JP2011057834A - Ink for inkjet, color filter and method for producing the same, and liquid crystal display and image display device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a blue ink for inkjet that forms a color pixel exhibiting good luminance and hue and having excellent heat resistance and light resistance, produces a color filter having excellent chemical resistance to various solvents, and is applicable to a thermosetting process; a color filter obtained from such an ink for inkjet; and a method for producing the color filter. <P>SOLUTION: The ink for inkjet includes: at least one dye selected from the group consisting of a dye represented by general formula (1), a dye represented by general formula (2-1), a dye represented by general formula (2-2), and a dye represented by general formula (2-3); a radically polymerizable monomer; an organic solvent; and a polyfunctional thiol compound which is bifunctional or more. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

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

  Conventionally, a so-called color resist method has been widely used as a method for producing a color filter. In this method, a photosensitive resin composition mainly containing a dye is applied on a predetermined substrate to form a coating film, and then the coating film is subjected to pattern exposure and development by repeating the operation a predetermined number of times. Manufacture filters. For example, Patent Document 1 discloses that a color filter is produced by a color resist method using a colored curable composition containing a tetraazaporphyrin dye and an azomethine dye. Patent Document 2 discloses a photosensitive colored curable composition containing a dipyrromethene compound.

  However, in this method, in order to color three colors of R, G, and B, it is necessary to repeat the same process three times, which causes a problem that the cost is increased and a yield is lowered. Therefore, in recent years, a method for forming a colored layer (color pixel) by spraying colored ink by an inkjet method has been proposed as a method for producing a color filter (Patent Document 3). The ink jet method is a recording method in which characters and images are obtained by ejecting and adhering ink droplets directly from a very fine nozzle to a recording member. The ink jet method has an advantage that a color filter having a large area can be manufactured with high productivity by sequentially moving the ink jet head, and the operability is low with low noise.

Normally, the ink ejected to a predetermined position by the ink jet method is then subjected to a curing process such as a light irradiation process or a heating process.
If light irradiation treatment is used as the curing treatment, curing in a short time can be expected. However, in order to perform the light irradiation process, it is necessary to use an expensive apparatus such as a UV irradiation apparatus, resulting in an increase in the size of the apparatus and an increase in manufacturing cost. Therefore, it is desired to use a curing means by heat treatment.

On the other hand, as the ink used in the ink jet method, an ink containing a pigment has been mainly proposed. In recent years, there has been a demand for higher-definition color filters. However, inks containing pigments have problems such as poor resolution and color unevenness due to coarse particles, which are always satisfactory in practice. It wasn't. In order to solve such a problem, it has been proposed to use an ink containing a dye, and it is expected to exhibit excellent optical characteristics such as contrast.
However, in the present situation, sufficient studies have not been made on research for obtaining a desired color pixel by discharging ink containing a dye by an ink jet method and curing it by only the above-described heat treatment. In particular, for blue inks, there is a high demand for practical use compared to other color inks, and the resulting color pixels exhibit good hue, brightness, excellent heat resistance, excellent chemical resistance, and the like. It is needed.

JP 2008-88222 A JP 2008-292970 A JP-A-8-146215

The present inventors have developed a blue ink-jet ink containing a dye that can form a color pixel that exhibits excellent brightness and hue and is excellent in heat resistance and chemical resistance by means of curing by heat treatment. For the purpose, a conventionally known composition was examined. Specifically, using a colored curable composition containing a tetraazaporphyrin-based dye and an azomethine-based dye that is specifically disclosed in the above-mentioned Patent Document 1, the ink is ejected by an ink jet method and cured by a thermosetting treatment. As a result of investigation, the hue of the obtained color pixel is easily deteriorated by heat, and so-called heat resistance is not always satisfactory in practice.
Furthermore, the present inventors have found that phase separation and aggregation of the dye may occur in the obtained color pixel. As a result, hue changes, contrast reduction, and the like have occurred, and further improvements are necessary.
Further, even when a colored curable composition containing a cyan dye and a dipyrromethene dye specifically disclosed in Patent Document 2 is used, the appearance, heat resistance, and light resistance of the obtained color pixel are not necessarily practical. It was not satisfactory.

  In order to solve such a problem, selecting a material (polymerizable monomer, etc.) that is compatible with the dye is one option. However, it has been difficult to select a material that simultaneously satisfies various requirements such as high ejection stability as an inkjet ink and the heat resistance and chemical resistance of the obtained color filter.

  The present invention has been made in view of the above circumstances, and its purpose is to exhibit good luminance and hue, to form a color pixel excellent in heat resistance and light resistance, and chemical resistance to various solvents. Blue ink-jet inks that can produce excellent color filters and are compatible with thermosetting processes, optical properties, light resistance, heat resistance, chemical resistance, etc. obtained by such ink-jet inks Color filter with excellent characteristics, a color filter manufacturing method that can stably manufacture a color filter having such characteristics without incurring a cost increase, and high contrast and high saturation capable of supporting a high-brightness backlight The liquid crystal display and the image display device are provided.

  As a result of intensive studies, the present inventors have found that by using an ink containing a cyan dye having a specific functional group, a dipyrromethene metal complex, and a polyfunctional thiol compound, the appearance, brightness, hue, various solvents It was found that a color pixel excellent in resistance to chemicals (chemical resistance), heat resistance, light resistance and the like can be produced.

The present inventors have found that the above problems are solved by the following configurations <1> to <10>.
<1> Dye represented by general formula (1) described later, dye represented by general formula (2-1) described later, dye represented by general formula (2-2) described later, and described later An ink-jet ink comprising at least one dye selected from the group consisting of dyes represented by formula (2-3), a radical polymerizable monomer, an organic solvent, and a bifunctional or higher polyfunctional thiol compound.
<2> The inkjet ink according to <1>, wherein at least one of R ^{1 in} the general formula (1) is a group having —COOH.
<3> The inkjet ink according to <1> or <2>, including a radical polymerizable monomer having 3 to 6 polymerizable groups as the radical polymerizable monomer.
<4> The inkjet ink according to any one of <1> to <3>, wherein the viscosity at 25 ° C. is 30 mPa · s or less.
<5> The inkjet ink according to any one of <1> to <4>, wherein the surface tension at 25 ° C. is 20 to 40 mN / m.

<6> The inkjet ink according to any one of <1> to <5>, further containing a surfactant.
<7> A drawing step of applying the ink-jet ink according to any one of <1> to <6> to a recess defined by a partition formed on a substrate by an ink-jet method;
A color filter manufacturing method comprising: a curing step of heating the inkjet ink ejected into the recess.
<8> A color filter manufactured by the method for manufacturing a color filter according to <7>.
<9> A liquid crystal display comprising the color filter according to <8>.
<10> An image display device comprising the color filter according to <8>.

  According to the present invention, it is possible to form a color pixel that exhibits good luminance and hue, has excellent heat resistance and light resistance, can produce color filters with excellent chemical resistance to various solvents, Blue ink-jet ink that can be used for the curing process, color filters excellent in optical characteristics, light resistance, heat resistance, chemical resistance, etc. obtained by such ink-jet ink, and such characteristics A color filter manufacturing method capable of stably manufacturing a color filter without incurring a cost increase, and a high-contrast, high-saturation liquid crystal display and an image display device capable of supporting a high-brightness backlight can be provided. .

It is a flowchart which shows the manufacturing process in one Embodiment of the manufacturing method of the color filter of this invention. (A)-(f) is typical sectional drawing of the board | substrate and color filter shown in order of the manufacturing process from the board | substrate to a color filter, respectively in the manufacturing method of the color filter of this invention. It is an optical microscope photograph (magnification 100 times) when a particulate matter and a phase-separation structure are not observed. It is an optical microscope photograph (magnification 100 times) when a particulate matter is observed. It is an optical microscope photograph (magnification 100 times) when a phase-separation structure is observed.

  Hereinafter, the inkjet ink according to the present invention, a color filter using the inkjet ink, a manufacturing method thereof, a liquid crystal display and an image display device using the same will be described in detail.

<Inkjet ink and method for producing the same>
First, the components of the inkjet ink of the present invention and the production method thereof will be described in detail.
The inkjet ink of the present invention is selected from the group consisting of a dye represented by the general formula (1) and a dye represented by the general formula (2-1) to a dye represented by the general formula (2-3). Containing at least one kind of dye, a radical polymerizable monomer, an organic solvent, and a polyfunctional thiol compound.
Hereinafter, each component will be described in detail.

<Dye represented by general formula (1)>
The ink-jet ink of the present invention contains a dye (cyan dye) represented by the general formula (1). By containing this dye, a color filter having excellent heat resistance, light resistance and chemical resistance can be produced. Moreover, by using together with the dye (dipyrromethene dye) represented by the general formula (2-1) to the general formula (2-3) described later, the dispersibility of the dye in the obtained color pixel is further improved, It is possible to form a color pixel that exhibits more excellent hue / luminance and excellent heat resistance. The dye represented by the general formula (1) and the dipyrromethene dye described later are partially similar in structure, and the intermolecular interaction is easy to work. Is presumed to be more suppressed.

In general formula (1), R ¹ each independently represents a hydrogen atom or a substituent.
The “substituent” represented by R ¹ may be any group that can be substituted. For example, an aliphatic group (an alkyl group having 1 to 15 carbon atoms, an alkenyl group, or an alkynyl group is preferable. For example, a methyl group , Ethyl group, vinyl group, allyl group, ethynyl group, isopropenyl group, 2-ethylhexyl group, etc.), halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), aryl group (total carbon number of 6 to 16, more preferably 6 to 12 carbon atoms, for example, phenyl group, 4-nitrophenyl group, 2-nitrophenyl group, 2-chlorophenyl group, 2,4-dichlorophenyl group, 2,4-dimethylphenyl group. , 2-methylphenyl group, 4-methoxyphenyl group, 2-methoxyphenyl group, 2-methoxycarbonyl-4-nitrophenyl group, and the like. Terocyclic group (3 to 15 carbon atoms are preferred, and 3 to 10 carbon atoms are more preferred. For example, 3-pyridyl group, 2-pyridyl group, 2-pyrimidinyl group, 2-pyrazinyl group, 1-piperidyl group, etc. ), Cyano group, carboxyl group, carbamoyl group (total carbon number of 1-16 is preferable, and total carbon number of 1-12 is more preferable. For example, carbamoyl group, dimethylcarbamoyl group, diethylcarbamoyl group, N-methyl -N-propylcarbamoyl group, N-ethyl-N-methoxyethylcarbamoyl group, bis (2-methylbutyl) carbamoyl group, bis (2-ethylhexyl) carbamoyl group, bis (methoxyethyl) carbamoyl group, bis (ethoxyethyl) carbamoyl Group, bis (propoxyethyl) carbamoyl group, N-carboxymethyl-N Methylcarbamoyl group and the like.),

Aliphatic oxycarbonyl group (preferably having 2 to 16 carbon atoms, more preferably 2 to 10 carbon atoms. Examples include methoxycarbonyl group and butoxycarbonyl group), aryloxycarbonyl group (7 carbon atoms in total) To 17 and more preferably 7 to 15 in total, for example, phenoxycarbonyl group and the like, acyl group (2 to 15 in total carbon is preferable, and 2 to 10 in total carbon is more preferable. , Acetyl group, pivaloyl group, benzoyl group, etc.), hydroxy group, aliphatic oxy group (total carbon number of 1-12 is preferable, and total carbon number of 1-10 is more preferable. For example, methoxy group, ethoxyethoxy Group, methoxyethoxy group, methoxydiethoxy group, phenoxyethoxy group, thiophenoxyethoxy group, etc.) An aryloxy group (preferably having a total carbon number of 6 to 18, more preferably a total carbon number of 6 to 14. For example, a phenoxy group, 4-methylphenoxy group, etc.), an acyloxy group (having a total carbon number of 2 to 14) Preferably, the total carbon number is 2 to 10. For example, an acetoxy group, a methoxyacetoxy group, a benzoyloxy group, etc.), a carbamoyloxy group (a total carbon number of 1 to 16 is preferable, and a total number of carbon atoms of 1 to 10). (For example, a dimethylcarbamoyloxy group, a diisopropylpropylcarbamoyl group, an N, N-bis (methoxyethyl) -carbamoyl group, an N, N-bis (ethoxyethyl) -carbamoyl group, etc.) may be mentioned. Ring oxy group (total carbon number of 1 to 15 is preferable, and total number of carbon atoms of 3 to 10 is more preferable. For example, 3-furyloxy group, 3- Rijiruokishi group, such as N- methyl-2-piperidyl group and the like.),

Acylamino group (total carbon number of 2 to 15 is preferable, and total carbon number of 3 to 12 is more preferable. Examples thereof include N-methylacetylamino group, N-ethoxyethylbenzoylamino group, and N-methylmethoxyacetylamino group. ), A carbamoylamino group (total carbon number of 1-16 is preferable, and total carbon number of 1-12 is more preferable. For example, N, N-dimethylcarbamoylamino group, N-methyl-N-methoxyethylcarbamoylamino group, etc. ), A sulfamoylamino group (total carbon number of 0 to 16 is preferable, and total carbon number of 0 to 12 is more preferable. Examples thereof include N, N-dimethylsulfamoylamino group), aliphatic Oxycarbonylamino group (total carbon number of 2 to 15 is preferable, and total carbon number of 2 to 10 is more preferable. For example, methoxycarbonylamino group Methoxyethoxycarbonylamino group, etc.), aryloxycarbonylamino group (total carbon number of 7-17 is preferable, and total carbon number of 7-15 is more preferable. For example, phenoxycarbonylamino group, 4-methoxycarbonylamino group An aliphatic sulfonylamino group (total carbon number of 1 to 12 is preferable, and total carbon number of 1 to 8 is more preferable. Examples thereof include a methanesulfonylamino group and a butanesulfonylamino group). Arylsulfonylamino group (total carbon number 6-17 is preferable, total carbon number 6-15 is more preferable, for example, phenylsulfonylamino group, 4-methylphenylsulfonylamino group, etc.), aliphatic thio group ( A total carbon number of 1 to 16 is preferable, and a total carbon number of 1 to 12 is more preferable, for example, methyl O group, ethylthio group, ethoxyethylthio group, etc.), arylthio group (total carbon number 6-22 is preferable, total carbon number 6-14 is more preferable. For example, phenylthio group, 2-t-butylthio group An aliphatic sulfonyl group (total carbon number of 1 to 15 is preferable, and total carbon number of 1 to 8 is more preferable. Examples thereof include a methanesulfonyl group, a butanesulfonyl group, a methoxyethanesulfonyl group, and the like. ),

Arylsulfonyl group (preferably having a total carbon number of 6 to 16, more preferably a total carbon number of 6 to 12. For example, a benzenesulfonyl group, 4-t-butylbenzenesulfonyl group, 4-toluenesulfonyl group, 2-toluenesulfonyl group, etc. ), A sulfamoyl group (preferably having a total carbon number of 0 to 16, more preferably a total carbon number of 0 to 12. For example, a sulfamoyl group, a dimethylsulfamoyl group, a N, N-diethylsulfamoyl group, etc. An aliphatic sulfonylcarbamoyl group (total carbon number of 2 to 17 is preferable, and total carbon number of 2 to 13 is more preferable. For example, methylsulfonylcarbamoyl group, butylsulfonylcarbamoyl group, 2-methylbutylsulfonylcarbamoyl group, etc. Arylsulfonylcarbamoyl group (total carbon number 7 to 2) The total number of carbon atoms is more preferably 7 to 17. For example, a phenylsulfonylcarbamoyl group and the like are exemplified, and an aliphatic carbonylsulfamoyl group (the total number of carbon atoms is preferably 2 to 17, and the total number of carbon atoms is 2 to 13). For example, methylcarbonylsulfamoyl group, butylcarbonylsulfamoyl group, 2-ethylhexylcarbonylsulfamoyl group, etc.), arylcarbonylsulfamoyl group (total number of carbon atoms of 7 to 21 is preferable, The total number of carbon atoms is more preferably 7 to 17. For example, a phenylcarbonylsulfamoyl group and the like are exemplified, and an aliphatic sulfonylsulfamoyl group (the total number of carbon atoms is preferably 1 to 16, and the total number of carbon atoms is 1 to 12). For example, methylcarbonylsulfamoyl group, butylcarbonylsulfamoyl group, 2-ethylhexylcarbonylsulfamoyl group, etc.), arylsulfonylsulfamoyl group (total carbon number 6-16 is preferable, total carbon number 6-12 is more preferable. For example, phenylsulfonylsulfamoyl group, etc. ), A sulfo group, an imide group, a phosphonic acid group, a heterocyclic thio group, or a combination thereof.

  As the “aliphatic group”, the aliphatic moiety may be linear, branched, or cyclic, and may be saturated or unsaturated. For example, an alkyl group, an alkenyl group, a cycloalkyl group, It contains a cycloalkenyl group and may be unsubstituted or substituted with a substituent. The “aryl group” may be either a single ring or a condensed ring, and may be unsubstituted or substituted with a substituent. A “heterocyclic group” is one in which the heterocyclic moiety has a heteroatom (eg, nitrogen atom, sulfur atom, oxygen atom) in the ring, and may be either a saturated ring or an unsaturated ring. It may be a ring or a condensed ring, and may be unsubstituted or substituted with a substituent.

When the substituent of R ¹ is a further substitutable group, it may further have the substituent, and when it has two or more substituents, these substituents are the same. Or different.

However, in general formula (1), at least one of R ¹ is a group having —SO ₃ H, —P═O (OH) ₂ , —P═O (H) (OH) or —COOH (hereinafter, Or at least one of the groups represented by —S (O) _m — (L) _n — (R ¹ ) _p , R ¹ is an OH group, and L is a single group. And represents a group in which m is 2. By having these substituents, the dispersibility in the color pixel of the dye used can be improved, and in turn, a color pixel having excellent color characteristics such as appearance, hue, and luminance can be formed. In addition, when several R < ¹ > represents the said functional group, it may be the same or different.

Among the polar functional groups, a group having —SO ₃ H and a group having —COOH are more preferable, and a group having —COOH is particularly preferable.
In addition, from the viewpoint of better solubility of the obtained color pixel in hue and solvent, one polar functional group having two or more —SO ₃ H, —P═O (OH) ₂ , —P═O ( H) (OH) or —COOH is preferable, and from the viewpoint of synthesis, 2 or 3 is preferable, and 2 is particularly preferable.
Incidentally, at least one of ^{R 1} is represents the polar functional group is one having 1 to 4 Among them preferably 1-2 Tsugayori preferred.

As a suitable aspect of a polar functional group, the aspect represented by the following formula | equation (A) is mentioned.
-Z- (Y) _q formula (A)
In formula (A), Z represents a single bond or a linking group. The linking group is not particularly limited, and examples thereof include a divalent linking group, a trivalent linking group, and a combination of these. For example, examples of the divalent linking group include an arylene group, an alkylene group, —S (O) ₂ —, —S—, —CO—, —O—, —CONH—, —NH—, or a combination thereof. Examples of the trivalent linking group include —N <(nitrogen atom), a methine group, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by combining them.
Wherein (A), Y _represents -SO 3 H, -P = O ( OH) 2, -P = O (H) (OH), or -COOH.
In the formula (A), q represents an integer of 1 or more, preferably 1 to 4, and more preferably 1 to 2. Among these, 2 is preferable from the viewpoint of further improving the hue, luminance, heat resistance, solubility in a solvent, and the like of the obtained color pixel, and the difficulty in synthesis.

When at least one of the groups represented by —S (O) _m — (L) _n — (R ¹ ) _p represents a group in which R ¹ is an OH group, L is a single bond, and m is 2. means that the -SO ₃ H group is bonded directly to a ring structure represented by ^{Z 1.}
One of the groups represented by —S (O) _m — (L) _n — (R ¹ ) _p in the general formula (1) may be the above group, and among these, preferably 1 to 4 groups. Yes, more preferably 1-2.

In terms of the effects of the present invention, R ¹ other than the polar functional group includes a halogen atom, aliphatic group, cyano group, carbamoyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, hydroxy group, aliphatic oxy group, Carbamoyloxy group, heterocyclic oxy group, aliphatic oxycarbonyloxy group, carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic thio group, arylthio Group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, aliphatic sulfonylcarbamoyl group, arylsulfonylcarbamoyl group, aliphatic carbonylsulfamoyl group, arylcarbonylsulfamoyl group, aliphatic sulfonylsulfamoyl group, arylsulfonyl Preferred is a sulfamoyl group, an imide group, or a combination thereof. An aliphatic group, a carbamoyl group, a hydroxy group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an aliphatic oxy group, an aliphatic oxycarbonyloxy group Carbamoylamino group, sulfamoylamino group, aliphatic oxycarbonylamino group, aliphatic sulfonylamino group, arylsulfonylamino group, aliphatic sulfonyl group, arylsulfonyl group, sulfamoyl group, aliphatic sulfonylcarbamoyl group, aliphatic carbonyl More preferably, it is a sulfamoyl group, an aliphatic sulfonylsulfamoyl group, an imide group, or a combination thereof. A carbamoyl group, a hydroxy group, an aliphatic oxycarbonyl group, an aliphatic oxy group, an aliphatic oxycarbo Ruoxy group, carbamoylamino group, aliphatic oxycarbonylamino group, arylsulfonyl group, aliphatic sulfonylcarbamoyl group, aliphatic carbonylsulfamoyl group, aliphatic sulfonylsulfamoyl group, imide group, aliphatic sulfonyl group, or these Most preferred is a group in which

In general formula (1), L represents an aliphatic or aromatic coupling group each independently. When these linking groups are used, the appearance, hue, luminance, heat resistance, and chemical resistance of the obtained color pixel are further improved. Each L may be the same or different.
The aliphatic linking group represented by L may be unsubstituted or substituted, and is preferably an aliphatic group having 1 to 20 carbon atoms, and an aliphatic group having 1 to 15 carbon atoms. More preferred. For example, a methylene group, ethylene group, propylene group, butylene group and the like can be mentioned.
The aromatic linking group represented by L may be unsubstituted or substituted, and is preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having 6 to 16 carbon atoms. preferable. For example, a phenylene group, a naphthylene group, etc. are mentioned, The most preferable is a phenylene group.
When n = 0, R ¹ and S (sulfur atom) are directly bonded.

In the general formula (1), Z ¹ represents a group of non-metallic atoms necessary for forming a 6-membered ring with two carbon atoms, and the four Z ¹ may be the same or different. The formed 6-membered ring may be either an aryl ring or a heterocyclic ring, may be condensed, and the condensed ring may further have a substituent. Examples of the 6-membered ring include a benzene ring, a pyridine ring, a cyclohexene ring, a naphthalene ring, and the like, and an embodiment that is a benzene ring is preferable.

In the general formula (1), M represents two hydrogen atoms, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. Examples of M include VO, TiO, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, AlCl, InCl, FeCl, TiCl ₂ , and SnCl _2. , SiCl ₂ , GeCl ₂ , Si (OH) ₂ , H _{2 and the} like, and VO, Zn, Mn, Cu, Ni, Co are preferable. In view of the effects of the present invention, M is preferably VO, Mn, Co, Ni, Cu, Zn or Mg, more preferably VO, Co, Cu or Zn, and most preferably Cu.

In the general formula (1), each m independently represents 1 or 2, and m is preferably 2.
Each n independently represents 0 or 1, and n is preferably 1. However, when R ¹ is a group having —SO ₃ H, —P═O (OH) ₂ , —P═O (H) (OH), or —COOH, n represents 1.
p represents the integer of 1-5 each independently, the case where it is 1-3 is preferable, and the case where it is 1 is more preferable.

In the present invention, a plurality of R ¹ in the molecule may be the same or different. Among them, R ¹ represents —OY, —COOY, —SO ₃ Y, —CON (Y) CO—, —CON (Y) SO ₂ — or —SO ₂ N (Y) CO—, —SO ₂ NH—. It is preferable to have. Thereby, the appearance characteristics and chemical resistance of the color pixel obtained are further improved.
The _{-OY, -COOY, -SO 3 Y,} -CON (Y) CO -, - CON (Y) SO 2 - ( sulfonylcarbamoyl group) or _-SO 2 N (Y) CO- (acylsulfamoyl group) , —SO ₂ NH— may be bonded to the linking group L in the general formula (1), or may be directly bonded to —S (═O) _m — without the linking group L. When it is directly bonded to —S (═O) _m — without the linking group L, R ¹ is preferably —OY, and directly bonded to the tetraazaporphyrin ring together with —S (═O) _m —. constituting a -SO ₃ Y to (m = 2) is preferred.

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

r ¹ , r ² , r ³ and r ⁴ each independently represent 0 or 1, r ¹ + r ² + r ³ + r ⁴ is 1 or more, and r ¹ + r ² + r ³ + r ⁴ is 2 to 4 Is preferred. It is also preferred that r ¹ , r ² , r ³ and r ⁴ are each 1.

Examples of the group represented by the above “—S (O) _m — (L) _n — (R ¹ ) _p ” will be shown below. However, the present invention is not limited to these. In the following examples, T-92, T-112, T-118, T-143, T-145, T-147 to T-157, T-159, and other functional groups are polar functional groups. Preferable examples include T-95, T-97, T-114, T-115, T-117, T-127, and T-130.

  The dye represented by the general formula (1) (tetraazaporphyrin-based dye) is described in, for example, JP-A-2006-58787, JP-A-2006-124379, JP-A-2006-124679, and the like. It can be synthesized by the method of

<Dye Represented by General Formula (2-1) to General Formula (2-3)>
The inkjet ink of the present invention is a group consisting of a dye represented by the general formula (2-1), a dye represented by the general formula (2-2), and a dye represented by the general formula (2-3). Containing at least one selected from. By using the dipyrromethene dye, a color pixel having more excellent hue and luminance can be formed. In addition, you may use 2 types together in the said dye.
The dye represented by each formula is described in detail below.

<Dye Represented by General Formula (2-1)>
Below, each substituent of the dye represented by general formula (2-1) is explained in full detail.

In General Formula (2-1), R _{11 to} R ₁₆ each independently represent a hydrogen atom or a substituent. Examples of the substituent in R _{11 to} R ₁₆ include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). A linear, branched or cyclic alkyl group such as 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 an 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 having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms). A reel group, for example, phenyl, naphthyl), a heterocyclic group (preferably a C1-C32, more preferably a C1-C18 heterocyclic group, for example, a thiophene ring, a pyridine ring, a furan ring, a pyrimidine ring Benzotriazole ring, pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, oxazole ring, thiadiazole ring, triazole ring, benzothiazole ring, benzoxazole ring, benzoisothiazole ring, benzimidazole ring, more specifically, 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 a silyl group having 3 to 18 carbon atoms, for example, Trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group, carboxyl group, alkoxy group (preferably having 1 to 48 carbon atoms, more preferably 1 carbon atom) -24, alkoxy groups such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy groups such as cyclopentyloxy, cyclohexyloxy), aryloxy groups ( An aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenoxy or 1-naphthoxy, or a heterocyclic oxy group (preferably having 1 to 32 carbon atoms, more preferably 1 carbon atom). ~ 18 heterocyclic oxy groups, for example 1 -Phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), silyloxy groups (preferably silyloxy groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyl) Oxy, diphenylmethylsilyloxy), acyloxy groups (preferably acyloxy groups having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), alkoxycarbonyloxy groups (Preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms such as ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy group such as cyclohexyl Ruoxycarbonyloxy), aryloxycarbonyloxy group (preferably aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonyloxy), carbamoyloxy group (preferably carbon A carbamoyloxy group having 1 to 48, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy ), A sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-diethylsulfamoyloxy, N-propylsulfamoyl). Oxy), alkylsulfonyloxy group (preferred) Is properly 1 to 38 carbon atoms, more preferably an alkylsulfonyloxy group having 1 to 24 carbon atoms, e.g., methyl sulfonyloxy, hexadecyl sulfonyloxy, cyclohexyl sulfonyloxy)

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

An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, such as phenoxycarbonyl), a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably a carbon number). 1 to 24 carbamoyl groups such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methyl-N -Phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), an amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as amino, methylamino, N, N-dibutylamino, Tetradecylamino, 2-ethylhexylamino, Rohexylamino), anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, for example, anilino, N-methylanilino), a heterocyclic amino group (preferably having 1 to 32 carbon atoms). More preferably a heterocyclic amino group having 1 to 18 carbon atoms, such as 4-pyridylamino), a carbonamido group (preferably having 2 to 48 carbon atoms, more preferably a carbonamido group having 2 to 24 carbon atoms, , Acetamide, benzamide, tetradecanamide, pivaloylamide, cyclohexaneamide), a ureido group (preferably a ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido, N, N-dimethylureido, N -Phenylureido), an imide group (preferably having a carbon number of 36 or less, more preferably a carbon number) An imide group having 4 or less, for example, N-succinimide, N-phthalimide), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, methoxycarbonyl Amino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 32 carbon atoms, more preferably having 7 to 24 carbon atoms) A group such as phenoxycarbonylamino), a sulfonamide group (preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methanesulfonamide, butanesulfonamide, Zensulfonamide, hexadecanesulfonamide, cyclohexanesulfonamide), sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-dipro Pyrsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenylazo, 3-pyrazolylazo ),

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

R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R ₁₄ and R ₁₅ , and / or R ₁₅ and R _{16 in} general formula (2-1) are each independently bonded to each other to form 5 or 6 members. Alternatively, a 7-membered saturated ring or an unsaturated ring may be formed. When the 5-membered, 6-membered, and 7-membered rings formed are further substitutable groups, they may be substituted with the substituents described above for R _{11 to} R ₁₆ , and two or more When substituted with a substituent, these substituents may be the same or different.

R ₁₇ in the general formula (2-1) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and the halogen atom, alkyl group, aryl group, and heterocyclic group of R ₁₇ are the R ₁₁ halogen atoms described to R _16, an alkyl group, an aryl group, and a have the same meanings heterocyclic group, the same applies to its preferable range. When the alkyl group, aryl group, and heterocyclic group of R ₁₇ are further substitutable groups, they may be substituted with the substituents described for R _{11 to} R ₁₆ above, and two or more substituents may be substituted. When substituted with a group, the substituents may be the same or different.

In the general formula (2-1), preferably, R ₁₁ and R ₁₆ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxy group, a cyano group, an alkoxy group, Aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group , Sulfonamido group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, phosphinoylamino group, or a combination thereof, R ₁₂ and R ₁₅ are each Independently, a hydrogen atom, a halogen atom, an alkyl group, Alkenyl group, aryl group, heterocyclic group, hydroxy group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxy Represents a carbonylamino group, a sulfonamido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a combination thereof, and R ₁₃ and R ₁₄ each represents Independently, hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxy group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, Carbamoyl group, anili Group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, sulfonamido group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, phosphinoylamino Represents a group or a combination thereof, and R ₁₇ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

More preferably, in the general formula (2-1), R ₁₁ and R ₁₆ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, or an alkoxycarbonyl group. Carbamoyl group, amino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, azo group, alkylsulfonyl group, arylsulfonyl group, phosphino Represents an ylamino group or a combination thereof, and R ₁₂ and R ₁₅ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, carbamoyl group, imide group, Represents an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or a combination thereof, and R ₁₃ and R ₁₄ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, Acyl group, alkoxycarbonyl group, carbamoyl group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, sulfonamido group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group Or a combination of these, R ₁₇ represents a hydrogen atom or an alkyl group.

Particularly preferably, in the general formula (2-1), R ₁₁ and R ₁₆ are each independently a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a heterocyclic amino group, a carbonamido group, or a ureido. Represents a group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, an azo group, an alkylsulfonyl group, an arylsulfonyl group, a phosphinoylamino group, or a combination thereof, and in the general formula (2-1), R ₁₂ and R ₁₅ each independently represents an alkyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a combination thereof. R ₁₃ and _{R 14} each independently represent a hydrogen atom, an alkyl group, an aryl , A heterocyclic group or a group comprising a combination thereof,, R ₁₇ represents a hydrogen atom.

Ma in the general formula (2-1) 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, may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or Divalent metal chlorides are included. For example, Zn, Mg, Si, Sn , Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, in addition to Fe, such _{as, AlCl, InCl, FeCl, TiCl} 2, SnCl 2, SiCl 2, GeCl Also included are metal chlorides such as ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ .
Among these, Fe, Zn, Co, V = O, or Cu is preferable, and Zn is most preferable from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex.

X ₁ in the general formula (2-1) may be any group that can be bonded to the metal atom Ma, and may be water, alcohols (eg, methanol, ethanol, propanol), carboxylic acids (eg, Acetic acid) and the like, and the compounds described in “Metal Chelate” [1] Takeichi Sakaguchi and Keihei Ueno (1995 Nanedo), [2] (1996), [3] (1997), etc. Can be mentioned.

X ₂ in the general formula (2-1) represents a group necessary for neutralizing the charge of Ma, and examples thereof include a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, and a sulfonic acid group.

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

<Dye Represented by General Formula (2-2)>
Below, each substituent of the dye represented by general formula (2-2) is explained in full detail.

In general formula (2-2), R < ₁₂ > -R < ₁₅ > represents a hydrogen atom or a substituent each independently. R ₁₇ 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 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 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, Y ₂ represents a nitrogen atom or a carbon atom. R ₁₈ and R ₁₉ each independently represents 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 amino group. R ₁₈ and Y ₁ may be bonded to each other to form a 5-, 6-, or 7-membered ring, and R ₁₉ and Y ₂ are bonded to each other to form a 5-, 6-, or 7-membered ring. The ring may be formed. X ₅ represents a group capable of binding to Ma, and a represents 0, 1 or 2.

_R 12 _{to R 15} in the general formula (2-2) wherein and _{R 17, R} 12 _{to R 15} each in the general formula (2-1), and _{R 17} and have the same meanings, a preferred embodiment also the same is there.
Ma in the general formula (2-2) represents a metal atom or a metal compound, and is synonymous with the metal atom or the metal compound described in the general formula (2-1), and a preferable range thereof is also the same.

In General Formula (2-2), R ₁₈ and R ₁₉ are each independently an alkyl group (preferably a linear, branched, or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms. Groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl groups (preferably having 2 to 2 carbon atoms) 24, more preferably an alkenyl group having 2 to 12 carbon atoms, such as vinyl, allyl, 3-buten-1-yl), an aryl group (preferably having 6 to 36 carbon atoms, more preferably having 6 to 18 carbon atoms) An aryl group, for example, phenyl or naphthyl), a heterocyclic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 1 carbon atoms) Heterocyclic groups such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), alkoxy groups (Preferably an alkoxy group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms such as methoxy, ethoxy, propyloxy, butoxy, hexyloxy, 2-ethylhexyloxy, dodecyloxy, cyclohexyloxy), aryloxy A group (preferably an aryloxy group having 6 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, such as phenoxy or naphthyloxy), an alkylamino group (preferably having 1 to 36 carbon atoms, more preferably 1 carbon atom). ~ 18 alkylamino groups such as methylamino, ethylamino Propylamino, butylamino, hexylamino, 2-ethylhexylamino, isopropylamino, t-butylamino, t-octylamino, cyclohexylamino, N, N-diethylamino, N, N-dipropylamino, N, N-dibutyl Amino, N-methyl-N-ethylamino), an arylamino group (preferably an arylamino group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, such as phenylamino, naphthylamino, N, N- Diphenylamino, N-ethyl-N-phenylamino), a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-aminopyrrole, 3- Aminopyrazole, 2-aminopyridine, 3-aminopyridine), or combinations thereof A representative.

In general formula (2-2), the alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylamino group, arylamino group, and heterocyclic amino group represented by R ₁₈ and R ₁₉ When the group is a further substitutable group, it may be substituted with a substituent represented by R _{11 to} R ₁₆ in the general formula (2-1), and substituted with two or more substituents. The substituents may be the same or different.

In General Formula (2-2), 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 or an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as methyl, ethyl , Propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 carbon atoms) -12 alkenyl groups, such as vinyl, allyl, 3-buten-1-yl), aryl groups (preferably 6-36, more preferably 6-18 carbons, such as phenyl, Naphthyl), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), an acyl group (preferably having a carbon number of 1 to 24, more preferably an acyl group having 2 to 18 carbon atoms, for example, acetyl, pivaloyl, 2-ethylhexyl, benzoyl, cyclohexanoyl), an alkylsulfonyl group (preferably having 1 to 24 carbon atoms, more preferably 1 carbon atom) A C-18 alkylsulfonyl group, for example, methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclohexylsulfonyl), an arylsulfonyl group (preferably a C6-C24, more preferably a C6-C18 arylsulfonyl group, for example, , Phenylsulfonyl, naphthylsulfur Representing a nil).
The alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkylsulfonyl group, and arylsulfonyl group represented by R and Ra are further represented by R _{11 to} R ₁₆ in the general formula (2-1). In the case of substitution with a plurality of substituents, these substituents may be the same or different.

In General Formula (2-2), Y ₁ represents NRc, a nitrogen atom, or a carbon atom, and Y ₂ represents a nitrogen atom or a carbon atom. Rc has the same meaning as R in X ₃ above.

In the general formula (2-2), R ₁₈ and Y ₁ are bonded to each other, and together with R ₁₈ , Y ₁ and the carbon atom, a 5-membered ring (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole) , Furan, thiophene, indole, benzofuran, benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline) Or a 7-membered ring (eg, cycloheptane, hexamethyleneimine).

In General Formula (2-2), R ₁₉ and Y ₂ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with R ₁₉ , Y ₂ , and the carbon atom. 5-membered to be formed, 6-membered, and 7-membered ring, from the ring formed by the above R ₁₈ and Y ₁ and carbon atom, the ring one binding has changed to the double bond.

In the general formula (2-2), when the 5-membered, 6-membered, and 7-membered rings formed by combining R ₁₈ and Y ₁ , and R ₁₉ and Y ₂ are further substitutable rings May be substituted with a substituent represented by R _{11 to} R ₁₆ in the general formula (2-1), and when substituted with two or more substituents, these substituents are They may be the same or different.

In General Formula (2-2), X ₅ represents a group capable of binding to Ma, and examples thereof include the same groups as X ₁ in General Formula (2-1). a represents 0, 1, or 2.

As a preferable aspect of the compound represented by the general formula (2-2), R _{12 to} R ₁₅ , R ₁₇ , and Ma are each preferably described in the description of the dye represented by the general formula (2-1). X ₃ is NR (R is a hydrogen atom, an alkyl group), a nitrogen atom, or an oxygen atom, and 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), a nitrogen atom or a carbon atom, Y ₂ is a nitrogen atom or a carbon atom, and X ₅ is a group bonded through an oxygen atom. , R ₁₈ and R ₁₉ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, or R ₁₈ and Y ₁ are bonded to each other to form a 5-membered or 6-membered ring. Or R ₁₉ and Y ₂ are bonded to each other to form a 5-membered or 6-membered ring, and a represents 0 or 1.

As a more preferable embodiment of the compound represented by the general formula (2-2), R _{12 to} R ₁₅ , R ₁₇ and Ma are particularly described in the description of the dye represented by the general formula (2-1). In a preferred embodiment, X ₃ and X ₄ are oxygen atoms, Y ₁ is NH, Y ₂ is a nitrogen atom, X ₅ is a group bonded via an oxygen atom, R ₁₈ and R 4 ₁₉ is each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, or R ₁₈ and Y ₁ are bonded to each other to form a 5-membered or 6-membered ring, or R ₁₉ and Z ₂ are bonded to each other to form a 5-membered or 6-membered ring, and a represents 0 or 1.

<Dye represented by general formula (2-3)>
Below, each substituent of the dye represented by general formula (2-3) is explained in full detail.

In General Formula (2-3), R _{11 to} R ₁₆ each independently represent a hydrogen atom or a substituent. R ₁₇ 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.

_R 11 _{to R 17} in the general formula (2-3) are respectively synonymous with _R 11 _{to R 17} in the general formula (2-1), preferable embodiments thereof are also the same.
Ma in the general formula (2-3) represents a metal atom or a metal compound, and is synonymous with the metal atom or metal compound described in the general formula (2-1), and the preferred range thereof is also the same.

  Next, specific examples of the dyes represented by the general formula (2-1) to the general formula (2-3) are shown below, but the present invention is not limited thereto. Other specific examples include dyes described in paragraph numbers [0058] to [0074] of Japanese Patent Application No. 2008-149467.

  The dyes represented by the general formula (2-1) to the general formula (2-3) are disclosed in U.S. Pat. Nos. 4,774,339, 5,433,896, and JP-A-2001-240761, 2002. -155052, Japanese Patent No. 3614586, Aust. J. et al. Chem, 1965, 11, 1835-1845, J. Am. H. Boger et al, Heteroatom Chemistry, Vol. 1, No. 1 5,389 (1990) and the like.

  In the inkjet ink, the total content of the dye represented by the general formula (1) and the dye represented by the general formula (2-1) to the general formula (2-3) is based on the total amount of the ink. 1 to 30% by mass is preferable, and 3 to 20% by mass is more preferable. When the content is too small, the film thickness is increased in order to achieve the optical density required for the color filter. Therefore, it is necessary to increase the thickness of the black matrix, which is not preferable because it is difficult to form the black matrix. When the content is too large, the ink viscosity becomes high and ejection becomes difficult, and it becomes difficult to dissolve in a solvent, which is not preferable.

  In the inkjet ink, the mass of the dye represented by the general formula (1) (cyan dye) and the dye represented by the general formula (2-1) to the general formula (2-3) (dipyrromethene dye) The ratio (cyan dye / dipyrromethene dye) is not particularly limited, but the mass ratio is preferably 0.3 to 4 in terms of the appearance of the color pixel obtained and excellent chemical resistance. 3 is more preferable.

<Organic solvent>
The ink jet ink contains an organic solvent. The organic solvent is not particularly limited as long as the solubility of each component is satisfied.
Specific examples of the organic solvent include water and esters such as amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, oxy Ethyl acetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate Such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc .; methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxypropionate 2-oxypropionic acid alkyl esters such as propyl acid, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate Methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc .; methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glyco 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, etc .; ketone Preferred examples thereof include cyclohexanone, 2-heptanone, and 3-heptanone; aromatic hydrocarbons such as xylene; and organic solvents such as dicyclohexylmethylamine. These may be used alone or in combination of two or more.

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

  As for the boiling point of the organic solvent used by this invention, 130-280 degreeC is preferable. If the boiling point is too low, it is not preferable in terms of uniformity of the shape of the pixels in the surface. If the boiling point is too high, it is not preferable in terms of solvent removal by pre-baking. The boiling point of the organic solvent means a boiling point under a pressure of 1 atm, and can be known from a physical property value table such as a compound dictionary (Chapman & Hall).

  As one of the preferable usage forms of the organic solvent, it is preferable that the organic solvent having a boiling point of 160 ° C. or higher is 10% by mass or more based on the total amount of the organic solvent. Especially, the organic solvent whose boiling point is 160-250 degreeC is preferable, and 180-240 degreeC is more preferable. The content of the organic solvent having a boiling point in the predetermined range is preferably 10% by mass or more, more preferably 20 to 100% by mass, and more preferably 25 to 75% by mass in the total amount of the organic solvent used. When the organic solvent having a predetermined boiling point is contained within the above range, it is preferable from the viewpoint of controlling the drying of the ink, providing the discharge stability, and improving the leveling property of the ink after the discharge. On the other hand, when an organic solvent having a low boiling point is contained, it quickly evaporates even on the ink jet head, so that it easily causes an increase in the viscosity of the ink on the head, precipitation of a solid content, and the like, and is often accompanied by a deterioration in ejection performance. In addition, even when ink lands on the substrate surface and wets and spreads on the substrate surface, the viscosity of the ink increases due to evaporation of the solvent at the edge of the wet spread, and the phenomenon of pinning (PINING) causes wet spread. It may be suppressed.

  Examples of the organic solvent having a boiling point of 160 ° C. or higher include 2-heptanol, cyclohexanol, 2-furaldehyde, N, N-diethylethanolamine, 2-methylcyclohexanol, N, N-dimethylacetamide, 2- (Methoxymethoxy) ethanol, diacetone alcohol, furfuryl alcohol, ethylene glycol monobutyl ether, monoethanolamine, 3-methylcyclohexanol, 4-methylcyclohexanol, 1-heptanol, N, N-ethylformamide, 2-octanol, Tetrahydrofuryl alcohol, N-methylformamide, ethylene glycol monoisoamyl ether, ethylene glycol monoacetate, 2,3-butanediol, glycerin monoacetate, 2-ethyl-1-hexano 1,2-propanediol, dimethyl sulfoxide, dipropylene glycol monomethyl ether, ethylene glycol diacetate, 1,2-butanediol, ethylene glycol monobutyl ether acetate, 3,3,5-trimethyl-1-hexanol, diethylene glycol Monomethyl ether, 1-octanol, 2-methyl-2,4-pentanediol, dipropylene glycol monoethyl ether, ethylene glycol, diethylene glycol monoethyl ether, N-methylpyrrolidone, γ-butyrolactone, benzyl alcohol, N-methylacetamide, 1,3-butanediol, ethylene glycol monohexyl ether, formamide, 1-nonanol, 1,3-propanediol, diethylene glycol monoethyl -Teracetate, α-terpineol, acetamide, 1,4-butanediol, diethylene glycol monobutyl ether, 1-decanol, dipropylene glycol, 1,3-butylene glycol diacetate, 2-butene-1,4-diol, ethylene carbonate, propylene Carbonate, 1,5-pentanediol, 1-undecanol, tripropylene glycol monomethyl ether, 2-ethyl-1,3-hexanediol, ethylene glycol monophenyl ether, diethylene glycol, 2-pyrrolidone, diethylene glycol monobutyl ether acetate, triethylene glycol Monomethyl ether, tetraethylene glycol dimethyl ether, tripropylene glycol monobutyl ether, triethylene glycol Such Lumpur, and the like.

<Radically polymerizable monomer>
The ink-jet ink of the present invention contains a radical polymerizable monomer. Addition of the radical polymerizable monomer improves the adhesion between the ink droplet and the substrate. In addition, it can be expected to improve the dispersion uniformity of the above-described dye in the ink and to improve the fastness such as weather resistance and heat resistance. Although there is no restriction | limiting in particular as this radically polymerizable monomer, It is preferable to contain radically polymerizable monomers, such as a (meth) acrylic-type monomer, from the point that there are many variations of various substituents and acquisition is easy.

As the polymerizable monomer, a monomer having two or more polymerizable groups is preferable. The polymerizable monomer is not particularly limited as long as it can be polymerized by active energy rays and / or heat, but is a monomer having three or more polymerizable groups from the viewpoint of film strength and chemical resistance. Is more preferable.
Especially, the polyfunctional monomer which has 3-6 polymerizable groups is preferable at the point which the fastness and heat resistance of the color pixel obtained are more excellent. Among these, the number of polymerizable groups is preferably 4-6. If it is in the said range, it is preferable at the point of durability of a color pixel, the availability of a monomer, and the difficulty at the time of a synthesis | combination.

  Although there is no restriction | limiting in particular as a kind of polymeric group mentioned above, As above-mentioned, an acryloyloxy group and a methacryloyloxy group are especially preferable. Specific examples of the polymerizable monomer include acrylate monomers and methacrylate monomers described in paragraph No. [0016] of JP-A No. 2002-371216, and monomers described in CM Publishing, “Reactive Monomer Market Outlook”. Can be mentioned.

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

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

<Multifunctional thiol compound>
The inkjet ink of the present invention contains a polyfunctional thiol compound having two or more thiol groups. By using a polyfunctional thiol compound with a specified number of functionalities, the dispersibility of the dye in the color pixel is improved, and it has excellent fastness, chemical resistance, heat resistance, hue, brightness, and leveling properties. Color pixels can be formed. Further, by using this polyfunctional thiol compound, the viscosity of the ink can be kept low without reducing the film strength of the ink itself, and an ink excellent in ejection stability can be obtained.

The polyfunctional thiol compound has two or more thiol groups in the molecule, and preferably has 3 to 6 thiol groups. If the number of thiol groups is less than 2, the resulting pixel may be inferior in heat resistance, chemical resistance, and light resistance. If the number of thiol groups is more than 6, the synthesis is very difficult, and the viscosity of the thiol compound to be used is too high, and the ink ejection stability may be inferior.
The molecular weight of the polyfunctional thiol compound is not particularly limited, but is preferably 200 to 1200, and more preferably 400 to 1000, from the viewpoint of ink ejection stability.

A polyfunctional thiol compound may use only 1 type and may use 2 or more types together.
Specific examples of the polyfunctional thiol compound include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipenta Examples include erythritol hexakis (3-mercaptopropionate) and pentaerythritol tetrakis (thioglycolate). Among them, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercapto) Propionate) is preferred.

  The content of the polyfunctional thiol compound in the inkjet ink is preferably 0.5 to 20% by mass and more preferably 2 to 12% by mass with respect to the total amount of the ink. When the content is too small, it is not preferable because the effect of fastness and heat resistance of the color pixel cannot be obtained sufficiently. When the content is too large, the film quality of the pixel such as the surface shape may deteriorate, which is not preferable.

The ink-jet ink described above may contain other additives (for example, a surfactant, a thermal polymerization initiator, etc.) as necessary.
Below, an arbitrary component is explained in full detail.

<Surfactant>
A surfactant may be further used in the inkjet ink of the present invention. As examples of the surfactant, the surfactants disclosed in JP-A-7-216276, paragraph [0021], JP-A-2003-337424, and JP-A-11-133600 are preferable. As mentioned.
The content of the surfactant is preferably 5% by mass or less, more preferably 0.01 to 2% by mass with respect to the total amount of the inkjet ink. If it is in the said range, it is preferable at the point which can obtain preferable surface tension, without impairing the other physical property of an ink.

<Thermal polymerization initiator>
The inkjet ink of the present invention may be used in combination with a thermal polymerization initiator for the purpose of promoting the polymerization reaction of the polymerizable monomer. The thermal polymerization initiator can be selected according to the kind of radical polymerizable monomer used in the ink jet ink and the polymerization route. As the thermal polymerization initiator, for example, thermal polymerization initiators described in paragraph numbers [0086] to [0117] of Patent Application 2007-303656 may be used.

  The content of the thermal polymerization initiator is preferably 0.01 to 50% by mass, more preferably 1 to 30% by mass, based on the total solid content in the inkjet ink. When the content is in the above-described range, a better sensitivity and a strong cured portion can be formed.

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

  The content of each component of the inkjet ink is the dye represented by the general formula (1) and the general formula (2-1) with respect to the total amount of the ink in that each characteristic of the obtained color pixel is more excellent. The total content of the dye represented by the dye represented by the general formula (2-3) (dipyrromethene dye) is preferably 1 to 30% by mass, more preferably 2 to 20% by mass. The content is preferably 30 to 90% by mass, more preferably 50 to 90% by mass, and the content of the radical polymerizable monomer is preferably 5 to 50% by mass, more preferably 7 to 30% by mass. The content of the functional thiol is preferably 0.5 to 20% by mass, more preferably 2 to 12% by mass.

<Inkjet ink manufacturing method>
For the production of the inkjet ink of the present invention, a known inkjet ink production method can be applied. For example, after dissolving a dye in a solvent, each component (for example, a radical polymerizable monomer and a polymerization initiator) necessary for the inkjet ink can be dissolved to prepare the inkjet ink.

<Physical properties of ink-jet ink>
The physical property value of the inkjet ink of the present invention is not particularly limited as long as it can be discharged by an inkjet head, but the ink viscosity is preferably 30 mPa · s or less at 25 ° C. from the viewpoint of stable discharge. More preferably, it is 30 mPa * s, and 2-20 mPa * s is still more preferable. Moreover, when ejecting with an apparatus, it is preferable to maintain the temperature of the inkjet ink at a substantially constant temperature in the range of 20 to 80 ° C. When the temperature of the apparatus is set to a high temperature, the viscosity of the ink decreases, and it becomes possible to eject higher viscosity ink. However, as the temperature rises, heat denaturation of the ink and thermal polymerization reactions occur in the head, and the solvent tends to evaporate on the nozzle surface that ejects the ink, so nozzle clogging easily occurs. The temperature is preferably in the range of 20-80 ° C.

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

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

  The above-described surface tension is measured by a Wilhelmy method using a commonly used surface tension meter (for example, surface tension meter FACE SURFACE TENSIOMETER CBVB-A3, manufactured by Kyowa Interface Science Co., Ltd.) at a liquid temperature of 25 ° C. and 60%. It is a value measured by RH.

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

<Color pixel (color image)>
When the chromaticity of a color pixel (color image, recording material) obtained by the method described later using the inkjet ink of the present invention is expressed in the CIE-XYZ color system measured using a C light source, When the value on the xy chromaticity diagram is 7 ≦ Y (stimulus value Y is 7 or more), it is within the range surrounded by 0.125 <x <0.145 and 0.075 <y <0.140. Preferably there is. More preferably, it is in the range surrounded by 0.130 <x <0.140 and 0.090 <y <0.120.

In the XYZ color system, the color can be expressed by the following equation using three variables (x, y, Y). At this time, the following x and y are variables representing hue and saturation, and X, Y, and Z are color stimulus values.
(Formula W)
x = X / (X + Y + Z), y = Y / (X + Y + Z)

  In addition, the luminance Y value when the hue of the obtained color pixel is in the above preferable range on the xy chromaticity diagram is preferably 7 or more, and preferably 10 or more from the viewpoint of application to a color filter. Is more preferable, and 12 or more is particularly preferable.

<Color filter and manufacturing method thereof>
Next, with reference to the preferred embodiments shown in the drawings, a color filter using the above-described ink jet ink and a manufacturing method thereof will be described in detail.
The color filter of the present invention is characterized by comprising color pixels formed by the inkjet method using the inkjet ink of the present invention, that is, manufactured by the inkjet method using the inkjet ink of the present invention. It is characterized by that. The color filter manufacturing method of the present invention includes a step of forming pixels by applying the inkjet ink of the present invention to a recess surrounded by a partition formed on a substrate by an inkjet method (hereinafter referred to as “pixel formation”). Process) ”. Preferably, the pixel forming step includes a drawing step of applying ink as droplets to the recesses defined by the partition walls on the substrate by an ink jet method, and further forming at least one colored pixel (ink in the recesses). After that, a curing process including a heating process for curing by heat to form color pixels can be provided, and another process such as a baking process can be provided if necessary.

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

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

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

The ink jet system used in the drawing step S110 is not particularly limited, a method of continuously ejecting charged ink jet ink and controlling it by an electric field, a method of intermittently ejecting ink jet ink using a piezoelectric element, and ink jet Various methods, such as a method of heating ink for heating and intermittently ejecting the foam, etc. can be used. As inkjet heads used, continuous and on-demand piezo methods, thermal methods, Various types of inkjet heads (discharge heads) such as a solid type and an electrostatic suction type can be used, and it is preferable to use various types of on-demand type inkjet heads. It is preferable to use an inkjet head. Further, the ejection units (nozzles) of the inkjet head are not limited to a single row arrangement, and may be arranged in a plurality of rows or in a staggered pattern.
Further, the head preferably has a temperature control function so that the temperature of the ink can be controlled. It is preferable to set the injection temperature so that the viscosity at the time of ejection is 5 to 25 mPa · s, and to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. Moreover, as a drive frequency, it is preferable to operate | move at 1-500 kHz. The shape of the nozzle is not necessarily circular, and is not limited to an elliptical shape, a rectangular shape, or the like. The nozzle diameter is preferably in the range of 10 to 100 μm. The nozzle opening itself is not necessarily a perfect circle, but in this case, the nozzle diameter is the diameter expressed by a circle equivalent to the area of the opening.

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

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

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

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

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

  In the present invention, as shown in FIG. 2C, after a droplet of ink 18 is applied to the recess 16 on the substrate 12 to form a layer of ink 18 in the drawing step S110, the layer shown in FIG. As shown in FIG. 2E, after the organic solvent contained in the ink 18 is dried and removed to form the ink remaining portion 18a in the preliminary treatment step S112, the heating step of heating the ink remaining portion 18a is performed as shown in FIG. The pixel 20 may be formed by polymerizing the remaining ink 18a in the curing step S114. In addition, when the temperature at which thermal polymerization of the remaining ink starts is T ° C., preheating (hereinafter also referred to as a preheating step) is performed at a temperature lower than T ° C. in the pretreatment step S112, and the ink is contained in the ink 18. The organic solvent to be removed is forcibly dried to form the ink residue 18a, and then the ink residue 18a is polymerized and cured by a heating process in which the ink residue 18a is heated at a temperature of T ° C. or higher to form the pixel 20. May be.

<Curing process>
In the method for producing a color filter of the present invention, a step of curing the uncured pixel ink 18a having a desired hue such as red (R), green (G), and blue (B) with heat can be provided.
The ink-jet ink of the present invention can form color pixels exhibiting excellent hue, brightness, heat resistance, and chemical resistance by thermosetting, and there is no need to provide a process such as light irradiation.

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

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

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

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

In the method for producing a color filter using the ink of the present invention, the pixel forming step S106 from the drawing step S110 to the preheating step (S112) and the curing step (S114) is preferably performed within 24 hours. Is more preferable, and it is even more preferable to be performed within 6 hours. By forming the pixels from the drawing step S110 to the curing step S114 within 24 hours, the surface shape of the pixels can be improved.
In the color filter manufacturing method of the present invention, the pixel formation step S106, that is, the drawing step S110, the preheating step (S112), and the curing step (S114) may be performed for each color or a plurality of colors. It may be performed every time, or all colors may be drawn in the drawing step S110, and the preliminary heating in the preheating step (S112) and the curing in the curing step S114 may be performed for all colors. Further, when the pixel formation step S106 is performed for each color or a plurality of colors, the order of the colors of the pixels to be formed is not particularly limited, and any color order may be used.

<Partition forming process>
In the method for manufacturing a color filter of the present invention, in the pixel forming step S106 described above, as shown in FIGS. 2C to 2E, the ink is applied to the concave portion 16 surrounded by the partition wall 14 formed on the substrate 12. A pixel 20 is formed by applying droplets of the inkjet ink 18 of the present invention by the method.
The partition 14 is not particularly limited, and a known partition can be used. Any partition may be used. When a color filter is manufactured, the partition 14 has a black matrix function and has a light blocking effect. It is preferable.
Therefore, in the example shown in FIG. 1, in the partition forming step S102, as shown in FIG. 2 (b), on the substrate 12 shown in FIG. A partition wall 14 is formed.

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

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

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

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

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

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

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

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

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, equipment, operations, 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 examples shown below. In the following examples, “%” and “parts” represent “mass%” and “parts by mass” unless otherwise specified, and the molecular weight indicates the weight average molecular weight.

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

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

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

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

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

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

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

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

<Blue (B) ink>
The following components were mixed at the blending ratio shown in Table 2 and stirred for 1 hour. Then, it filtered under reduced pressure with the micro filter with an average hole diameter of 0.25 micrometer, and prepared the blue ink liquid (B-1-B-7, B comparison-1-B comparison-6).

Details of each material used for preparing the blue (B) ink are shown below.
(Organic solvent)
・ Cyclohexanone (Wako Pure Chemical Industries, Ltd.)
・ Benzyl alcohol (Wako Pure Chemical Industries, Ltd.)
・ Diethylene glycol monomethyl ether (Wako Pure Chemical Industries, Ltd.)
(Polymerizable monomer)
・ Denacol acrylate DA-314 (manufactured by Nagase ChemteX Corporation)
: ECH-modified glycerol triacrylate SR-399E (manufactured by Sartomer)
: Dipentaerythritol hydroxypentaacrylate AD-TMP (manufactured by Shin-Nakamura Chemical Co., Ltd. (NK ester AD-TMP))
: Ditrimethylolpropane tetraacrylate / DPCA-20 (manufactured by Nippon Kayaku Co., Ltd. (KAYARAD DPCA-20))
: Caprolactone-modified dipentaerythritol hexaacrylate

(Multifunctional thiol)
TPMP: trimethylolpropane tris (3-mercaptopropionate)
-Karenz MT-PE1 (manufactured by Showa Denko (Karenz MT-PE1))
: Pentaerythritol tetrakis (3-mercaptobutyrate)
DPMP: dipentaerythritol hexakis (3-mercaptopropionate)
(Surfactant)
KF-353 (manufactured by Shin-Etsu Silicone): polyether-modified silicone oil F781-F (manufactured by Dainippon Ink and Chemicals (Megafac F781F))

(dye)
Specific dye C-1 (corresponds to the dye represented by the above general formula (1))
Specific dye C-2 (corresponds to the dye represented by the general formula (1))
Specific dye C-3 (corresponds to the dye represented by the general formula (1))
Specific dye C-4 (corresponds to the dye represented by the general formula (1) above)
Specific dye C-5 (corresponds to the dye represented by the above general formula (1))
・ Specific dye C-6 (corresponds to comparative example)
・ Specific dye C-7 (corresponds to comparative example)
・ Specific dye C-8 (corresponds to comparative example)
Specific dye M-1 (Exemplary compound I-21 of a dye represented by the above general formula (2-2))
Specific dye M-2 (Exemplary compound III-58 of a dye represented by the above general formula (2-2))
・ Specific dye M-3 (corresponds to comparative example)
Specific dye M-4 (Exemplary compound III-1 of a dye represented by the above general formula (2-2))

<Manufacture of color filters by inkjet method>
Using the ink of B-1 prepared above, an inkjet printer DMP-2831 manufactured by Fuji Film Dimatix Co., Ltd. is formed in the region (the concave portion surrounded by the convex portion) divided by the partition on the substrate obtained above. Then, discharging was performed, followed by heating in an oven at 100 ° C. for 2 minutes.
Next, the monochromatic color filter was produced by leaving still for 30 minutes in 220 degreeC oven. The film thickness of the obtained color pixel was 2.0 μm.
For each of the other B-2 to B-7 inks, a color filter was prepared using these inks in the same manner.

<Measurement of viscosity and surface tension>
The viscosity and surface tension of the ink prepared above were measured.
The ink viscosity was measured under the following conditions using an E-type viscometer (RE-80L) manufactured by Toki Sangyo Co., Ltd. while adjusting the temperature of the obtained ink to 25 ° C. The results are shown in Table 3.
(Measurement condition)
-Rotor used: 1 ° 34 'x R24
・ Measurement time: 2 minutes ・ Measurement temperature: 25 ° C

  The surface tension was measured using a surface tension meter (FACE SURFACE TENSIOMETER CBVB-A3) manufactured by Kyowa Interface Science Co., Ltd. while adjusting the temperature of the obtained ink to 25 ° C. The results are shown in Table 3.

<Appearance inspection>
The monochromatic color filter produced above was observed with an optical microscope with a magnification of 100 times. When a particulate matter with a size of 1 μm or more is observed in the field of view, or when a phase separation structure is observed, it is judged as rejected (x), and when a particulate matter is not observed in the field of view, it is passed (◯). did. As an example, FIG. 3 shows a case of acceptance, FIG. 4 shows a case of failure in which particulate matter is observed, and FIG. 5 shows an observation view in case of failure where a phase separation structure is observed. The results are shown in Table 3 below.

<Hue>
If the hue of the single color filter produced above is in the range of 0.130 <x <0.140 and 0.090 <y <0.120 (range A) when a C light source is used as the light source, Although not included in the range A, the range was 0.1 if it was in the range of 0.125 <x <0.145 and 0.075 <y <0.140, and x if it was in any other range. For the measurement of hue, UV-560 (manufactured by JASCO Corporation) was used. The results are shown in Table 3 below.

<Luminance>
When the hue of the single color filter produced above is in the range of 0.125 <x <0.145 and 0.075 <y <0.140 when a C light source is used as the light source, the brightness at that time Y values of 12 or more were rated as ◎, 10 or more as ◯, 7 or more as Δ, and less than 7 as ×. For the measurement of luminance, UV-560 (manufactured by JASCO Corporation) was used. The results are shown in Table 3 below.

<Heat resistance evaluation>
The single color filter produced above was placed in an oven heated to 220 ° C. and left for 1 hour, and then the hue was measured. For the measurement of hue, UV-560 (manufactured by JASCO Corporation) was used, and ΔEab before and after the evaluation was rated as less than 3. ΔEab is 3 or more and less than 7, and ΔEab is 7 or more and less than 15, and ΔEab is 15 or more. The results are shown in Table 3 below.
ΔEab is a value obtained from the following color difference formula based on the CIE 1976 (L *, a *, b *) space color system (Japanese Color Society edited by Color Science Handbook (Showa 60) p.266).
ΔEab = {(ΔL) ² + (Δa) ² + (Δb) ² } ^1/2

  In the evaluation results in Table 3 below, it is necessary that x is not included from the viewpoint of practical use.

  In Table 3 above, “-” represents that the experiment was not performed (not performed).

As can be seen from Table 3, the color pixels obtained by the thermosetting process using the inkjet ink of the present invention were excellent in optical properties such as appearance, hue and luminance, and also in heat resistance.
On the other hand, in B comparison-1 to B comparison-6, “x” was included in any of the above items, and a color pixel having desired characteristics could not be obtained.
More specifically, as shown in B comparison-1 and 2, when a dye not corresponding to the dye represented by the general formula (1) is used, particulate matter is confirmed in the color pixel, Aggregation occurred, and the desired hue could not be obtained.
Moreover, as shown in B Comparative-3, in the inkjet ink that does not contain a thiol compound, only a color pixel inferior in heat resistance and inferior in luminance was obtained. In particular, when the composition was substantially the same and it compared with Example B-3 which contains a thiol compound, when it did not contain a thiol compound, it was inferior in all the evaluation items.

Furthermore, as shown in B Comparison-4, when a cyan dye and an azomethine dye specifically disclosed in Japanese Patent Application Laid-Open No. 2008-88222 were used in combination, only a color pixel inferior in heat resistance was obtained.
Further, as shown in Comparative B-5, when a cyan dye and a dipyrromethene dye specifically disclosed in Japanese Patent Application Laid-Open No. 2008-292970 were used in combination, particulate matter was confirmed in the color pixel.
Moreover, as shown in B comparison-6, when only the dipyrromethene dye was used, the obtained color pixel was inferior in heat resistance.
In addition, B comparison-4 which does not contain the dye represented by the general formula (2) and B comparison-6 which contains the dye represented by the general formula (2) were both inferior in heat resistance. On the other hand, in the present application, excellent heat resistance was obtained, and it was confirmed that excellent heat resistance was obtained only when two dyes were used in combination and a thiol compound was used.

<Chemical resistance evaluation>
The monochromatic color filter produced above was immersed in the chemical to be evaluated (N-methylpyrrolidone, 2-propanol, 5% sulfuric acid aqueous solution, 5% sodium hydroxide aqueous solution) for 20 minutes, and the hue before and after that was measured. For the measurement of hue, UV-560 (manufactured by JASCO Corporation) was used, and ΔEab was less than 3 as ◎. ΔEab is 3 or more and less than 7, and ΔEab is 7 or more and less than 15, and ΔEab is 15 or more. The results are shown in Table 4 below.
In the following evaluation results, it is necessary that x is not included from the viewpoint of practical use.

As can be seen from Table 4, the color pixels obtained by the thermosetting process using the inkjet ink of the present invention were also excellent in chemical resistance.
For example, when Example B-2 using the dye represented by the general formula (1) is compared with B Comparison-2 which is not used, in Example B-2, N-methylpyrrolidone and It was confirmed that the chemical resistance related to 2-propanol was improved.
Moreover, when Example B-3 which uses the thiol compound and B comparison-3 which is not used are compared, it was confirmed that the chemical resistance is improving more.
Furthermore, even when Examples B-3 and B-4 were compared with B Comparison-4 and B Comparison-5, respectively, it was confirmed that the chemical resistance (solvent resistance) was further improved.

DESCRIPTION OF SYMBOLS 10 Color filter 12 Board | substrate 14 Partition 16 Recessed part 18 Ink 18a Uncured pixel ink 20 Pixel 22 Protective film

Claims (10)

Dye represented by general formula (1), dye represented by general formula (2-1), dye represented by general formula (2-2), and represented by general formula (2-3) An inkjet ink comprising at least one dye selected from the group consisting of dyes, a radical polymerizable monomer, an organic solvent, and a bifunctional or higher polyfunctional thiol compound.
(In General Formula (1), each R ¹ independently represents a hydrogen atom or a substituent. L independently represents an aliphatic or aromatic linking group. Z ¹ together with two carbon atoms. Represents a group of non-metallic atoms necessary to form a 6-membered ring, and four Z ¹ may be the same or different, and M represents two hydrogen atoms, a divalent metal atom, a divalent atom Represents a metal oxide, a divalent metal hydroxide or a divalent metal chloride, m represents 1 or 2 each independently, n represents each independently 0 or 1, p represents each independently 1 to 2 Represents an integer of 5. r ¹ , r ² , r ³ and r ⁴ each independently represent 0 or 1, and satisfy r ¹ + r ² + r ³ + r ⁴ ≧ 1, provided that at least one of R ¹ is _{-SO 3 H, -P = O (} OH) 2, a -P = O (H) (OH ) or -COOH Yes Or represents radicals, _{or, -S (O) m - (} L) n - at least one of the groups represented by (R ¹⁾ _p is at R ¹ is OH group, L represents a single bond, m Represents a group in which n is 2. When R ¹ is a group having —SO ₃ H, —P═O (OH) ₂ , —P═O (H) (OH) or —COOH, n is 1 is represented.)
(In general formula (2-1), R _{11 to} R ₁₆ each independently represents a hydrogen atom or a substituent. R ₁₇ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. represents .Ma is .X ₁ representing a metal atom or metal compound represents a group capable of being bonded to Ma, _{X 2} is .X ₁ and _{X 2} represents a group necessary for neutralizing a charge of Ma May be bonded to each other to form a 5-membered, 6-membered or 7-membered ring.)
(In General Formula (2-2), R _{12 to} R ₁₅ each independently represents a hydrogen atom or a substituent. R ₁₇ 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 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. Represents a nitrogen atom, an oxygen atom, or a sulfur atom, and 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). Represents an oxygen atom or a sulfur atom, and Y ₁ represents NRc (Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group). Represents an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, or a carbon atom, Y ₂ represents a nitrogen atom or a carbon atom, and R ₁₈ and R ₁₉ are each independently Represents 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 amino group, wherein R ₁₈ and Y ₁ are bonded to each other and are 5-membered; A 6-membered or 7-membered ring may be formed, and R ₁₉ and Y ₂ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and X ₅ represents Ma. And a represents 0, 1 or 2.)
(In the general formula (2-3), R _{11 to} R ₁₆ each independently represents a hydrogen atom or a substituent. R ₁₇ 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.) The inkjet ink according to claim 1, wherein at least one of R ^{1 in} the general formula (1) is a group having —COOH.   The inkjet ink according to claim 1, wherein the radical polymerizable monomer includes a radical polymerizable monomer having 3 to 6 polymerizable groups.   The inkjet ink according to any one of claims 1 to 3, wherein the viscosity at 25 ° C is 30 mPa · s or less.   The inkjet ink according to any one of claims 1 to 4, wherein the surface tension at 25 ° C is 20 to 40 mN / m.   Furthermore, the inkjet ink in any one of Claims 1-5 containing surfactant. A drawing step of applying the ink-jet ink according to any one of claims 1 to 6 to the concave portion defined by the partition formed on the substrate by an ink-jet method;
A color filter manufacturing method comprising: a curing step of heating the inkjet ink ejected into the recess.   A color filter manufactured by the method for manufacturing a color filter according to claim 7.   A liquid crystal display comprising the color filter according to claim 8.   An image display device comprising the color filter according to claim 8.