and may be automatically performed, for example, every predetermined time, every period, every drawing on a predetermined number of substrates, It may be automatically performed according to the amount of ink in the ink tank 52 detected by the level detection unit 78, or may be performed according to an input instruction based on a judgment of an operator who observes the drawn pixel. There may be timing determination means, which may be selectively performed.

The ink jet drawing apparatus shown in FIGS. 3 to 5 is basically configured as described above. Hereinafter, an operation of the ink jet drawing apparatus and an ink jet drawing method for producing a color filter by the ink jet drawing apparatus will be described. Will be explained.
FIG. 6 is a flowchart showing a flow of an embodiment before starting drawing of an ink jet drawing method performed as a drawing process for manufacturing a color filter in the ink jet drawing apparatus shown in FIGS.

  First, as shown in FIG. 6, in step S <b> 120, the substrate 12 in which the partition wall 14 is formed on the platen 32 via the substrate transport mechanism 40 by the substrate supply unit (not shown) in the inkjet drawing apparatus 30 shown in FIG. 3. Supply. Next, in step S122, the supplied substrate 12 is transported onto the platen 32 by the feed roller 46 and the restraining roller 48 of the substrate transport mechanism 40, positioned and stopped at the predetermined position, and the substrate 12 is placed on the platen 32. For example, it is attached and fixed by adsorption or the like. Next, in step S124, the substrate alignment is taken using the alignment mark on the substrate 12, and the drawing start position is set.

On the other hand, in step S130, as shown in FIG. 3, the drive screw 42 is driven by the head moving mechanism 38 to move the head unit 36 along the guide rail 43, and the head unit 36 is moved to the region of the substrate 12 or the platen 32. The nozzle head 34a is moved to a maintenance position (discharge inspection position; not shown) for inspecting the ejection state of the ink jet head 34, which is out of the region, and the nozzle surface 34a of the ink jet head 34 is moved to a cap 58 as shown in FIG. Make them face each other. At this time, the head unit 36 has been moved to a predetermined position facing the cap 58.
Next, in step S132, the cap 58 is raised and brought into contact with the nozzle surface 34a of the inkjet head 34, and ink is discharged from each nozzle to detect ink discharge. The ink discharge detection, that is, the inspection of the discharge state, may be performed by detecting the presence or absence of discharged ink droplets in an optical sensor provided for each nozzle of the inkjet head 34 in the cap 58, for example, a light emitting / receiving element. . Alternatively, the amount of ejected ink droplets is measured for each nozzle of the inkjet head 34, and the ejection state of each nozzle is inspected depending on whether the amount is within a preset specification, that is, within a predetermined range. good. The discharged ink at the time of discharge detection is collected in the collection tank 64 through the ink collection pipe 66.

Next, in step S134, it is determined whether all the nozzles of the inkjet head 34 are within the preset specification, that is, whether they are in an appropriate discharge state.
If it is determined in step S134 that all the nozzles of the inkjet head 34 are within the set specifications (appropriate ejection state) (Y), the process proceeds to step S126, and the cap 58 is moved from the nozzle surface 34a of the inkjet head 34. 3, the drive screw 42 is driven by the head moving mechanism 38 to move the head unit 36 along the guide rail 43, and the head unit 36 is moved to a predetermined drawing start position on the substrate 12 by the substrate alignment. Move to.
Next, in step S128, drawing is performed on the substrate 12.

On the other hand, if it is determined in step S134 that even one nozzle of the inkjet head 34 is out of the set specification (appropriate ejection state) (N), the process proceeds to step S136, and each nozzle of the inkjet head 34 is Perform dummy discharge (preliminary discharge).
Next, in step S138, as in step S132, ink ejection is detected at each nozzle of the inkjet head 34, and the ejection state of each nozzle is inspected. Note that the ink ejected during dummy ejection and ejection detection is collected in the collection tank 64 through the ink collection pipe 66 (see FIG. 5).
Next, in step S140, as in step S134, it is determined whether or not all the nozzles of the inkjet head 34 are within the set specification. If they are within the set specification (Y), the process proceeds to step S126. As described above, the cap 58 is removed from the nozzle surface 34a of the inkjet head 34, the drive screw 42 is driven by the head moving mechanism 38, and the head unit 36 is moved along the guide rail 43 (see FIG. 3). The unit 36 is moved to a predetermined drawing start position on the substrate 12 by the substrate alignment.
Next, in step S128, drawing is performed on the substrate 12.

On the other hand, if it is determined in step S140 that even one nozzle of the inkjet head 34 is out of the set specification (N), the process proceeds to step S142, and each nozzle of the inkjet head 34 is moved by the suction pump 62. The ink in the nozzles is sucked, or the head pressure is applied to each nozzle by the head pressurizing pump 68 to forcibly eject the ink in each nozzle (see FIG. 5). Note that both the nozzle suction operation by the suction pump 62 and the forced discharge operation by the head pressurizing pump 68 may be performed.
Next, in step S144, the cap 58 is removed from the nozzle surface 34a of the inkjet head 34, the nozzle surface 34a is wiped by the cleaning blade 60, and deteriorated ink such as solidified ink or high viscosity ink attached to the nozzle surface 34a. The nozzle surface 34a is cleaned (see FIG. 5).

Thereafter, in step S146, dummy ejection is performed from each nozzle of the inkjet head 34, as in step S136.
Next, in step S148, as in step S138, the ejection of ink from each nozzle of the inkjet head 34 is detected, and the ejection state of each nozzle is inspected. The ejected ink at the time of nozzle suction operation and / or forced ejection operation, dummy ejection and ejection detection is collected in the collection tank 64 through the ink collection pipe 66 (see FIG. 5).
Next, in step S150, as in step S140, it is determined whether all the nozzles of the inkjet head 34 are within the set specification. If they are within the set specification (Y), the process proceeds to step S126. As described above, the cap 58 is removed from the nozzle surface 34a of the inkjet head 34, the drive screw 42 is driven by the head moving mechanism 38, the head unit 36 is moved along the guide rail 43, and the head unit 36 is aligned with the substrate. To the drawing start position on the substrate 12 (see FIG. 3).
Next, in step S128, drawing is performed on the substrate 12.

On the other hand, if it is determined in step S150 that even one nozzle of the inkjet head 34 is out of the set specification (N), the process returns to step S142 again, and the above-described nozzle suction operation by the suction pump 62 and / or A forced discharge operation is performed by the head pressurizing pump 68, and nozzle wiping by the cleaning blade 60 in step S144, dummy discharge in step S146, discharge detection in step S148, and whether all nozzles in step S150 are within the above set specifications. Are sequentially determined.
In step S150, if all the nozzles are within the set specifications (Y), the process proceeds to step S126, and similarly, the head unit 36 is moved to the drawing start position on the substrate 12 by the substrate alignment (see FIG. 3). In step S128, although drawing is performed on the substrate 12, if even one nozzle of the inkjet head 34 is out of the set specification (N), the process returns to step S142 described above again, and step S142. , S144, S146, S148, and S150 are repeated until all nozzles are within the set specifications (Y). When the number of repetitions exceeds a predetermined number set in advance, it is preferable to stop the drawing method as an error.

In the drawing step of step S128, in the ink jet drawing apparatus 30 shown in FIG. 3, the head unit 36 is moved (scanned) in the main scanning (X) direction by the head moving mechanism 38, that is, a predetermined position on the substrate 12, that is, A droplet of ink 18 is ejected from an inkjet head 34 into a predetermined recess 16 between the partition walls 14 on the substrate 12 and is drawn to form a pixel (uncured pixel ink 18a) of the color filter.
In this way, the head unit 36 is moved and scanned from the start end in the main scanning (X) direction and / or from the end to the start end in the drawing region (region in which the partition wall 14 is formed) of the substrate 12 to form pixels in the main scanning direction. finish.
Thereafter, the suction and fixation of the substrate 12 to the platen 32 is released, the feed roller 46 is rotated by the substrate moving mechanism 40, and the substrate 12 is moved in the sub-scanning direction by a predetermined distance (for example, the length ΔY for the drawing area (color The filter cell is transported and moved by one pitch (one pitch) or two pitches (reciprocating)) and stopped on the platen 32, and the substrate 12 is again fixed to the platen 32 by suction. As a result, the head unit 36 that has reached the start or end of the substrate 12 in the main scanning direction is moved in the sub-scanning direction by a certain amount (the length ΔY corresponding to the drawing area).
Subsequently, as described above, the head unit 36 is again moved in the main scanning (X) direction by the head moving mechanism 38 from the drawing start position in the main scanning direction to the substrate 12 thus sucked and fixed on the platen 32. Thus, drawing by the inkjet head 34 is performed, and drawing of the substrate 12 in the main scanning direction is completed.
Thereafter, the suction of the substrate 12 to the platen 32 is released again, the substrate 12 is transported by a predetermined distance ΔY in the sub-scanning direction, the suction of the substrate 12 to the platen 32 is fixed, and the drawing of the substrate 12 in the main scanning direction by the inkjet head 34 is performed. The head unit 36 is moved in the main scanning (X) direction while moving the substrate 12 by the length ΔY corresponding to the drawing area from the start end to the end in the sub-scanning direction. In response, ink is ejected to draw one color on the entire surface of the substrate 12 to form color filter pixels (uncured pixel ink 18a).

In this way, for other colors of the color filter, ink is ejected while moving the head unit 36 in the main scanning direction on the substrate 12, and then the substrate 12 is moved by a certain distance in the sub-scanning direction. Repeatedly, other colors are sequentially drawn on the substrate 12 to form pixels of the color filter (uncured pixel ink 18a), and all pixels (uncured pixel ink 18a) can be formed for all colors of the color filter. .
In the present invention, the nozzle arrangement of the inkjet head 34 of the head unit 36 is not particularly limited, and may be a single row or a plurality of rows, and the number of nozzles in each nozzle row is also particularly limited. Instead, it may be one or plural. In addition, the drawing format on the cells and pixels of the color filter by the ink jet head 34 having such a nozzle arrangement is not particularly limited and may be any type.

  For example, as shown in FIG. 9A, an inkjet head 34R that has four nozzle rows in the nozzle portion and ejects R ink, and an inkjet head 34G that has four nozzle rows in the nozzle portion and ejects G ink. FIG. 9B shows the nozzle spacing of each nozzle row of each of the inkjet heads 34R, 34G, and 34B using an inkjet head 34B that has four nozzle rows in the nozzle portion and discharges G ink. As described above, when the dot interval to be drawn in one cell (pixel) 20R, 20G, 20B of each color of the color filter is small, the inkjet heads 34R, 34G, 34B are moved in the main scanning (X) direction and the cell of the color filter. 4 to one cell of the color filter from one inkjet head by scanning so that the longitudinal direction of Using two nozzles in each row of the ink, ink droplets are ejected from a total of eight nozzles to form eight dots in one cell of the color filter, and a cell for each color (that is, cell 20R, 20G, 20B) may be formed. Further, as shown in FIG. 9C, the nozzle row 35R in which nozzles for discharging R ink are arranged in the nozzle portion, the nozzle row 35G in which nozzles for discharging G ink are arranged, and the nozzle for discharging B ink are arranged. An ink jet head 34 ′ having three nozzle rows of the nozzle row 35B is used, and the ink jet head 34 ′ is scanned so that the main scanning (X) direction thereof coincides with the longitudinal direction of the color filter cell. Using one nozzle in one nozzle row (that is, one of the nozzle rows 35R, 35G, and 35B) for one cell, a total of eight ink droplets are ejected from one nozzle. Thus, one cell of the color filter shown in FIG. 9D, that is, one corresponding cell among the cells 20R, 20G, 20B, and 20R ′ in FIG. 9D. It may be formed eight dots. In the example shown in FIG. 9D, three dots (specifically, cells 20R, 20G, and 20B) among the four cells of the color filter have eight dots of three different types of ink. 9 (d), the uppermost cell and the lowermost cell (specifically, cell 20R and cell 20R ′) in FIG. 9 (d) are formed in the inkjet head 34 ′ shown in FIG. 9 (c). It shows that 8 dots are formed by different nozzles of the nozzle row 35R and are respectively formed of the same kind of ink.

  Here, the shape of the pixel array (pixel pattern) of the color filter formed by the ink jet drawing method shown in FIG. 6 using the ink jet drawing apparatus 30 shown in FIGS. ), A grid pattern shown in FIG. 7B, or a delta array pattern shown in FIG. 7C, but the present invention is not particularly limited.

In addition, when the color pixel array (color pixel pattern) of the color filter shown in FIGS. 7A to 7C is drawn and cured, one color, for example, an R color pixel pattern is first formed. Drawing and curing to form the color pixel 20, and sequentially drawing and curing the other colors one by one, for example, in the order of G and then B, to form all color pixels 20 color pixel patterns may be formed. First, after drawing two or more colors, for example, three color pixel patterns of RGB sequentially or simultaneously, or multiple colors, two or more drawn colors, for example, The uncured pixels 18a of the three color pixel patterns of RGB may be cured to form the cured color pixels 20 of a color pixel pattern of a plurality of colors or all colors.
As described above, in the production of the color filter, for example, the pixel arrangement of three primary colors such as RGB, that is, the pixel pattern is regular, so that a normal image composed of random color pixel patterns is drawn with an inkjet head. Alternatively, or different from these, the nozzles used in the inkjet head are determined, and among all the nozzles of the inkjet head, nozzles that are not used for a long time are generated. For this reason, in the ink jet drawing method in the color filter manufacturing method of the present invention, as shown in FIG. 6, it is preferable to inspect the discharge state of each nozzle of the ink jet head and perform ink jet drawing while confirming the discharge. .

In the above-described embodiment, the pixel is formed by moving the head unit in the main scanning direction and the sub-scanning direction. However, the present invention is not limited to this. For example, the head unit is moved only in the main scanning direction and the substrate is moved. You may make it move a fixed distance at a time in a subscanning direction.
Alternatively, the inkjet head may be a full line head, and pixels may be formed on the entire surface of the printing plate precursor in one scan of the head unit. Here, when the inkjet head is a full line head, the inkjet head may be scanned or the substrate may be scanned.

In the example shown in FIG. 5, the ink tank 52 is directly connected to the inkjet head 34 via the ink supply pipe 54. However, the present invention is not limited to this, and the damper effect and refill for preventing fluctuations in the internal pressure of the head are improved. In order to provide a function to perform this, a supply sub tank may be provided between the ink tank 52 and the inkjet head 34.
FIG. 8 schematically shows a schematic configuration of another embodiment of the ink supply system applied to the ink jet drawing apparatus shown in FIGS. 3 and 4 instead of the ink supply system shown in FIG.
As shown in FIG. 8, the ink jet drawing apparatus 31 and the ink supply system 90 used therefor basically include an ink jet head (ejection head) 34, a cap 58, an ink tank 52, a supply sub tank 92, and a recovery. A tank 64 and a replenishment tank 94 are provided.

  The ink jet drawing apparatus 31 and the ink supply system 90 shown in FIG. 8 have the ink jet drawing apparatus 30 and the ink supply system 50 shown in FIGS. 3 to 5 and a supply sub tank 92, and overflow the recovery tank 64 and the ink tank 52. Since it has the same structure except that it is different in that it is connected by a pipe 98, the same reference numeral is given to the same component, and the detailed description thereof is omitted. Note that the scanning system of the ink jet drawing apparatus 31 not shown in FIG. 8 may be one to which the scanning system of the ink jet drawing apparatus 30 shown in FIGS. 3 and 4 is applied, or a conventionally known scanning system may be used. It may be applied.

  The ink supply system 90 mainly includes an ink supply system in a narrow sense for supplying ink from the ink tank 52 to the inkjet head 34, and an ink recovery system for recovering and reusing the ink purged by the cap 58. Is done. The ink supply system includes an ink pump 96, a supply sub tank 92, a first ink supply pipe 54a connecting the ink pump 96 and the supply sub tank 92, a second ink supply pipe 54b connecting the supply sub tank 92 and the inkjet head 34, and This is mainly composed of an overflow pipe 98a that opens inside the supply subtank 92 that also functions as a third ink recovery pipe (flow path) 98 that overflows the ink in the supply subtank 92 and sends it to the ink tank 52 for recovery. The ink recovery system also includes a recovery tank 64, a first ink recovery pipe 66 that connects the cap 58 and the recovery tank 64, and a second ink recovery that overflows the ink in the recovery tank 64 and sends it to the ink tank 52 for recovery. It is mainly composed of an overflow pipe 100a that opens inside the collection tank 64 that also functions as the pipe 100. The second ink collection tube 100 (overflow tube 100a) is provided with a density detector 86 for measuring the collected ink transmittance in order to detect the density of the collected ink flowing inside. The supply subtank 92 is provided with an atmosphere release valve 102 and a pressure adjustment valve 104. The ink supply pipe serving as the ink supply flow path and the ink collection pipe serving as the ink collection flow path can be configured from, for example, a pipe or a flexible tube.

  FIG. 8 mainly shows the characteristic portions of the present invention, but the ink jet drawing apparatus 31 and the ink supply system 90 are not shown in FIG. Scanning that transports (scans and conveys) the recording medium P in a direction orthogonal to the nozzle row direction (row direction), which will be described later, along a driver that discharges droplets, a scanning unit of the inkjet head 34, and a predetermined path that faces the inkjet head 34. It goes without saying that various components of a known ink jet drawing apparatus such as a conveying means are included.

The cap 58 is attached to the nozzle side of the ink jet head 34 when the ink circulation is stopped or when drawing is not performed for a long time, so that all the nozzles of the ink jet head 34 are disconnected from the outside air. This prevents dry fixation due to evaporation of the remaining ink. Various types of caps that are normally used in various ink jet recording apparatuses can be used.
The ink tank 52 has the function of mixing the solvent from the replenishing tank 94, the concentrated ink, and the ink recovered from the recovery tank 64 to make the liquid properties and optical characteristics constant, and the function of storing the ink. The ink tank 52 preferably has a stirring means for preventing the precipitation of dye and a temperature adjusting means for improving the stability of ink ejection.
An ink pump 96 for feeding ink from the ink tank 52 to the supply sub tank 92 is disposed on the first ink supply pipe 54a. The amount of liquid fed by the ink pump 96 is set to be larger than the amount of ink supplied from the supply sub tank 92 to the inkjet head 34.

The supply sub tank 92 is a sealed ink tank to which the first ink supply pipe 54a and the second ink supply pipe 54b are connected, and is disposed below the inkjet head 34 in the vertical direction. The other end of the second ink supply pipe 54 b connected to the supply sub tank 92 is connected to the inkjet head 34.
In the supply sub tank 92, the ink supplied from the ink tank 52 by the first ink supply pipe 54a is stored, and the stored ink is supplied to the inkjet head 34 through the second ink supply pipe 54b.
In addition, an overflow pipe 98a serving as a third ink recovery pipe 98 is disposed in the supply subtank 92, and the second ink supply pipe 54b is connected below the upper end of the overflow pipe 98a. In the illustrated example, a connection portion with the second ink supply pipe 54 b is provided on the bottom surface of the supply sub tank 92.

The ink stored in the supply sub tank 92 is supplied to the inkjet head 34 from the second ink supply pipe 54b by pressurizing the supply sub tank 92 to the nozzle meniscus by the surface tension or supply sub tank pressure adjustment mechanism.
Further, in the supply sub tank 92, even if the ink supplied by the ink pump 96 exceeds the height of the overflow pipe 98a, it overflows and is discharged from the overflow pipe 98a, so that the liquid level in the tank is constant. Kept. As a result, if the supply subtank 92 is opened to the atmosphere, the pressure of the supply subtank 92 is kept constant.
The ink discharged from the overflow pipe 98 is returned to the ink tank 52 through the third ink collection pipe 98 and is again circulated.

The collection tank 64 is a sealed ink tank connected to the cap 58, and is disposed below the inkjet head 34 in the vertical direction. As described above, the other end of the first ink recovery tube 66 is connected to the cap 58, and the other end of the second ink recovery tube 100 is connected to the ink tank 52.
The recovery tank 64 stores ink discharged to the cap 58 by purge and dummy discharge. The ink stored in the recovery tank 64 is returned from the second ink recovery pipe 100 to the ink tank 52.

The ink replenishment tank 94 is a sealed tank that replenishes the ink tank 52 with consumed ink, and is connected to the ink tank 52 by an ink replenishment pipe 106.
The replenishment tank 94 replenishes the ink tank 52 with ink so that the ink in the ink tank 52 has a predetermined concentration and a predetermined amount. The configuration of the replenishment tank 94 is not particularly limited. For example, as in the ink replenishment system 70 illustrated in FIG. 5, a concent tank that stores conch ink (high-concentration ink), and a dilution liquid tank that stores ink dilution liquid. The ink tank may be replenished with a determined amount of concentrated ink and diluent so as to have a predetermined concentration and a predetermined amount. Note that a solvent may be used as the diluent.

In the ink jet drawing apparatus 31 and the ink supply system 90, the ink replenishment timing is not particularly limited. For example, it may be automatically performed every time a predetermined number of drawings are performed, or may be automatically performed by detecting the amount of ink in the ink tank 52. It may be performed according to the above, or may be performed selectively by having a plurality of timing determination means.
Also, there is no particular limitation on the method for determining the replenishment amount of the concentrate and the diluent. For example, in addition to the expected ink evaporation amount, the total ink ejection number detected from the pixel data, the density measurement result of the circulating ink, the ink amount in the ink tank 52, etc. are used to predict the ink consumption amount, The replenishment amount of ink may be determined so that the ink in the ink tank 52 becomes a predetermined amount at a predetermined concentration.

The method of mixing the diluted solution, the concentrated ink, and the recovered ink can also be performed by the following method. A transparent portion is provided as an ink concentration measurement area in the middle of the third ink recovery tube 100 serving as a flow path from the recovery tank 64 to the ink tank 52, and a density detector 86 is disposed in that portion. The density detection unit 86 calculates the solvent evaporation amount of the ink collected in the ink tank by measuring the light transmittance of the ink in the measurement area. As for the relationship between the light transmittance and the solvent evaporation amount, the relationship between the ink having different dye concentration and the light transmittance is measured in advance or the light transmittance exp (−α · t) (α: absorption coefficient (dye It can be calculated from (proportional to concentration) and t: thickness). In order to measure the transmittance, the ink density measurement area includes a light source, a light receiving sensor, and a flow path of a transparent member such as glass. It is desirable that the flow path be a plane for the part through which the measurement light is transmitted, the surface is AR-coated, and it is desirable that the flow path is inclined several degrees from the perpendicular to the optical axis. This is to prevent measurement accuracy from being deteriorated by reflected light.
The mixing ratio of the diluted liquid, the concentrated ink, and the recovered ink is determined from the concentration of the recovered ink.
The ink jet drawing apparatus 31 and the ink supply system 90 shown in FIG. 8 are basically configured as described above.

  The color filter manufactured as described above can be suitably used as a color filter for color image display devices such as liquid crystal displays, electronic paper, and organic EL.

  As described above, the ink-jet ink, the color filter and the manufacturing method thereof, and the liquid crystal display and the image display device using the same have been described in detail with reference to various embodiments and examples. It goes without saying that the present invention is not limited to examples and embodiments, and various improvements and modifications may be made without departing from the scope of the present invention.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, equipment, operations, etc. shown in the following examples can be appropriately changed without departing from the scope of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the following examples, “%” and “parts” represent “% by mass” and “parts by mass” unless otherwise specified, and the molecular weight indicates the weight average molecular weight.

(Preparation of dark color composition for barrier rib formation)
The dark color composition K1 is first weighed in the amount of K pigment dispersion 1 and propylene glycol monomethyl ether acetate listed in Table 1, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 10 minutes, While stirring, the amounts of methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisdiethoxycarbonylmethyl) shown in Table 1 Amino-3′-bromophenyl] -s-triazine and surfactant 1 are weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.) and stirred at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes. It is obtained by doing. In addition, the quantity of Table 1 is a mass part, and has the following composition in detail.

<K pigment dispersion 1>
・ Carbon black (Nippex 35 manufactured by Degussa) 13.1%
・ Dispersant (Compound 1 below) 0.65%
-Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.72%
Propylene glycol monomethyl ether acetate 79.53%

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27%
・ Propylene glycol monomethyl ether acetate 73%

<DPHA solution>
・ Dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD
DPHA) 76%
・ Propylene glycol monomethyl ether acetate 24%

<Surfactant 1>
・ The following structure 1 30%
・ Methyl ethyl ketone 70%

(Formation of partition walls)
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., a dark color prepared as described above with a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. Composition K1 was applied. Subsequently, a part of the solvent was dried with a VCD (vacuum dryer, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a thick film with a thickness of 2.3 μm. A composition layer K1 was obtained.
With a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) that has an ultra-high pressure mercury lamp, the exposure mask surface and the dark color photosensitive film with the substrate and mask (quartz exposure mask with image pattern) standing vertically The distance between the layers K1 was set to 200 μm, and pattern exposure was performed under a nitrogen atmosphere with an exposure amount of 300 mJ / cm ² to a partition wall width of 20 μm and a space width of 100 μm.

Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the dark color composition layer K1, and then a KOH developer (containing a nonionic surfactant, trade names: CDK-1, Fuji Film). Electronics Materials Co., Ltd. 100-fold diluted) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water is sprayed at a pressure of 9.8 MPa with an ultrahigh pressure cleaning nozzle to remove the residue, and a dark color composition layer K1 of the substrate is formed at an exposure amount of 2500 mJ / cm ^{2 in} the atmosphere. The film was post-exposed from the surface side and heated in an oven at 240 ° C. for 50 minutes to obtain a stripe-shaped partition wall having an opening having a thickness of 2.0 μm, an optical density of 4.0, and a width of 100 μm.

(Ink-repellent plasma treatment)
The substrate on which the barrier ribs were formed was subjected to ink repellent plasma treatment under the following conditions using a cathode coupling parallel plate type plasma treatment apparatus.
Gas used: CF ₄
Gas flow rate: 80sccm
Pressure: 40Pa
RF power: 50W
Processing time: 30 sec

<Blue (B) Ink> Preparation Method (Part 1)
The following components were mixed and stirred for 1 hour. Then, it filtered under reduced pressure with the micro filter with an average hole diameter of 0.25 micrometer, and prepared the blue ink liquid (ink B-1 and ink B-2).

Details of the materials used are shown below.
Dye: Illustrative compound III-4 of the compound represented by the general formula (I)
-Dye: Illustrative compound CI-29 of the compound represented by formula (B)
DPCA-60 (manufactured by Nippon Kayaku Co., Ltd. (KAYARAD DPCA-60)): caprolactone-modified dipentaerythritol hexaacrylate KF-353 (manufactured by Shin-Etsu Silicone): polyether-modified silicone oil

(Measurement of viscosity and surface tension)
While the temperature of the obtained ink was adjusted to 25 ° C., measurement was performed under the following conditions using an E-type viscometer (RE-80L) manufactured by Toki Sangyo Co., Ltd.
(Measurement condition)
-Rotor used: 1 ° 34 'x R24
・ Measurement time: 2 minutes ・ Measurement temperature: 25 ° C

  The obtained ink was measured using a surface tension meter (FACE SURFACE TENSIOMETER CBVB-A3) manufactured by Kyowa Interface Science Co., Ltd. while adjusting the temperature to 25 ° C.

<Contrast measurement method>
As a backlight unit, a cold cathode tube light source (light source emitting light having a wavelength spectrum distribution shown in FIG. 10) provided with a diffusion plate is used, and a monochromatic substrate between two polarizing plates (POLAX-15N manufactured by Luceo) And the Y value of the chromaticity of the light that passes when the polarizing plate is installed in parallel Nicol is divided by the Y value of the chromaticity of the light that passes when installed in crossed Nicol. A color luminance meter (BM-5A manufactured by Topcon Co., Ltd.) was used for the measurement of chromaticity. The monochromatic substrate was produced by the following method. A solid film is formed on a glass substrate by an ink jet method or a spin coat method using one color of the B inks (ink B-1 and ink B-2) constituting the color filter, and a color filter described later is formed. In the same manner as above, pre-baking (preheating) (temperature 100 ° C., 2 minutes) and post-baking (post-heating) (temperature 220 ° C., 30 minutes) were performed to form a film thickness of 2 μm.

The measurement angle of the color luminance meter was set to 1 °, and the measurement was performed with a visual field of 5 mm on the sample. The amount of light of the backlight was set so that the luminance was 400 cd / m ² when two polarizing plates were installed in parallel Nicol without a sample.

  When the contrast of the monochromatic substrates (two types) obtained above was measured, a value of 50000 or more was obtained with any monochromatic substrate.

<Production of ITO layer>
Next, using a sputtering apparatus on the monochromatic substrate obtained above, ITO (indium tin oxide) is sputtered at a film surface temperature of 200 ° C. for 15 minutes to form an ITO film having a thickness of 1500 mm. A color filter substrate was produced.

<Change in spectral characteristics before and after ITO sputtering>
Before and after ITO sputtering, a spectral transmittance curve in a wavelength range of 400 nm to 700 nm was obtained using an ultraviolet-visible absorption spectrometer (V-570 manufactured by JASCO Corporation). If the change in spectral transmittance at the maximum peak before and after sputtering is small, it means that the heat resistance is good.

  From the ultraviolet-visible absorption spectrum before and after ITO sputtering of the produced monochromatic substrate (ink B-1), it was found that the spectrum shape hardly changed before and after ITO sputtering, and it had high heat resistance. Similarly, in the monochromatic substrate of B ink (ink B-2), the spectral shape hardly changed before and after ITO sputtering.

<Blue (B) Ink> Preparation Method (Part 2)
The following components were mixed at the blending ratio shown in Table 5 and stirred for 1 hour. Then, it filtered under reduced pressure with the micro filter with an average hole diameter of 0.25 micrometer, and prepared the blue ink liquid (B Examples 1-10). In addition, the numerical value in a table | surface represents the mass%.

Details of each material used for preparing the blue (B) ink are shown below.
(Organic solvent)
・ Cyclohexanone (Wako Pure Chemical Industries, Ltd.)
・ N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.)
・ Benzyl alcohol (Wako Pure Chemical Industries, Ltd.)
MMPGAC (manufactured by Daicel Kogyo): propylene glycol monomethyl ether acetate 1,3-BGDA (manufactured by Daicel Kogyo): 1,3-butylene glycol diacetate (polymerizable monomer)
DPCA-60 (manufactured by Nippon Kayaku Co., Ltd. (KAYARAD DPCA-60)): caprolactone-modified dipentaerythritol hexaacrylate DPHA (manufactured by Nippon Kayaku Co., Ltd. (KAYARAD DPHA)): dipentaerythritol hexaacrylate AD-TMP (new Nakamura Chemical Co., Ltd. (NK Ester AD-TMP)): Ditrimethylolpropane tetraacrylate (surfactant)
KF-353 (manufactured by Shin-Etsu Silicone): polyether-modified silicone oil BYK-377 (manufactured by Big Chemie): polyether-modified dimethylsiloxane mixture Solsperse 20000 (manufactured by Lubrizol)
・ F781-F (Dainippon Ink and Chemicals (Megafac F781F))
(dye)
-Dye C-1 (using the exemplified compound CI-29 of the tetraazaporphyrin-based dye represented by the general formula (A) described above)
-Dye C-2 VALIFAST BLUE 2620 (manufactured by Orient Chemical Industries)
-Dye C-3 (using the exemplified compound CA-19 of the tetraazaporphyrin-based dye represented by the general formula (A) described above)
-Dye C-4 (using the exemplified compound CC-5 of the tetraazaporphyrin-based dye represented by the general formula (A) described above)
-Dye M-1 (uses exemplified compound III-4 of the dipyrromethene-based boron complex compound represented by the general formula (I) described above)
-Dye M-2 (Use of Exemplified Compound II-3 of the above-described dipyrromethene-based boron complex compound represented by the general formula (I))
-Dye M-3 (using the exemplified compound IIIa-20 of the dipyrromethene-based boron complex compound represented by the above general formula (I))
-Dye M-4 (using the exemplified compound IIIa-40 of the dipyrromethene-based boron complex compound represented by the general formula (I) described above)

<Preparation of pigment dispersion>
C. I. P. B. Table 4 below shows the dispersant and solvent (1,3-butanediol diacetate) (hereinafter abbreviated as 1,3-BGDA) in 15: 6 (trade name: Rionol Blue ES, manufactured by Toyo Ink Manufacturing Co., Ltd.). After mixing as shown, premixing, motor mill M-50 (manufactured by Eiger Japan), using zirconia beads with a diameter of 0.65 mm at a filling rate of 80%, dispersed for 25 hours at a peripheral speed of 9 m / s, A pigment dispersion for B (B1) was prepared. A pigment dispersion for B (B2) was prepared in the same manner as for the pigment dispersion for B (B1) except that the pigment and other components were blended as shown in Table 4 in the pigment dispersion for B (B2). The number average particle size of the pigment dispersion was measured using Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd.

In addition, the colorant used for preparation of a pigment dispersion liquid is as follows.
・ C. I. P. B. 15: 6 (manufactured by Toyo Ink Co., Ltd.): Rionol Blue ES
・ C. I. P. V. 23 (manufactured by Clariant Japan): Hostaperm Violet RL-NF

<Ink for Comparative Example>
As a comparative example, a pigment ink prepared in the amount shown in Table 5 below was prepared using the above pigment dispersion. The materials used are as follows.
DPS100 (Nippon Kayaku Co., Ltd.): KAYARAD DPS100
・ TMPTA (Nippon Kayaku Co., Ltd.): KAYARAD TMPTA
Surfactant: Surfactant 1 (structure described in Compound 2)
V-40 (manufactured by Wako Pure Chemical Industries): Azobis (cyclohexane-1-carbonitrile)

<Method for producing evaluation color filter>
Using each of the inks prepared above, an inkjet printer DMP-2831 manufactured by Fuji Film Dimatix was used to eject the ink in the region (the concave portion surrounded by the convex portion) divided by the partition on the substrate obtained above. And then heated in a 100 ° C. oven for 2 minutes.
Next, the monochromatic color filter was produced by leaving still for 30 minutes in 220 degreeC oven. The film thickness of the obtained color pixel was 2.0 μm.

<Ink storage stability evaluation>
Each ink prepared above is stored in a thermostatic chamber at 50 ° C., the viscosity after 30 days is measured, and the difference (%) from the value immediately after ink preparation [(viscosity after 30 days−viscosity immediately after preparation) / preparation. Evaluation was performed according to [Viscosity immediately after]. Evaluation criteria were classified as follows.
A: Difference from viscosity immediately after ink preparation is less than 10% B: Difference from viscosity immediately after ink preparation is 10% or more and less than 20% Δ: Difference from viscosity immediately after ink preparation is 20% or more and less than 30% X: The difference from the viscosity immediately after ink preparation is 30% or more

<Continuous discharge stability evaluation>
The continuous ejection stability was evaluated using each ink prepared above. The evaluation method was an inkjet printer DMP-2831, manufactured by Fuji Film Dimatix, a head cartridge with a droplet ejection volume of 10 pl, and a droplet ejection frequency of 10 kHz, and the state when continuously ejected for 30 minutes was observed. Evaluation criteria were classified as follows.
◎: Continuous discharge is possible without problems ○: Slight non-ejection, ejection disturbance, etc. are observed during ejection, but it returns during ejection, and there is almost no problem Δ: Non-ejection, ejection disturbance occurs during ejection, State that does not return during discharge but returns to normal state due to maintenance x: State where non-discharge or discharge disturbance occurs during discharge, normal discharge cannot be performed, and discharge does not return even after maintenance DMP-2831 Purging (pressurizing ink in the head and forcibly ejecting ink from the nozzle) and blotting (sucking ink on the nozzle surface by slightly bringing the head nozzle surface into contact with the cleaning pad).

<Evaluation of ejection stability after rest>
Using each ink prepared above, the ejection stability after rest was evaluated. The evaluation method is the same as the continuous discharge stability evaluation, using a Fujifilm inkjet printer DMP-2831, a head cartridge with a droplet ejection volume of 10 pl, ejecting once for 5 minutes at a droplet ejection frequency of 10 kHz, and again after a 24-hour pause. The state when the discharge was started under the same conditions was observed. Evaluation criteria were classified as follows.
◎: Discharge can be performed without any problems at the same time as the droplet ejection instruction ○: Immediately after the droplet ejection instruction, a slight non-ejection, ejection disturbance, etc. are observed, but it returns during ejection and there is almost no problem Δ: Non-ejection, ejection disturbance Occurs, but does not return during discharge, but returns to normal state by maintenance ×: non-discharge, discharge disturbance occurs, normal discharge cannot be performed, and discharge does not return to normal level even by maintenance. Purging with DMP-2831 (pressurizing ink in the head and forcibly ejecting ink from the nozzle) and blotting (with the head nozzle surface slightly in contact with the cleaning pad and sucking ink from the nozzle surface) were performed.

<Heat resistance evaluation>
Each color filter prepared above was placed in an oven heated to 230 ° C. and allowed to stand for 1 hour, and then the hue was measured. For the measurement of hue, UV-560 (manufactured by JASCO Corporation) was used, and ΔEab before and after the evaluation was evaluated as ○ when less than 5. ΔEab is 5 or more and less than 15, and ΔEab is 15 or more. ΔEab is a value obtained from the following color difference formula based on the CIE 1976 (L *, a *, b *) space color system (Japanese Color Society edited by Color Science Handbook (Showa 60) p.266).
ΔEab = {(ΔL) ² + (Δa) ² + (Δb) ² } ^1/2

<Chemical resistance evaluation>
Each color filter produced above was immersed in the chemicals to be evaluated (N-methylpyrrolidone, 2-propanol, 5% sulfuric acid aqueous solution, 5% sodium hydroxide aqueous solution) for 20 minutes, and the hue before and after that was measured. For the measurement of hue, UV-560 (manufactured by JASCO Corporation) was used, and ΔEab was less than 5 as ◯. ΔEab is 5 or more and less than 15, and ΔEab is 15 or more. The evaluation method for ΔEab is the same as described above.

Tables 6 to 7 below collectively show the evaluation results of each ink-jet ink and color filter.
In Table 7, “B Examples 1 to 10” refer to the evaluation results of the color filters prepared using the inks described in B Examples 1 to 10, respectively.
In the following evaluation results, it is necessary that x is not included from the viewpoint of practical use.

As shown in Tables 6 to 7, the ink-jet ink described in the present invention was excellent in storage stability and in terms of ejection stability. More specifically, excellent ejection characteristics (continuous ejection stability and ejection stability after rest) were exhibited in B Example 2 and B Example 7 in which the solid content in the ink was 21% by mass or less. Moreover, the color filter manufactured using the ink-jet ink described in the present invention had excellent chemical resistance and heat resistance comparable to those obtained when pigment ink was used. In particular, the amount of hexafunctional acrylate used was large and B Example 1 showed excellent heat resistance and chemical resistance.
On the other hand, in the comparative example using the pigment ink, the ejection stability was poor and lacked practicality.

DESCRIPTION OF SYMBOLS 10 Color filter 12 Board | substrate 14 Bulkhead 16 Recessed part 18 Ink 18a Uncured pixel ink 20 Pixel 22 Protective film 30,31 Inkjet drawing apparatus 32 Platen 34 Inkjet head 36 Head unit 38 Head moving mechanism 40 Substrate transport mechanism 42 Drive screw 43 Guide rail 44 Drive support section 45 Support section 46 Feed roller 48 Retaining roller 50, 90 Ink supply system 52 Ink tank 54, 54a, 54b Ink supply pipe 56, 84 Filter 58 Cap 60 Cleaning blade 62 Suction pump 64 Collection tank 66, 100 Ink collection pipe 68 Head pressurization pump 70 Ink replenishment system 72 Conc ink replenishment tank 74 Diluent replenishment tank 76, 86 Concentration detection unit 78 Level detection unit 80 Replenishment control unit 82 Refill tank 92 Supply sub tank 94 Refill tank 96 Ink pump 98 Overflow pipe 102 Atmospheric release valve 104 Pressure adjustment valve

Claims (15)

Inkjet ink containing at least a dipyrromethene-based boron complex compound represented by the general formula (I):

[In General Formula (I), R ^{1 to} R ⁶ each independently represent a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, X ¹ and Y ¹ each independently represent a halogen atom, an alkoxy group, an aryloxy group, a hydroxyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group. ] In the general formula (I), at least one of R ¹ and R ⁶ represents an amino group, a carbonamido group, a ureido group, an alkoxycarbonylamino group, or an imide group, and at least one of R ² and R ⁵ represents The inkjet ink according to claim 1, wherein the inkjet ink represents the following formula (i):

The inkjet ink according to claim 1 or 2, further comprising a tetraazaporphyrin-based cyan dye represented by the following general formula (A).

[In General Formula (A), M ¹ represents a metal atom or a metal compound, and Z ¹ , Z ² , Z ³ , and Z ⁴ are each independently selected from a carbon atom, a nitrogen atom, and a hydrogen atom. This represents an atomic group necessary for forming a 6-membered ring composed of atoms. ] The inkjet ink according to claim 3, wherein the tetraazaporphyrin-based cyan dye represented by the general formula (A) is a phthalocyanine-based dye represented by the following general formula (B).

[In General Formula (B), R ^{101 to} R ¹¹⁶ each independently represent a hydrogen atom or a substituent, and M ² represents a metal atom or a metal compound. ]   The inkjet ink according to claim 1, further comprising a polymerizable monomer.   The inkjet ink according to claim 5, wherein the polymerizable group of the polymerizable monomer is selected from the group consisting of an epoxy group, an acryloyloxy group, and a methacryloyloxy group.   The inkjet ink according to claim 1, further comprising a surfactant.   The ink-jet ink according to any one of claims 1 to 7, which has a viscosity at 25 ° C of 2 to 30 mPa · s.   The ink for inkjet according to any one of claims 1 to 8, wherein the surface tension at 25 ° C is 20 to 40 mN / m.   10. A pixel forming step of forming a color pixel of a color filter by applying ink-jet ink droplets according to any one of claims 1 to 9 to a recess defined by a partition formed on a substrate by an ink-jet method. A method for producing a color filter.   A color filter manufactured by the method for manufacturing a color filter according to claim 10.   The color filter manufactured by the inkjet method using the ink for inkjets in any one of Claims 1-9.   A color filter provided with the color pixel formed using the ink for inkjets in any one of Claims 1-9.   A liquid crystal display provided with the color filter in any one of Claims 11-13.   An image display device comprising the color filter according to claim 11.

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