KR20090127232A - Inkjet ink, color filter and process for preparing color filter, and liquid crystal display and image display device using color filter - Google Patents

Abstract

PURPOSE: Inkjet ink is provided to ensure excellent discharge stability and good color, to form color pixel with excellent with excellent light-proof property and heat resistance, and to prepare a color filter with excellent optical property such as contrast or haze. CONSTITUTION: Inkjet ink comprises a dipyrromethene-based complex compound obtained from a dipyrromethene-based compound represented by chemical formula (I), metal element or metal compound. In chemical formula I, R1~R6 are independently hydrogen atom or substituent, R7 is hydrogen atom, halogen atom, alkyl group, aryl group, or heterocyclic group.

Description

INKJET INK, COLOR FILTER AND PROCESS FOR PREPARING COLOR FILTER, AND LIQUID CRYSTAL DISPLAY AND IMAGE DISPLAY DEVICE USING COLOR FILTER}

 The present invention relates to an inkjet ink, a color filter and 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, especially large-screen liquid crystal televisions, the demand for liquid crystal displays (LCDs), especially color liquid crystal displays, tends to increase. However, since color liquid crystal displays are expensive, the demand for cost reduction is increasing. In particular, there is a high demand for cost reduction for costly color filters. Such a color filter is normally equipped with the coloring pattern of three primary colors of red (R), green (G), and blue (B). In the liquid crystal display provided with this color filter, the liquid crystal acts as a shutter by turning on and off electrodes corresponding to the pixels of R, G, and B, and light passes through the pixels of R, G, and B. Color display is made.

As a manufacturing method of a conventional color filter, a dyeing method is mentioned, for example. This dyeing method first forms a water-soluble high molecular material which is a material for dyeing on a glass substrate, and patterning it into a desired shape by a photolithography step, and then, the obtained pattern is immersed in a dye bath to obtain a colored pattern. By repeating this three times, R, G, and B color filter layers are formed.

In addition, there is a pigment dispersion method as another method. This method first forms the photosensitive resin layer which disperse | distributed the pigment on the board | substrate, and patterns this, and obtains a monochromatic pattern. In addition, this process is repeated three times to form color filter layers of R, G, and B.

However, either method requires repeating the same process three times in order to color the three colors of R, G, and B, resulting in a problem of high cost or a problem of lowering the yield since the same process is repeated. As a manufacturing method of the color filter which solves these problems, the method of spraying a coloring ink by the inkjet method and forming a colored layer (color pixel) is proposed (patent document 1, 2).

The inkjet method is a recording method in which ink droplets are directly discharged and adhered to a recording member from a very fine nozzle to obtain a character or an image. The inkjet method has the advantage of being able to manufacture a large area color filter with high productivity by sequentially moving the inkjet head, low noise, and good operability.

 Inkjet ink using a pigment is used for manufacture of the color filter by such an inkjet method. As inkjet inks using such a pigment, for example, a binder component, a pigment, and a color filter inkjet ink containing a solvent having a boiling point of 180 ° C to 260 ° C and a vapor pressure of 0.5 mmHg or less at room temperature have been proposed. There is (patent document 3).

When the inkjet ink using such a pigment is used for the production of a color filter, the manufactured color filter is excellent in light resistance and heat resistance, but on the other hand, contrast is reduced due to scattering due to pigment particles, or an increase in haze. A problem arises. Moreover, since nozzle clogging frequently occurs due to pigment aggregation of the ink, it is not preferable also in terms of discharge stability. Further, due to the aggregated pigment, the recovery function of the ink ejection state due to the ejection recovery operation such as wiping or purging is also deteriorated. In addition, at the time of wiping, the nozzle surface may be rubbed by the aggregated pigment, causing warping in the discharge direction of the ink.

On the other hand, in the case of ink using a dye, improvement of optical characteristics such as contrast and haze of a color filter is expected. In addition, even when the ejection stability is generally high and there is a nozzle clogging with an increase in ink viscosity or the like, it is expected that the ink ejection state is easily recovered by wiping or purging. However, the fastness such as light resistance and heat resistance of the color pixel is still insufficient, and it is not necessarily satisfactory in practical use.

Therefore, there has been a problem that it is difficult to cope with the recent high brightness backlight.

Moreover, there existed a problem that the characteristics, such as the said optical characteristic, changed with the high temperature at the time of film-forming of ITO (indium tin oxide) which is used abundantly as electrodes for FPD (flat panel displays), such as a liquid crystal display (LCD).

For example, in the blue ink, ink using a violet dye is known, but as described above, the level of light resistance and heat resistance of the color pixel is not sufficient, and further improvement has been desired.

Patent Document 1: Japanese Patent Application Laid-Open No. 59-75205

Patent Document 2: Japanese Unexamined Patent Publication No. 2004-339332

Patent Document 3: Japanese Unexamined Patent Publication No. 2002-201387

This invention is made | formed in view of the said situation, The objective is to show the favorable hue, and can form the color pixel excellent in light resistance and heat resistance, Especially, it is excellent in optical characteristics, such as contrast and a haze, and also light resistance and heat resistance An excellent color filter can be produced, an inkjet ink exhibiting excellent ejection stability, a color filter excellent in the above-described optical properties obtained by such an inkjet ink, light resistance and heat resistance, and the like, and a color having such characteristics The present invention provides a method for producing a color filter that can stably produce a filter without incurring a cost increase, and a high contrast, high chroma liquid crystal display and an image display device that can cope with a high brightness backlight.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the said subject is solved by the structure of following <1>-<28>.

Ink for inkjet containing the dipyrromethene type compound represented by <1> general formula (I), and the dipyrromethene type metal complex compound obtained from a metal atom or a metal compound.

 General formula (Ⅰ)

(In General Formula (I), R <_1> -R <_6> respectively independently represents 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.)

The ink for inkjets as described in <1> whose <2> above-mentioned dipyrromethene type metal complex compounds are compounds represented by General formula (II-1).

 General formula (Ⅱ-1)

(In General Formula (II-1), 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.) Ma Represents a metal atom or a metal compound, X ₂ represents a group necessary to neutralize the charge of Ma, X ₁ represents a group capable of bonding to Ma. X ₁ and X ₂ are bonded to each other 5 atoms, 6 atoms, Or may form a 7-membered ring)

The ink for inkjets as described in <1> whose <3> above-mentioned dipyrromethene type metal complex compounds are compounds represented by General formula (II-2).

General formula (Ⅱ-2)

(In General Formula (II-2), R ₁ to R ₆ and R ₈ to R ₁₃ each independently represent a hydrogen atom or a substituent. R ₇ and R ₁₄ each independently represent a hydrogen atom or a halogen atom. , An alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound.)

The ink for inkjets as described in <1> whose <4> above-mentioned dipyrromethene type metal complex compound is a compound represented by General formula (III), or a tautomer of this compound.

 General formula (Ⅲ)

(In General Formula (III), R <_2> -R <_5> represents a hydrogen atom or a substituent each independently. R <_7> represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma is a metal atom. Or a metal compound, X ₃ represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, an oxygen atom, or Represents a sulfur atom, X ₄ represents NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or a sulfur atom , Y ₁ represents NRc (Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, or a carbon atom, and Y ₂ Is a nitrogen atom, or carbon atom Produce. R ₈ and R ₉ are, each independently, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic group represents an amino group. R ₈ and Y ₁ is being optionally, and bonded to each other to form a five atoms, six atoms, or 7-membered ring, and R ₉ and Y ₂ may optionally form a five atoms, six atoms, or 7-membered ring by combining to each other. X ₅ is Ma and Represents a group which can be bonded, and a represents 0, 1, or 2)

<5> The inkjet ink according to <1>, wherein the dipyrromethene compound represented by General Formula (I) is a compound represented by General Formula (IV).

General formula (Ⅳ)

(In General Formula (IV), R <_1> -R <_4> and R <_6> respectively 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.)

<6> The inkjet ink according to any one of <1> to <5>, wherein the metal atom or metal compound is Fe, Zn, Co, V = O, or Cu.

<7> The inkjet ink according to any one of <1> to <6>, wherein the metal atom or the metal compound is Zn.

<8> The inkjet ink according to any one of <1> to <7>, further containing a tetraaza porphyrin-based dye represented by General Formula (A).

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 composed of an atom selected from a carbon atom, a nitrogen atom, and a hydrogen atom. Represents a group of atoms forming a six-membered ring)

The ink for inkjets as described in <8> whose <9> said tetraaza porphyrin type pigment | dye is a phthalocyanine type pigment | dye represented by General formula (B).

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 as described in any one of <1>-<9> which further contains a <10> polymerizable monomer.

<11> The inkjet ink according to <10>, wherein the polymerizable group of the polymerizable monomer is any one selected from the group consisting of an epoxy group, acryloyloxy group, and methacryloyloxy group.

The inkjet ink in any one of <1>-<11> containing <12> binder resin further.

Ink for inkjets in any one of <1>-<12> which further contains a <13> surfactant.

The ink for inkjets in any one of <1>-<13> whose viscosity at the time of <14> discharge is 2-3 mPa * s.

The ink for inkjets in any one of <1>-<14> whose surface tension in <15> 25 degreeC is 20-40 mN / m.

The pixel formation process of forming the color pixel of a color filter by giving the droplet of the inkjet ink in any one of <1>-<15> by the inkjet method to the recessed part partitioned by the partition formed on the <16> board | substrate. Method for producing a color filter having a.

<17> The pixel forming step includes a drawing step of applying the ink to the concave portion by dropping by the inkjet method, and a curing step of forming the color pixel by curing the ink provided to the concave portion. The manufacturing method of the color filter as described in <16> which has.

<18> The said hardening process is equipped with the irradiation process of irradiating an active energy ray to the said ink remainder, and / or the heating process of heating the said ink remainder after removing the solvent contained in the said ink to make an ink remainder, The manufacturing method of the color filter as described in <17> which superpose | polymerizes the said ink remainder and forms the said color pixel by the said irradiation process and / or the said heating process.

In the drawing step, the droplets of the inkjet ink are discharged from the ejection nozzles of the inkjet head and applied to the recessed portions of the substrate.

Furthermore, before the said drawing process, the inspection process which examines the discharge state of the discharge nozzle of the said inkjet head,

And a pretreatment step of performing an ink ejection operation on ejection nozzles corresponding to the out of the prescribed prescribed range outside the drawing region by the inkjet head when the inspection result of the ejected state is outside the prescribed prescribed range,

After the pretreatment step, the process returns to the inspection step, and the discharge state is re-inspected, and when the color is within the prescribed range, the color according to <17> or <18> for starting the drawing of the color pixel by the drawing step. Method of making a filter.

In the drawing step, the droplets of the ink jet ink are discharged from the discharge nozzles of the ink jet head and applied to the recesses of the substrate.

Furthermore, before the said drawing process, the inspection process which examines the discharge state of the discharge nozzle of the said inkjet head,

When the ink jet head has a discharge nozzle by the inspection in the inspection step, the head pressurization is applied to a part or all of the fire discharge nozzles in the plurality of discharge nozzles of the ink jet head. A pretreatment step of carrying out part or all of the ink purge of the discharge nozzle by the ink, suction of the ink from the discharge nozzle, and wiping of the nozzle face of the inkjet head;

After the pretreatment step, the process returns to the inspection step, and the discharge state is re-inspected, and when the color is within the prescribed range, the color according to <17> or <18> for starting the drawing of the color pixel by the drawing step. Method of making a filter.

And a recovery step of recovering ink discharged by the ink ejecting operation in the pretreatment step, ink purged by the ink purge, and ink sucked by the ink suction;

A storage process for storing the collected recovery ink;

An evaluation step of evaluating ink characteristics including the concentration of recovered ink stored;

The color filter as described in <19> or <20> which has a manufacturing liquid process which recycles the said collection ink as the said inkjet ink for forming the said color pixel based on the evaluation result of the evaluated recovery ink. Method of preparation.

<22> Furthermore, the 1st preservation process of previously storing high density ink in a high concentration ink storage tank, and dilution ink in a dilution ink storage tank,

A supply step of 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-liquid process for producing a liquid-liquid ink as the ink-jet ink for forming the color pixel by roughening the supplied high concentration ink and the supplied dilution ink;

It has a 2nd preservation process which saves the said preparation liquid prepared as said inkjet ink in the preparation liquid ink storage tank,

The manufacturing method of the color filter in any one of <16>-<21> which supplies the said crude liquid ink stored in the crude liquid ink storage tank as the said inkjet ink in the said drawing process.

<23> The method for producing a color filter according to any one of <16> to <22>, wherein the ink for dilution is the solvent.

<24> The color filter manufactured by the manufacturing method of the color filter in any one of <16>-<26>.

<25> The color filter manufactured by the inkjet method using the inkjet ink in any one of <1>-<15>.

<26> The color filter provided with the color pixel formed using the inkjet ink in any one of <1>-<15>.

<27> Liquid crystal display provided with the color filter in any one of <24>-<26>.

<23> The image display device provided with the color filter in any one of <24>-<16>.

According to the present invention, it is possible to form an image having good color and excellent in light resistance and heat resistance, and in particular, a color filter having excellent optical properties such as contrast and haze, and excellent light resistance and heat resistance, and can be produced. The inkjet ink exhibiting ejection stability, the color filter excellent in the above-described optical properties, light resistance and heat resistance, etc. obtained by such an inkjet ink, and the color filter having such characteristics are stabilized, resulting in no increase in cost. A high contrast, high saturation liquid crystal display and an image display device can be provided that can cope with a color filter that can be produced without a high brightness backlight.

EMBODIMENT OF THE INVENTION Hereinafter, the inkjet ink which concerns on this invention, the color filter using this inkjet ink, its manufacturing method, and the liquid crystal display and image display device using the same are demonstrated in detail.

<Inkjet ink and its manufacturing method>

 First, the ink for inkjet of this invention, its component, and its manufacturing method are demonstrated in detail.

The inkjet ink of the present invention contains a dipyrromethene-based compound represented by General Formula (I) and a dipyrromethene-based metal complex compound obtained from a metal or a metal compound.

<Dipyrromethene Compounds Represented by General Formula (I) and General Formula (IV)>

Below, each group of the dipyrromethene type compound represented by General formula (I) and General formula (IV) is demonstrated.

General formula (Ⅰ)

General formula (Ⅳ)

R ₁ to R ₆ in General Formula (I) and R ₁ to R ₄ and R ₆ in General Formula (IV) each independently represent a hydrogen atom or a substituent. The substituent is, for example, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably C1-C48, more preferably C1-C24, a straight chain, a branched chain, Or a cyclic alkyl group, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl , Cyclohexyl, 1-norbornyl, 1-adamantyl), alkenyl group (preferably alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms), for example, vinyl, allyl, 3 -Buten-1-yl), an aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, for example, phenyl, naphthyl), a heterocyclic group (preferably 1 carbon atom) To 32, more preferably a heterocyclic group having 1 to 18 carbon atoms, for example, 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, it is a C3-C18 silyl group, For example, trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), a hydroxyl group, a carboxyl group, a cyano group, a nitro Group, alkoxy group (preferably alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t -Butoxy, dodecyloxy, cycloalkyloxy groups, for example cyclopentyloxy, cyclohexyloxy),

Aryloxy group (preferably C6-C48, more preferably C6-C24 aryloxy group, for example, phenoxy, 1-naphthoxy), heterocyclic oxy group (preferably C1-C32) More preferably, it is a C1-C18 heterocyclic oxy group, For example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), a silyloxy group (preferably C1-C32, More preferably, it is a C1-C18 silyloxy group, For example, trimethylsilyloxy, t-butyl dimethyl silyloxy, diphenylmethyl silyloxy), an acyloxy group (preferably C2-C48), More preferable Preferably it is a C2-C24 acyloxy group, For example, an acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), the alkoxycarbonyloxy group (preferably C2-C48), More preferably, Examples of the alkoxycarbonyloxy group having 2 to 24 carbon atoms For example, an ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy group, for example, cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably carbon number 7) To 32, more preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms, for example, a phenoxycarbonyloxy group, a carbamoyloxy group (preferably 1 to 48 carbon atoms), more preferably 1 to 24 carbon atoms. 24 carbamoyloxy groups, for example, N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy) , Sulfamoyloxy group (preferably a C1-C32, more preferably C1-C24 sulfamoyloxy group, for example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), alkyl Sulfonyloxy groups (preferably C1-C38, more preferably C1-C1) As the alkylsulfonyloxy group of 24, for example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), an arylsulfonyloxy group (preferably C6-C32, more preferably C6-C1-C) As the arylsulfonyloxy group of 24, for example, phenylsulfonyloxy), an acyl group (preferably an acyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms), for example, formyl, acetyl, Pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, methoxycarbonyl, ethoxy Carbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl), aryloxycarbonyl group (preferably having 7 to 32 carbon atoms, More preferably, C7-24 carbon atoms An oxycarbonyl group, for example, phenoxycarbonyl), a carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms), for example carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methyl-N-phenyl Carbamoyl, N, N-dicyclohexylcarbamoyl), amino group (preferably amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, for example, amino, methylamino, N, N-di Butylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), an anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms), for example, an aniline, N-methylanilino), heterocyclic amino group (preferably C1-C32, More preferably, it is C1-C1) Heterocyclic amino group of -18, for example, 4-pyridylamino), carboxyamide group (preferably carboxyamide group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, acetamide , Benzamide, tetradecanamide, pivaloylamide, cyclohexaneamide),

A ureido group (preferably C1-C32, More preferably, it is a C1-C24 ureido group, For example, a ureido, N, N- dimethyl ureido, N-phenyl ureido), an imide group (preferably Preferably an imide group of 36 or less carbon atoms, more preferably 24 or less carbon atoms, for example, N-succinimide, N-phthalimide), an alkoxycarbonylamino group (preferably 2 to 48 carbon atoms) Preferably an alkoxycarbonylamino group having 2 to 24 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxyca An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, phenoxycarbonylamino), and a sulfonamide group ( Preferably carbon 1-48, More preferably, it is a C1-C24 sulfonamide group, For example, methane sulfonamide, butane sulfonamide, benzene sulfonamide, hexadecane sulfonamide, cyclohexane sulfonamide), sulfamoylamino group (preferably Is a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino) or azo group (preferably Preferably it is a C1-C32, More preferably, it is a C1-C24 azo group, for example, a phenyl azo, 3-pyrazolyl azo), an alkylthio group (preferably C1-C48, More preferably, carbon number) 1-24 alkylthio group, for example, methylthio, ethylthio, octylthio, cyclohexylthio), arylthio group (preferably C6-C48, more preferably C6-C24 arylthio group) , For example phenylthio), he Terocyclic thi groups (preferably heterocyclic thi groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 2-benzothiazolylthio, 2-pyridylthio, and 1-phenyltetrazolylthio ), An alkylsulfinyl group (preferably having 1 to 32 carbon atoms, more preferably an alkylsulfinyl group having 1 to 24 carbon atoms, for example, dodecanesulfinyl) and an arylsulfinyl group (preferably having 6 to 32 carbon atoms) Preferably an arylsulfinyl group having 6 to 24 carbon atoms, for example, phenylsulfinyl, an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms) For example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), arylsulfonyl group (preferably Preferably it is C6-C48, More preferably, it is carbon number 6-24 arylsulfonyl group, for example, phenylsulfonyl, 1- naphthylsulfonyl), sulfamoyl group (preferably 32 or less carbon atoms, more preferably 24 or less carbon sulfamoyl groups), for example , Sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl) sulfo groups, phosphonyl groups (preferably Preferably it is a C1-C32, More preferably, it is a C1-C24 phosphonyl group, For example, a phenoxy phosphonyl, octyloxy phosphonyl, phenyl phosphonyl), a phosphinoylamino group (preferably C1-C1-C) 32, More preferably, it is a C1-C24 phosphinoylamino group, For example, diethoxy phosphinoylamino, dioctyloxy phosphinoylamino), or group which combined these is shown.

In the case where the substituents of R ₁ to R ₆ in General Formula (I) and the substituents of R ₁ to R ₄ and R ₆ in General Formula (IV) can be further substituted, General Formula (I) described above It may have a substituent demonstrated by R <_1> -R <_6> , and when it has two or more substituents, those substituents may be same or different.

R ₁ and R ₂ in Formula (I), R ₂ and R ₃ , R ₄ and R ₅ , or / and R ₅ and R ₆ , and R ₁ and R ₂ in Formula (IV), or / and R Each of ₂ and R ₃ independently may be bonded to each other to form a 5, 6, or 7 membered saturated ring or an unsaturated ring. Five atoms, six atoms is formed, and a 7-membered ring is, if due to further substituted, then the optionally substituted by a substituent described above as R ₁ ~ R ₆ of the above-mentioned general formula (Ⅰ), 2 or more When substituted with a substituent, those substituents may be same or different.

R <_7> in 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 demonstrated by the substituent of R <_1> -R <_6> of general formula (I) mentioned above, It is synonymous with an aryl group and a heterocyclic group, and its preferable range is also the same.

When the alkyl group, the aryl group, and the heterocyclic group of R <_7> are the group which can be substituted further, they may be substituted by the substituent demonstrated by the substituent of R <_1> -R <_6> of general formula (I) mentioned above, When substituted with a substituent, those substituents may be same or different.

<Metal atom or metal compound>

In order to obtain specific metal complex compound-I and specific metal complex compound-IV contained in the inkjet ink of this invention, in addition to the said specific compound (Dipyrromethene type compound represented by general formula (I) or general formula (IV)), , Metal atoms or metal compounds are required. In addition, specific metal complex compound-I refers to the dipyrromethene type metal complex compound containing the dipyrromethene type compound represented by General formula (I), and a metal atom or a metal compound. Moreover, specific metal complex compound-IV refers to the dipyrromethene type metal complex compound containing the dipyrromethene type compound represented by general formula (IV), and a metal atom or a metal compound.

As the metal atom or the metal compound which forms the specific metal complex compound-I, the specific metal complex compound-IV together with the specific compound, any metal atom or metal compound capable of forming a complex may be used, and a divalent metal atom, Divalent metal oxides, divalent metal hydroxides, or divalent metal chlorides. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, etc., AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ , GeCl Metal chlorides, such as ₂ , metal oxides, such as TiO and VO, and metal hydroxides, such as Si (OH) ₂ , are also included.

Among these, Fe, Zn, Co, V = O, or Cu is preferable, and Zn is the most preferable from a viewpoint of stability of a complex, spectral characteristic, heat resistance, light resistance, manufacturing suitability, etc.

Next, the preferable range of the dipyrromethene type compound represented by General formula (I) and General formula (IV) is demonstrated.

Preferably, in general formula (I) and general formula (IV), R <_1> and R <_6> is respectively independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, and a cyan. No group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, alinino group, heterocyclic amino group, carboxyamide group, ureido group, imide group, alkoxycarbonylamino group , Aryloxycarbonylamino group, sulfonamide group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, or phosphinoylamino group, R ₂ and R ₅ are each independently Such as hydrogen atom, 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, aryl jade A carbonyl group, a carbamoyl group, an imide group, alkoxycarbonylamino group, sulfonamide group, an azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl represents a group, or a sulfamoyl group, R ₃ And R ₄ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group , Alkoxycarbonyl group, carbamoyl group, alinino group, carboxyamide group, ureido group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group, alkylthio group, arylthio group, heterocyclic thi group, alkylsulfonyl group, An arylsulfonyl group, sulfamoyl group, or phosphinoylamino group; R ₇ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group; and a metal atom or a metal compound Water represents Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or VO.

More preferably, in General Formula (I) and General Formula (IV), R ₁ and R ₆ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, and alkoxy. Carbonyl group, carbamoyl group, amino group, heterocyclic amino group, carboxyamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, azo group, alkylsulfonyl group, arylsulfonyl group, or phosphino A monoamino group, R ₂ and R ₅ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imide group, An alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, Alkoxycarbonyl group, carbamoyl group, carboxyamide group, ureido group, imide group, alkoxycarbonylamino group, sulfonamide group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, or sulfamo Represents a diary, R ₇ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and the metal atom or metal compound represents Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or VO Indicates.

Especially preferably, in general formula (I) and general formula (IV), R <_1> and R <_6> is respectively independently a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a heterocyclic amino group, a carboxyamide group, A ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an azo group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, and R <_2> and R <_5> respectively independently represents an alkyl group, an aryl group, and a hetero ring Group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group, or arylsulfonyl group, R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group , R ₇ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and the metal atom or metal compound represents Zn, Cu, Co, or VO.

R ₁ and R ₂ in Formula (I), R ₂ and R ₃ , R ₄ and R ₅ , or / and R ₅ and R ₆ , and R ₁ and R ₂ in Formula (IV), or / and R _{When 2} and R ₃ are each independently, bonded to each other to form a 5-membered, 6-membered, or 7-membered saturated or unsaturated ring having no substituent, for example, a pyrrole ring, a furan ring, a 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 A ring is mentioned, Preferably a benzene ring and a pyridine ring are mentioned.

Moreover, when it has a substituent, the substituent demonstrated by R <_1> -R <_6> of general formula (I) mentioned above is mentioned, for example, and a preferable substituent is also the same as R <_1> -R <_6> .

In addition, a tautomer may be sufficient as the compound represented by general formula (IV).

<Compound represented by General Formula (II-1)>

Dipyrromethene metal complex (specific metal complex compound-I) obtained from the dipyrromethene compound represented by the general formula (I) and the metal atom or the metal compound and the dipyrromethene compound represented by the general formula (IV) and the metal atom Or as a preferable embodiment of the dipyrromethene metal complex (specific metal complex compound-IV) obtained with a metal compound, it is a compound represented by the following general formula (II-1) (Hereinafter, it is suitably called "specific metal complex compound-II-I". ).

General formula (Ⅱ-1)

R <_1> -R <_6> in general formula (II-1) represents a hydrogen atom or a substituent each independently, is the same meaning as R <_1> -R <_6> in general formula (I), and its preferable aspect is also the same.

Ma in general formula (II-1) represents a metal atom or a metal compound, is synonymous with the metal atom or metal compound demonstrated in the said specific metal complex compound-I, and its preferable range is also the same.

R <_7> in general formula (II-1) is synonymous with R <_7> in general formula (I), and its preferable aspect is also the same.

X <_1> in general formula (II-1) represents group which can couple | bond with Ma, and any group can be any group which can couple | bond with metal atom Ma, and water, alcohols (for example, methanol, ethanol, propanol) And the compounds described in &quot; metal chelates &quot; [1] Sakaguchi Takechi Ueno Keihei (1995 Nanko sugar), copper [2] (1996), copper [3] (1997) and the like. .

X <_2> in general formula (II-1) represents group required in order to neutralize the electric charge of Ma, For example, a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, etc. are mentioned.

X ₁ and X ₂ in General Formula (II-1) may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring with Ma. The 5-membered, 6-membered, and 7-membered ring formed may be a saturated ring or an unsaturated ring. In addition, the 5-membered, 6-membered, and 7-membered rings may be composed of only carbon atoms, and may form a hetero ring having at least one atom selected from a nitrogen atom, an oxygen atom, and / or a sulfur atom.

<Compound represented by General Formula (II-2)>

Dipyrromethene metal complex (specific metal complex compound-I) obtained from the dipyrromethene compound represented by the general formula (I) and the metal atom or the metal compound, and the dipyrromethene compound represented by the general formula (IV) and the metal atom Or as a preferable embodiment of the dipyrromethene metal complex (specific metal complex compound-IV) obtained from a metal compound, it is represented by the following general formula (II-2) (Hereinafter, it is suitably "specific metal complex compound-II-2." Can be used as appropriate.

General formula (Ⅱ-2)

R <_1> -R <_6> in general formula (II-2) is synonymous with R <_1> -R <_6> in general formula (I), and its preferable aspect is also the same.

The substituent represented by R <_8> -R <_13> in general formula (II-2) is synonymous with the substituent represented by R <_1> -R <_6> of the compound represented by general formula (I), and its preferable aspect is also the same. When the substituent represented by R <_8> -R <_13> of the compound represented by general formula (II-2) is a group which can be substituted further, it is substituted by the substituent demonstrated by R <_1> -R <_6> of the compound represented by general formula (I). May be sufficient, and when substituted by two or more substituents, those substituents may be same or different.

R <_7> in general formula (II-2) is synonymous with R <_7> in general formula (I), and its preferable aspect is also the same.

R <_14> in general formula (II-2) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and each of those groups is synonymous with R <_7> in general formula (I). The preferable range of R <_14> is the same as the preferable range of said R <_7> . When R <_14> is group which can be substituted further, it may be substituted by the group demonstrated by the substituent of R <_1> -R <_6> of the compound represented by general formula (I), and when they are substituted by two or more substituents, those substituents May be the same or different.

Ma in general formula (II-2) represents a metal atom or a metal compound, is synonymous with the metal atom or metal compound demonstrated in the said specific metal complex compound-I, and its preferable range is also the same.

R <_8> and R <_9> , R <_9> and R <_10> , R <_11> and R <_12> , R <_12> and R <_{13> in} General formula (II-2) respectively independently combine with each other and saturate 5, 6, or 7 atoms. A ring or an unsaturated ring may be formed, and these have the same meaning as R ₁ and R ₂ , R ₂ and R ₃ , R ₄ and R ₅ , or / and R ₅ and R ₆ of the compound represented by General Formula (I). The preferable aspect is also the same.

<Compound represented by General Formula (III)>

Preferred embodiments of specific metal complex compound-I and specific metal complex compound-IV include compounds represented by the following general formula (III) (hereinafter, appropriately referred to as “specific metal complex compound-II”).

  General formula (Ⅲ)

Formula (Ⅲ) of R ₂ ~ R _5, and R ₇ are each formula (Ⅰ) means the same as in R ₁ ~ R _6, and R _7, are also the same preferred embodiment.

Ma in General formula (III) represents a metal atom or a metal compound, is synonymous with the metal atom or metal compound demonstrated by the said specific metal complex compound-I, and its preferable range is also the same.

In general formula (III), R <_8> and R <_9> are respectively independently an alkyl group (preferably C1-C36, More preferably, it is a C1-C12 linear, branched chain, or cyclic alkyl group, for example, For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl groups (preferably Preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, vinyl, allyl, 3-buten-1-yl), and an aryl group (preferably 6 to 36 carbon atoms) Preferably an aryl group having 6 to 18 carbon atoms, for example, phenyl, naphthyl), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms), for example, 2 -Thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazole , Benzotriazol-1-yl), an alkoxy group (preferably an alkoxy group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms), for example, methoxy, ethoxy, propyloxy, butoxy, hex Siloxy, 2-ethylhexyloxy, dodecyloxy, cyclohexyloxy), aryloxy (preferably an aryloxy group having 6 to 24 carbon atoms, more preferably 1 to 18 carbon atoms), for example, phenoxy , Naphthyloxy), an alkylamino group (preferably an alkylamino group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms), for example, methylamino, ethylamino, propylamino, butylamino, hexylamino, 2 Ethylhexylamino, isopropylamino, t-butylamino, t-octylamino, cyclohexylamino, N, N-diethylamino, N, N-dipropylamino, N, N-dibutylamino, N-methyl -N-ethylamino), arylamino (preferably C6-C36, more preferably carbon Examples of the arylamino group having 6 to 18 carbon atoms include phenylamino, naphthylamino, N, N-diphenylamino, N-ethyl-N-phenylamino, or heterocyclic amino groups (preferably having 1 to 24 carbon atoms). And, more preferably, a heterocyclic amino group having 1 to 12 carbon atoms, for example, 2-aminopyrrole, 3-aminopyrazole, 2-aminopyridine, 3-aminopyridine).

The group which the alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylamino group, arylamino group, or heterocyclic amino group of R <_8> and R <_9> can further substitute in general formula (III). In the case, it may be substituted by the substituent demonstrated by R <_1> -R <_6> of the said General formula (I), and when substituted by two or more substituents, those substituents may be same or different.

In General Formula (III), X ₃ represents NR, a nitrogen atom, an oxygen atom, or a sulfur atom, and X ₄ represents NRa, an oxygen atom, or a sulfur atom. R and Ra are each independently a hydrogen atom, an alkyl group (preferably a linear, branched, or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, for example, methyl, ethyl , Propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl group (preferably 2 carbon atoms) To 24, more preferably an alkenyl group having 2 to 12 carbon atoms, for example, vinyl, allyl, 3-buten-1-yl), and an aryl group (preferably having 6 to 36 carbon atoms, more preferably 6 to 6 carbon atoms). As an aryl group of -18, for example, phenyl, naphthyl), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms), for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, Zotriazol-1-yl) and acyl groups (preferably acyl groups having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms), for example, acetyl, pivaloyl, 2-ethylhexyl, benzoyl and cyclo Hexanoyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms), for example, methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclohexylsul And arylsulfonyl group (preferably arylsulfonyl group having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms), for example, phenylsulfonyl and naphthylsulfonyl.

The alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkyl sulfonyl group, and arylsulfonyl group of R and Ra are further substituted with groups described by the substituents of R ₁ to R ₆ of the general formula (I). May be sufficient, and when replacing by the some substituent, those substituents may be same or different.

In General Formula (III), Y ₁ represents NRc, a nitrogen atom, or a carbon atom, and Y ₂ represents a nitrogen atom or a carbon atom. Rc is synonymous with R of said X <_3> .

In general formula (III), R <_8> and Y <_1> combine with each other, and together with R <_8> , Y <_1> and a carbon atom, a 5-membered ring (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, Tetrahydrothiophene, pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, 6-membered ring (e.g. cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, You may form pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline), or a seven-membered ring (for example, cycloheptane, hexamethyleneimine).

In general formula (III), R <_9> and Y <_2> may combine with each other and may form the 5-membered, 6-membered, or 7-membered ring with R <_9> , Y <_2> and a carbon atom. Examples of the 5-membered, 6-membered, and 7-membered ring formed include rings in which one bond is changed to a double bond from the ring formed of R ₈ , Y _1, and a carbon atom.

In the general formula (III), in the case where the 5-membered, 6-membered and 7-membered rings formed by R ₈ and Y ₁ , and R ₉ and Y ₂ are bonded to each other are rings which can be further substituted, the above general formula (III) _{May be} substituted with the group described by the substituent of R ₂ to R ₅ , and when substituted with two or more substituents, those substituents may be the same or different.

In general formula (III), X <_5> represents group which can couple with Ma, and the group similar to X <_1> in the said General formula (II-1) is mentioned.

a represents 0, 1, or 2.

As a preferable aspect of a compound represented by general formula (III), R <_2> -R <_5> , R <_7> and Ma are the preferable aspect described in description of the compound represented by general formula (I), respectively, X <_3> is NR (R Is a hydrogen atom, an alkyl group), a nitrogen atom or an oxygen atom, X ₄ is NRa (Ra is a hydrogen atom, an alkyl group, a heterocyclic group) or an oxygen atom, Y ₁ is NRc (Rc is a hydrogen atom, or an alkyl group), nitrogen An atom or a carbon atom, Y ₂ is a nitrogen atom or a carbon atom, X ₅ is a group bonded through an oxygen atom, R ₈ and R ₉ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group Or an alkylamino group, or R ₈ and Y ₁ are bonded to each other to form a 5 or 6 membered ring, or R ₉ and Y ₂ are bonded to each other to form a 5 or 6 membered ring, and a is 0 or 1 is shown.

As a more preferable aspect of the compound represented by general formula (III), R <_2> -R <_5> , R <_7> , Ma are the especially preferable aspect described in description of the compound represented by general formula (I), respectively, X <_3> and X <_4> Is an oxygen atom, Y ₁ is NH, Y ₂ is a nitrogen atom, X ₅ is a group bonded through an oxygen atom, R ₈ and R ₉ are each independently an alkyl group, an aryl group, a heterocyclic group, alkoxy A group or an alkylamino group, or R ₈ and Y ₁ are bonded to each other to form a 5 or 6 membered ring, or R ₉ and Z ₂ are bonded to each other to form a 5 or 6 membered ring, a is 0 Or 1 is represented.

Although the molar extinction coefficient of specific metal complex compound-I-specific metal complex compound-IV (dipyrromethene type metal complex compound) in this invention differs with the structure of a compound, it is very high. From the viewpoint of the film thickness, the molar extinction coefficient is preferably as high as possible. Moreover, 520 nm-580 nm are preferable and, as for the maximum absorption wavelength (lambda) max, from a viewpoint of color purity improvement, 530 nm-570 nm are more preferable. Moreover, compared to a pyrazoloazole-type azomethine pigment | dye, the dipyrromethene type metal complex compound used for this invention is 1) absorption is sharp, and the absorption of 450 nm which is a requirement which is essential for the blue color of a color filter is small (transmittance) High color). 2) The extinction coefficient of the dipyrromethene-based metal complex compound is about 130000, while the extinction coefficient of the pyrazoloazole-based azomethine pigment is about 60000, and the absorption coefficient is high (high color value). 3) The dipyrromethene-based metal complex compound is excellent in heat resistance and light resistance, and further improves heat resistance and light resistance by being used together with a phthalocyanine-based dye described later. In addition, a maximum absorption wavelength and molar extinction coefficient are measured by the spectrophotometer UV-2400PC (made by Shimadzu Corporation).

It is preferable that melting | fusing point of specific metal complex compound-I in this invention is not too high from a soluble viewpoint.

Next, specific metal complex compound-I in the present invention (including specific metal complex compound-II-I, specific metal complex compound-II-2, specific metal complex compound III, and specific metal complex compound-IV) Although the specific example of is shown below, this invention is not limited to these.

Metal complex compound-I (specific metal complex compound II-1, specific metal complex compound II-2, specific metal complex compound III, and specific metal complex compound IV) obtained from the dipyrromethene-based compound represented by the general formula (I) Include U.S. Patent Nos. 4,774,339, 5,433,896, Japanese Patent Laid-Open No. 2001-240761, 2002-155052, Patent 3614586, Aust. J. Chem, 1965, 11, 1835-1845, J. H. Boger et al, Heteroatom Chemistry, Vol. 1, No. 5,389 (1990) and the like.

The ink for inkjet of this invention may be used individually by 1 type, and may use 2 or more types of said specific metal complex compound-I-the said specific metal complex compound-IV, respectively.

Dipyrromethene-based metal complex compounds (specific metal complex compound-I, specific metal complex compound-II-I, specific metal complex compound-II-2, specific metal complex compound-III, and specific metal complex compound-IV described above) It is preferable that the total content in the inkjet ink of 1 to 20% by mass is included. When it is less than 1 mass%, the film thickness becomes thick in order to achieve the optical density required as a color filter. Therefore, it is not preferable because the black matrix also needs to be thickened and black matrix formation may be difficult. When it exceeds 20 mass%, since an ink viscosity becomes high and discharge becomes difficult and dissolution to a solvent may become difficult, it is unpreferable.

<Tetraazaporphyrin-based cyan dye represented by General Formula (A)>

The ink for ink jet of the present invention is the above-described dipyrromethene-based metal complex compound (specific metal complex compound-I, specific metal complex compound-II-1, specific metal complex compound-II-2, specific metal complex compound-III, In addition to the specific metal complex compound-IV), by using together the tetraaza porphyrin-based cyan pigment (henceforth "specific pigment-A" suitably) represented by the following general formula (A), it is excellent in color purity It is excellent in color fastness and can manufacture the color filter using the inkjet ink. In particular, it can use suitably for CCD and CMOS.

Below, each group of the tetraaza porphyrin type cyan pigment represented by general formula (A) is demonstrated.

General formula (A)

In General Formula (A), M ¹ represents a metal atom or a metal compound. The metal atom or metal compound may be any metal atom or metal compound capable of forming a complex, and includes divalent metal atoms, divalent metal oxides, divalent metal hydroxides, or divalent metal chlorides.

M ¹ in General Formula (A) is, for example, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, etc., and AlCl, InCl, Metal chlorides such as FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ , GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ .

Z ¹ , Z ² , Z ³ , and Z ⁴ in General Formula (A) each independently represent an atomic group necessary for forming a 6-membered ring composed of atoms selected from carbon atoms, nitrogen atoms, and hydrogen atoms . The 6-membered ring may be a saturated ring, an unsaturated ring, an unsubstituted ring, or may have a substituent. In addition, other 5- or 6-membered rings may be condensed. The six-membered ring includes benzene ring, cyclohexane ring, pyridine ring, pyrimidine ring, pyrazine ring and the like.

580 nm-700 nm are preferable, and, as for the maximum absorption wavelength (lambda) max of the specific pigment | dye -A in this invention, from a viewpoint of color purity improvement, 600 nm-680 nm are more preferable. In addition, the maximum absorption wavelength was measured similarly to specific metal complex compound-I.

<Phthalocyanine-based dye represented by general formula (B)>

Among the tetraaza porphyrin-based cyan dyes represented by the general formula (A), particularly, phthalocyanine-based dyes represented by the following general formula (B) (hereinafter, appropriately referred to as "specific pigments -B") are preferable.

 General formula (B)

In general formula (B), M <^2> is synonymous with the example of M <^{1> in} the compound represented by said general formula (A), and its preferable aspect is also the same.

In General Formula (B), R ¹⁰¹ to R ¹¹⁶ each independently represent a hydrogen atom or a substituent, and the substituents represented by R ¹⁰¹ to R ¹¹⁶ are represented by R ₁ to R ₆ in General Formula (I) described above. It is synonymous with the illustration of a substituent, and its preferable aspect is also the same. When the substituent of R <^101> -R <^116> of the compound represented by general formula (B) is a group which can be substituted further, you may substitute by the substituent demonstrated by R <_1> -R <_6> in general formula (I) mentioned above, When substituted with two or more substituents, those substituents may be the same or different.

Moreover, as one of the preferable aspects of the substituent represented by R <^101> -R <^116> , group represented by "* -S (= O) _m- (L) _n- (A) _p " (henceforth a substituent A) is mentioned. have. A each independently represents a hydrogen atom or a substituent, and the definition of the substituent is the same as the substituent represented by R ¹⁰¹ to R ¹¹⁶ . * Represents a bonding position with a benzene ring. Moreover, it is preferable that at least 1 of R <^101> -R <^116> is substituent A, and it is preferable that 1-4 are substituent A. It is also preferable that substituent A is one with each benzene ring group in general formula (B). When several substituent A is contained, they may be same or different.

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

L represents an aliphatic or aromatic linking group, and a plurality of Ls may be the same or different. As an aliphatic coupling group represented by L, it may be unsubstituted or may have a substituent, a C1-C20 aliphatic group is preferable, and a C1-C15 aliphatic group is more preferable. For example, a methylene group, ethylene group, a propylene group, butylene group, etc. are mentioned.

The aromatic linking group represented by L may be unsubstituted or may have a substituent, an aromatic group having 6 to 20 carbon atoms is preferable, and an aromatic group having 6 to 16 carbon atoms is more preferable. For example, a phenylene group, a naphthylene group, etc. are mentioned, Most preferably, it is a phenylene group.

In addition, when n is 0, A and S are directly bonded.

Further, in view of the effects of the present invention, A represents a halogen atom, an aliphatic group (alkyl group, etc.), cyano group, carboxy group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, hydroxy group, aliphatic oxy group, carbamoyloxy group, hetero Cyclic oxy, aliphatic oxycarbonyloxy group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio group, arylthio group, aliphatic sulfonyl group, arylsulfo Nyl group, sulfamoyl group, aliphatic sulfonylcarbamoyl group, arylsulfonylcarbamoyl group, aliphatic carbonyl sulfamoyl group, arylcarbonyl sulfamoyl group, aliphatic sulfonyl sulfamoyl group, aryl sulfonyl sulfamoyl group, imide group, sulf It is preferred to give up or combine these.

In the present invention, the plurality of A's in the molecule may be the same as or different from each other, and at least one of the plurality of A's is -OY, -COOY, -SO ₃ Y, -CON (Y) CO-, CON It is preferred to have (Y) SO ₂ -or -SO ₂ N (Y) CO-.

The _{-OY, -COOY, -SO 3 Y,} -CON (Y) CO-, CON (Y) SO 2 - or -SO ₂ N (Y) CO- is, and may be bonded to the linking group L, a linking group L It may be directly bonded to -S (= O) _m -without interposing. When directly bonded to -S (= O) _m -without intervening the linking group L, R ¹ is preferably -OY, and is directly bonded to the tetraazaporphyrin ring together with -S (= O) _m-. Preference is given to (m = 2) constituting —SO ₃ Y.

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, and Li, Na and K are preferable. Examples of the base forming the conjugated acid represented by Y include tertiary amines (for example, triethylamine, tripropylamine, tributylamine, diisopropylethylamine, N-methylpiperidine, and 4-methylmor). Pauline), guanidines (for example, guanidine, N, N-diphenylguanidine, 1,3-di-o-tolylguanidine), pyridines (for example, pyridine, 2-methylpyridine), etc. are mentioned. have. Among them, triethylamine, tripropylamine, tributylamine, N, N-diphenylguanidine and 1,3-di-o-tolylguanidine are preferable.

Hereinafter, the example (T-1-T141) of the substituent of R <^101> -R <^116> of specific pigment | dye-B is shown. However, in this invention, it 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, T-128, T-129, T-140, and T-141 are mentioned.

Next, the preferable range of the phthalocyanine type pigment | dye represented by General formula (B) is demonstrated.

위치의 치환체 (

치환체) 로서, (R¹⁰¹ 과 R¹⁰⁴), (R¹⁰⁵ 와 R¹⁰⁸), (R¹⁰⁹ 와 R¹¹²), 및 (R¹¹³ 과 R¹¹⁶) 의 조합 중 적어도 1 조에 치환기를 갖고 있거나, β 위치의 치환체 (β 치환체) 로서 (R¹⁰² 와 R¹⁰³), (R¹⁰⁶ 과 R¹⁰⁷), (R¹¹⁰ 과 R¹¹¹), 및 (R¹¹⁴ 와 R¹¹⁵) 의 조합 중 적어도 1 조에 치환기를 갖고 있거나, 혹은

위치, 및 β 위치의 치환체로서 (R¹⁰¹ 과 R¹⁰³ 및/또는 R¹⁰² 와 R¹⁰⁴), (R¹⁰⁵ 와 R¹⁰⁷ 및/또는 R¹⁰⁶ 과 R¹⁰⁸), (R¹⁰⁹ 와 R¹¹¹ 및/또는 R¹¹⁰ 과 R¹¹²), 및 (R¹¹³ 과 R¹¹⁵ 및/또는 R¹¹⁴ 와 R¹¹⁶) 의 조합 중에서 적어도 1 조에 치환기를 갖고 있는 것이 바람직하다. The phthalocyanine pigment | dye represented by the said general formula (B),

Substituent at position (

Substituent) and has a substituent in at least one of a combination of (R ¹⁰¹ and R ¹⁰⁴ ), (R ¹⁰⁵ and R ¹⁰⁸ ), (R ¹⁰⁹ and R ¹¹² ), and (R ¹¹³ and R ¹¹⁶ ), A substituent (β substituent) has a substituent in at least one group of a combination of (R ¹⁰² and R ¹⁰³ ), (R ¹⁰⁶ and R ¹⁰⁷ ), (R ¹¹⁰ and R ¹¹¹ ), and (R ¹¹⁴ and R ¹¹⁵ ), or

Position, and substituents at the 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 It is preferable to have a substituent in at least 1 group among the combination of ¹¹⁰ and ^R112 ), and ( ^R113 and ^R115 and / or ^R114 and ^R116 ).

Here, as a substituent represented by said R <^101> -R <^116> , 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, an alkoxy group, an aryl jade Time period, 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, heterocyclic amino group, amino group, anilino group, carboxyamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, sulfamoylamino group, Azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group, phosphonyl A group and a pocifinoylamino group are mentioned. Examples of M ² include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, TiO, VO, and the like.

치환체 (모노 치환체) 로서 (R¹⁰¹ 또는 R¹⁰⁴), (R¹⁰⁵ 또는 R¹⁰⁸), (R¹⁰⁹ 또는 R¹¹²), 및 (R¹¹³ 또는 R¹¹⁶) 중 적어도 하나에 치환기를 갖거나, 또는, β 치환체 (모노 치환체) 로서 (R¹⁰² 또는 R¹⁰³), (R¹⁰⁶ 또는 R¹⁰⁷), (R¹¹⁰ 또는 R¹¹¹), 및 (R¹¹⁴ 또는 R¹¹⁵) 중 적어도 하나에 치환기를 갖는 화합물이다. As a preferable range of the phthalocyanine type pigment | dye represented by the said General formula (B),

A substituent (mono substituent) has a substituent on at least one of (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ), or β As a substituent (mono substituent), it is a compound which has a substituent in at least one of (R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and (R ¹¹⁴ or R ¹¹⁵ ).

Here, as a substituent represented by said R <^101> -R <^116> , Preferably, they are 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 , Aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, alinino group, carboxyamide group, ureido group, imide group, alkoxy Carbonylamino group, aryloxycarbonylamino group, sulfonamide group, sulfamoylamino group, azo group, alkylthio group, arylthio group, heterocyclic thi group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulf A pamoyl group, a sulfo group, and a phosphinoylamino group are mentioned. Examples of M ² include Zn, Pd, Cu, Ni, Co, TiO, VO, and the like.

치환체로서 (R¹⁰¹ 또는 R¹⁰⁴), (R¹⁰⁵ 또는 R¹⁰⁸), (R¹⁰⁹ 또는 R¹¹²), 및 (R¹¹³ 또는 R¹¹⁶) 내의 적어도 3 개에 치환기를 갖거나, 또는 β 치환체로서 (R¹⁰² 또는 R¹⁰³), (R¹⁰⁶ 또는 R¹⁰⁷), (R¹¹⁰ 또는 R¹¹¹), 및 (R¹¹⁴ 또는 R¹¹⁵) 내의 적어도 3 개에 치환기를 갖는 화합물이다. As a more preferable range of the phthalocyanine-based pigment represented by the general formula (B),

At least three substituents in (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) as substituents, or (R) as β substituents ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and at least three of (R ¹¹⁴ or R ¹¹⁵ ) are compounds having a substituent.

Here, as a substituent represented by said R <^101> -R <^116> , Preferably, it is 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, an aryl octane. Time period, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, carboxyamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, sulfamoyl Amino groups, azo groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, sulfamoyl groups, and sulfo groups are mentioned. M ² is, there may be mentioned Zn, Pd, Cu, Ni, Co, VO, etc.

치환체로서 (R¹⁰¹ 또는 R¹⁰⁴), (R¹⁰⁵ 또는 R¹⁰⁸), (R¹⁰⁹ 또는 R¹¹²), 및 (R¹¹³ 또는 R¹¹⁶) 내의 적어도 3 개에 동일한 치환기를 갖거나, 또는 β 치환체로서 (R¹⁰² 또는 R¹⁰³), (R¹⁰⁶ 또는 R¹⁰⁷), (R¹¹⁰ 또는 R¹¹¹), 및 (R¹¹⁴ 또는 R¹¹⁵) 내의 적어도 3 개에 동일한 치환기를 갖는 화합물이다. As a more preferable range of the phthalocyanine pigment | dye represented by the said General formula (B),

At least three of (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) as substituents, or as β substituents ( R ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and at least three of (R ¹¹⁴ or R ¹¹⁵ ) are compounds having the same substituent.

Here, as a substituent represented by said R <^101> -R <^116> , Preferably, they are 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, a heterocyclic oxy group, Acyl group, alkoxycarbonyl group, carbamoyl group, carboxyamide group, ureido group, imide group, sulfonamide group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, sulfo group. . Examples of M ² include Zn, Pd, Cu, Ni, Co, or VO.

치환체로서 (R¹⁰¹ 또는 R¹⁰⁴), (R¹⁰⁵ 또는 R¹⁰⁸), (R¹⁰⁹ 또는 R¹¹²), 및 (R¹¹³ 또는 R¹¹⁶) 내의 적어도 3 개에 치환기를 갖거나, 또는 β 치환체로서 (R¹⁰² 또는 R¹⁰³), (R¹⁰⁶ 또는 R¹⁰⁷), (R¹¹⁰ 또는 R¹¹¹), 및 (R¹¹⁴ 또는 R¹¹⁵) 내의 적어도 3 개에 치환기를 가지며, 그 치환기가 전부 동일한 화합물이다. As an especially preferable range of the phthalocyanine type pigment | dye represented by the said General formula (B),

At least three substituents in (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) as substituents, or (R) as β substituents ¹⁰² or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and at least three of (R ¹¹⁴ or R ¹¹⁵ ) have substituents, all of which are the same compounds.

Here, as a substituent represented by said R <^101> -R <^116> , Preferably, they are 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, and carbamoyl group , An alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a sulfo group. Examples of M ² include Zn, Pd, Cu, Ni, Co, or VO.

치환체로서 (R¹⁰¹ 또는 R¹⁰⁴), (R¹⁰⁵ 또는 R¹⁰⁸), (R¹⁰⁹ 또는 R¹¹²), 및 (R¹¹³ 또는 R¹¹⁶) 내의 적어도 3 개에 치환기를 갖거나, β 치환체로서 (R¹⁰² 또는 R¹⁰³), (R¹⁰⁶ 또는 R¹⁰⁷), (R¹¹⁰ 또는 R¹¹¹), 및 (R¹¹⁴ 또는 R¹¹⁵) 내의 적어도 3 개에 치환기를 가지며, 그 치환기 전부가 동일한 화합물로서, 그 R¹⁰¹ ∼ R¹¹⁶ 으로 나타내는 치환기로는, 할로겐 원자, 알킬기, 헤테로 고리기, 카르복실기, 알콕시기, 아릴옥시기, 헤테로 고리 옥시기, 알콕시카르보닐기, 카르바모일기, 알킬술포닐기, 아릴술포닐기, 술파모일기, 또는 술포기를 들 수 있다. M² 로는, Zn 등을 들 수 있다. As a most preferable range of the phthalocyanine pigment | dye represented by the said General formula (B),

At least three substituents in (R ¹⁰¹ or R ¹⁰⁴ ), (R ¹⁰⁵ or R ¹⁰⁸ ), (R ¹⁰⁹ or R ¹¹² ), and (R ¹¹³ or R ¹¹⁶ ) as substituents, or (R ¹⁰² as β substituents) Or R ¹⁰³ ), (R ¹⁰⁶ or R ¹⁰⁷ ), (R ¹¹⁰ or R ¹¹¹ ), and at least three substituents in (R ¹¹⁴ or R ¹¹⁵ ), and all of the substituents are the same compound, wherein R ¹⁰¹ to ^Examples of the substituent represented by R ¹¹⁶ include a halogen atom, an alkyl group, a heterocyclic group, a carboxyl 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 sulfo groups. Examples of M ² include Zn.

Below, the specific example of the tetraaza porphyrin-type cyano pigment | dye represented by general formula (A) (containing the phthalocyanine pigment | dye represented by general formula (B)) is shown. However, in this invention, it is not limited to these.

<Synthesis example>

Next, the synthesis example of the pigment | dye represented by the said General formula (A) or (B) is explained in full detail with reference to the following scheme D which takes the synthesis | combination of the exemplary compound CI-29 mentioned above as an example.

(Synthesis of Intermediate A)

Sodium carbonate (16.5 g, 0.156 mol) is 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), and 60 ° C. Heated to and stirred for 3 hours. The reaction mixture was poured into 10% saline (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 solid obtained here, and 31% hydrogen peroxide (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 intermediate A24g (yield 49% from 3-nitrophthalonitrile).

(Synthesis of Intermediate B)

200 ml of acetonitrile were added to 67.3 g (0.2 mol) of intermediates A, and it heated and stirred at 70 degreeC-75 degreeC. 37 ml of phosphorus oxychloride was added dropwise to this dispersion. After completion of the dropwise addition, the mixture was stirred at 70 ° C to 75 ° C for 4 hours to complete the reaction. After completion of the reaction, the reaction solution was cooled to room temperature and then poured into 2000 ml of water with stirring to precipitate crystals. The crystals were filtered off and washed with water and then dispersed in 300 ml of 2-propanol. The dispersion was stirred for 1 hour, then filtered and dried. 63.0g (yield: 99.5%) of intermediate B was obtained.

(Synthesis of Intermediate C)

250 ml of acetonitrile were added to the intermediate B50.0g (0.15 mol) obtained by the above method, and cooled to 5 ° C and stirred. 31.0 g of 3-ethoxypropylamine were added dropwise to this solution. After completion of dropping, 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 off and washed with water and then dispersed in 500 ml of 2-propanol. After stirring at room temperature for 2 hours, it was filtered and dried. 52.6g (yield: 87.7%) of intermediate C was obtained.

(Synthesis of CI-29)

30 ml of diethylene glycol and 100 ml of 2-methoxypropanol were prepared in 7.99 g (0.02 mol) of intermediate C and 1.28 g (0.01 mol) of o-phthalonitrile obtained by the above-described method, and 3.36 g (0.01 mol) of intermediate A. Added and heated to 100 ° C. and stirred. 3.87 g of ammonium benzoate and 1.26 g of copper acetate were added to this solution. After the addition was completed, the mixture was stirred at 95 ° C to 100 ° C for 6 hours to complete the reaction. After cooling this reaction liquid to room temperature, 60 ml of methanol was added, and 75 ml of hydrochloric acid was poured into the aqueous solution diluted with 800 ml of water, stirring. The precipitated crystals were filtered off, washed with water and dried. The crystals were dissolved by heating in 250 ml of methanol and filtered to remove insoluble matters. This filtrate was concentrated under reduced pressure, and 250 ml of ethyl acetate was added to the residue, followed by stirring. The dispersed crystals were filtered off 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 (lambda) max = 665.6 nm and (epsilon) = 84600, respectively.

The maximum absorption wavelength (lambda max) and the molar extinction coefficient ((epsilon)) of the obtained pigment | dye were measured by the spectrophotometer UV-2400PC (made by Shimadzu Corporation) of the maximum absorption wavelength ((lambda) max) and molar extinction coefficient ((epsilon)) in ethyl acetate. Were 623.4 nm and 47000, respectively.

Moreover, also about other exemplary compounds other than the pigment | dye CI-29 mentioned above, it can synthesize | combine by the same method as the above.

From a viewpoint of color purity improvement, 580 nm-700 nm are preferable, and, as for the maximum absorption wavelength (lambda) max of the specific pigment | dye-B in this invention, 600 nm-680 nm are more preferable. In addition, the maximum absorption wavelength was measured with the spectrophotometer UV-2400PC (made by Shimadzu Corporation).

Although content in the inkjet ink when containing the said specific pigment | dye-A or specific pigment | dye-B differs by each molar extinction coefficient, the required spectral characteristic, film thickness, etc., it is for the inkjet in this invention It is preferable that it is 1 mass%-80 mass% with respect to the total solid of ink, and it is more preferable that it is 10 mass%-70 mass%.

Specific dye-A and specific dye-B may be contained individually in the inkjet ink in this invention, respectively, and may be used in combination of 2 or more type.

Moreover, in order to produce a blue filter array, a dipyrromethene type metal complex compound (The said specific metal complex compound -I-the said specific metal complex compound -IV is included), the said specific pigment | dye-A, and the said specific pigment | dye-B. It is preferable to mix and use at least 1 sort (s) of.

At this time, the respective mixing ratios differ depending on the respective molar extinction coefficients, the required spectroscopic characteristics, the film thickness, and the like, but preferably in the content ratio (weight ratio) (total content of the dipyrromethene-based metal complex compound): ( Total content of specific dye-A and specific dye-B) = 20: 1 to 1:20. Preferably it is used in the range of 10: 1-1:10.

The dipyrromethene-based metal complex compound described above is excellent in light resistance and heat resistance, and has resistance (alkali resistance) to alkaline solvents used for washing at the time of color filter production, repair of alignment film, and the like. Moreover, the compound hardly inhibits the polymerization reaction of the polymerizable monomer described later, and the polymerization reaction can be advanced by adding a smaller amount of heat and light energy than conventionally.

<Solvent>

It is preferable that the ink for inkjets of this invention contains a solvent. The solvent is not particularly limited as long as it satisfies the solubility of each component and the boiling point of the solvent described later. However, the solvent is preferably selected in consideration of the solubility, applicability, 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 and oxy. Ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and the like; 3-oxypropionic acid such as methyl 3-oxypropionate and ethyl 3-oxypropionate Alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate and the like; 2-oxypropionate alkyl esters, such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate, for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate and 2-methoxypropionic acid Propyl, 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2-methylpropionate, 2-e Ethyl oxy-2-methylpropionate, etc .; Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate and the like; Ethers such as diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl 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 and the like; Ketones such as cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons such as xylene and the like; Dicyclohexylmethylamine etc. are mentioned preferably. You may use these 1 type or in combination or 2 or more types.

30-90 mass% is preferable with respect to ink whole quantity, and, as for content of the solvent in the inkjet ink of this invention, 50-90 mass% is more preferable. If it is 30 mass% or more, the amount of ink to be beaten in one pixel is maintained, and it spreads while the ink satisfies well in a pixel. Moreover, if it is 90 mass% or less, the amount of components other than the solvent for forming the functional film (for example, a pixel) in ink can be kept more than predetermined amount. For this reason, when forming a color filter, the ink required amount per pixel does not become large too much, for example, when ink is provided to the recessed part partitioned by the partition by the inkjet method, it is the case of the ink from a recessed part. It is possible to suppress the occurrence of overflowing and color mixing with the adjacent pixels.

It is preferable that the inkjet ink of this invention contains the solvent with a high boiling point among the above-mentioned solvents from the discharge property of the ink with respect to a nozzle, and the wettability with respect to a board | substrate. Since the solvent having a low boiling point evaporates quickly even on the inkjet head, the viscosity of the ink on the head, precipitation of solids, etc. are easily caused, and the discharge property is often accompanied. In addition, even when the ink reaches the substrate surface and spreads while wet on the substrate surface, the solvent evaporates at the edges which spread while wet, resulting in an increase in viscosity of the ink, which is caused by the phenomenon of pinning. It may be suppressed.

It is preferable that the boiling point of the solvent used by this invention is 130-280 degreeC. If it is lower than 130 ° C, it may be undesirable in view of the uniformity of the in-plane pixel shape. When it is higher than 280 degreeC, it may not be preferable from the solvent removal by prebaking. In addition, the boiling point of a solvent means the boiling point under pressure of 1 atm, and it can know it from the physical-property table of a compound dictionary (Chapman & Hall). These may use together 1 type (s) or 2 or more types.

Moreover, when the inkjet ink mentioned above does not contain the polymerizable monomer etc. which are mentioned later, since the thickness of the ink remainder (color pixel) obtained by removing the solvent contained in ink becomes thin, it is a board | substrate for the purpose of prevention of mixed color etc. Since the height of the partition formed in the phase can be made low, it is preferable at the point of cost and productivity.

<Polymerizable monomer>

The inkjet ink of the present invention may contain a polymerizable monomer. By addition of a polymerizable monomer, the adhesiveness of an ink droplet and a board | substrate improves. Moreover, the improvement of dispersion uniformity in ink of the dipyrromethene type metal complex compound mentioned above, and improvement of the fastness, such as weather resistance and heat resistance, can be expected. Although there is no restriction | limiting in particular as this polymerizable monomer, Since there are many barrier properties of various substituents, and it is easy to obtain, it contains 1 or more types chosen from a (meth) acrylic-type monomer, an epoxy-type monomer, and an oxetanyl-type monomer. It is desirable to.

As the polymerizable monomer, a monomer having two or more polymerizable groups (hereinafter also referred to as "monofunctional 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 monomers having three or more polymerizable groups in terms of film strength, solvent resistance, and the like (hereinafter referred to as "monofunctional monomers"). More preferably).

Although there is no restriction | limiting in particular as a kind of polymerizable group mentioned above, As above, an acryloyloxy group, a methacryloyloxy group, an epoxy group, and an oxetanyl group are especially preferable. As a specific example of a polymerizable monomer, The epoxy group containing monomer of Paragraph No. [0061]-[0065] of Unexamined-Japanese-Patent No. 2001-350012, The acrylate monomer of Paragraph No. [0016] of Unexamined-Japanese-Patent No. 2002-371216 And paragraphs [0021] to 0084 and JP 2004-91556 in methacrylate monomers, JP 2001-220526, JP 2001-310937 and JP 2003-341217. The oxetanyl group containing monomer as described in numbers [0022] -0058, etc., and the monomer as described in CMC publication "The market prospect of reactive monomer", etc. are mentioned.

Moreover, as an acrylate monomer and a methacrylate monomer which are (meth) acrylic-type monomers, monofunctional, such as polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, etc. Acrylate and methacrylate, polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentylglycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaeryte Lithitol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylol Acrylates such as propane tri (acryloyloxypropyl) ether and tri (acryloyloxyethyl) isocyanurate or Trimethylolpropane PO (propylene oxide) modified tri (meth) acrylate and trimethyl obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as methacrylate, glycerin or trimethylol ethane and then (meth) acrylate All propane EO (ethylene oxide) modified tri (meth) acrylate, caprolactone modified dipentaerythritol hexaacrylate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, Japanese Patent Application Publication No. 51 The urethane acrylates described in each of -37193, the polyester acrylates described in each of JP-A-48-64183, JP-A-49-43191, JP-A-52-30490, and epoxy Polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of resins with (meth) acrylic acid, A mixture thereof. Moreover, what is introduced as a photocurable monomer and oligomer is further mentioned to Japanese adhesive association Vol.20, No.7, pages 300-308. It is preferable to adjust a viscosity by combining suitably a monofunctional monomer, a bifunctional monomer, a trifunctional or more than trifunctional monomer, and an oligomer. When a monofunctional monomer and a bifunctional monomer are used together, the viscosity of ink falls and the effect which can prevent a nozzle clogging is acquired. In order to supplement the strength of the film or to provide adhesion to the substrate, a small amount of a high-functional monomer such as a polyfunctional monomer having a viscosity at 25 ° C. of 700 mPa · s or higher, a urethane acrylate, oligomer, or the like may be used in combination.

Moreover, as an oxetanyl group containing monomer which is an oxetanyl-type monomer, the compound of Paragraph No. [0021]-[0084] of Unexamined-Japanese-Patent No. 2003-341217 can be used preferably. Moreover, the compound of Paragraph No. [0022]-0058 of Unexamined-Japanese-Patent No. 2004-91556 can also be used.

30-80 mass% is preferable in solid content of the inkjet ink, and, as for content of the polymerizable monomer mentioned above, 40-80 mass% is more preferable. When the amount of the monomer used is within the above range, since the polymerization of the pixel portion is sufficient, scratches due to the lack of film strength of the pixel portion are less likely to occur. In addition, when the transparent conductive film is provided, cracks and reticulation are less likely to occur, the solvent resistance when forming the alignment film is improved, or the voltage retention is not reduced. Here, the solid content of the inkjet ink for specifying the blending ratio includes all components except the solvent, and the liquid polymerizable monomer and the like are also included in the solid content.

<Binder resin>

In the inkjet ink of the present invention, a binder resin may be added for the purpose of adjusting the viscosity, adjusting the ink hardness, and the like. As binder resin, you may use the binder resin which simply dry-solidifies which consists only of resin which is not polymerizable by itself. However, in order to give sufficient strength, durability, and adhesiveness to a coating film, after forming the pattern of a pixel on a board | substrate by the inkjet method, it is preferable to use the binder resin which can harden the pixel by a polymerization reaction, For example, the photocurable binder resin which can be polymerized and hardened by visible light, an ultraviolet-ray, an electron beam, etc., and the binder resin which can be polymerized and cured like the thermosetting binder resin which can be polymerized and cured by heating can be used.

<Polymerization initiator>

The ink for inkjet of this invention may use together a polymerization initiator for the purpose of promoting the polymerization reaction of a polymerizable monomer and binder resin. A polymerization initiator can be selected according to the kind of polymeric monomer and binder used for an inkjet ink, and a polymerization route. A photoinitiator is used when making a polymerization reaction by an active energy ray, and a thermal polymerization initiator is used when making a polymerization reaction by heat. Examples of the photopolymerization initiator include at least one active halogen compound, a 3-aryl substituted coumarin compound, a lophine dimer, a benzophenone compound, an acetophenone compound, and a halomethyloxadiazole compound and a halomethyl-s-triazine compound. Derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds.

As the thermal polymerization initiator, generally known organic peroxide compounds and azo compounds can be used.

It is preferable that content of the polymerization initiator mentioned above is 0.01-50 mass% with respect to the total solid in an inkjet ink, More preferably, it is 1-30 mass%. If content is in the above-mentioned range, a more favorable sensitivity and firm hardening part can be formed. Moreover, the said compound which produces | generates an acid can be used 1 type or in mixture of 2 or more types.

<Hardener>

An epoxy type monomer (epoxy group containing monomer) and thermosetting binder resin can be mix | blended normally, combining a hardening | curing agent. As a hardening | curing agent, the hardening | curing agent described in Chapter 3 of the "General Epoxy Resin Basic Part I" issued by the Epoxy Resin Technical Association, and the accelerator described in Chapter 3 can be preferably used, for example, polyhydric carboxylic anhydride or Polyhydric carboxylic acid can be used.

<Heat latent catalyst>

Moreover, in this invention, when using an epoxy-group containing monomer and thermosetting binder resin, you may add the catalyst which can accelerate the thermosetting reaction between acid-epoxy in order to improve the hardness and heat resistance of ink. As such a catalyst, a heat latent catalyst which shows activity at the time of heat curing can be used.

<Surfactant>

You may use surfactant for the inkjet ink of this invention. As an example of surfactant, Paragraph No. 0021 of Unexamined-Japanese-Patent No. 7-216276, surfactant disclosed in Unexamined-Japanese-Patent No. 2003-337424, and Unexamined-Japanese-Patent No. 11-133600 are mentioned as a preferable thing. Can be. As for content of surfactant, 5 mass% or less is preferable with respect to the inkjet ink whole quantity.

As another additive, the other additive of Paragraph No. [0058]-[0071] of Unexamined-Japanese-Patent No. 2000-310706 is mentioned.

In order to adjust the color tone of the inkjet ink of the present invention, other coloring agents may be used in combination with the dyes described above.

As content of each component of the inkjet ink of this invention, 1-20 mass% is preferable, as for content of said dipyrromethene type metal complex compound, 5-15 mass% is more preferable, and content of a solvent is 30- 90 mass% is preferable, 50-85 mass% is more preferable, 5-50 mass% is preferable, as for content of a polymerizable monomer, 7-30 mass% is more preferable, and content of surfactant is 5 mass% The following are preferable and 0.1-5 mass% is more preferable.

<Manufacturing Method of Ink for Inkjet>

The well-known manufacturing method of inkjet ink can be applied to manufacture of the inkjet ink of this invention. For example, after dissolving a dipyrromethene type metal complex compound in a solvent, each component (for example, a polymerizable monomer, a binder, etc.) which are necessary for inkjet ink can be melt | dissolved, and inkjet ink can be prepared.

When manufacturing a monomer liquid, when the solubility of the raw material used with respect to a solvent is low, processing, such as heating and an ultrasonic treatment, can be performed suitably within the range which a monomer liquid does not produce a polymerization reaction.

<Physical Properties of Inkjet Inks>

Although it will not specifically limit, if it is a range which can be discharged with an inkjet head as a physical property value of the inkjet ink of this invention, It is preferable that the viscosity at the time of discharge is 2-30 mPa * s from a stable discharge viewpoint, and 2-20 mPa * s is more desirable. Moreover, when discharging to an apparatus, it is preferable to keep the temperature of inkjet ink at substantially constant temperature in the range of 20-80 degreeC. When the temperature of the apparatus is set to a high temperature, the viscosity of the ink is lowered, and the ink of higher viscosity can be discharged. However, as the temperature increases, heat denaturation or thermal polymerization reaction occurs in the head, or Since a solvent becomes easy to evaporate and nozzle clogging will generate | occur | produce easily on the nozzle surface which discharge | releases the inside, the temperature of an apparatus has the preferable range of 20-80 degreeC.

In addition, a viscosity is a value measured using the E-type clay meter (For example, the E-type clay meter (RE-80L) manufactured by Toki Industries Co., Ltd.) generally used in the state which hold | maintained the inkjet ink at 25 degreeC. to be.

Moreover, as surface tension (static surface tension) of 25 degreeC of inkjet ink, 20-40 mN / m is preferable and 20-35 mN / m is more preferable from a wettability improvement with respect to a non-invasive board | substrate, and discharge stability. Do. Moreover, when discharging from an apparatus, it is preferable to keep the temperature of the inkjet ink at substantially constant temperature in the range of 20-80 degreeC, and it is preferable to make surface tension at that time into 20-40 mN / m. In order to keep the temperature of the inkjet ink constant at a predetermined precision, it is preferable to include ink temperature detecting means, ink heating or cooling means, and control means for controlling heating or cooling according to the detected ink temperature. Alternatively, it is preferable to have a means for reducing the influence on the change in ink physical properties by controlling the energy applied to the means for discharging ink in accordance with the ink temperature.

The surface tension mentioned above is 25-degree liquid temperature by the Wilhelmi method using the surface tension meter (For example, Kyowa Interface Science, Ltd. make, surface tension meter FACE SURFACE TENSIOMETER CBVB-A3 etc.) generally used, It is a value measured at 60% RH.

In addition, in order to properly maintain the shape in which the inkjet ink wets and spreads after the substrate is reached, it is preferable to maintain the liquid physical properties of the inkjet ink after the substrate is landed. 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 increase the heat capacity of the pedestal for supporting the substrate and to reduce the influence of temperature change.

<Color filter and its manufacturing method>

Next, with reference to the preferable embodiment shown in drawing, the color filter using the inkjet ink of this invention and its manufacturing method are demonstrated in detail.

The color filter of this invention is characterized by including the color pixel formed by the inkjet method using the inkjet ink of this invention, ie, the thing manufactured by the inkjet method using the inkjet ink of this invention. It is characterized by. Moreover, the manufacturing method of the color filter of this invention is a process of forming a pixel by providing the inkjet ink of this invention by the inkjet method to the recessed part enclosed by the partition formed on the board | substrate ("pixel formation process" hereafter). It is characterized by having). Preferably, the pixel forming step includes a drawing step of applying ink as droplets to the recesses partitioned by partition walls on the substrate by the inkjet method, and further, active pixels of at least one color pixel (ink in the recesses) drawn. And a curing step including a irradiation step of curing by irradiation of lines to form a color pixel, and a heating step of forming a color pixel by curing with heat after forming all the pixels (inks in the recesses) of a desired color. According to this, other processes, such as a baking process, can be formed and comprised.

BRIEF DESCRIPTION OF THE DRAWINGS It is a flowchart which shows the manufacturing process in one Embodiment of the manufacturing method of the color filter of this invention, and FIG.2 (a)-(f) is a board | substrate in the manufacturing method of the color filter of this invention. It is typical sectional drawing of the board | substrate and a color filter shown in the manufacturing process order to the color filter.

As shown to FIG. 1 and FIG.2 (a)-(f), the manufacturing method of the color filter 10 of this invention makes the partition (bank) 14 which becomes a black matrix (BM) to the board | substrate 12. The recessed part between the partition formation process S102 (refer FIG. 2 (b)) to form, the liquid-repellent processing process S104 which imparts liquid repellency (ink repellency) to the partition 14, and the adjacent partition 14 The pixel formation step (S106) (refer FIG. 2 (c)-(e)) which forms the color pixel 20 by giving the inkjet ink 18 of this invention by the inkjet method to (16), and formed The protective film 22 which protects the color pixel 20 is formed, and the protective film formation process S108 (refer FIG. 2 (f)) which manufactures the color filter 10 is carried out.

In addition, in the pixel formation step S106, as described above, the writing step S110 of discharging the ink 18 as a droplet by the inkjet method to the recesses 16 between the partition walls 14 is provided (FIG. 2). (c)) and the preliminary processing step S112 which dries the ink 18 provided to the recessed part 16, removes the solvent in the ink 18, and makes it the ink remainder 18a (FIG. 2 (d)). And the ink remaining portion 18a by a irradiation step of irradiating an active energy ray to the ink remaining portion 18a in the recessed portion 16 on the substrate 12 and / or a heating step of heating the ink remaining portion 18a. It has the hardening process S114 (refer FIG. 2 (e)) which superposes | polymerizes and hardens and forms the color pixel 20. FIG.

In addition, the partition 14 is previously formed on the board | substrate 12 in the partition formation process S102 before pixel formation process S106, and the partition formation process S102 of the partition 14 and its formation method Details will be described later. First, the pixel forming step (S106) will be described.

<Pixel formation process>

As shown in FIG.2 (c)-(e), in the pixel formation process S106, in the drawing process S110, in the recessed part 16 between the partitions (color separation wall) 14 of this invention, The droplet of the inkjet ink 18 is given by the inkjet method, and the ink 18 provided in the hardening process S114 is hardened | cured, and the pixel 20 is formed. This pixel 20 becomes color pixels, such as red (R), green (G), and blue (B), which constitute the color filter 10. The detail of the inkjet method and drawing process S110 used by this invention is mentioned later. By using the inkjet ink of this invention, the color filter 10 which has the color pixel of blue (B) can be manufactured. Moreover, it does not specifically limit as the board | substrate 12 of a color filter, Resin boards, such as a glass plate, a polycarbonate, polymethyl methacrylate, and a polyethylene terephthalate, can be used.

As a color filter manufactured using the inkjet ink of this invention, not only a monochromatic color filter but the color pixel of red (R) consisting of yellow (Y) and magenta (M), yellow (Y) and cyan (C) A three-color color filter having a color pixel of green (G), magenta (M) and blue (B) consisting of cyan (C), or yellow (Y), magenta (M), The color filter etc. which have 4-6 color pixels which have a color pixel of cyan (C) are mentioned.

As ink for inkjet of blue (B), the ink for inkjet containing the dipyrromethene type metal complex compound mentioned above and the tetraaza porphyrin type cyan pigment represented by General formula (A) is used preferably. Moreover, the pigment | dye used as inkjet ink of other colors (red (R), green (G)) is not specifically limited, For example, in patent application 2007-303595 specification [0156]-[0288] You may use the pigment | dye described.

A well-known thing can be used as each coloring ink for forming the color filter which has magenta (M) and other color pixels other than this. For example, in the case of a magenta hue ink, as a coupling component (henceforth a coupler component), phenols, naphthols, anilines, hetero rings, such as pyrazine, a branched active methylene compound, etc. Aryl or hetaryl azo dyes having; For example, Azomethine dye which has a cleavage type active methylene compound etc. as a coupler component; Ink containing an anthrapyridone dye (for example, the compound of No. 20 in Table 1 described in US2004 / 0239739 A1 specification, the compound (13) described in International Publication No. 04/104108 pamphlet), and the like. .

Examples of the yellow tint ink include aryl or heteraryl azo dyes having heterocycles such as phenols, naphthols, anilines, pyrazolone and pyridones, and branched active methylene compounds as the coupler component; For example, Azomethine dye which has a cleavage type active methylene compound etc. as a coupler component; Methine dyes such as, for example, benzylidene dyes and monomethynoxonol dyes; For example, quinone dyes such as naphthoquinone dye, anthraquinone dye, and the like, and the like, and other types of dyes include quinophthalone dyes, nitro-nitroso dyes, acridine dyes, and acridinone dyes. The ink containing these is mentioned.

As a dye for cyan color tone, For example, Aryl or hetaryl azo dye which has a phenol, naphthol, aniline, etc. as a coupler component; For example, Azomethine dye which has heterocyclic rings, such as phenols, naphthol, a pyrrolotriazole, etc. as a coupler component; Polymethine dyes such as cyanine dye, oxonol dye, merocyanine dye and the like; Carbonium dyes such as diphenylmethane dye, triphenylmethane dye and xanthene dye; Phthalocyanine dyes; Anthraquinone dyes; Ink containing an indigo thio indigo dye etc. are mentioned.

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

In the present invention, as shown in FIG. 2C, in the drawing step S110, droplets of the ink 18 are applied to the recessed portions 16 on the substrate 12 to form the ink 18 layer. Then, as shown in FIG.2 (d), after drying and removing the organic solvent contained in the ink 18 in the pretreatment process S112, it is set as the ink remainder 18a, and it shows in FIG.2 (e). Similarly, curing comprising an irradiation step of irradiating an active energy ray to the ink remaining part 18a (hereinafter also referred to as a first curing step) and / or a heating step of heating the ink remaining part (hereinafter also referred to as a second curing step). You may superpose | polymerize the ink remainder 18a by the process S114, and the pixel 20 may be formed. In addition, when the temperature at which thermal polymerization of the ink remainder is started is set to T ° C, in the preliminary processing step (S112), the ink 18 is preheated (hereinafter also referred to as a preheating step) at a temperature below T ° C. After forcibly drying and removing the organic solvent contained therein to make the ink residue 18a, the irradiation step of irradiating the active energy ray to the ink residue 18a and / or the ink residue 18a is heated at a temperature of T 占 폚 or more. You may superpose | polymerize and harden the ink remainder 18a by a heating process, and the pixel 20 may be formed.

<1st hardening process>

A step of irradiating and curing an active energy ray to the ink remaining portion (hereinafter referred to as uncured pixel ink) 18a in the recessed portion 16 for pixel formation of at least one color formed in the drawing step S110 (first curing) Process) can be formed. In the 1st hardening process, the hardened pixel 20 can be formed by hardening the ink of each color containing red (R), green (G), and blue (B). Hardening may be performed every time one color uncured pixel ink 18a is formed, and may be performed after forming the uncured pixel ink 18a of plural colors or all colors.

In the first curing step, when the ink in the concave portion 16, that is, the uncured pixel ink 18a, is cured for each color or plural colors, the order of curing is not particularly limited, and any order may be used.

Moreover, hardening of ink, such as R, G, B, can be performed by performing exposure processing which accelerates polymerization hardening using the energy source which emits an active energy ray of the wavelength range corresponding to the photosensitive wavelength which ink has.

As an energy source, 400-200 nm ultraviolet-ray, ultraviolet-ray, g-ray, h-ray, i-ray, KrF excimer laser beam, ArF excimer laser beam, an electron beam, an X-ray, a molecular beam, an ion beam, etc. are mentioned, for example. What is sensitive to the polymerization initiator mentioned above can be selected suitably, and can be used. Specifically, a light source emitting active rays belonging to a wavelength range 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 lamps, xenon lamps, chemical lamps and the like can be preferably used. Preferred light sources include LEDs, high pressure mercury lamps, and metal halide lamps.

As irradiation time of an active energy ray, it can set suitably according to the combination of a monomer and a polymerization initiator, for example, can be made into 1 to 30 second.

<2nd hardening process>

In the manufacturing method of the color filter of this invention, the process (2nd hardening process) which hardens the uncured pixel ink 18a of desired color, such as red (R), green (G), and blue (B), by heat. Can be formed. As mentioned above, the manufacturing efficiency of the color filter 10 and display characteristics can be made compatible by forming a 1st hardening process and forming a 2nd hardening process. Moreover, you may harden only by a 2nd hardening process.

In this 2nd hardening process, after forming a hardening pixel ink which consists of a partition and a desired color, and after performing a 1st hardening process, heat processing (so-called baking process) can be performed further and hardening by heat can be performed. . That is, the board | substrate in which the photopolymerized pixel is formed by a partition and light irradiation can be heated in an electric furnace, a dryer, etc., or can be heated by irradiating an infrared lamp.

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

Moreover, in the manufacturing method of the color filter using the inkjet ink of this invention, before performing superposition | polymerization of the ink in the recessed part (uncured pixel) for pixel formation by exposure and / or heat processing of an active energy ray, a pretreatment process ( You may provide a preheating process as S112). The heating temperature in the preliminary heating step is not particularly limited, but when the temperature at which the thermal polymerization of the uncured pixel ink is started is set to T ° C., a temperature below T ° C. and a temperature at which polymerization of the uncured pixel ink does not occur is preferable. And 50-100 degreeC is more preferable, and 60-90 degreeC is further more preferable. By introducing the preliminary heating step, evaporation of the organic solvent in the ink imparted by the inkjet method is promoted, and not only can the color filter be efficiently produced, but also the viscosity of the ink residue is lowered by heat, resulting in higher fluidity. Can be obtained, and a color filter having a high flatness pixel can be obtained.

The preliminary heating step is effective not only for the ink polymerized by heat inside the pixel, but also for the ink polymerized by light as long as the ink residue as in the present invention has fluidity. In the case of the ink polymerized by light, the temperature T at which the above-mentioned ink starts thermal polymerization is a temperature at which the photopolymerization initiator is decomposed by heat, and the polymerization reaction is initiated, or the monomer itself is decomposed by heat, It means the temperature to be started. Although the time of a preheating process is not specifically limited, It is preferable to carry out for 1 to 5 minutes.

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

In the manufacturing method of the color filter using the ink of this invention, the pixel formation process (S106) from drawing process (S110) to the preliminary heating process (S112) and the hardening process (S114) which consists of a 1st hardening process and a 2nd hardening process (S106). ) Is preferably performed within 24 hours, more preferably within 12 hours, even more preferably within 6 hours. The surface shape of a pixel can be improved by forming the pixel from drawing process S110 to final hardening process (2nd hardening process) (S114) within 24 hours.

In addition, in the manufacturing method of the color filter of this invention, one color from a pixel formation process (S106), ie, drawing process (S110), to preheating process (S112), a 1st hardening process, and a 2nd hardening process (S114) is carried out. Every color may be performed, every color may be performed, or drawing may be performed about all the colors in drawing process S110, and preheating by preheating process S112 and hardening by the curing process S114 may be performed by all colors. You may carry out about. In addition, when performing pixel formation process S106 for every one color or multiple colors, the color order of the formed pixel is not restrict | limited in particular, Any order of color may be sufficient.

<Partition formation process>

In the manufacturing method of the color filter of this invention, in the pixel formation process (S106) mentioned above, as shown to FIG.2 (c)-(e), it is surrounded by the partition 14 formed on the board | substrate 12. The recessed part 16 is provided with the droplet of the inkjet ink 18 of this invention by the inkjet method, and the pixel 20 is formed.

The partition wall 14 is not particularly limited, and any known partition wall may be used, and any partition wall may be used. However, when the color filter is manufactured, it is preferable that the partition wall 14 has a light shielding function having a black matrix function.

Therefore, in the example shown in FIG. 1, as shown in FIG.2 (b), in the partition formation process S102, the function of such a black matrix on the board | substrate 12 shown in FIG.2 (a) is The partition 14 which has light shielding property is formed.

In addition, this partition 14 can be manufactured by the same well-known method using the same material as the well-known black matrix for color filters. For example, Paragraph No. [0108]-[0126] of Unexamined-Japanese-Patent No. 2007-193090, Paragraph No. of Unexamined-Japanese-Patent No. 2005-3861, or Unexamined-Japanese-Patent No. 2004-240039 The black matrix (so-called resin black matrix) described in paragraph numbers [0012] to [0021], paragraph numbers [0015] to [0020] of Japanese Patent Laid-Open No. 2006-17980, and paragraph number of Japanese Patent Laid-Open No. 2006-10875 The black matrix for inkjets as described in [0009]-[0044] is mentioned. In addition, the partition 14 may have a two-layer structure composed of a layer having a black matrix function and a partition function separately. For example, Paragraph No. [0054]-[0057] of Unexamined-Japanese-Patent No. 2004-361491, Paragraph No. of Unexamined-Japanese-Patent No. 2004-295039, or Unexamined-Japanese-Patent No. 2006-86128 The two-layer structure consisting of the metal light shielding film of paragraph numbers [0068]-[0069], [0103], [0109]-[0110], and a partition (bank) layer made of a resin, preferably a liquid-repellent resin, formed thereon. It may be.

In this invention method, it is preferable to use the photosensitive resin transfer material among the well-known manufacturing methods mentioned above from a viewpoint of cost reduction. The photosensitive resin transfer material is formed by forming a resin layer having at least light shielding properties on a temporary support, and can be pressed onto a substrate to transfer the resin layer having light shielding properties onto the substrate.

It is preferable to form the photosensitive resin transfer material using the photosensitive resin transfer material described in Unexamined-Japanese-Patent No. 5-72724, ie, the integral film. As a structural example of this integrated film, a temporary support body / a thermoplastic resin layer / an intermediate | middle layer / photosensitive resin layer (In this invention, "photosensitive resin layer" means resin which can be hardened by light irradiation, and when it has light-shielding property, It is also called "the resin layer which has light-shielding property," and when it is colored by the target color, it is also called the "colored resin layer." The structure which laminated | stacked the protective film in this order is mentioned. About the temporary support which comprises the photosensitive resin transfer material, a thermoplastic resin layer, an intermediate | middle layer, a protective film, or the manufacturing method of a transfer material, Paragraph No. 0023-Japanese Unexamined-Japanese-Patent No. 2005-3861 The thing of Paragraph No. [0108]-[0126] of Unexamined-Japanese-Patent No. 2007-193090 is mentioned as a preferable thing.

Moreover, in order to prevent the mixed color of the inkjet ink, such a partition 14 may perform an ink process.

Therefore, in the example shown in FIG. 1, after the partition formation step S102, the liquid repellent treatment, that is, ink repellent treatment, is performed on the partition 14 on the substrate 12 shown in FIG. 2B in the liquid repellent treatment step S104. Perform the process.

As such ink repellent treatment, for example, the ink repellent treatment method described in paragraphs [0086] to [0087] of JP-A-2007-187884, specifically, (1) ink repellent material (2) A method of forming a ink repellent layer (see, for example, JP-A-5-241011), ( 3) Method of imparting ink repellency by plasma treatment (for example, see Japanese Laid-Open Patent Publication No. 2002-62420), (4) Method of applying ink repellent material to the upper surface of a wall of a partition (for example, Japan And Japanese Patent Application Laid-Open No. Hei 10-123500).

In addition to these, as the ink repellent treatment method applicable to the present invention method, the ink repellent treatment method described in paragraph No. [0058] of JP 2004-361491 A (for example, JP 9-203803 A). (See Japanese Patent Application Laid-Open No. 9-230129 and Japanese Patent Laid-Open No. 9-230127) or paragraphs [0074] to [0075], [0111] to [0118] of Japanese Patent Laid-Open No. 2006-86128, The ink repellent processing method as described in [0130] is mentioned.

In addition, in the above-mentioned example, although the ink repellent process is given to the partition 14 on the board | substrate 12, this invention is not limited to this, At the same time, the inking process on the recessed part 16 on the board | substrate 12 is carried out. You may carry out.

In addition, when the partition 14 is equipped with ink repellency, the liquid repelling process S104 is unnecessary, but in that case, you may perform a parent ink process in the recessed part 16 on the board | substrate 12. FIG.

As shown in FIG. 2E, after the partition 14 and the pixel 20 are formed on the substrate 12 and the color filter 10 is manufactured, FIG. 2F is used for the purpose of improving the resistance. ), The overcoat layer 22 can be formed as a protective layer so as to cover the entire surfaces of the pixel 20 and the partition wall 14. The overcoat layer 22 can flatten the surface while protecting the pixels 20 and the partitions 14 such as R, G, and B. However, it is preferable not to form in the point which a process number increases. The overcoat layer 22 can be comprised using resin (made by OC), and an acrylic resin composition, an epoxy resin composition, a polyimide resin composition etc. are mentioned as resin (made by OC). Especially, an acrylic resin composition is preferable at the point which is excellent in transparency in a visible light region, and the resin component of the inkjet ink has an acrylic resin as a main component, and is excellent in adhesiveness. As an example of an overcoat layer, Paragraph No. 0018 of Unexamined-Japanese-Patent No. 2003-287618, and Optimus SS6699G by JSR Corporation are mentioned as a commercial item of an overcoating agent.

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

The color filter of this invention is restrict | limited especially to the use of image display, such as a liquid-crystal display, a television, a personal computer, a liquid crystal projector, a game machine, a mobile telephone, a digital camera, car navigation, etc., especially a color image display. It can be preferably applied. Moreover, the color filter of this invention is applicable also to image display devices, such as an electronic paper and an organic EL element device, especially a color image display device.

Next, the drawing process of the manufacturing method of the color filter of this invention, the inkjet drawing method used for this, the inkjet drawing apparatus which implements this, and the inkjet head used for this are demonstrated.

FIG. 3 is a perspective view showing a part of an embodiment of an inkjet drawing apparatus used for carrying out a drawing step of the method for manufacturing a color filter of the present invention, FIG. 4 is a partial cross-sectional view of the inkjet drawing apparatus shown in FIG. 3, FIG. 5 is a schematic diagram showing a schematic configuration of an embodiment of an ink circulation system in the inkjet drawing apparatus shown in FIG. 3.

The inkjet drawing apparatus (henceforth simply a drawing apparatus) 30 shown to FIG. 3 and FIG. 4 is the platen 32 which mounts and supports the board | substrate 12, and the ink for color filter manufacture on the board | substrate 12. FIG. The head unit 36 of the carriage-type head unit 36 including the inkjet head 34 for discharging the ink, and the head unit 36 on the substrate 12 supported on the platen 32 in the main scanning direction (arrow X in FIG. 3). Head moving mechanism 38 for moving in the direction shown) and the substrate 12 mounted on the platen 32 in the sub-scan direction (arrow Y in FIGS. 3 and 4) orthogonal to the main scanning direction (X direction). The substrate supply mechanism 40 to convey in the direction shown, the ink supply system 50 (refer FIG. 5) which supplies ink to the inkjet head 34 of the head unit 36, and the board | substrate conveyance mechanism 40 It has a substrate supply means not shown which supplies the board | substrate 12 to the platen 32 via. In addition, as long as the board | substrate supply means can supply the board | substrate 12 to the board | substrate conveyance mechanism 40 so that the board | substrate conveyance mechanism 40 can convey the board | substrate 12 to the platen 32, what kind of board | substrate supply means For example, a well-known board | substrate supply means or the automatic feeder apparatus which automatically supplies the board | substrate 12 to the platen 32 via the board | substrate conveyance mechanism 40 may be sufficient.

Here, the platen 32 has a flat plate shape, and mounts and supports the board | substrate 12 supplied from the board | substrate supply means on the surface. Here, the surface of the platen 32 forms an air suction hole to adsorb the substrate 12 during the drawing by the head unit 36, that is, during the drawing by the inkjet head 34 of the head unit 36. It is desirable to. Thereby, the planarity of the board | substrate 12 can be maintained suitably. Moreover, when conveying the board | substrate 12 in the sub scanning direction (Y direction) by the board | substrate conveyance mechanism 40, it is preferable that the surface of the platen 32 is small in friction with the back surface of the board | substrate 12. In addition, the platen 32 is attached to the casing (not shown) of the drawing apparatus 30.

The head unit 36 has an inkjet head 34, is disposed to face the platen 32, and is movable in parallel with the surface of the platen 32 by the head moving mechanism 38 described later. It is supported in a state. The head unit 36 is also connected with an ink supply pipe 54 for supplying ink in the ink tank 52 (see FIG. 5) of the ink supply system 50 to the ink jet head 34.

The inkjet head 34 discharges the inkjet ink 18 for producing the color filter of the present invention described above according to the ink ejection signal of the predetermined color for forming the color filter, and the pixel (on the substrate 12) The uncured pixel 18a is drawn to form the cured pixel 20 (see FIGS. 2E and 2F). Here, the discharge signal is a discharge signal for discharging droplets so as to selectively apply ink to a portion that becomes a pixel of the color filter based on the image signal.

As the inkjet head, various types of inkjet heads (ejection heads) such as continuous, on-demand piezo, thermal, solid, and electrostatic suction methods can be used. It is preferable to use a head, and in particular, it is preferable to use an on-demand piezo type inkjet head. In addition, the discharge part (nozzle) of an inkjet head is not limited to a single row arrangement | positioning, You may be multiple rows, and you may arrange | position in a grid pattern shape. In addition, the arrangement | positioning of the nozzle of an inkjet head and the drawing method according to it are mentioned later.

In addition, in the drawing apparatus 30 shown to FIG. 3 and FIG. 4, although R pixel of a color filter is formed using one color, for example, magenta ink, two or more colors of a color filter, for example, 3 In order to form RGB pixels of color, one drawing device 30 may be replaced with different inks to sequentially form pixels of different colors, and three drawing devices 30 each using inks of different colors. The pixel of a different color may be formed, respectively, or the drawing apparatus 30 shown in FIG. 3 and FIG. 4 may be a structure provided with two or more head units which can move to a two-dimensional direction.

In addition, in the example of illustration, although the head unit 36 is equipped with the 1 type of inkjet head 34 which discharges one color of ink, this invention is not limited to this, For example, two or more colors, for example Or two or more ink jet heads 34 that discharge three or four full color inks, respectively, for example. In this case, for each of the three or four inkjet heads 34, three or four kinds of ink for supplying the respective ink supply systems 50, that is, three or four full color inks, respectively. An ink supply system 50 is required, and three or four ink supply pipes 54 are connected to the head unit 36 according to each of them.

The head movement mechanism 38 scan-moves the head unit 36 in the main scanning direction (arrow X direction in FIG. 3), and includes a drive screw 42, a guide rail 43, a drive support 44, and And a support 45. The drive screw 42 and the guide rail 43 are spaced apart from each other by a predetermined interval, and both are parallel to the main scanning direction (the X direction in FIG. 3) orthogonal to the conveying direction (the Y direction in FIG. 3) of the substrate 12, Moreover, the board | substrate 12 of the largest usable (length of the main scanning direction is long) is arrange | positioned from the left end to the right end.

The drive screw 42 consists of a ball screw (not shown) etc. which have a male screw part (not shown) formed in the head unit 36 and the male screw part screwed together, and rotates to move the head unit 36. FIG. The guide rail 43 is a guide inserted into the through hole formed in the head unit 36 to guide the posture of the inkjet head 34 moving by the rotation of the drive screw 42 so as not to change.

Moreover, the drive support part 44 is formed in the one end part of the drive screw 42 and the guide rail 43, and the support part 45 is formed in those other end parts, and the drive screw 42 is forward-reversed. It is supported in a rotatable state and is supported so that the guide rail 43 may not move. The drive support part 44 is equipped with drive sources (not shown), such as a motor which drives the drive screw 42. FIG. In addition, the drive support part 44 and the support part 45 are all supported by the casing of the drawing apparatus 30 which is not shown in the above.

The head unit 36 is supported by the drive screw 42 and the guide rail 43 so that the movement is possible, and the drive screw 42 is forward-reversely rotated by the drive support part 44 to the guide rail 43. While being guided, it is reciprocated (scanned) in the main scanning direction (X direction). In addition, in order to maintain the attitude | position of the head unit 36, the head movement mechanism 38 may be equipped with the some guide rail, and may have other attitude maintenance means. In addition, the head unit 36 maintains a predetermined posture by which the guide rail 43 discharges ink droplets, that is, the ink droplet ejecting surface of the inkjet head 34 is opposed to the platen 32. Is moved.

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 the guide wires are attached to both sides of the end portion in the X-direction of the inkjet head, respectively, to wind the guide wire in the moving direction and move along the guide rail. It is also possible to use a configuration to make. Moreover, you may move with a timing belt instead of a guide wire. In this case, the timing belt sprocket may be used instead of the wire reel. Moreover, you may use a rack and pinion mechanism. It may also be a self-propelled meal. In addition, a linear motor may be used.

The board | substrate conveyance mechanism 40 conveys the board | substrate 12 mounted in the platen 32 with respect to the head unit 36 to a sub scanning direction (Y direction), and is predetermined in a sub scanning direction (Y direction). Intervals, for example, spaced apart by a distance slightly shorter than the length of the substrate 12 having the minimum usable (shortest in the sub-scanning direction), extending in the main scanning direction (X direction), and connected with a drive source (not shown) To each conveying roller 46 which is arrange | positioned in the position which interposes both ends of one conveying roller 46 and the main scan X direction of the board | substrate 12 mounted on each conveying roller 46, respectively. It has one set of narrow press rollers 48, and sandwiches the board | substrate 12 between the feed roller 46 and the press roller 48, and conveys it to the sub scanning Y direction. The pair of feed rollers 46 is composed of two long driving rollers longer than the maximum usable (longest in the scanning direction) length of the main scanning direction of the substrate 12, and the drive shafts of the two driving rollers are By synchronous drive means such as a drive belt, they are connected to each other and driven synchronously. On the other hand, the press roller 48 is comprised with the narrow short-acting driven roller which is formed with two and four pieces in total with respect to each feed roller 46, and is the longest board | substrate 12 in the usable main scanning direction. It is preferable to be able to move to the main scanning direction between the positions of both ends of the shortest board | substrate 12 in the main scanning direction which can be used at the positions of both ends, and to adjust to the position of the both ends of the board | substrate 12 used suitably. One conveying roller 46 and two pressing rollers 48 are arranged so that the conveyance path | route of the board | substrate 12 is formed up and down. The board | substrate 12 supplied from the automatic sheet feeding apparatus is inserted by the predetermined | prescribed nip pressure between the feed roller 46 and the press roller 48, and the feed roller 46 is moved by the drive source (not shown) by the predetermined direction (FIG. 4). In the anti-scan direction (Y) by rotating in the counterclockwise direction.

Here, when drawing the board | substrate 12 on the surface of the platen 32 during the drawing by the head unit 36, rotation of all the conveying rollers 46 and the pressing rollers 48 is stopped, and the head While the drawing by the unit 36 is not performed, the feed roller 48 is driven to rotate by a drive source (not shown), and the substrate 12 sandwiched between the pressing roller 48 in the sub-scan Y direction. It is preferable to comprise so that conveyance may be carried out. That is, it is preferable that the board | substrate conveyance mechanism 40 carries out subscanning of the board | substrate 12 intermittently. In addition, both the feed roller 46 and the press roller 48 are supported by the casing of the drawing apparatus 30 which is not shown in figure so that rotation is possible. In addition, as long as the board | substrate conveyance mechanism 40 used for this invention can convey the board | substrate 12 to a subscanning direction, what kind of form may be sufficient and all the well-known subscanning conveyance mechanisms can be applied.

Thus, the board | substrate conveyance mechanism 40 can move the head unit 36 relatively to the board | substrate 12 to a sub scanning direction by conveying the board | substrate 12 to a sub scanning direction.

As mentioned above, the head movement mechanism 38 and the board | substrate conveyance mechanism 40 can move the head unit 36 with respect to the board | substrate 12 in the main scanning direction and the sub-scanning direction, and the head unit 36 Two-dimensional scanning (XY scanning) of the substrate 12 by the inkjet head 34 of FIG. In addition, in this invention, if the drive source of the head movement mechanism 38 and the board | substrate conveyance mechanism 40 can be made to draw correctly for manufacture of a color filter etc., it is preferable that it is a step motor although it does not restrict | limit especially.

In addition, the head movement mechanism 38 moves the head unit 36 to a predetermined head retracted position when the ink jet head 34 is not used, and to the predetermined maintenance position at the time of maintenance. Moreover, it is preferable that the predetermined head retracting position and the predetermined maintenance position are a position away from the substrate 12 on the platen 32 or a position away from the platen 32, more preferably the predetermined position. It is preferable that the head retracted position is a position away from the substrate 12 on the platen 32, and the predetermined maintenance position is a position away from the platen 32.

In the illustrated example, the head unit 36 is moved by the main scanning direction of the head unit 36 by the head moving mechanism 38 and by the sub scanning direction of the substrate 12 by the substrate transfer mechanism 40. Although two-dimensional scanning (XY scanning) of the substrate 12 by the inkjet head 34 is realized, the present invention is not limited thereto, and the substrate 12 is mounted on the platen 32 as a support. And the head unit 36 is moved and scanned in the main scanning (X) direction and the sub scanning (Y) direction by a head unit scanning means or the like, and the two-dimensional scanning (XY scanning) of the fixed substrate 12 is performed. May be performed.

The two-dimensional scanning of the substrate by the head unit 36 will be described later in detail along with the inkjet drawing method for producing the color filter of the present invention.

5, the schematic structure of the ink supply system 50 in the inkjet drawing apparatus 30 is shown.

The ink supply system 50 includes an ink tank 52 for storing ink supplied to the ink jet head 34, an ink supply pipe 54 for connecting the ink jet head 34 and the ink tank 52, and an ink supply pipe. The cleaning blade 60 which cleans the filter 56 formed in the middle of 54, the cap 58 which covers the nozzle area of the inkjet head 34, and the nozzle surface 34a of the inkjet head 34 is cleaned. And a suction pump 62 connected to the cap 58 to perform nozzle suction of the inkjet head 34, a recovery tank 64 to recover ink sucked by the suction pump 62, and a cap 58 ) And an ink recovery pipe 66 connecting the recovery tank 64 via the suction pump 62 and branched to the ink supply pipe 54 to form a pressure chamber (not shown) of the nozzle of the ink jet head 34. Ink pressurizing system for replenishing ink to the head pressurizing pump 68 and ink tank 52 for pressurizing Have (70).

In addition, the cap 58, the cleaning blade 60, the suction pump 62, and the head pressurizing pump 68 constitute a maintenance system of the inkjet head 34, and the cap 58, the recovery tank 64, The ink recovery tube 66 and the recovery ink replenishment tube 82, the filter 84, and the concentration detector 86 of the ink replenishment system 70 described later constitute an ink recovery system.

Here, the ink supply system 50 is not only a narrow supply system for supplying ink from the ink tank 52 to the inkjet head 34, but also the maintenance system, ink recovery system, and ink replenishment system of the inkjet head 34. (70) is also included.

The ink tank 52 is a main tank for supplying ink to the inkjet head 34, and is for storing various inks, including the inkjet ink of the present invention for producing the color filter described above. In addition, in the example of illustration, when the ink replenishment system 70 is provided as a form of the ink tank 52, and the remaining amount of ink in the ink tank 52 becomes small, the refill port (illustration omitted) from the ink replenishment system 70 is omitted. ), But the present invention is not limited to this, and the cartridge method of replacing the ink tank 52 as an ink cartridge for each ink tank may be employed.

In the case of mass production of color filters, for example, the ink jet head 34 and the ink supply system 50 are provided for each color and each type, and when a large amount of ink is consumed, the ink replenishment method is also used in terms of ink replacement and cost. Although this is suitable, when a small amount of ink consumption changes an ink type according to a use use, a cartridge system is suitable. In the case of the cartridge system, it is preferable to identify the type information of the ink by a bar code or the like and to perform discharge control in accordance with the type of ink.

As shown in FIG. 5, in the middle of the ink supply pipe 54 which connects the ink tank 52 and the inkjet head 34, the filter 56 is formed in order to remove a foreign material and air bubbles. It is preferable that the mesh size of the filter 56 is the same as the nozzle diameter of the inkjet head 34 or is below the nozzle diameter (generally about 20 micrometers). In addition, although details are mentioned later, the pressure chamber of the nozzle of the inkjet head 34 (not shown) is further formed branching in the middle of the ink supply pipe 54, and when the ink jet head 34 discharged ink badly. ), A head pressurizing pump 68 for forcibly pressurizing and forcing discharge is formed. In addition, the portion of the ink supply pipe 54 connected to the inkjet head 34, for example, the portion on the inkjet head 34 side rather than the head pressurizing pump 68 is two-dimensional in the head unit 36. In order to realize smooth movement at the time of movement (XY direction), it is good to set it as a flexible tube.

In addition, although not shown in FIG. 5, it is also preferable to set it as the structure which forms the sub tank in the vicinity of the inkjet head 34 or integrally with the inkjet head 34. As shown in FIG. The sub tank has a function of improving the dumper effect and the refill to prevent fluctuations in the internal pressure of the head.

In addition, in the inkjet drawing apparatus 30 of the illustrated example, the cap 58 and the cleaning blade (for maintaining the proper ejection state of the inkjet head 34) in order to properly eject ink from each nozzle of the inkjet head 34. And a maintenance unit including 60). These maintenance units can be moved relative to the inkjet head 34 by a moving mechanism not shown, and are moved below the inkjet head 34 at the maintenance position from the predetermined retracted position as necessary. In the inkjet drawing apparatus 30 shown in FIG. 3, the retracted position and the maintenance position of the maintenance unit are also positions away from the substrate 12 on the platen 32, preferably, positions away from the platen 32. It is good to be

The cap 58 is deposited so as to cover the nozzle area of the nozzle face 34a of the inkjet head 34 so as to prevent drying of the nozzle when the inkjet head 34 is not in use or to increase ink viscosity near the nozzle. It is formed as a means. The cap 58 is a preliminary ejection (hereinafter also referred to as a dummy ejection) for inspecting the ejection state of the nozzle (not shown) of the inkjet head 34 and / or eliminating ejection defects, or the head pressurizing pump 68. The nozzle suction by the suction pump 62 is also possible in order to recover the discharged ink, even at the time of forced discharge from the nozzle by the nozzle or suction of the ink jet head 34 by the suction pump 62. And the ink jet head 34 is used to cover the nozzle face 34a so as to recover the sucked ink.

This cap 58 is lifted and displaced relative to the inkjet head 34 by a lifting mechanism not shown in the maintenance position. The elevating mechanism raises the cap 58 to a predetermined raised position at the time of power supply OFF or drawing waiting, and closes the cap region to the cap 58 by bringing the cap 58 into close contact with the ink jet head 34. It is supposed to cover.

The cleaning blade 60 is formed as a cleaning means for the nozzle face 34a of the inkjet head 34 and is composed of an elastic member such as rubber, and at the maintenance position, the inkjet head is provided by a blade moving mechanism (not shown). The ink ejecting surface (nozzle surface 34a) of 34 can be slid. When ink droplets or foreign matter adhere to the nozzle face 34a, the nozzle face 34a is wiped off by sliding the cleaning blade 60 onto the nozzle face 34a to clean the nozzle face 34a.

The suction pump 62 is connected to the cap 58 by the ink recovery pipe 66. This suction pump 62 has a cap 58 on the nozzle face 34a of the inkjet head 34 at the time of loading the inkjet head 34 of the initial ink to each nozzle, or at the start of use after a long stop. It is used to perform suction operation (nozzle suction operation) by bringing into contact and to suck out and remove the deteriorated ink whose viscosity rises and solidifies. In addition, the suction pump 62 feeds and collects the deteriorated ink removed by suction to the recovery tank 64.

In addition, when the frequency of use of a particular nozzle is lowered during printing or in the atmosphere and the ink viscosity in the vicinity of the nozzle is increased, preliminary ejection is performed toward the cap 58 in order to discharge the deteriorated ink by increasing the viscosity. However, even when preliminary ejection is performed from each nozzle of the inkjet head 34, a nozzle of ejection failure may exist as a result of the inspection of the ejection state of each nozzle.

In this way, even when preliminary ejection does not recover so that the ejection failure nozzle can be easily ejected, that is, the ejection failure is not easily solved, for example, the ink in the inkjet head 34 (in the pressure chamber) Even when bubbles are mixed in the ink or when the ink becomes high in the nozzle or solidifies and becomes deteriorated ink, the suction pump 62 is brought into contact with the cap 58 against the ink jet head 34. It is used to remove the ink (bubble mixed) or the high viscosity or solidified deterioration ink in the chamber by suction (nozzle suction). Of course, even in this case, the suction pump 62 transfers the bubble-blended ink and the deterioration ink suctioned and removed to the recovery tank 64 for recovery.

The head pressurizing pump 68 is formed branched to the ink supply pipe 54 connected to the inkjet head 34. This head pressurizing pump 68 is similar to the suction pump 62 described above, when the discharge failure is not easily eliminated even during preliminary discharge at the time of loading of the initial ink or at the start of use after a long stop. The pressure chamber of the nozzle of the inkjet head 34 is pressurized to forcibly eject (force discharge) ink containing bubble mixing ink in the pressure chamber and deteriorated ink in the nozzle from each nozzle. Also in this case, the cap 58 is pressed by the inkjet head 34 and receives ink containing bubble mixing ink or deterioration ink forcedly discharged by the head pressurizing pump 68, and the suction pump 62 and the ink recovery The liquid is sent to the recovery tank 64 through the pipe 66 to be recovered.

In addition, since the suction pump 62 and the head pressurizing pump 68 have the same function, what is necessary is just to provide either, but may provide both as shown in the example.

The recovery tank 64 includes ink preliminarily discharged, ink or deterioration ink sucked out by the suction pump 62, bubble mixing ink forcibly discharged by the head pressurizing pump 68, and deterioration ink in the nozzle. It is for recovering ink and storing it as recovered ink.

In addition, the recovered ink collected and stored in this recovery tank 64 and stored in a predetermined amount may be discarded. However, as described later, the ink is sent to the ink replenishment system 70 to detect ink characteristics such as ink concentration and electrical conductivity. After the evaluation, based on the evaluation result, for the manufacture of the color filter, it is preferable to replenish the ink tank 52 after being re-liquidized as a reusable ink.

By the way, if the inkjet head 34 continues to be discharged for a predetermined time or more, the ink solvent in the vicinity of the nozzle is evaporated and the viscosity of the ink in the vicinity of the nozzle becomes high, and even if the discharge driving pressure generating means (not shown) operates. No ink is discharged from the nozzle. Therefore, the pressure generating means is operated toward the cap 58 serving as the ink receiver (in the range of the viscosity at which the ink can be discharged by the operation of the pressure generating means) before such a state, so that the viscosity is increased in the vicinity of the nozzle. "Preliminary ejection" for ejecting ink is performed. Moreover, after cleaning the contamination of the nozzle surface 34a with the wiper of the cleaning blade 60 etc. which are formed as a cleaning means of the nozzle surface 34a, it is understood that a foreign material mixes in a nozzle by the sliding operation of this wiper. In order to prevent this, preliminary ejection is performed. In addition, preliminary discharge may be called "dummy discharge", "empty discharge", "purge", "other discharge", etc.

In addition, if bubbles are mixed in the nozzle or pressure chamber of the inkjet head 34, or if the viscosity rise of the ink in the nozzle exceeds a certain level, the ink cannot be discharged in the preliminary ejection. A suction operation by the pump 62 and a head press operation by the head pressurizing pump 68 are performed.

That is, when bubbles are mixed into the ink of the nozzle of the inkjet head 34 or the pressure chamber, or when the ink viscosity in the nozzle rises above a certain level, ink cannot be discharged from the nozzle even when the pressure generating means is operated. . In such a case, the cap 58 is brought into contact with the nozzle face 34a of the inkjet head 34 to suck the ink or the thickened ink or the solidified ink in which the bubbles in the pressure chamber are mixed with the suction pump 62, Alternatively, an operation of forcibly pressurizing the inside of the pressure chamber with the head pressurizing pump 68 and forcibly discharging from the nozzle is performed.

However, the ink consumption is large because the suction operation and the forced ejection operation by the head press are performed on the entire ink in the pressure chamber. Therefore, when there is little viscosity increase, it is preferable to perform preliminary discharge as much as possible. In addition, it is needless to say that the cap 58 described with reference to FIG. 5 functions as a suction means and can function as an ink receiver for preliminary ejection.

Moreover, it is preferable to set it as the structure which the inside of the cap 58 is divided into several area | region corresponding to the nozzle row by the partition wall, and each of these divided areas can be selectively suctioned by a selector etc.

Next, as shown in FIG. 5, the ink replenishment system 70 of the ink refilling tank 72 which stores the cone ink, the diluent replenishment tank 74 which stores the dilution liquid, and the ink tank 52 A concentration detector 76 for detecting the concentration of the ink, a level detector 78 for detecting the storage amount of the ink in the ink tank 52, and a detected density from the concentration detector 76 and the ink from the level detector 78 And a replenishing control unit 80 for receiving the information of the storage amount of the liquid, and controlling the replenishment amount of the dike solution from the dike replenishment tank 74 and the replenishment amount of the dike solution from the dike replenishment tank 74.

In the ink replenishment system 70 shown in FIG. 5, the ink tank 52 and the recovery tank 64 are connected by the recovery ink replenishment pipe 82. In the recovery ink refilling pipe 82, a filter 84 for removing deteriorated ink such as solidified ink contained in the recovery ink recovered in the recovery tank 64 is formed, and the recovery ink refilling pipe 82 is provided. On the side close to the ink tank 52, the density detection part 86 is formed. Here, the replenishment control unit 80 also receives information on the detected concentration of the recovered ink from the concentration detection unit 86, adds the replenishment amount of the cone ink and the replenishment amount of the dilution liquid, and recovers it from the recovery tank 64. Control the ink replenishment amount.

The cone ink replenishment tank 72 is a tank for filling the ink (high concentration ink), and is provided with a pump (not shown) for supplying the ink of the ink in the ink replenishment tank 72 to the ink tank 52. According to the instruction from the replenishment control unit 80, the ink ink 52 is replenished in the ink tank 52.

On the other hand, the diluent replenishment tank 74 is a tank for filling a solvent used as a diluent of ink when replenishing ink, and has a pump or the like for supplying the diluent to the ink tank 52, and the replenishment control unit 80 According to the instruction from the above, the diluent is replenished in the ink tank 52.

Here, in the present invention, the concentration of the cone ink is not particularly limited, and may be higher than the target concentration of the ink. Preferably it is 1.5 to 5 times of concentration range as colorant amount, More preferably, it is 2 to 4 times of concentration range. That is, the ink having a higher concentration than the target concentration of the ink may be used as the ink having a predetermined concentration for replenishment. Also, the diluent is not particularly limited, and an ink having a lower concentration than the target concentration of the ink may be used. That is, in this invention, you may replenish using the ink of several predetermined density | concentrations from which the density | concentration mutually differs including the ink of high density | concentration and the ink of low density | concentration rather than the target density | concentration of ink as a cone ink and a diluent liquid.

The density detection unit 76 detects the density of the ink using the optical detection means and supplies it to the replenishment control unit 80.

For example, in the ink supply system 50 of the inkjet drawing apparatus 30, the ink supply pipe 54 has a permeation | transmission part formed with a light transmissive member, such as a part and glass, and the density | concentration detection part 76 emits light. The measurement light emitted from the element is incident on the light transmitting portion, and the light amount of the transmitted light passing through the light transmitting portion is measured by the light receiving element. The density detector 76 has a look-up table (LUT) indicating the relationship between the measurement result of the transmitted light and the ink concentration, which is prepared in advance by an experiment or the like, and calculates the ink concentration from the measurement result of the transmitted light using this LUT. Alternatively, instead of the LUT, the density of the ink may be determined by a calculation formula using the measurement result of the transmitted light as a parameter.

In addition, in this invention, the detection method and means of the ink density in the density detection part 76 are not limited to an optical method and means, Various methods and means can be used, For example, the ink tank 52 Ink characteristics such as electrical conductivity of the ink in the ink) may be detected to determine the ink concentration. Moreover, in this invention, such an optical density detection method and means can be used preferably from the point of detecting the density | concentration of ink directly and with high precision.

The level detection unit 78 detects the ink level (the liquid level of the ink, that is, the amount of ink) in the ink tank 52 and supplies it to the replenishment control unit 80. That is, in the example of illustration, by detecting the ink level in the ink tank 52, the ink amount in the ink supply system 50 is detected.

In the present invention, the ink level detection means and method are not particularly limited, and electrical level detection means using electrodes, etc., level detection means using floats, ultrasonic level detection means, capacitive level detection means, Various well-known means and methods, such as a detection method using these means, can be used. In addition, the ink amount in the ink tank 52 may be directly detected by measuring the ink weight in the ink tank, or the like, instead of detecting the ink level.

When the refill control unit 80 refills the ink tank 52, the concentration information of the ink and the recovered ink from the concentration detectors 76 and 86 and the inside of the ink tank 52 from the level detector 78 are changed. Receive the ink amount information, and determine the refilling amount of the cone ink and the diluent, or the refilling amount of the recovered ink, the cone ink and the diluent, and the refilling amount of the conk ink and the diluent replenishing tank 74 with respect to the conk ink refilling tank 72. ) And the supplemented amount of the recovered ink with respect to the recovery tank 64, respectively.

In addition, in the recording apparatus 10 using the present invention, the timing of ink replenishment is not particularly limited, and for example, may be automatically performed for each predetermined time or period, or every drawing of a predetermined number of substrates, and the like. It may be performed automatically according to the amount of ink in the ink tank 52 detected by the detection unit 78, or may be performed in accordance with an input instruction by a judgment of an operator or the like who observed the drawn pixel, and a plurality of timing determining means. You may carry out selectively with.

Although the inkjet drawing apparatus shown to FIG. 3 thru | or FIG. 5 is comprised basically as mentioned above, the action of this inkjet drawing apparatus and the inkjet drawing method for color filter manufacture by an inkjet drawing apparatus are demonstrated below.

FIG. 6: is a flowchart which shows the flow of one Embodiment before the start of drawing of the inkjet drawing method performed as a drawing process for manufacture of a color filter in the inkjet drawing apparatus shown in FIGS.

First, as shown in FIG. 6, in the step S120, in the inkjet drawing apparatus 30 shown in FIG. 3, on the platen 32 via the board | substrate conveyance mechanism 40 by the board | substrate supply means which is not shown in figure. The board | substrate 12 in which the partition 14 is formed is supplied. Next, in step S122, the supplied substrate 12 is conveyed onto the platen 32 by the transfer roller 46 and the pressing roller 48 of the substrate transfer mechanism 40 and positioned at the predetermined position. After the crystallization is stopped, the substrate 12 is fixed to the platen 32 by, for example, adsorption or the like. Next, in step S124, the substrate alignment is adopted 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 movement mechanism 38, the head unit 36 is moved along the guide rail 43, and the head unit 36 ) Is moved to a maintenance position (ejection inspection position; not shown) for inspecting the ejection state of the inkjet head 34, which is separated from the region of the substrate 12 or the region of the platen 32, and is shown in FIG. 5. Similarly, the nozzle face 34a of the inkjet head 34 is opposed to the cap 58. At this time, the head unit 36 is moved to the predetermined position facing the cap 58.

Next, in step S132, the cap 58 is raised to abut on the nozzle face 34a of the inkjet head 34, and ink is ejected from each nozzle to detect ejection of ink. The ejection detection of the ink, that is, the inspection of the ejection state, may be performed by detecting the presence or absence of the ejected ink droplets by an optical sensor formed in each nozzle of the inkjet head 34 in the cap 58, for example, a light emitting light receiving element. Alternatively, the amount of ejected ink droplets may be measured for each nozzle of the inkjet head 34, and the ejected state of each nozzle may be inspected according to whether or not the amount is within a predetermined specification, i.e., a predetermined range. In addition, the discharge ink at the time of discharge detection is collect | recovered to the recovery tank 64 via the ink recovery pipe 66.

Next, in step S134, a determination is made as to whether all the nozzles of the inkjet head 34 are within a preset specification, that is, in an appropriate ejection state.

In the judgment of this step S134, when all the nozzles of the inkjet head 34 are in the above-mentioned set specification (suitable ejection state) (Y), it moves to step S126 and the cap 58 of the inkjet head 34 It removes from the nozzle surface 34a, and as shown in FIG. 3, the drive screw 42 is driven by the head movement mechanism 38, the head unit 36 is moved along the guide rail 43, and the head unit The 36 is moved to a predetermined drawing start position on the substrate 12 by substrate alignment.

Next, in step S128, the drawing is performed on the substrate 12.

On the other hand, in the judgment of said step S134, if even one nozzle of the inkjet head 34 deviates from the said set specification (suitable discharge state), it transfers to step S136 and the angle of the inkjet head 34 Dummy discharge (preliminary discharge) is performed from the nozzle.

Next, in step S138, discharge of ink from each nozzle of the inkjet head 34 is detected similarly to step S132, and the discharge state of each nozzle is inspected. In addition, discharge ink at the time of dummy discharge and discharge detection is recovered to the recovery tank 64 through the ink recovery pipe 66 (see FIG. 5).

Next, in step S140, it is determined whether or not all the nozzles of the inkjet head 34 are within the set specification as in step S134, and when it is within the set specification (Y), the process moves to step S126. As described above, the cap 58 is removed from the nozzle face 34a of the inkjet head 34, and the drive screw 42 is driven by the head moving mechanism 38 to guide the head unit 36. It moves along the rail 43 (refer FIG. 3), and moves the head unit 36 to the predetermined drawing start position on the board | substrate 12 by board alignment.

Next, in step S128, the drawing is performed on the substrate 12.

On the other hand, in the judgment of the step S140, if even one nozzle of the inkjet head 34 is out of the above set specification (N), the process moves to step S142 and each nozzle of the inkjet head 34 is suction pump. Ink in each nozzle is sucked by 62, or head pressure is applied to each nozzle by the head pressurizing pump 68 to forcibly discharge ink in each nozzle (see FIG. 5). In addition, you may perform both the nozzle suction operation | movement by the suction pump 62, and the forced discharge operation | movement by the head pressurization pump 68. FIG.

Next, in step S144, the cap 58 is removed from the nozzle face 34a of the inkjet head 34, and the nozzle face 34a is wiped by the cleaning blade 60, and the nozzle face ( Degradation ink such as solidification ink and high viscosity ink attached to 34a) is rubbed off and the nozzle face 34a is cleaned (see Fig. 5).

After that, in step S146, dummy discharge is performed from each nozzle of the inkjet head 34 in the same manner as in step S136.

Next, in step S148, the ejection detection of the ink in each nozzle of the inkjet head 34 is performed similarly to step S138, and the ejection state of each nozzle is examined. In addition, the discharge ink at the time of the nozzle suction operation and / or the forced discharge operation, the dummy discharge and the discharge detection is recovered to the recovery tank 64 through the ink recovery pipe 66 (see FIG. 5).

Next, in step S150, a judgment is made as to whether or not all the nozzles of the inkjet head 34 are within the set specifications in the same manner as in step S140, and when it is within the set specifications (Y), the process goes to step S126. In addition, as described above, the cap 58 is removed from the nozzle face 34a of the inkjet head 34, the drive screw 42 is driven by the head moving mechanism 38 to drive the head unit 36. It moves along the guide rail 43, and moves the head unit 36 to the drawing start position on the board | substrate 12 by board alignment (refer FIG. 3).

Next, in step S128, the drawing is performed on the substrate 12.

On the other hand, in the judgment of said step S150, if even one nozzle of the inkjet head 34 is out of the said set specification (N), it will return to step S142 again and the nozzle by the suction pump 62 mentioned above. The suction operation and / or the forced discharge operation by the head pressurizing pump 68 are performed, the nozzle wiping by the cleaning blade 60 in step S144, the dummy discharge in step S146, and the discharge in step S148. Detection and determination as to whether or not all the nozzles in step S150 are within the set specification are sequentially performed.

In step S150, when all the nozzles are within the above set specification (Y), the process moves to step S126, and the head unit 36 is similarly moved to the drawing start position on the substrate 12 by substrate alignment ( 3), in step S128, the image is drawn on the substrate 12, but even if one nozzle of the inkjet head 34 deviates from the set specification (N), the process returns to the above-described step S142 again. Each operation of steps S142, S144, S146, S148, and S150 is repeated until all the nozzles are in the above-mentioned setting specification (Y). If the number of repetitions exceeds the predetermined number of times, it is better to stop the drawing method as an error.

In addition, in the drawing step of step S128, in the inkjet drawing apparatus 30 shown in FIG. 3, the head moving mechanism 38 moves (scans) the head unit 36 to the main scanning X direction, and is a board | substrate. Droplets of ink 18 are discharged from the inkjet head 34 to a predetermined recessed portion 16, that is, a predetermined recessed portion 16 between the partitions 14 on the substrate 12, and drawn. Cured pixel ink 18a is formed.

In this way, the head unit 36 is moved from the start end to the drawing region of the substrate 12 (the region where the partition wall 14 is formed) from the start end in the main scanning X direction and / or from the end end to the start end. Scanning is performed to finish pixel formation in the main scanning direction.

Thereafter, the adsorption 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 rotated a predetermined distance (in the sub-scanning direction). For example, it conveys and moves by the length (DELTA) Y (1 pitch (one way) or 2 pitches (reciprocation) of the cell of a color filter)) for the drawing area, it stops on the platen 32, and again the platen 32 The substrate 12 is fixed by suction. Thereby, the head unit 36 which reached the start or end of the main scanning direction of the board | substrate 12 will be in the state moved to the sub-scanning direction by the fixed amount (length (DELTA Y) for drawing area).

Subsequently, from the drawing start position in the main scanning direction to the substrate 12 adsorbed and fixed on the platen 32 in this way, as described above, the head unit 36 is further moved by the head moving mechanism 38. It moves to the main scanning X direction, it draws by the inkjet head 34, and the drawing of the main scanning direction of the board | substrate 12 is complete | finished.

 Thereafter, the suction of the substrate 12 to the platen 32 is again released, the substrate is transported by the predetermined distance ΔY in the sub-scanning direction of the substrate 12, and the suction of the substrate 12 to the platen 32 is fixed. The head unit 36 is scanned in the main scan direction by repeating the drawing of the substrate 12 by the inkjet head 34 and moving the substrate 12 by the length ΔY of the drawing region from the start to the end in the sub-scan direction. Move in the (X) direction, eject ink from the nozzle of the inkjet head in accordance with the ejection signal, and draw the entire surface of the substrate 12 with respect to one color, so that the pixel of the color filter (uncured pixel ink 18a) is Form.

In this manner, ink is also ejected while moving the head unit 36 on the substrate 12 in the main scanning direction with respect to the other colors of the color filter, and thereafter, the substrate 12 is fixed at a certain distance in the sub scanning direction. By repeating the movement, the pixels 12 of the color filter (uncured pixel ink 18a) are formed on the substrate 12 in succession to form other colors, and the entire pixels (not applied to all the colors of the color filter). The cured pixel ink 18a can be formed.

In addition, in this invention, the nozzle arrangement | positioning of the inkjet head 34 of the head unit 36 is not specifically limited, A single row | line | column may be sufficient, a plurality of rows may be sufficient, and the number of nozzles of each nozzle row is not specifically limited, either It may be sufficient as it or a plurality. Moreover, the drawing format of the color filter by the inkjet head 34 which has such a nozzle arrangement to the cell and the pixel is not restrict | limited in particular, What kind of thing may be sufficient as it.

For example, as shown in Fig. 9 (a), the inkjet head 34R which discharges R ink with four rows of nozzles in the nozzle portion, and the inkjet which discharges G ink with four rows of nozzles in the nozzle portion Using the head 34G and the inkjet head 34B having four rows of nozzles in the nozzle portion and discharging B ink, the nozzle intervals of the nozzle rows of the respective inkjet heads 34R, 34G, and 34B are illustrated. As shown in 9 (b), when the dot spacing 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 subjected to main scanning. The ink droplets are scanned from the eight nozzles in total by using two nozzles in each row of four rows from one inkjet head to one cell of the color filter by scanning so that the (X) direction and the longitudinal direction of the cells of the color filter are orthogonal. Discharged to form eight dots in one cell of the color filter, Or it formed of a cell (i.e., cell (20R, 20G, 20B)) for the respective colors. In addition, as shown in Fig. 9C, the nozzle row 35R in which the nozzles for discharging R ink are arranged, the nozzle row 35G in which the nozzles for discharging G ink are disposed, and the B ink are discharged. Using the inkjet head 34 'having three rows of nozzles in the nozzle row 35B in which the nozzles are arranged, the inkjet head 34' is made to coincide with the main scanning X direction and the longitudinal direction of the cells of the color filter. 8 ink in total from one nozzle by scanning, using one nozzle of one nozzle row (i.e., one of the nozzle rows 35R, 35G, 35B) for one cell of the color filter. The droplets are discharged and eight dots are placed in one cell of the color filter shown in FIG. 9 (d), that is, in one of the cells 20R, 20G, 20B, 20R 'in FIG. 9 (d). You may form. In the example shown in FIG. 9 (d), three of the four cells of the color filter (specifically, cells 20R, 20G, and 20B) each have eight dots of three different inks. It is formed, and the top and bottom two cells (specifically, cells 20R and 20R ') of FIG. 9 (d) are nozzle rows of the inkjet head 34' shown in FIG. 9 (c). 35R is formed by different nozzles, indicating that eight dots each of the same kind of ink are formed.

Here, the shape of the pixel array (pixel pattern) of the color filter formed by the inkjet drawing method shown in FIG. 6 using the inkjet drawing apparatus 30 shown in FIGS. Although it can be set as the stripe shape shown to 7 (a), the lattice shape shown to FIG. 7 (b), or the delta arrangement shape shown to FIG. 7 (c), this invention is not restrict | limited in particular.

In addition, when drawing and hardening the color pixel arrangement (color pixel pattern) of the color filter shown to FIG.7 (a)-FIG.7 (c), one color, for example, first the color pixel pattern of R Draw and harden to form the color pixels 20, and sequentially draw different colors one by one, for example, in the order of G, then B, draw and harden the color pixel pattern to form color pixels of all colors ( 20) a color pixel pattern may be formed, and two or more colors, for example, three or more colors of RGB, for example, may be sequentially or simultaneously or plural colors drawn, and then two or more colors drawn, for example The uncured pixel 18a of the three-color RGB pixel pixel pattern may be cured to form the cured color pixel 20 of the color pixel pattern of a plurality of colors or all colors.

As described above, in manufacturing the color filter, for example, since the pixel array of three primary colors such as RGB, that is, the pixel pattern is regular, an inkjet head is used to draw a normal image composed of a random color pixel pattern. Or different from these, the nozzle used for an inkjet head is determined, and the nozzle which does not use for a long time among all the nozzles of an inkjet head arises. For this reason, in the inkjet drawing method in the manufacturing method of the color filter of this invention, as shown in FIG. 6, it is preferable to perform the inkjet drawing, checking the discharge state of each nozzle of an inkjet head, and confirming discharge. Do.

In the above-described embodiment, the head unit is moved in the main scanning direction and the sub scanning direction to form pixels, but the present invention is not limited thereto. For example, the head unit is moved only in the main scanning direction and the substrate is attached. You may make it move by a fixed distance in a scanning direction.

Further, the inkjet head may be a full line head, and pixels may be formed on the entire surface of the printing plate original plate by one scan of the head unit. In this case, 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, although the ink tank 52 is connected to the inkjet head 34 directly by the ink supply pipe 54, this invention is not limited to this, and prevents the fluctuation of internal pressure of a head. In order to impart a function of improving the dumper effect and the refilling, the supply sub tank may be formed between the ink tank 52 and the inkjet head 34.

In FIG. 8, instead of the ink supply system shown in FIG. 5, the schematic structure of another embodiment of the ink supply system applied to the inkjet drawing apparatus shown in FIG. 3 and FIG. 4 is shown typically.

As shown in FIG. 8, the inkjet drawing apparatus 31 and the ink supply system 90 used for this are basically an inkjet head (discharge head) 12, the cap 58, and the ink tank 52 ), A supply sub tank 92, a recovery tank 64, and a replenishment tank 94.

The inkjet drawing apparatus 31 and the ink supply system 90 shown in FIG. 8 have the inkjet drawing apparatus 30 and the ink supply system 50 and the supply sub tank 92 which are shown in FIGS. Since the recovery tank 64 and the ink tank 52 have the same configuration except for being different from each other by the overflow pipe 98, the same components are assigned the same reference numerals, and the detailed description thereof is omitted. do. In addition, as for the scanning system of the inkjet drawing apparatus 31 which is not shown in FIG. 8, the scanning system of the inkjet drawing apparatus 30 shown in FIG. 3 and FIG. 4 may be applied, or the conventionally well-known scanning system may be applied. do.

The ink supply system 90 mainly serves as a narrow ink supply system for supplying the ink of the ink tank 52 to the inkjet head 34, and an ink recovery system for recovering and reusing ink purged in the cap 58. It is composed. 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 supply sub tank 92, and an inkjet head. It also functions as a second ink supply pipe 54b for connecting the 34 and a third ink recovery pipe (euro) 98 that overflows the ink in the supply sub tank 92 and transfers the liquid to the ink tank 52. It consists mainly of the overflow pipe 98A opened inside the supply sub tank 92. As shown in FIG. In addition, the ink recovery system overflows the ink in the first ink recovery pipe 66, which connects the recovery tank 64, the cap 58, and the recovery tank 64, and the recovery tank 64 to the ink tank 52. It mainly consists of the overflow pipe 100a opened in the recovery tank 64 which also functions as the 2nd ink recovery pipe 100 which collects and collect | recovers liquids. The second ink recovery tube 100 (overflow tube 100a) is equipped with a concentration detector 86 for measuring the transmittance of the recovered ink in order to detect the concentration of the recovered ink flowing therein. In addition, an air release valve 102 and a pressure regulating valve 104 are attached to the supply sub tank 92. The ink supply pipe serving as the ink supply passage and the ink collecting vessel serving as the ink recovery passage can be constituted by, for example, a pipe or a flexible tube.

In addition, although FIG. 8 mainly shows the characteristic site | part of this invention, the inkjet drawing apparatus 31 and the ink supply system 90 drive the inkjet head 34, for example, in addition to what is shown in the figure. Transfer the recording medium P in a direction orthogonal to the nozzle column direction (row direction), which will be described later, in a predetermined path facing the driver for ejecting the droplets, the scanning means of the inkjet head 34, or the inkjet head 34 (scan conveyance). It goes without saying that it has various components of a known inkjet drawing apparatus, such as a scanning conveying means.

The cap 58 is attached to the nozzle side of the inkjet head 34 at the time of stopping the circulation of the ink or not drawing for a long time, and keeps all the nozzles of the inkjet head 34 in a state where communication with the outside air is blocked. This is to prevent dry fixation by evaporation of the ink remaining in the nozzle. Such a cap 58 can be variously used that is commonly used in various inkjet recording apparatuses.

The ink tank 52 mixes the solvent from the replenishment tank 94, the conk ink, and the recovered ink from the recovery tank 64, so that the liquid properties and optical characteristics are constant, and the ink storage function is provided. Have It is preferable that the ink tank 52 has stirring means for preventing precipitation of dye and temperature control means for improving stability of ink discharge.

On the first ink supply pipe 54a, an ink pump 96 for feeding ink from the ink tank 52 to the supply sub tank 92 is disposed. The liquid supply amount by the ink pump 96 is set more than the ink supply amount from the supply sub tank 92 to the inkjet head 34.

The supply sub tank 92 is a hermetically sealed ink tank to which the first ink supply pipe 54a and the second ink supply pipe 54b are connected, and are disposed below the ink jet head 34 in the vertical direction. The other end of the second ink supply pipe 54b connected to the supply sub tank 92 is connected to the ink jet head 34.

In the supply sub tank 92, 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. do.

Moreover, in the supply sub tank 92, the overflow pipe 98a used as the 3rd ink recovery pipe 98 is arrange | positioned, and the 2nd ink supply pipe 54b is compared with the upper end of the overflow pipe 98a. It is connected below. In the example of illustration, the connection part with the 2nd ink supply pipe 54b is formed in the bottom face of the supply sub tank 92. As shown in FIG.

The ink stored in the supply sub tank 92 is pressurized from the second ink supply pipe 54b to the nozzle meniscus by pressurizing the supply sub tank 92 by the surface tension or the supply sub tank pressure adjusting mechanism. Supplied to.

Moreover, in the supply sub tank 92, even if the ink supplied by the ink pump 96 exceeds the height of the overflow pipe 98a, since it overflows and discharges from the overflow pipe 98a, the liquid level in a tank The height of is kept constant. As a result, when the supply sub tank 92 is opened to the atmosphere, the pressure of the supply sub tank 92 is kept constant.

Moreover, the ink which overflowed and discharged from the overflow pipe 98 is returned to the ink tank 52 via the 3rd ink recovery pipe 98, and is circulated again.

The recovery tank 64 is a sealed ink tank connected to the cap 58, and is disposed below the ink jet head 34 in the vertical direction. As described above, the other end of the first ink recovery pipe 66 is connected to the cap 58, and the other end of the second ink recovery pipe 100 is connected to the ink tank 52, respectively.

The ink discharged to the cap 58 by the purge and dummy discharge is stored in the recovery tank 64. 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 hermetic tank for replenishing the consumed ink to the ink tank 52, and is connected to the ink tank 52 by the ink replenishment pipe 106.

The replenishment tank 94 replenishes the ink in the ink tank 52 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, and for example, a condensate tank for storing the conk ink (high concentration ink) and a diluent for storing the dilution liquid of the ink, as in the ink replenishment system 70 shown in FIG. 5. The tank may have a tank, and the ink tank may be replenished with a predetermined amount of the cone ink and the diluent so as to have a predetermined concentration and a predetermined amount. Moreover, what is necessary is just to use a solvent as a diluent liquid.

In the inkjet drawing apparatus 31 and the ink supply system 90, the replenishment timing of ink is not specifically limited. For example, the drawing may be automatically performed for each drawing of a predetermined number of sheets, or the like may be automatically detected by detecting the amount of ink in the ink tank 52, or according to an input instruction by an operator or the like who has observed the drawn pixels. It may be implemented, and may have a some timing determination means, and may implement selectively.

In addition, the method of determining the replenishment amount of the cone ink and the diluent is not particularly limited. For example, the consumption amount of the ink is estimated using the total number of ink ejections detected from the pixel data or the like, the concentration measurement result of the circulating ink, the ink amount in the ink tank 52, etc., in addition to the estimated amount of ink evaporation, What is necessary is just to determine the replenishment amount of ink so that it may become a predetermined amount with the ink Q predetermined density | concentration in the ink tank 52.

·t) (

：흡수 계수 (염료 농도에 비례), t：두께) 인 것으로부터 산출할 수 있다. 투과율의 측정을 위해, 잉크 농도 측정 에어리어에는 광원, 수광 센서 및 유리 등의 투명 부재의 유로를 구비한다. 유로는, 측정광이 투과되는 부분에 대해서는 평면인 것이 바람직하고, 표면은 AR 코트되어 있는 것, 광축에 대해 수직으로부터 몇 도 기울어져 있는 것이 바람직하다. 반사광에 의한 측정 정밀도의 악화 방지를 위해서이다. The mixing method of a dilution liquid, a cone ink, and a collection ink can also be performed with the following method. A transparent portion is set as an ink concentration measuring area in the middle of the third ink recovery pipe 100 serving as a flow path from the recovery tank 64 to the ink tank 52, and the density detection unit 86 is disposed therein. The concentration detection part 86 calculates the solvent evaporation amount of the ink collect | recovered to an ink tank by measuring the light transmittance of the ink in a measurement area. The relationship between the light transmittance and the solvent evaporation amount is to measure the relationship between the ink and the light transmittance having different dye concentrations in advance, and the light transmittance exp (-

T) (

: It can calculate from absorption coefficient (proportional to dye concentration), and t: thickness. In order to measure the transmittance, the ink concentration measuring area includes a flow path of a transparent member such as a light source, a light receiving sensor, and glass. It is preferable that a flow path is planar with respect to the part to which measurement light permeate | transmits, and it is preferable that the surface is AR-coated and it inclines several degrees from perpendicular | vertical with respect to an optical axis. This is to prevent deterioration of measurement accuracy due to reflected light.

The mixing ratio of the diluent, the cone ink and the recovered ink is determined from the concentration of the recovered ink.

The inkjet drawing apparatus 31 and the ink supply system 90 shown in FIG. 8 are comprised as mentioned above basically.

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

As mentioned above, although the inkjet ink of this invention, the color filter, its manufacturing method, and the liquid crystal display and image display device using the same have been described in detail with reference to various embodiment and Example, this invention is the said Example or It is a matter of course that various modifications and changes may be made without departing from the spirit and scope of the present invention.

Example

An Example is given to the following and this invention is demonstrated to it further more concretely. Materials, reagents, ratios, instruments, operations, and the like 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 example shown below. In addition, in the following Examples, "%" and "part" show a "mass%" and a "mass part" unless there is particular notice, and molecular weight shows a weight average molecular weight.

(Preparation of deep color composition for partition formation)

The thickening composition K1 first takes K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 10 minutes, and further stirred, Methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA liquid, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisdiethoxycarbonylmethyl) in the amounts shown in Table 1 ) Amino-3'-bromophenyl] -s-triazine and surfactant (1) were taken and added in this order at a temperature of 25 deg. C (± 2 deg. C), and at 150 rpm at a temperature of 40 deg. It is obtained by stirring for 30 minutes. In addition, the quantity of Table 1 is a mass part, and has the following composition in detail.

<K pigment dispersion 1>

Carbon black (Degusa Nipex35) 13.1%

Dispersant (compound 1 below) 0.65%

Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio

         Random copolymer, molecular weight 3.7 million) 6.72%

Propylene glycol monomethyl ether acetate 79.53%

<Binder 2>

Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio

         Random copolymer, molecular weight 3.8 million) 27%

Propylene glycol monomethyl ether acetate 73%

 <DPHA liquid>

Dipentaerythritol hexaacrylate

 (Contains 500ppm of polymerization inhibitor MEHQ, manufactured by Nippon Gunpowder Co., Ltd.,

  KAYARAD DPHA) 76%

Propylene glycol monomethyl ether acetate 24%

<Surfactant 1>

The following structure 1 30%

70% methyl ethyl ketone

(Formation of bulkhead)

The alkali free glass substrate was wash | cleaned with the UV cleaning apparatus, and then brush-cleaned using a washing | cleaning agent, and also ultrasonic cleaning with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.

After cooling a board | substrate and temperature-controlling at 23 degreeC, the deep color composition K1 prepared as mentioned above is apply | coated with the coater for glass substrates (F * A * S Asia company make, brand name: MH-1600) which has a slit-shaped nozzle. It was. Subsequently, a part of the solvent was dried for 30 seconds with a VCD (vacuum drying device, manufactured by Tokyo Oka Industries Co., Ltd.) to remove fluidity of the coating layer, and then prebaked at 120 ° C. for 3 minutes to give a thick composition layer K1 having a thickness of 2.3 μm. Got it.

With a proximity type exposure machine (manufactured by Hitachi Hi-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the distance between the exposure mask surface and the deep photosensitive layer K1 is 200 while the substrate and the mask (quartz exposure mask having an image pattern) are placed vertically. It set to micrometer, and it pattern-exposed to 20 micrometers of partition widths, and 100 micrometers of space widths by exposure amount 300mJ / cm <2> in nitrogen atmosphere.

Next, pure water is sprayed with a shower nozzle, and the surface of the deep color composition layer K1 is uniformly wetted, and then KOH-based developer (containing nonionic surfactant, trade name: CDK-1, manufactured by Fuji Film Electronics Co., Ltd.) 100 times diluted) was shower-developed at 23 degreeC for 80 second and the flat nozzle pressure 0.04 Mpa, and the patterning image was obtained. Subsequently, ultrapure water is sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove the residue, and post exposure is performed from the surface side on which the deep color composition layer K1 of the substrate is formed at an exposure dose of 2500 mJ / cm 2 under an atmosphere, at 240 ° C. in an oven. It heated for 50 minutes and obtained the stripe-shaped partition wall which has opening part of 2.0 micrometers of film thickness, optical density 4.0, and 100 micrometer width.

Ink repellent plasma treatment

The ink repellent plasma process was performed to the board | substrate with which the partition was formed using the cathode coupling type parallel plate type plasma processing apparatus on condition of the following.

Working gas ： CF ₄

Gas Flow Rate: 80sccm

Pressure: 40Pa

RF power: 50W

Processing time: 30sec

Preparation method of <ink for blue (B)> (1)

The following components were mixed and stirred for 1 hour. Then, it filtered under reduced pressure with the microfilter of the average pore diameter of 0.25 micrometer, and the blue ink liquid (ink B-1 and ink B-2) was prepared.

The detail of the used material is shown below.

Dyes: exemplary compound Ia-5 of the specific metal complex compound-I

Dye: VALIFAST BLUE 2620 (manufactured by Orient Chemical Industry Co., Ltd.)

DPCA-60 (manufactured by Nippon Kayaku Co., Ltd. (KAYARAD DPCA-60)): caprolactone modified dipentaerythritol hexaacrylate

KF-353 (manufactured by Shin-Etsu Silicone Co., Ltd.): polyether modified silicone oil

 (Measurement of viscosity and surface tension)

In the state which adjusted the temperature of the obtained ink at 25 degreeC, it measured on condition of the following using the Toki Sangyo Co., Ltd. E-type viscosity meter (RE-80L).

(Measuring conditions)

Rotor: 1 ° 34 '× R24

Measurement time: 2 minutes

Measurement temperature: 25 ℃

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

<Contrast Measurement Method>

A monochromatic substrate was provided between two polarizing plates (POLAX-15N manufactured by Rukeo) using a diffuser plate provided in a cold cathode tube light source (a light source for emitting light having a wavelength spectrum distribution shown in FIG. 10) as a backlight unit. The contrast was calculated | required by dividing the Y value of the chromaticity of the light which passes when installing a polarizing plate in parallel nicotine, and the Y value of the chromaticity of the light which passes when installing a polarizing plate in cross nicol. The chromaticity meter (BM-5A by Topcon Co., Ltd.) was used for the measurement of chromaticity. The monochromatic substrate was manufactured by the following method. A beta film is formed on the glass substrate by an inkjet method or a spin coat method using the ink of one color among the B inks constituting the color filter (ink B-1 and ink B-2), in the same manner as the color filter formation. Prebaking (preheating) (temperature 100 degreeC, 2 minutes) and post-baking (post-heating) (temperature 220 degreeC, 30 minutes) were performed, and the film thickness 2um (micrometer) was formed.

The measurement angle of the color luminance meter was set to 1 °, and measured by the field of view 5 mm on the sample. The light quantity of the backlight was set so that the brightness | luminance at the time of providing two polarizing plates in parallel nicol in the state which did not provide a sample was 400 cd / m <2>.

As a result of measuring the contrast of the monochromatic substrates (six kinds) obtained above, even a monochromatic substrate obtained the value 50000 or more.

<ITO layer manufacture>

Next, using a sputtering apparatus on the above-mentioned monochromatic substrate, ITO (indium tin oxide) was sputtered for 15 minutes at the film surface temperature of 200 degreeC, the ITO film of a film thickness of 1500 Pa was formed, and the color filter substrate with ITO adhered. Was prepared.

<Changes in spectral characteristics before and after ITO sputtering>

Before and after ITO sputtering, the spectral transmittance curve in the wavelength range of 400 nm-700 nm was obtained using the ultraviolet-visible absorption spectroscopy apparatus (Nippon spectroscopy V-570). When the amount of change in the 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 turned out that the spectrum shape hardly changes before and after ITO sputtering, and has high heat resistance. Similarly for the monochromatic substrates of the other B inks (ink B-2), the spectral shapes were almost unchanged before and after the ITO specter.

Preparation method of <ink for blue (B)> (2)

The following components were mixed at the blending ratios shown in Table 3 and stirred for 1 hour. Thereafter, the resultant was filtered under reduced pressure with a microfilter having an average pore diameter of 0.25 µm to prepare blue ink solutions (B Examples 1 to 16). In addition, the numerical value in a table | surface shows mass%.

The detail of each material used for preparation of the ink for blue (B) is shown below.

(Organic solvent)

Cyclohexanone (made by Wako Pure Chemical Industries, Ltd.)

N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.)

Benzyl alcohol (made by Wako Pure Chemical)

MMPGAC (manufactured by Daicel Industries, Ltd.): propylene glycol monomethyl ether acetate

1,3-BGDA (manufactured by Daicel Industries Co., Ltd.): 1,3-butylene glycol diacetate

DCHMA (Tokyo Chemical Co., Ltd.): Dicyclohexylmethylamine

(Polymerizable monomer)

DPCA-60 (manufactured by Nippon Kayaku Co., Ltd. (KAYARAD DPCA-60): caprolactone-modified dipentaerythritol hexaacrylate

DPHA (KAYARAD DPHA): Dipentaerythritol hexaacrylate

AD-TMP (manufactured by Shin-Nakamura Chemical Co., Ltd. (NK ester AD-TMP)): ditrimethylolpropane tetraacrylate

(Surfactants)

KF-353 (manufactured by Shin-Etsu Silicone Co., Ltd.): polyether modified silicone oil

BYK-377 (manufactured by Vicchemy): Polyether-modified dimethylsiloxane mixture

Solsperse20000 (manufactured by Lubrizol)

F781-F (Dainippon Ink Chemical Industry Co., Ltd. (Megapack F781F))

(dyes)

Dye C-5 VALIFAST BLUE 2620 (manufactured by Orient Chemical Industries, Ltd.)

Dye C-6 (exemplary compound CA-19 of the compound represented by General Formula (A))

Dye C-7 (exemplary compound CC-5 of the compound represented by the general formula (A))

Dye C-8: the following exemplary compound F-2 (corresponding to the compound represented by General Formula (A))

Dye M-5 (exemplary compound Ia-5 of the compound represented by the general formula (II-2))

Dye M-6 (exemplary compound Ia-28 of the compound represented by General Formula (II-2))

Dye M-7 (example compound III-40 of the compound represented by the said General formula (III))

Dye M-8 (Example compound III-58 of the compound represented by the general formula (III))

Dye M-9 (exemplary compound III-92 of the compound represented by General Formula (III))

Dye M-10 (exemplary compound I-23 of the compound represented by General Formula (III))

<Preparation of pigment dispersion>

Dispersant and solvent (1,3-butanediol diacetate) (hereinafter abbreviated as 1,3-BGDA) in CIPB 15: 6 (brand name: Rionol Blue ES, manufactured by Toyo Inky Co., Ltd.) are shown in Table 6 below. After mixing and premixing, the motor mill M-50 (manufactured by Aiga Japan Co., Ltd.) was used to disperse the zirconia beads having a diameter of 0.65 mm at a filling rate of 80% for 25 hours at a circumferential speed of 9 m / s for 25 hours. Pigment dispersion (B1) was prepared. In the pigment dispersion (B2) for B, the pigment dispersion (B2) for B was prepared like B pigment dispersion (B1) except having mix | blended pigment and other components as shown in a table | surface. In addition, the number average particle diameter of this pigment dispersion liquid was measured using the Nikkiso company nano truck UPA-EX150.

In addition, the coloring agent used for manufacture of a pigment dispersion liquid is as follows.

C. I. P. B. 15: 6 (manufactured by Toyo Inki Maker): Rionol Blue ES

C. I. P. V. 23 (manufactured by Clariant Japan): Hostaperm Violet RL-NF

<Comparative ink>

As a comparative example, the pigment ink manufactured by the quantity of following Table 5 was prepared using said pigment dispersion liquid. In addition, the used material is as follows.

DPS100 (manufactured by Nippon Gunpowder): KAYARAD DPS100

TMPTA (manufactured by Nippon Kayaku Co., Ltd.): KAYARAD TMPTA

Surfactant: Surfactant 1 (structure described in compound 2)

V-40 (manufactured by Wako Pure Chemical Industries, Ltd.): azobis (cyclohexane-1-carbonitrile)

[Formula 33]

<Manufacturing method of color filter for evaluation>

Using the ink prepared above, discharge was carried out using the inkjet printer DMP-2831 made by FUJIFILM Dimatix, in a region (concave region surrounded by convex portions) separated by the partition on the substrate thus obtained, and then, Heated in 100 ° C. oven for 2 minutes.

Next, the monochromatic color filter was manufactured by leaving still for 30 minutes in 220 degreeC oven. In addition, the film thickness of the obtained color pixel was 2.0 micrometers.

<Ink preservation stability evaluation>

Each color ink prepared above was stored in a constant temperature chamber at 50 ° C., and the viscosity after 30 days was measured, and the difference (%) from the value immediately after ink preparation [(viscosity immediately after 30 days after preparation) / preparation Immediate viscosity] was evaluated. Evaluation criteria were classified as follows.

(Double-circle): The difference with the viscosity immediately after ink preparation is less than 10%

(Circle): The difference with the viscosity immediately after ink preparation is 10% or more and less than 20%

(Triangle | delta): The difference with the viscosity immediately after ink preparation is 20% or more and less than 30%.

X: The difference with the viscosity immediately after ink preparation is 30% or more

<Continuous discharge stability evaluation>

Using the ink prepared above, continuous discharge stability was evaluated. The evaluation method was performed with the FUJIFILM Dimatix Co. inkjet printer DMP-2831, the head cartridge of 10 pl. Of quantity, and the frequency of 10 kHz, and observed the state when it discharged continuously for 30 minutes. Evaluation criteria were classified as follows.

◎: Continuous discharge is possible without any problem

(Circle): Although discharge | disappearance a little, discharge unevenness etc. are observed during discharge, it returns during discharge, and is a state without a problem generally.

(Triangle | delta): A state in which discharge | emission does not return during discharge, and it does not return during discharge, but returns to a normal state by maintenance.

X: A state in which unejection and discharge nonuniformity occurred during discharge, it was impossible to discharge normally, and discharge did not return even by maintenance.

The maintenance was performed by a DMP-2831 purge (pressing ink in the head to forcibly eject ink from the nozzle) and a blot (a head nozzle surface was slightly brought into contact with a cleaning pad to suck ink from the nozzle surface). .

<Evaluation stability after discharge>

The ejection stability was evaluated using the ink prepared above. The evaluation method was carried out for 5 minutes at a frequency of 10 kHz at a frequency of 10 Hz using a Fujifilm Dimatix inkjet printer DMP-2831 manufactured by Fujifilm, Inc. Then, the state when discharge was started again on the same conditions was observed. Evaluation criteria were classified as follows.

◎: Dispensing is possible without problem at the same time as other instructions.

(Circle): Although a little discharge | emission, a discharge nonuniformity, etc. are observed immediately after a strike instruction, it returns during discharge and is generally a problem-free state.

(Triangle | delta): A state which returns to a normal state by maintenance, although un ejection and discharge unevenness generate | occur | produce and it does not return during discharge.

X: The discharge and discharge unevenness generate | occur | produce, and it cannot discharge normally, and even the maintenance does not return to normal level.

The maintenance was performed by a DMP-2831 purge (pressing ink in the head to forcibly eject ink from the nozzle) and a blot (a head nozzle surface was slightly brought into contact with a cleaning pad to suck ink from the nozzle surface). .

<Heat resistance evaluation>

The color filter of each color manufactured above was put into the oven heated at 230 degreeC, and left to stand for 1 hour, and the color was measured. As for the measurement of the hue, (DELTA) Eab before and after evaluation used the UV-560 (made by Nippon spectroscopy) as less than 5 as (circle). ΔEab was 5 or more and less than 15, and ΔEab was 15 or more. In addition, ΔEab is a value obtained from the following color difference formula by the CIE1976 (L *, a *, b *) spatial colorimeter (Nippon Color Society, New Monochromatic Color Science Handbook (1985) p.266).

ΔEab = {(ΔL) ² + (Δa) ² + (Δb) ² } ^1/2

<Chemical Resistance Evaluation>

The color filter of each color manufactured above was immersed in the chemical (N-methylpyrrolidone, 2-propanol, 5% sulfuric acid aqueous solution, 5% sodium hydroxide aqueous solution) evaluated for 20 minutes, and the color before and behind was measured. . As for the measurement of hue, (DELTA) Eab made less than 5 into (circle) using UV-560 (made by Nippon spectroscopy). ΔEab was 5 or more and less than 15, and ΔEab was 15 or more. The evaluation method of ΔEab is as described above.

In the following Tables 6-7, the evaluation result of each inkjet ink and a color filter is put together, and is shown.

In addition, in Table 7, "B Examples 1-16" points out the evaluation result of the color filter manufactured using the ink of B Examples 1-16, respectively.

 In the following evaluation results, x must not be included from a practical use viewpoint.

As shown in Tables 6-7, the inkjet ink of this invention was excellent also in the storage stability, and was excellent also in discharge stability. Moreover, the color filter manufactured using the inkjet ink of this invention had the same outstanding chemical-resistance and heat resistance as the case where a pigment ink was used.

On the other hand, in the comparative example using the pigment ink, discharge stability was bad and the practicality was lacking.

 BRIEF DESCRIPTION OF THE DRAWINGS It is a flowchart which shows the manufacturing process in one Embodiment of the manufacturing method of the color filter of this invention.

FIG.2 (a)-(f) are typical sectional drawing of the board | substrate and color filter shown in the manufacturing process order from a board | substrate to a color filter in the manufacturing method of the color filter of this invention, respectively.

FIG. 3 is a perspective view showing a part of one embodiment of an inkjet drawing apparatus used for carrying out a drawing step of the method for manufacturing a color filter of the present invention. FIG.

4 is a partial cross-sectional view of the inkjet 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.

FIG. 6 is a flowchart showing a flow of an embodiment of a drawing method performed in the inkjet drawing apparatus shown in FIG. 3.

(A)-(c) is a schematic diagram which shows the pixel arrangement 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 another embodiment of the ink circulation system applied to the inkjet drawing apparatus shown in FIG.

(A)-(d) of FIG. 9 each show an example of the nozzle arrangement of the inkjet head of the inkjet drawing apparatus shown in FIG. 3 and the dot formation of the color filter pixel drawn by the inkjet head having the nozzle arrangement. It is a schematic diagram.

FIG. 10 is a diagram showing a wavelength spectral distribution of light emitted from a cold cathode tube light source used in contrast measurement. FIG.

Explanation of the sign

10: color filter

12: substrate

14: bulkhead

16: concave

18: ink

18a: uncured pixel ink

20 pixels

22: protective film

30, 31: inkjet drawing apparatus

32: platen

34: inkjet head

36: head unit

38: head moving mechanism

40: substrate transfer mechanism

42: drive screw

43: guide rail

44: drive support

45: support

46: feed roller

48: pressing 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: recovery tank

66, 100: ink recovery tube

68: head pressurized pump

70: ink replenishment system

72: Conk Ink Refill Tank

74: diluent replenishment tank

76, 86: concentration detection unit

78 level detection unit

80: supplementary control unit

82: recovery ink refill tube

92: supply sub tank

94: replenishment tank

96: ink pump

98: overflow pipe

102: atmospheric release valve

104: pressure regulating valve

Claims (19)

The ink for inkjet containing the dipyrromethene type compound represented by general formula (I), and the dipyrromethene type metal complex compound obtained from a metal atom or a metal compound. [Formula 1] General formula (Ⅰ)

(In General Formula (I), R <_1> -R <_6> respectively independently represents 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.) The method of claim 1, The ink for inkjet, wherein the dipyrromethene metal complex compound is a compound represented by General Formula (II-1). [Formula 2] General formula (Ⅱ-1)

(In General Formula (II-1), 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. Ma is represents a metal atom or a metal compound, X ₂ represents a group required to neutralize a charge of Ma, X ₁ represents a group capable of binding to Ma. X ₁ and X ₂ are bonded to each other to five atoms, six atoms, or May form a 7-membered ring) The method of claim 1, The ink for ink jet, wherein the dipyrromethene metal complex compound is a compound represented by General Formula (II-2). [Formula 3] General formula (Ⅱ-2)

(In General Formula (II-2), R ₁ to R ₆ and R ₈ to R ₁₃ each independently represent a hydrogen atom or a substituent. R ₇ and R ₁₄ each independently represent a hydrogen atom or a halogen atom. , An alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound.) The method of claim 1, An inkjet ink, wherein said dipyrromethene metal complex compound is a compound represented by General Formula (III) or a tautomer thereof. [Formula 4] General formula (Ⅲ)

(In General Formula (III), R <_2> -R <_5> represents a hydrogen atom or a substituent each independently. R <_7> represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma is a metal atom. Or a metal compound, X ₃ represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, an oxygen atom, or Represents a sulfur atom, X ₄ represents NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or a sulfur atom , Y ₁ represents NRc (Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, or a carbon atom, and Y ₂ represents Represents a nitrogen atom, or carbon atom Produce. R ₈ and R ₉ are, each independently, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic group represents an amino group. R ₈ and Y ₁ is and optionally, and bonded to each other to form a five atoms, six atoms, or 7 membered ring, or may, and R ₉ and Y ₂ may form a five atoms, six atoms, or 7-membered ring by combining to each other. X ₅ is a bond and Ma Represents a possible group, a represents 0, 1, or 2) The method of claim 1, The ink for ink jet, wherein the dipyrromethene compound represented by the general formula (I) is a compound represented by the general formula (IV). [Formula 5] General formula (Ⅳ)

(In General Formula (IV), R <_1> -R <_4> and R <_6> respectively 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.) The method of claim 1, The inkjet ink, wherein the metal atom or metal compound is Fe, Zn, Co, V = O, or Cu. The method of claim 6,  An inkjet ink, wherein the metal atom or metal compound is Zn. The method of claim 1, Furthermore, the inkjet ink containing the tetraaza porphyrin type pigment | dye represented by General formula (A). [Formula 6] 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 composed of an atom selected from a carbon atom, a nitrogen atom, and a hydrogen atom. Represents a group of atoms forming a six-membered ring) The method of claim 8, The ink for inkjet of which the said tetraaza porphyrin type pigment | dye is a phthalocyanine type pigment | dye represented by General formula (B). [Formula 7] 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 method of claim 1, An ink jet ink further containing a polymerizable monomer. The method of claim 10, An inkjet ink, 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. The method of claim 1, Inkjet ink further containing a surfactant. The method of claim 1, Inkjet ink whose viscosity in 25 degreeC is 2-30 mPa * s.  The method of claim 1, Inkjet ink whose surface tension in 25 degreeC is 20-40 mN / m. The pixel formation process of forming the color pixel of a color filter by giving the droplet of the inkjet ink of any one of Claims 1-14 by the inkjet method to the recessed part partitioned by the partition formed on the board | substrate. Method for producing a color filter.  The color filter manufactured by the inkjet method using the inkjet ink in any one of Claims 1-14. The color filter provided with the color pixel formed using the inkjet ink of any one of Claims 1-14. The liquid crystal display provided with the color filter of Claim 16. An image display device comprising the color filter according to claim 16.

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