JP2007291198A - Copper chelate pigment, colored composition, colored microparticle dispersion, inkjet ink using the same, inkjet recording method, and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored composition containing a novel copper chelate pigment and being excellent in hue and image fastness. <P>SOLUTION: The copper chelate pigment is represented by formula (1): Cu<SP>2+</SP>[(X<SB>1</SB>)<SB>l</SB>(X<SB>2</SB>)<SB>m</SB>(X<SB>3</SB>)<SB>n</SB>]-(W<SB>1</SB>)<SB>s</SB>(wherein X<SB>1</SB>, X<SB>2</SB>, and X<SB>3</SB>are each a monodentate or bidentate ligand, provided that at least one of them is represented by formula (2); l, m, n, and s are each an integer of 0 to 2, provided that l+m+n>1; and (W<SB>1</SB>)<SB>s</SB>is a counterion necessary to neutralize the charge). In formula (2), Q is a 5- or 6-membered nitrogen-containing heterocyclic ring; and Z<SB>2</SB>is an atomic group which forms a 4- to 6-membered ring; L<SB>1</SB>to L<SB>5</SB>are each a substituted or unsubstituted methine group; n1 is an integer of 0 to 4; n2 is 0 or 1; Y<SB>2</SB>is an oxygen atom or =NR<SB>3</SB>-; and R and R<SB>1</SB>to R<SB>3</SB>are each a substituent, provided that at least one of them has a chelatable group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel copper chelate dye, an inkjet ink using the same, and a color filter.

  In recent years, recording materials for forming color images have been mainly used as image recording materials. Specifically, application fields using colored compositions include inkjet recording materials and thermal transfer recording. Examples thereof include materials, electrophotographic recording materials, optical recording media, transfer type silver halide photosensitive materials, printing inks, and recording pens. Further, a color filter is used for recording / reproducing a color image in an image pickup device such as a CCD in a photographing apparatus and on an LCD or PDP in a display. These color image recording materials and color filters use so-called additive and subtractive primary colorants to reproduce or record full-color images, but they have absorption characteristics that can realize a preferable color gamut. It is desired to have a fast and durable dye that can withstand various use conditions and environmental conditions.

  Among the above image recording methods, the ink jet recording method is rapidly spread because the material cost is low, high-speed recording is possible, noise during recording is low, and color recording can be easily obtained. However, it is developing further. Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals. There are a method of discharging bubbles, a method of generating bubbles in the ink by heat and discharging droplets, a method of using ultrasonic waves, and a method of sucking and discharging droplets by electrostatic force. Further, as ink for inkjet recording, water-based ink, oil-based ink, solid (melting type) ink, or the like is used.

  The dyes used in such inks for ink jet recording have good solubility or dispersibility in solvents, high density recording, good hue, light, heat, and environmental activity. It is robust against gases (NOx, ozone, and other oxidizing gases, SOx, etc.), excellent in water and chemical fastness, has good fixability to image receiving materials and is difficult to bleed, and ink It is required to have excellent storage stability, non-toxicity, high purity, and availability at low cost. However, at present, it is extremely difficult to search for pigments that satisfy these required performances at a high level. In particular, there is a strong demand for a pigment that exhibits a good magenta hue and is robust against an active gas under light and a storage environment, particularly an oxidizing gas such as ozone. Although a method of using an azo dye for ink jet recording ink is disclosed, these disclosed inks are excellent in ozone gas resistance, but are not yet sufficient in terms of color tone and light resistance (for example, Patent Document 1, 2).

  Conventionally, phenol, naphthol, aniline, and the like have been widely used as coupling components for azo dyes. Although azo dyes having good hues obtained by these coupling components have been disclosed, they have the problem of poor light fastness (see, for example, Patent Documents 3 and 4). In order to improve this, recently, a dye having a good hue and improved light fastness has been disclosed (for example, see Patent Document 5). However, all of the dyes proposed in Patent Documents 3 to 5 have extremely insufficient fastness to oxidizing gases such as ozone.

  On the other hand, since a high transparency is required for the color filter, a method called a dyeing method for coloring with a dye has been performed. For example, a color filter can be produced by sequentially repeating a method of forming a pattern by pattern exposure and development of a dyeable photoresist and then dyeing with a filter color dye for all filter colors. It is disclosed that a color filter can be produced by a method using a positive resist in addition to a staining method (see, for example, Patent Documents 6 and 7).

In addition, color filters using dyes are disclosed (for example, see Patent Documents 8 to 10). Since these methods use dyes, the transmittance is high and the optical characteristics of the color filter are excellent, but there are limitations on light resistance, heat resistance, etc., and pigments with excellent various resistances and high transparency are desired. It was. On the other hand, a method using an organic pigment having excellent light resistance and heat resistance in place of a dye is widely known. However, it is difficult to obtain optical characteristics like a dye with a color filter using a pigment.
JP 2003-64275 A Japanese Patent Laid-Open No. 2003-246942 Japanese Patent Application Laid-Open No. 11-209673 Japanese Patent No. 3020660 JP 2001-335714 A US Pat. No. 4,808,501 JP-A-6-35182 JP 2002-228830 A JP 2001-66421 A JP 2000-345059 A

  The present invention has been made in view of the above-mentioned problems, and its purpose is excellent in hue and image fastness, and is used in an ink jet recording ink used in an ink jet recording method and an image pickup device such as a display such as LCD and PDP, and a CCD. Another object of the present invention is to provide a coloring composition that can be preferably used for a color filter. Furthermore, the present invention is to provide an ink for ink jet recording and an ink jet recording method which have a good hue and can form an image having high fastness against an active gas, particularly ozone gas, under light and storage conditions. Another object of the present invention is to provide a color filter excellent in color reproducibility and light fastness.

  As a result of intensive studies in view of the above-mentioned problems, the present inventors have used a novel copper chelate dye represented by the general formula (1), so that hue (spectral absorption characteristics), light resistance, and oxidizing gas can be obtained. A colored composition having excellent resistance can be obtained, and further, by using the colored composition of the present invention, it has a good hue and color reproducibility, and is excellent in image storability under light and various storage environments. As soon as an ink for ink jet recording, an ink jet recording method, and a color filter can be realized, the present invention has been achieved.

  The above object of the present invention is achieved by the following means.

  1. A copper chelate dye represented by the following general formula (1).

General formula (1)
Cu ²⁺ [(X ₁ ) _l (X ₂ ) _m (X ₃ ) _n ] · (W ₁ ) _s
[Wherein, X ₁ , X ₂ and X ₃ each independently represent a monodentate or bidentate ligand, which may be the same or different, and at least one of them represents the following general formula (2) . l, m, n, and s each represent an integer of 0 to 2, l + m + n> 1, and (W ₁ ) _s represents a counter ion necessary to neutralize the charge. ]

[Wherein Q represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and Q may be condensed or may have a substituent. Z ₂ represents an atomic group necessary for forming a 4- to 6-membered ring. L _1, represents a L _2, L _3, L ₄ and L ₅ methine group having each independently unsubstituted or substituted. n1 represents an integer of 0 to 4, and n2 is 0 or 1. Y ₂ represents an oxygen atom or ═NR ₃ —, R and R _{1 to} R ₃ each represent a substituent, at least one has a chelatable group, and R ₂ and R ₃ are bonded to form a 5-membered ring. May be formed. ]
2. 2. The copper chelate dye as described in 1 above, wherein the ring formed by Z ₂ in the general formula (2) is represented by the following general formula (3).

[Wherein Y ₁ represents an oxygen atom, a sulfur atom or ═C (CN) R ₁₃ . R ₁₃ represents a cyano group, a carboxylic acid group, a carboxylic acid ester group or a carbonamido group, and is bonded to L ₃ by * and Z ₁ by **. ]
3. In the general formula (2), Y ₂ represents ═NR ₃ —, and the condensed ring structure formed by combining R ₂ and R ₃ is represented by the following general formula (4-1) or (4-2). 3. The copper chelate dye as described in 1 or 2 above.

[Wherein, R _{41 to} R ₄₃ each represent a substituent, at least one of which has a chelatable group, and is bonded to Z ₂ at the * moiety. ]
4). In the general formula (4-1) or (4-2), the chelatable group represented by R _{41 to} R ₄₃ is represented by the following general formula (5), The copper chelate dye according to item 1.

[Wherein W represents ═N— or ═C (OR ₇₁ ) —, Z ₃ represents an atomic group necessary for forming a 5- or 6-membered ring, and may have a substituent, R ₇₁ represents a substituent, and is bonded to Z ₁ by *. ]
5). In Formula (1), one of the 1-4 at least one ligand represented by X _1, X ₂ or X _3, characterized by being represented by the following general formula (6) 1 The copper chelate dye described in the item.

[Wherein E ₁ and E ₂ represent an electron-withdrawing group having a Hammett substituent constant (σp) of 0.1 or more and 0.9 or less, R ₆₁ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, Represents an aryloxy group and an amino group, and may have a substituent. ]
6). The coloring composition characterized by containing the copper chelate pigment | dye of any one of said 1-5.

  7). 6. A colored fine particle dispersion comprising the copper chelate dye according to any one of 1 to 5 and a thermoplastic resin or a high-boiling solvent.

  8). An ink-jet ink comprising the colored composition according to claim 6 or the colored fine particle dispersion according to claim 7.

  9. 9. An ink jet recording method, wherein recording is performed using the ink jet ink described in 8 above.

  10. 6. A color filter comprising the copper chelate dye according to any one of 1 to 5 above.

  According to the present invention, it is possible to provide a coloring composition excellent in hue and image fastness, whereby an image having a good hue and having high fastness to an active gas, particularly ozone gas, in a light and storage environment. An ink for ink jet recording and an ink jet recording method that can be formed can be provided, and a color filter excellent in color reproducibility and light fastness can be provided.

  The coloring composition of the present invention contains a novel copper chelate dye represented by the general formula (1).

  As a result of intensive studies to solve the above problems, the present inventors have found a novel copper chelate dye represented by the above general formula (1), a coloring composition containing the dye, and a colored fine particle dispersion It was found that an ink-jet ink and a color filter excellent in hue and fastness can be provided by using.

  Hereinafter, the structures represented by the general formulas (1) to (6) will be described.

<< Compound Represented by Formula (2) >>
In the general formula (2), Q represents an atomic group necessary for forming a 5-membered or 6-membered nitrogen-containing heterocycle, and Q may be condensed or may have a substituent. Z ₂ represents an atomic group necessary for forming a 4- to 6-membered ring. L ₁ , L ₂ , L ₃ , L ₄ and L ₅ each independently represents an unsubstituted or substituted methine group. n1 represents an integer of 0 to 4, and n2 is 0 or 1. Y ₂ represents an oxygen atom or ═NR ₃ —, R and R _{1 to} R ₃ each represent a substituent, at least one has a chelatable group, and is bonded to R ₂ and R ₃ to form a 5-membered ring. May be formed.

  Preferred examples of the heterocyclic ring formed by Q include benzothiazole nucleus, benzoxazole nucleus, benzoselenazole nucleus, benzotelrazole nucleus, 2-quinoline nucleus, 4-quinoline nucleus, benzimidazole nucleus, thiazoline nucleus, indolenine. Nuclei, oxadiazole nuclei, thiazole nuclei, imidazole nuclei are mentioned, more preferably benzothiazole nuclei, benzoxazole nuclei, benzimidazole nuclei, benzoselenazole nuclei, 2-quinoline nuclei, 4-quinoline nuclei, indolenine nuclei. Particularly preferred are a benzothiazole nucleus, a benzoxazole nucleus, a 2-quinoline nucleus, a 4-quinoline nucleus, and an indolenine nucleus. Examples of substituents on the ring include carboxylic acid, phosphonic acid, sulfonic acid, halogen (F, Cl, Br, I), cyano, alkoxy (methoxy, ethoxy, methoxyethoxy, etc.), aryloxy (phenoxy, etc.), alkyl ( Methyl, ethyl, cyclopropyl, cyclohexyl, trifluoromethyl, methoxyethyl, allyl, benzyl, etc., alkylthio (methylthio, ethylthio, etc.), alkenyl (vinyl, 1-propenyl, etc.), aryl (phenyl, thienyl, toluyl, Chlorophenyl, etc.).

Z ₂ represents an atomic group necessary for forming a 4- to 6-membered ring composed of atoms selected from a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a hydrogen atom. The ring formed by Z ₂ is preferably a ring having a skeleton formed by 4 or 5 carbons, and more preferably a ring represented by the general formula (3).

In the general formula (3), Y ₁ represents an oxygen atom, a sulfur atom or ═C (CN) R ₁₃ , R ₁₃ represents a cyano group, a carboxylic acid group, a carboxylic acid ester group or a carbonamido group, and * represents L ₃ and ** bind to a nitrogen-containing 5-membered ring. Y ₁ is preferably an oxygen atom.

In the general formula (2), L ₁ , L ₂ , L ₃ , L ₄ and L ₅ each independently represents a methine group which may have a substituent. Examples of the substituent include a substituted or unsubstituted alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 7 carbon atoms such as methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, 2-carboxyl. Ethyl, benzyl, etc.), substituted or unsubstituted aryl groups (preferably having 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms, such as phenyl, toluyl, chlorophenyl, o-carboxyphenyl), heterocyclic rings Groups (eg pyridyl, thienyl, furanyl, pyridyl, barbituric acid), halogen atoms (eg chlorine, bromine), alkoxy groups (eg methoxy, ethoxy), amino groups (preferably having 1 to 12 carbon atoms, Preferably 6 to 12, for example diphenylamino , Methylphenylamino, 4-acetyl-piperazin-1-yl), etc. oxo group. These substituents on the methine group may be linked to each other to form a ring such as a cyclopentene ring, a cyclohexene ring, a squarylium ring, or a ring with an auxiliary color group.

  n1 represents an integer of 0 to 4, preferably 0 to 3, and more preferably 0 to 2. n2 is 0 or 1.

  R represents a substituent. The substituent is preferably an aromatic group which may have a substituent or an aliphatic group which may have a substituent, and the aromatic group preferably has 1 to 16 carbon atoms, more preferably 5 Or 6. The number of carbon atoms in the aliphatic group is preferably 1-18, more preferably 2-10. Examples of the unsubstituted aliphatic group and aromatic group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, a phenyl group, and a naphthyl group.

The substituent represented by R ₁ and R ₂ is not particularly limited as long as it can be substituted, but an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group) Group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, trifluoromethyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg, vinyl group, allyl group) Group), alkynyl group (for example, ethynyl group, propargyl group, etc.), aryl group (for example, phenyl group, naphthyl group, etc.), heteroaryl group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group) , Pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzimid Dazolyl group, benzoxazolyl group, quinazolyl group, phthalazyl group, etc.), heterocyclic group (also called heterocyclic group, for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group) , Ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (for example, phenoxy group) , Naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.) Arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (Eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octyl) Aminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), a Group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc. ), Acyloxy groups (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide groups (for example, methylcarbonylamino group, ethylcarbonyl) Amino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group Group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentyl) Aminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (eg methyl Ureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthyl Raid group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, Naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentyl) Amino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), cyano group, nitro group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.) Can be mentioned. These may be further substituted with the same substituent.

R ₁ is preferably an alkyl group, aryl group, heterocyclic group, heteroaryl group, alkoxy group, sulfamoyl group, ureido group, amino group, amide group, acyl group, alkoxycarbonyl group, carbamoyl group, cyano group, halogen atom, etc. More preferred are an alkyl group, an aryl group, an alkoxycarbonyl group, a carbamoyl group, a cyano group, and an amide group.

R ₂ is preferably the same group as R ₁ , may be further substituted with another group, and has a chelatable group.

  A chelatable group represents a substituent containing an atom having an unshared electron pair. Specifically, a heterocyclic group (pyridine ring, pyrazine ring, pyrazole ring, quinoline ring, etc.), hydroxy group, carbonyl group, oxy Carbonyl group, carbamoyl group, alkoxy group, heterocyclic oxy group, carbonyloxy group, urethane group, sulfonyloxy group, amino group, imino group, sulfonylamino group, sulfamoylamino group, acylamino group, ureido group, sulfonyl group, Examples include a sulfamoyl group, an alkylthio group, an arylthio group, and a heterocyclic thio group. Preferred examples of the substituent include a hydroxy group, a carbonyl group, an oxycarbonyl group, a carbamoyl group, an alkoxy group, a carbonyloxy group, a urethane group, a sulfonyloxy group, an amino group, an imino group, a sulfonylamino group, an acylamino group, a ureido group, an alkylthio group, An arylthio group is mentioned. More preferred substituents include a hydroxy group, a carbonyl group, a carbamoyl group, an alkoxy group, a sulfonylamino group, an acylamino group, a heterocyclic ring and the like.

In the general formula (2), Y ₂ is preferably ═NR ₃ —, and is preferably bonded to R ₂ to form a 5-membered ring. Examples of the condensed ring formed include pyrazolotriazole and pyrazoloimidazolepyra Zolotetrazole and the like can be mentioned, and it is preferably a pyrazolotriazole represented by the general formula (4-1) or (4-2).

In the general formulas (4-1) and (4-2), R _{41 to} R ₄₃ each represent a substituent, at least one of which has a chelatable group, and is bonded to Z ₂ with *.

The substituent represented by R _{41 to} R ₄₃ has the same meaning as R ₁ in the general formula (2), and R ₄₁ is preferably an alkyl group, aryl group, heterocyclic group, heteroaryl group, carbamoyl group, cyano group, An alkoxycarbonyl group etc. are mentioned.

R ₄₂ and R ₄₃ are preferably an alkyl group, an aryl group, a heterocyclic group, a heteroaryl group, etc., more preferably an aryl group, a heterocyclic group, or a heteroaryl group, which has a chelatable group. It is preferable.

In the general formulas (4-1) and (4-2), the chelatable group represented by R _{41 to} R ₄₃ is preferably a group represented by the general formula (5).

In the general formula (5), W represents = N- or = C (OR ₅₁ )-, Z ₃ represents an atomic group necessary for forming a 5- or 6-membered ring, and has a substituent. R ₅₁ represents a substituent, and is bonded to a nitrogen-containing 5-membered ring by *.

R ₅₁ has the same meaning as R ₁ , preferably an alkyl group, an aryl group, a heterocyclic group, an acyl group, and the like, more preferably an alkyl group and a heterocyclic group.

Preferred examples of the 5- or 6-membered ring formed by Z ₃ include a benzene ring, naphthalene ring, quinoline ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrazole ring, pyrrole ring, and imidazole ring. And a ring, a quinoline ring, a pyridine ring, a pyrazine ring, and a pyrazole ring.

<< Compound Represented by Formula (1) >>
In the general formula (1), X ₁ , X ₂ and X ₃ each independently represent a monodentate or bidentate ligand, which may be the same or different, and at least one of the general formula (2) ). l, m, n, and s represent an integer of 0 to 2, l + m + n> 1, and (W ₁ ) _s represents a counter ion necessary to neutralize the charge.

Examples of X ₁ , X _2, and X ₃ include JP 2000-251957, JP 2000-31723, JP 2000-323191, JP 2001-6760, JP 2001-59062, and JP 2001. Examples thereof include those described in -60467. Specifically, halogen ion, hydroxide ion, ammonia, pyridine, amine (such as methylamine, diethylamine, tributylamine, etc.), cyanide ion, cyanate ion, thiolate ion, thiocyanate ion, and bipyridines, aminopolycarboxylic acid Various chelate ligands such as acids, 8-hydroxyquinoline and the like can be mentioned, and the chelate ligands are exemplified in “Chelical Chemistry” by Keihei Ueno.

  As a monodentate ligand, a ligand coordinated by an acyl group, carbonyl group, thiocyanate group, isocyanate group, cyanate group, isocyanate group, halogen atom, cyano group, alkylthio group, arylthio group, alkoxy group or aryloxy group Or a ligand composed of dialkyl ketone or carbonamide is preferred.

  As bidentate ligands, acyloxy group, oxalylene group, acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group, thiocarbonate group, dithiocarbonate group, trithiocarbonate A ligand coordinated by a group, an alkylthio group or an arylthio group, or a ligand comprising a dialkyl ketone or a carbonamide is preferred.

  Specific examples are shown below, but the present invention is not limited thereto. It should be noted that the structural formula shown here is only one of the limit structures among the possible resonance structures, and the distinction between a covalent bond (indicated by-) and a coordination bond (indicated by ...) is also formal. It does not represent an absolute distinction.

  Moreover, the compound represented by the following general formula (6) is more preferable as a ligand.

In the general formula (6), E ₁ and E ₂ Hammett substituent constant (.sigma.p) represents a 0.1 to 0.9 electron attractive group, R ₆₁ is an alkyl group, an aryl group, a heterocyclic group, Represents an alkoxy group, an aryloxy group, or an amino group, and may have a substituent.

A substituent having a σp value represented by E ₁ and E ₂ of 0.1 or more and 0.9 or less will be described.

  As the value of Hammett's substituent constant σp here, Hansch, C .; It is preferable to use the values described in the report of Leo et al. (For example, J. Med. Chem. 16, 1207 (1973); ibid. 20, 304 (1977)).

  For example, a substituent or atom having a value of σp of 0.10 or more includes a chlorine atom, a bromine atom, an iodine atom, a carboxyl group, a cyano group, a nitro group, a halogen-substituted alkyl group (for example, trichloromethyl, trifluoromethyl, chloro Methyl, trifluoromethylthiomethyl, trifluoromethanesulfonylmethyl, perfluorobutyl), aliphatic / aromatic or heterocyclic acyl groups (eg formyl, acetyl, benzoyl), aliphatic / aromatic or heterocyclic sulfonyl groups (eg trifluoromethane) Sulfonyl, methanesulfonyl, benzenesulfonyl), carbamoyl groups (eg carbamoyl, methylcarbamoyl, phenylcarbamoyl, 2-chloro-phenylcarbamoyl), alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl) Bonyl, diphenylmethylcarbonyl), substituted aromatic groups (eg pentachlorophenyl, pentafluorophenyl, 2,4-dimethanesulfonylphenyl, 2-trifluoromethylphenyl), heterocyclic residues (eg 2-benzoxazolyl, 2-benzthiazolyl, 1-phenyl-2-benzimidazolyl, 1-tetrazolyl), azo group (eg phenylazo), ditrifluoromethylamino group, trifluoromethoxy group, alkylsulfonyloxy group (eg methanesulfonyloxy), acyloxy group ( For example, acetyloxy, benzoyloxy), arylsulfonyloxy group (for example, benzenesulfonyloxy), phosphoryl group (for example, dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl group (for example, N-ethylsulfuryl) Amoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl) and the like.

  In addition, as a substituent having a value of σp of 0.35 or more, a cyano group, a nitro group, a carboxyl group, a fluorine-substituted alkyl group (for example, trifluoromethyl, perfluorobutyl), an aliphatic / aromatic or heterocyclic acyl group (Eg, acetyl, benzoyl, formyl), aliphatic / aromatic or heterocyclic sulfonyl groups (eg, trifluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl), carbamoyl groups (eg, carbamoyl, methylcarbamoyl, phenylcarbamoyl, 2-chloro) -Phenylcarbamoyl), alkoxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl, diphenylmethylcarbonyl), fluorine or sulfonyl group substituted aromatic group (eg pentafluorophenyl, 2,4-dimethanesulfonylphenol) ), Heterocyclic residues (eg, 1-tetrazolyl), azo groups (eg, phenylazo), alkylsulfonyloxy groups (eg, methanesulfonyloxy), phosphoryl groups (eg, dimethoxyphosphoryl, diphenylphosphoryl), sulfamoyl groups, etc. Is mentioned.

  Examples of the substituent having a value of σp of 0.60 or more include a cyano group, a nitro group, an aliphatic / aromatic or heterocyclic sulfonyl group (for example, trifluoromethanesulfonyl, difluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl) and the like. It is done.

E ₁ and E ₂ are preferably a halogenated alkyl group (particularly a fluorine-substituted alkyl group), a carbonyl group, a cyano group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfonyloxy group, and the like.

Preferred examples of the substituent include an alkyl group having 2 to 20 carbon atoms R _61, alkoxy group having 2 to 20 carbon atoms, an aryloxy group, and an amino group, more preferably an alkyl group or a carbon number of 4 to 18 carbon atoms 4 to 18 alkoxy groups and aryloxy groups. Most preferably, it is a C6-C16 alkoxy group.

  Specific examples of the ligand represented by the general formula (6) are shown below, but the present invention is not limited thereto.

(W ₁ ) _s represents the counter ion when a counter ion is required to neutralize the charge. For example, whether a certain dye is a cation, an anion, or has a net ionic charge, Depends on the metal, ligand, and substituent. When the substituent has a dissociable group, it may be dissociated to have a negative charge, and in this case as well, the charge of the entire molecule is neutralized by (W ₁ ) _s . Typical cations are inorganic or organic ammonium ions (eg tetraalkylammonium ions, pyridinium ions), alkali metal ions and protons, whereas anions are specifically either inorganic or organic anions. For example, halogen anion (for example, fluoride ion, chloride ion, bromide ion, iodide ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion) ), Aryl disulfonate ions (for example, 1,3-benzenedisulfonate ions, 1,5-naphthalenedisulfonate ions, 2,6-naphthalenedisulfonate ions), alkyl sulfate ions (for example, methyl sulfate ions), sulfate ions , Thiocyanate ion , Perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion, and the like.

  Hereinafter, typical specific examples of the ligand represented by the general formula (2) and the copper chelate dye represented by the general formula (1) are shown, but the present invention is not limited thereto. .

  Examples of the dye represented by the general formula (2) according to the present invention include JP-A-6-250357, JP-A-7-175187, JP-A-3-82255, JP-A-3-261539, JP-A-4-13834, The compound can be synthesized with reference to conventionally known methods described in JP-A Nos. 63-210167, 2000-251958, 2000-285978, 2000-345059, etc. ) Can be synthesized with reference to JP-A Nos. 2002-332259 and 2003-237246, and chelate dyes having this ligand are disclosed in JP-A No. 2001-159832. And JP-A-2000-191934.

  Specific examples of the method for synthesizing the compounds represented by the general formulas (1) and (2) are shown below, but other compounds can be synthesized in the same manner. It is not limited.

[Synthesis Example 1]
<< D-22 synthesis route >>

<Synthesis of Intermediate 3>
Intermediate 2: 50 ml of 1-butanol and 4.04 g of triethylamine are added to 5.43 g and dissolved by stirring at 60 ° C. Next, what melt | dissolved the intermediate 1: 8.00g in 1-butanol: 20ml is dripped over 1 hour. After completion of the dropwise addition, the mixture is stirred at the same temperature for 2 hours, concentrated, dissolved in 200 ml of ethyl acetate and separated, neutralized, washed with water and concentrated. The concentrate was purified by column chromatography. Next, the concentrate was dissolved in 200 ml of acetone, 2N-HCl: 70 ml was added, and the mixture was heated to reflux for 6 hours. The reaction solution was concentrated to 100 ml, dropped into water: 300 ml, and the precipitated crystals were filtered to obtain Intermediate 3: 5.52 g. It was identified by MASS, H-NMR, and IR spectrum, and confirmed to be the target product.

<Synthesis of D-22>
1-Butanol: 40 ml and toluene: 40 ml were added to Intermediate 3: 3.67 g and Intermediate 4: 2.86 g, and the mixture was heated to reflux for 8 hours. The reaction solution was cooled, and the precipitated crystals were filtered to obtain D-22: 4.83 g. It was identified by MASS, H-NMR, and IR spectrum, and confirmed to be the target product.

[Synthesis Example 2]
《MD-7 synthesis route》

<Synthesis of MD-7>
Methanol: 100 ml was added to D-22: 6.36 g and copper chloride dihydrate: 1.85 g, and the mixture was heated to reflux for 2 hours. The reaction solution was cooled to room temperature, and the precipitated crystals were filtered to obtain MD-7: 7.06 g. It identified by the MASS spectrum and elemental analysis, and confirmed that it was the target object.

[Synthesis Example 3]
《MD-38 synthesis route》

<Synthesis of Intermediate 8>
Intermediate 5: While stirring to 35.0 g, acetonitrile: 200 ml, calcium chloride: 26.3 g, and triethylamine: 36.3 g are sequentially added and cooled to 15 ° C. Next, while maintaining the internal temperature at 20 ° C. or lower, 32.0 g of Intermediate 6 is added dropwise and reacted at room temperature for 2 hours. Extract by adding 200 ml of ethyl acetate and 100 ml of water, neutralize, wash with water and concentrate. The concentrate was purified by column chromatography to obtain Intermediate 7: 45.2 g. It was identified by MASS, H-NMR, and IR spectrum, and confirmed to be the target product.

  Next, 50 ml of water was added and dissolved in 2.73 g of copper chloride dihydrate: a solution obtained by adding 5 ml of methanol to 10.27 g of the intermediate 7 was added dropwise with stirring, and the precipitated crystals were filtered. Recrystallization from acetonitrile gave Intermediate 8: 9.20 g. It identified by the MASS spectrum and elemental analysis, and confirmed that it was the target object.

<Synthesis of MD-38>
Methanol: 100 ml was added to D-22: 6.36 g and intermediate 8: 8.25 g and heated to reflux for 2 hours. To the reaction solution, 50 ml of tolyl was added to aceto and cooled to 5 ° C., and the precipitated crystals were filtered to obtain MD-7: 7.58 g. It identified by the MASS spectrum and elemental analysis, and confirmed that it was the target object.

  Other compounds according to the present invention can also be synthesized according to the above synthesis method.

  Applications of the compounds according to the present invention include image recording materials for forming images, particularly color images, and specifically include recording materials (color toners) using an electrophotographic method, thermal transfer recording materials (inks). Sheet), pressure-sensitive recording material, optical recording material, transfer type silver halide photosensitive material, printing ink, recording pen, ink jet ink, and the like. In addition, color filters used in solid-state imaging devices such as LCDs and CCDs described in US Pat. No. 4,808,501 and JP-A-6-35182, and dyeing solutions for dyeing various fibers. Applicable.

  The compound according to the present invention is used by adjusting the physical properties such as solubility and heat mobility of the dye contained therein with a substituent. Further, the compound according to the present invention can be used in a uniform dissolved state, a dispersed dissolved state such as an emulsified dispersion, or a solid dispersed state depending on the system used.

  Next, various inks (especially ink jet ink) and color filters of the present invention will be described in detail.

  The ink containing the coloring matter according to the present invention can be used for various inks such as water-based ink, oil-based ink, and solid (phase change) ink. The water-based ink generally uses water and a water-soluble organic solvent as a solvent in addition to the compound according to the present invention. Examples of water-soluble organic solvents include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols (For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol ether (E.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl Glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl Ether, propylene glycol monophenyl ether, etc.), amines (eg ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, tri Tylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclics (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (eg dimethyl sulfoxide etc.), sulfones (eg sulfolane) Etc.), urea, acetonitrile, acetone and the like.

  In the water-based ink as described above, if the dye is soluble in the solvent system, it can be dissolved and used as it is. On the other hand, when it is an insoluble solid as it is, the compound according to the present invention is dispersed in various dispersing machines (for example, ball mill, sand mill, attritor, roll mill, agitator mill, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, jet mill). , And the like, or after dissolving the dye in a soluble organic solvent, it can be dispersed in the solvent system together with a polymer dispersant and a surfactant. Furthermore, when it is an insoluble liquid or a semi-molten product as it is, it can be dissolved in an organic solvent as it is or in a soluble state and can be dispersed in the solvent system together with a polymer dispersant or a surfactant.

  With regard to a specific method for preparing such water-based ink, for example, the methods described in JP-A Nos. 5-148436, 5-295313, 7-97541, 7-82515, 7-118584, etc. You can refer to it.

  The oil-based ink uses an organic solvent as a solvent in addition to the coloring matter according to the present invention. Examples of the solvent for the oil-based ink include alcohols (eg, pentanol, heptanol, octanol, phenylethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, in addition to those exemplified as the water-soluble organic solvent in the water-based ink. Anil alcohol, etc.), esters (ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol diacetate, ethyl acetate, amyl acetate, benzyl acetate, phenylethyl acetate, phenoxyethyl acetate, phenyl ethyl acetate, Benzyl propionate, ethyl benzoate, butyl benzoate, butyl laurate, isopropyl myristate, triethyl phosphate, tributyl phosphate, Diethyl tartrate, dibutyl phthalate, diethyl malonate, dipropyl malonate, diethyl diethyl malonate, diethyl succinate, dibutyl succinate, diethyl glutarate, diethyl adipate, dipropyl adipate, dibutyl adipate, di (2 -Methoxyethyl), diethyl sebacate, diethyl maleate, dibutyl maleate, dioctyl maleate, diethyl fumarate, dioctyl fumarate, cinnamate-3-hexenyl, etc.), ethers (eg, butyl phenyl ether, benzyl ethyl) Ethers, hexyl ethers, etc.), ketones (eg benzyl methyl ketone, benzylacetone, diacetone alcohol, cyclohexanone etc.), hydrocarbons (eg petroleum ether, petroleum benzyl, tetralin, decalin, Over-tertiary amyl benzene, dimethyl naphthalene, etc.), amides (e.g., N, N-diethyldodecanamide, etc.).

  In the oil-based ink as described above, the coloring matter can be used by dissolving it as it is, or it can also be used by dispersing or dissolving it together with a resinous dispersant or binder. For specific methods for preparing such oil-based inks, methods described in JP-A-3-231975, JP-A-5-508883 and the like can be referred to. The solid (phase change) ink uses a phase change solvent which is a solid at room temperature as a solvent and a molten liquid when the ink is heated and jetted, in addition to the compound according to the present invention.

  Such phase change solvents include natural waxes (eg, beeswax, carnauba wax, rice wax, wood wax, jojoba oil, whale wax, candelilla wax, lanolin, montan wax, ozokerite, ceresin, paraffin wax, microwax. Crystallin wax, petrolactam, etc.), polyethylene wax derivatives, chlorinated hydrocarbons, organic acids (eg palmitic acid, stearic acid, behenic acid, tiglic acid, 2-acetonaphthone behenic acid, 12-hydroxystearic acid, dihydroxystearic acid) Acid), organic acid esters (for example, esters of the above-mentioned organic acids with alcohols such as glycerin, diethylene glycol, and ethylene glycol), alcohols (for example, dodecanol, tetradecanol, hexadecanol, eicosano) , Docosanol, tetracosanol, hexacosanol, octacosanol, dodecenol, myricyl alcohol, tetrasenol, hexadecenol, eicosenol, docosenol, pinene glycol, hinokiol, butynediol, nonanediol, isophthalyl alcohol, mesythelin, teleaphthalyl alcohol , Hexanediol, decanediol, dodecanediol, tetradecandiol, hexadecanediol, docosandiol, tetracosanediol, tvneol, phenylglycerin, eicosanediol, octanediol, phenylpropylene glycol, bisphenol A, paraalphacumylphenol Etc.), ketones (eg benzoylacetone, diacetobenzene, benzophenone, tricho Non, heptacosanone, heptatriacontanone, hentriacontanone, heptatriacontanone, stearone, laurone, dianisole, etc.), amides (eg oleic acid amide, lauric acid amide, stearic acid amide, ricinoleic acid amide, palmitic acid amide) , Tetrahydrofuran acid amide, erucic acid amide, myristic acid amide, 12-hydroxystearic acid amide, N-stearyl erucic acid amide, N-oleyl stearic acid amide, N, N'-ethylenebislauric acid amide, N, N'- Ethylene bis stearic acid amide, N, N'-ethylene bis oleic acid amide, N, N'-methylene bis stearic acid amide, N, N'-ethylene bis behenic acid amide, N, N'-xylylene bis stearic acid amide , N, N'-Buchi Lenbis stearic acid amide, N, N′-dioleyl adipic acid amide, N, N′-distearyl adipic acid amide, N, N′-dioleyl sebacic acid amide, N, N′-cysteallyl sebacic acid amide, Like N, N′-distearyl terephthalamide, N, N′-distearylisophthalamide, phenacetin, toluamide, acetamide, oleic acid dimer / ethylenediamine / stearic acid (1: 2: 2 molar ratio) A reaction product of dimer acid, diamine and fatty acid such as tetraamide), sulfonamide (eg, paratoluenesulfonamide, ethylbenzenesulfonamide, butylbenzenesulfonamide, etc.), silicones (eg, silicone SH6018 (Toray Silicone), Silicone KR215, 216, 220 (Shin-Etsu Corn), etc.), coumarones (for example, Escron G-90 (Nippon Chemical Co., Ltd.)), cholesterol fatty acid esters (for example, stearic acid cholesterol, palmitic acid cholesterol, myristic acid cholesterol, behenic acid cholesterol, lauric acid cholesterol, melisin) Acid cholesterol, etc.), saccharide fatty acid esters (sucrose stearate, sucrose palmitate, saccharose behenate, saccharose laurate, saccharose melicate, lactose stearate, lactose palmitate, lactose myristate, lactose behenate, lactose laurate, melicine Acid lactose, etc.).

  The phase change temperature in the solid-liquid phase change of the solid ink is preferably 60 ° C. or higher, and more preferably 80 to 150 ° C.

  In the solid ink as described above, the dye according to the present invention can be used as it is by dissolving it in a heated molten solvent, or it can also be used by dispersing or dissolving it together with a resinous dispersant or binder. it can.

  For a specific method for preparing such a solid ink, the methods described in JP-A Nos. 5-186723 and 7-70490 can be referred to.

  The water-based, oil-based, and solid inks as described above have a flying viscosity of preferably 0.04 Pa · s or less, and more preferably 0.03 Pa · s or less.

  In the ink of the present invention, the surface tension at the time of flight is preferably 0.02 N / m or more, and more preferably 0.03 to 0.08 N / m.

  The pigment according to the present invention is preferably used in the range of 0.1 to 25% by mass of the total ink amount, and more preferably in the range of 0.5 to 10% by mass.

  In the ink of the present invention, viscosity adjusting agent, surface tension adjusting agent, specific resistance adjustment according to the purpose of improving ejection stability, print head and ink cartridge compatibility, storage stability, image storage stability and other various performances. An agent, a film-forming agent, a dispersant, a surfactant, an ultraviolet absorber, an antioxidant, a discoloration inhibitor, an antifungal agent, a rust inhibitor, and the like can also be added.

  The ink of the present invention is not particularly limited with respect to the recording method used, but can be preferably used as an ink for an on-demand ink jet printer. As an on-demand type, an electro-mechanical conversion type (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a shared wall type, etc.), an electro-thermal conversion type (for example, a thermal type) Specific examples include an ink jet type, a bubble jet (registered trademark) type, an electrostatic suction type (for example, an electric field control type, a slit jet type, etc.), and a discharge type (for example, a spark jet type). it can.

  The coloring composition of the present invention is characterized by containing a copper chelate dye represented by the general formula (1), and is preferably dispersed in an aqueous medium. The aqueous medium only needs to contain at least water. Specifically, water or a mixture of water and a water-miscible organic solvent, if necessary, a surfactant and an anti-drying agent (wetting agent). Preferred are those added with additives such as stabilizers and preservatives.

  The coloring composition of the present invention preferably has an embodiment containing a colored fine particle dispersion or an embodiment containing a pigment dispersion.

  The colored fine particle dispersion is obtained by dispersing colored fine particles containing the oil-soluble pigment and the oil-soluble polymer in the aqueous medium.

  There is no restriction | limiting in particular as said oil-soluble polymer, A conventionally well-known thing can be selected suitably, For example, a vinyl polymer, a condensation type polymer (a polyurethane, polyester, polyamide, polyurea, polycarbonate) etc. are mentioned.

  The oil-soluble polymer may be any of a water-insoluble type, a water-dispersed (self-emulsifying) type, and a water-soluble type, but is a water-dispersed type in terms of ease of production of colored fine particles and dispersion stability. Is preferred.

  The water-dispersed polymer may be any of an ionic polymer, a nonionic dispersible group-containing polymer, and a mixed polymer thereof.

  Examples of the ionic polymer include a polymer having a cationic group such as a tertiary amino group and a polymer containing an anionic dissociative group such as a carboxylic acid and a sulfonic acid. Examples of the nonionic dispersible group-containing polymer include polymers containing a nonionic dispersible group such as a polyethyleneoxy group. Among these, an ionic polymer containing an anionic dissociable group, a nonionic dispersible group-containing polymer, and a mixed polymer thereof are preferable from the viewpoint of dispersion stability of the colored fine particles.

  Examples of the monomer that forms the vinyl polymer include acrylic acid esters and methacrylic acid esters (the esters include esters of alkyl groups and aryl groups which may have a substituent, alkyl groups, aryl groups, and the like. As, for example, methyl, ethyl, n-butyl, sec-butyl, tert-butyl, hexyl, 2-ethylhexyl, tert-octyl, 2-chloroethyl, cyanoethyl, 2-acetoxyethyl, tetrahydrofurfuryl, 5-hydroxypentyl , Cyclohexyl, adamantyl, norbornyl, benzyl, hydroxyethyl, 3-methoxybutyl, 2- (2-methoxyethoxy) ethyl, 1,1,2,2-tetrafluoroethyl, perfluorodecyl, phenyl, 2,4,5 -Trimethylphenyl, - vinyl esters chlorophenyl, etc.) and the like, and the like.

  Examples of the vinyl esters include aliphatic carboxylic acid vinyl esters (specifically, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, etc.), aromatic Group carboxylic acid vinyl esters (specifically, vinyl benzoate, vinyl 4-methylbenzoate, vinyl salicylate, etc.) and the like, and these may have a substituent.

  Examples of other monomers that form the vinyl polymer include acrylamides, methacrylamides, olefins, and other monomers.

  Specific examples of the acrylamides include acrylamide, N-monosubstituted acrylamide, N, N-disubstituted acrylamide (the substituent includes an alkyl group, an aryl group, a silyl group, etc., for example, a methyl group , Ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, tert-octyl group, cyclohexyl group, adamantyl group, norbornyl group, benzyl group, hydroxymethyl group, ethoxyethyl group, phenyl group, 2,4,5-tetramethylphenyl group, 4-chlorophenyl group, trimethylsilyl group, and these may further have a substituent.

  Specific examples of the methacrylamides include methacrylamide, N-monosubstituted methacrylamide, N, N-disubstituted methacrylamide (for example, a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group, tert-butyl group, tert-octyl group, cyclohexyl group, adamantyl group, norbornyl group, benzyl group, hydroxymethyl group, ethoxyethyl group, phenyl group, 2,4,5-trimethylphenyl group , 4-chlorophenyl group, trimethylsilyl group, and these may further have a substituent.

  Examples of the olefins include olefins (eg, ethylene, propylene, 1-pentene, vinyl chloride, vinylidene, isoprene, chloroprene, butadiene), styrenes (eg, styrene, methylstyrene, isopropylstyrene, methoxystyrene, acetoxystyrene, Chlorostyrene), vinyl ethers (for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether) and the like.

  Examples of the other monomers include crotonic acid esters, itaconic acid esters, maleic acid esters, fumaric acid esters, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, N-vinyl oxazolidone, N-vinyl pyrrolidone, And vinylidene chloride, methylenemalonnitrile, vinylidene, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate, dioctyl-2-methacryloyloxyethyl phosphate, and the like.

  Examples of the monomer having an ionic group include a monomer having an anionic group and a monomer having a cationic group. Examples of the monomer having an anionic dissociable group include a carboxylic acid monomer, a sulfonic acid monomer, and a phosphoric acid monomer.

  Examples of the carboxylic acid monomer include acrylic acid, methacrylic acid, itaconic acid maleic acid, fumaric acid, citraconic acid, crotonic acid, itaconic acid monoalkyl ester (for example, itaconic acid monomethyl, itaconic acid monoethyl, itaconic acid monobutyl), maleic acid And monoesters (for example, monomethyl maleate, monoethyl maleate, monobutyl maleate) and the like.

  Examples of the sulfonic acid monomer include styrene sulfonic acid, vinyl sulfonic acid, acryloyloxyalkanesulfonic acid (for example, acryloyloxyethanesulfonic acid, acryloyloxypropanesulfonic acid), and methacryloyloxyalkanesulfonic acid (for example, methacryloyloxyethanesulfonic acid). Acid, methacryloyloxypropanesulfonic acid), acrylamide alkanesulfonic acid (for example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid), methacrylamide alkanesulfonic acid (for example, 2-methacrylic acid) Amido-2-methylethanesulfonic acid, 2-methacrylamideamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid) Etc., and the like.

  Examples of the phosphoric acid monomer include vinylphosphonic acid and methacryloyloxyethylphosphonic acid.

  Among these, as the monomer having an anionic group, acrylic acid, methacrylic acid, styrene sulfonic acid, vinyl sulfonic acid, acrylamide alkyl sulfonic acid, and methacrylamide alkyl sulfonic acid are preferable. Acrylic acid, methacrylic acid, styrene sulfonic acid 2-acrylamido-2-methylpropanesulfonic acid and 2-acrylamido-2-methylbutanesulfonic acid are more preferable.

  Examples of the monomer having a cationic group include monomers having a tertiary amino group such as dialkylaminoethyl acrylate and dialkylaminoethyl methacrylate.

  Examples of the monomer having a nonionic dispersible group include esters of polyethylene glycol monoalkyl ether and carboxylic acid monomer, esters of polyethylene glycol monoalkyl ether and sulfonic acid monomer, polyethylene glycol monoalkyl ether and phosphorus. Examples thereof include esters with acid monomers, vinyl group-containing urethanes formed from polyethylene glycol monoalkyl ether and isocyanate group-containing monomers, and macromonomers containing a polyvinyl alcohol structure. The repeating number of the ethyleneoxy part of the polyethylene glycol monoalkyl ether is preferably 8 to 50, more preferably 10 to 30. As carbon number of the alkyl group of the said polyethyleneglycol monoalkyl ether, 1-20 are preferable and 1-12 are more preferable.

  Next, the condensation polymer will be described in detail. The polyurethane is basically synthesized by a polyaddition reaction using a diol compound and a diisocyanate compound as raw materials. Specific examples of the diol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 2,2 as non-dissociable diols. , -Dimethyl-1,3-propanediol, 1,4-pentanediol, 2,4-pentanediol, 3,3-dimethyl-1,2-butanediol, 2-ethyl-2-methyl-1,3- Propanediol, 1,6-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,2-diethyl-1,3-propanediol, 2,4-dimethyl-2,4 -Pentanediol, 2-methyl-2-propyl 1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 2-ethyl-1,3-he Sundiol, 1,2-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol ( Average molecular weight = 200, 300, 400, 600, 1000, 1500, 4000), polypropylene glycol (average molecular weight = 200, 400, 1000), polyester polyol, 4,4′-dihydroxy-diphenyl-2,2-propane, 4 , 4-dihydroxyphenyl sulfone and the like.

  Examples of the diol compound having an anionic group include 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butanoic acid, 2,5,6-trimethoxy-3,4-dihydroxyhexanoic acid. 2,3-dihydroxy-4,5-dimethoxypentanoic acid, 2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid, and salts thereof, but are not particularly limited thereto. Absent.

  Preferable specific examples of the diisocyanate compound include ethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,4-toluene diisocyanate, 1,3-xylene diisocyanate, 1,5-naphthalene diisocyanate, m- Examples include phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 3,3′-dimethylbiphenylene diisocyanate, dicyclohexylmethane diisocyanate, and methylenebis (4-cyclohexylisocyanate).

  The polyester is basically easily synthesized by dehydration condensation from a diol compound and a dicarboxylic acid compound.

  Specific examples of the dicarboxylic acid compound include oxalic acid, malonic acid, succinic acid, glutaric acid, dimethylmalonic acid, adipic acid, pimelic acid, α, α-dimethylsuccinic acid, acetone dicarboxylic acid, sebacic acid, 1,9 -Nonanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, 2-butyl terephthalic acid, tetrachloroterephthalic acid, acetylenedicarboxylic acid, poly (ethylene terephthalate) dicarboxylic acid, 1 , 2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, ω-poly (ethyleneoxy) dicarboxylic acid, p-xylylene dicarboxylic acid, and the like. These compounds may be used in the form of an alkyl ester of carboxylic acid (for example, dimethyl ester) or an acid chloride of dicarboxylic acid when polycondensation with the diol compound, maleic anhydride or succinic anhydride, You may use in the form of an acid anhydride like phthalic anhydride.

  Preferred examples of the dicarboxylic acid compound having a sulfonic acid group and a diol compound include sulfophthalic acids (for example, 3-sulfophthalic acid, 4-sulfophthalic acid, 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, etc. ), Sulfosuccinic acid, sulfonaphthalenecarboxylic acids (for example, 4-sulfo-1,8-naphthalenedicarboxylic acid, 7-sulfo-1,5-naphthalenecarboxylic acid, etc.), 2,4-di (2-hydroxy) ethyloxy Examples thereof include carbonylbenzenesulfonic acid and salts thereof.

  As the diol compound, a compound selected from the same group as the diols described in the polyurethane is used. A typical method for synthesizing the polyester is a condensation reaction of the diols with a dicarboxylic acid or a derivative thereof, but can also be obtained by condensing a hydroxycarboxylic acid (for example, 1,2-hydroxystearic acid). Polyesters obtained by methods such as ring-opening polymerization methods of cyclic ethers and lactones (lecture polymerization reaction 6 ring-opening polymerization (I), detailed by Takeo Saegusa (chemical compound, 1971)) are also suitable for the present invention. Used for.

  The polyamide can be obtained by polycondensation of a diamine compound and a dicarboxylic acid compound, polycondensation of an aminocarboxylic acid compound, ring-opening polymerization of lactams, and the like. Examples of the diamine compound include ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, hexamethylenediamine, octamethylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, piperazine, and 2,5. -Dimethylpiperazine, 4,4'-diaminophenyl ether, 3,3'-diaminodiphenyl sulfone, xylylenediamine and the like. Examples of the aminocarboxylic acid include glycine, alanine, phenylalanine, ω-aminohexanoic acid, ω-aminodecanoic acid, ω-aminoundecanoic acid, and anthranilic acid. Examples of the monomer used for the ring-opening polymerization include ω-caprolactam, azetidinone, and pyrrolidone. As the dicarboxylic acid compound, a compound selected from the same group as the dicarboxylic acids described in the polyester is used.

  The polyurea can be basically obtained by polyaddition of a diamine compound and a diisocyanate compound or a deammonification reaction of a diamine compound and urea. As the diamine compound as a raw material, a compound selected from the same group as the diamines described in the polyamide can be used. As the diisocyanate compound as a raw material, a compound selected from the same group as the diisocyanates described in the polyurethane can be used.

  The polycarbonate can be basically obtained by reacting a diol compound with phosgene or a carbonate derivative (for example, an aromatic ester such as diphenyl carbonate). As the diol compound which is a raw material, compounds consisting of the same group as the diols described in the above polyurethane are used.

  For the oil-soluble polymer, necessary constituent materials may be used one by one or for various purposes (for example, adjustment and solubility of the glass transition temperature (Tg) of the polymer, compatibility with the dye, stability of the dispersion). Etc.), two or more of them can be used in an arbitrary ratio.

  Among the oil-soluble polymers, those having the ionic group are preferable, and those having at least one of a carboxyl group and a sulfonic acid group are more preferable as the ionic group. Those having a carboxyl group as the ionic group are particularly preferred.

  In addition, after polymerization of each polymer, an ionic group can be introduced by reaction by reacting an acid anhydride (for example, maleic acid) with a reactive group such as a hydroxy group or an amino group. .

  The content of the ionic group is preferably 0.1 to 3.0 mmol / g. When the content is small, the self-emulsifying property of the polymer is small, and when the content is large, the water-solubility becomes high and tends to be unsuitable for dye dispersion.

  In addition, as the ionic group, the anionic group may be a salt of an alkali metal (for example, sodium, potassium, etc.) or an ammonium ion, and the cationic group may be further an organic acid ( For example, it may be a salt such as acetic acid, propionic acid, methanesulfonic acid, etc.) or inorganic acid (eg, hydrochloric acid, sulfuric acid, phosphoric acid).

  As the oil-soluble polymer, vinyl polymers, polyurethanes, polyesters, and the like are preferable in consideration of imparting compatibility with oil-soluble dyes, providing excellent dispersion stability, and ease of introduction of ionic groups. .

  Particularly preferred polymers are a polymer containing an acetal group as a main functional group, a polymer containing a carbonate group, a polymer containing a hydroxyl group and a polymer having an ester group. The above polymer may have a substituent, and the substituent may have a linear, branched or cyclic structure. Various polymers having the above functional groups are commercially available, but can also be synthesized by a conventional method. These copolymers can also be obtained, for example, by introducing an epoxy group into one polymer molecule and then performing polycondensation with another polymer or graft polymerization using light or radiation.

Specific examples of the vinyl polymer are listed below. The ratio in parentheses represents the mass ratio. The present invention is not limited to these specific examples.
(PA-1) Methyl methacrylate-ethyl acrylate copolymer (50:50)
(PA-2) Butyl acrylate-styrene copolymer (50:50)
(PA-3) poly n-butyl methacrylate (PA-4) polyisopropyl methacrylate (PA-5) poly (4-tert-butylphenyl) acrylate (PA-6) n-butyl methacrylate-N-vinyl-2-pyrrolidone Copolymer (90:10)
(PA-7) Methyl methacrylate-vinyl chloride copolymer (70:30)
(PA-8) Isobutyl methacrylate-butyl acrylate copolymer (55:45)
(PA-9) Vinyl acetate-acrylamide copolymer (85:15)
(PA-10) n-butyl acrylate-methyl methacrylate-n-butyl methacrylate copolymer (35:35:30)
(PA-11) Ethyl methacrylate-n-butyl acrylate copolymer (70:30)
(PA-12) tert-butyl methacrylate-methyl methacrylate-acrylic acid copolymer (60:30:10)
(PA-13) n-butyl acrylate-acrylic acid copolymer (80:20)
(PA-14) sec-butyl acrylate-acrylic acid copolymer (85:15)
(PA-15) Isopropyl acrylate-acrylic acid copolymer (90:10)
(PA-16) Butyl methacrylate-2-hydroxyethyl methacrylate-acrylic acid copolymer (85: 5: 10)
(PA-17) Isobutyl methacrylate-tetrahydrofurfuryl acrylate-acrylic acid copolymer (60:30:10)
(PA-18) n-butyl methacrylate-1H, 1H, 2H, 2H-perfluorodecyl acrylate-acrylic acid copolymer (75: 20: 5)
(PA-19) Methyl methacrylate-n-butyl acrylate-acrylic acid copolymer (50: 45: 5)
(PA-20) 3-methoxybutyl methacrylate-styrene-acrylic acid copolymer (35:50:15)
(PA-21) Ethyl acrylate-phenyl methacrylate-acrylic acid copolymer (72:25:13)
(PA-22) Methacrylic acid ester-acrylic acid copolymer of isobutyl methacrylate-polyethylene glycol monomethyl ether (ethyleneoxy chain repeat number 23) (70:20:10)
(PA-23) Ethyl methacrylate-acrylic acid copolymer (95: 5)
(PA-24) Isobutyl acrylate-methoxystyrene-acrylic acid copolymer (75:15:10)
(PA-25) Isobutyl acrylate-N-vinyl pyrrolidone-acrylic acid copolymer (60:30:10)
(PA-26) 2,2,2-tetrafluoroethyl methacrylate-methyl methacrylate-methacrylic acid copolymer (25:60:15)
(PA-27) Ethyl methacrylate-2-ethoxyethyl methacrylate-methacrylic copolymer (75:15:15)
(PA-28) tert-octylacrylamide-propyl methacrylate-methacrylic acid copolymer (20:65:15)
(PA-29) n-butyl methacrylate-diphenyl-2-methacryloyloxydiethylphosphonate-methacrylic acid copolymer (80: 5: 15)
(PA-30) n-butyl methacrylate-phenylacrylamide-methacrylic acid copolymer (70:15:15)
(PA-31) n-butyl methacrylate-N-vinylpyrrolidone-methacrylic acid copolymer (70:15:15)
(PA-32) n-butyl methacrylate-styrene sulfonic acid copolymer (90:10)
(PA-33) Isobutyl methacrylate-styrene sulfonic acid copolymer (90:10)
(PA-34) n-butyl methacrylate-2-acrylamido-2-methylethanesulfonic acid copolymer (90:10)
(PA-35) Isobutyl acrylate-n-butyl methacrylate-2-acrylamido-2-methylethanesulfonic acid copolymer (70:20:10)
(PA-36) Ethyl acrylate-tert-butyl methacrylate-2-acrylamido-2-methylpropanesulfonic acid copolymer (60:30:10)
(PA-37) tert-butyl acrylate-tetrahydrofurfuryl acrylate-2-methylpropane sulfonic acid copolymer (50:40:10)
(PA-38) tert-butyl acrylate-polyethylene glycol monomethyl ether (ethyleneoxy chain repeat number 23) methacrylate ester-2-acrylamido-2-methylpropanesulfonic acid copolymer (60:30:10)
(PA-39) Isobutyl acrylate-N-vinylpyrrolidone-2-acrylamido-2-methylpropanesulfonic acid copolymer (60:30:10)
(PA-40) n-butyl methacrylate-2-acrylamido-2-methylpropanesulfonic acid soda copolymer (98:12)
(PA-41) n-butyl methacrylate-tert-butyl methacrylate-2-acrylamido-2-methylbutanesulfonic acid soda copolymer (50:35:15)
Specific examples (PC-1) to (PC-21) of the condensation polymer are exemplified below in the form of raw material monomers (however, PC-17 and later are exemplified in the form of a polymer), but the present invention is limited to these. Is not to be done. All acidic groups in each polymer are expressed in non-dissociated form. In addition, regarding components produced by a condensation reaction such as polyester and polyamide, the constituent components are all expressed as dicarboxylic acids, diols, diamines, hydroxycarboxylic acids, aminocarboxylic acids, etc., regardless of the raw materials. The ratio in parentheses means the mole percentage ratio of each component.
(PC-1) Toluene diisocyanate / ethylene glycol / 1,4-butanediol (50/15/35)
(PC-2) Tolue diisocyanate / hexamethylene diisocyanate / ethylene glycol / polyethylene glycol (Mw = 600) 1,4-butanediol (40/20/10/20)
(PC-3) 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate / tetraethylene glycol / ethylene glycol / 2,2-bis (hydroxymethyl) propionic acid (40/10/20/20/10)
(PC-4) 1,5-naphthalene diisocyanate / butanediol / 4,4′-dihydroxy-diphenyl-2,2′-propane / polypropylene glycol (Mw = 400) / 2,2-bis (hydroxymethyl) propionic acid (50/20/5/10/15)
(PC-5) Isophorone diisocyanate / diethylene glycol / neopentyl glycol / 2,2-bis (hydroxymethyl) propionic acid (50/20/20/10)
(PC-6) Diphenylmethane diisocyanate / hexamethylene diisocyanate / tetraethylene glycol / butanediol / 2,4-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid (40/10/10/33/7)
(PC-7) terephthalic acid / isophthalic acid / cyclohexanedimethanol / 1,4-butanediol / ethylene glycol (25/25/25/15/10)
(PC-8) terephthalic acid / isophthalic acid / 4,4′-dihydroxy-diphenyl-2,2-propane / tetraethylene glycol / ethylene glycol (30/20/20/15/15 /)
(PC-9) terephthalic acid / isophthalic acid / 4,4'-benzenedimethanol / diethylene glycol / neopentyl glycol (25/25/25/15/10)
(PC-10) terephthalic acid / isophthalic acid / 5-sulfoisophthalic acid / ethylene glycol / neopentyl glycol (24/24/2/25/25)
(PC-11) 11-aminoundecanoic acid (100)
(PC-12) Reaction product of poly (12-aminododecanoic acid) and maleic anhydride (PC-13) Hexamethylenediamine / Adipic acid (50/50)
(PC-14) N, N-dimethylethylenediamine / adipic acid / cyclohexanedicarboxylic acid (50/20/30)
(PC-15) Toluene diisocyanate / 4,4′-diphenylmethane diisocyanate / hexamethylenediamine (30/20/50)
(PC-16) Hexamethylenediamine / Nonamethylenediamine / Urea (25/25/50)
Examples of the polymer containing acetal as a main functional group include polyvinyl butyral resin. For example, # 2000-L, # 3000-1, # 3000-2, # 3000-4, # 3000-K, # 4000-1, # 4000-2, # 5000-A, manufactured by Denki Kagaku Kogyo Co., Ltd. # 6000-C, # 6000-EP, or BL-1, BL-1H, BL-2, BL-2H, BL-5, BL-10, BL-S, BL-SH manufactured by Sekisui Chemical Co., Ltd. , BX-10, BX-L, BM-1, BM-2, BM-5, BM-S, BM-SH, BH-3, BH-6, BH-S, BX-1, BX-3, BX -5, KS-10, KS-1, KS-3, KS-5, and the like.

  The resin is obtained as a derivative of PVA (polyvinyl alcohol). The degree of acetalization of the hydroxyl group of the original PVA is at most about 80 mol%, and usually about 50 mol% to 80 mol%. In the case of polyvinyl butyral, a 1,1′-butylene dioxy group is formed as an acetal group. Here, the degree of acetalization does not refer to such a narrowly defined acetal but is more general. An acetal group means a compound having an acetal group formed from a compound having a hydroxyl group (in this case, polyvinyl alcohol) and a compound having an aldehyde group (in this case, butanal). The hydroxyl group is not particularly defined but is preferably contained in an amount of 10 to 40 mol%. Moreover, although there is no prescription | regulation in particular in the content rate of an acetyl group, it is preferable that it is 10 mol% or less. The polymer containing an acetal group as a main functional group means that at least 30 mol% or more of oxygen atoms contained in the polymer forms an acetal group.

  In addition, as a polymer containing acetal as a main functional group, Iupital series manufactured by Mitsubishi Engineering Plastics Co., Ltd. can be used.

  Polycarbonate resin is mentioned as a polymer which contains carbonate ester as a main functional group. For example, there are Iupilon series and Novalex series manufactured by Mitsubishi Engineering Plastics. The Iupilon series is made with bisphenol A as a raw material, and various molecular weights can be used although the values differ depending on the measurement method. In the NOVAREX series, those having a molecular weight of 20,000 to 30,000 and a glass transition point of around 150 ° C. can be used, but are not limited thereto.

  The polymer containing a carbonate group as a main functional group means that at least 30 mol% or more of oxygen atoms contained in the polymer contribute to the formation of the carbonate group.

  Examples of the polymer containing a hydroxyl group as a main functional group include PVA. Although the solubility of PVA in organic solvents is often small, the solubility in organic solvents increases with PVA having a low saponification value. PVA having high water solubility can be used by adding it to the aqueous phase and adsorbing it to the polymer suspension after removing the organic solvent.

  Commercially available PVA can be used, for example, Kuraray's Poval PVA-102, PVA-117, PVA-CSA, PVA-617, PVA-505, and other special brands of sizing agents, PVA As PVA for molding and other functional polymers, KL-506, C-118, R-1130, M-205, MP-203, HL-12E, SK-5102, and the like can be used.

  The saponification degree is generally 50 mol% or more, but even when it is about 40 mol% as in LM-10HD, it can be used. In addition to PVA, those having a hydroxyl group as a main functional group can be used, but those having at least 20 mol% or more of oxygen atoms contained in the polymer can be used.

Examples of the polymer containing an ester group as a main functional group include a methacrylic resin. Asahi Kasei Delpet series 560F, 60N, 80N, LP-1, SR8500, SR6500, etc. can be used. A polymer containing an ester group as a main functional group means that at least 30 mol% or more of oxygen atoms contained in the polymer form an ester group.
These polymers may be used alone or in combination of two or more. Moreover, as long as 50% or more of these polymers are contained by mass ratio, the other polymer and the inorganic filler may be contained.

  Although it is also preferable to use a copolymer of these polymers, for example, as a method of copolymerizing a polymer containing a hydroxyl group with various polymers, the hydroxyl group is reacted with a monomer having an epoxy group such as glycidyl methacrylate, It can be copolymerized with methacrylate monomers by suspension polymerization.

  The molecular weight (Mw) of the oil-soluble polymer is usually 1,000 to 200,000, preferably 2,000 to 50,000. When the molecular weight is less than 1,000, it tends to be difficult to obtain a stable colored fine particle dispersion. When the molecular weight exceeds 200,000, the solubility in an organic solvent is deteriorated or the viscosity of the organic solvent solution is increased. It tends to be difficult to disperse.

  Next, preparation of the colored fine particle dispersion will be described. The colored fine particle dispersion can be produced by dispersing the oil-soluble dye and the oil-soluble polymer in the form of colored fine particles in an aqueous medium (a liquid containing at least water). For example, a method of preparing a latex of the oil-soluble polymer in advance and impregnating the latex with the oil-soluble dye, a co-emulsification dispersion method, or the like can be given. Among these, the co-emulsification dispersion method is preferable. As the co-emulsification dispersion method, fine particles are obtained by emulsifying the organic solvent by adding water to the organic solvent containing the oil-soluble polymer and the oil-soluble dye and adding the organic solvent to water. More preferred is a method of making them.

  The latex means that the oil-soluble polymer insoluble in water is dispersed as fine particles in an aqueous medium. As the dispersion state, the oil-soluble polymer is emulsified in the aqueous medium, emulsion-polymerized, micelle-dispersed, or the oil-soluble polymer is partially hydrophilic in the molecule. And the molecular chain itself may be molecularly dispersed.

  Here, a method for preparing the polymer latex in advance and impregnating the polymer latex with the oil-soluble dye will be described. As a first example of this method, there are a first step of preparing a polymer latex, a second step of preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent, and the dye solution and the polymer latex. And a third step of preparing a colored fine particle dispersion by mixing. As a second example of this method, a first step of preparing a polymer latex, a dye solution in which the oil-soluble dye is dissolved in an organic solvent are prepared, and the dye solution and a liquid containing at least water are mixed. A second step of preparing a dye fine particle dispersion, and a third step of mixing the polymer latex and the dye fine particle dispersion to prepare a colored fine particle dispersion. As a third example of this method, there is a method described in JP-A-55-139471.

  Here, the emulsion dispersion method will be described. A first example of this method comprises a first step of preparing a solution in which the oil-soluble dye and the oil-soluble polymer are dissolved in an organic solvent, the organic solvent solution containing the polymer and the dye, and a liquid containing at least water. And a second step of preparing a colored fine particle dispersion by mixing. A second example of this method includes a first step of preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent, a second step of preparing a polymer solution in which the oil-soluble polymer is dissolved in an organic solvent, And a third step of preparing a colored fine particle dispersion by mixing the dye solution, the polymer solution, and a liquid containing at least water. A third example of this method is a first step of preparing a dye fine particle dispersion by preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent and mixing the dye solution and a liquid containing at least water. A second step in which an oil-soluble polymer is dissolved in an organic solvent to prepare a polymer solution, and the polymer solution and a liquid containing at least water are mixed to prepare a polymer fine particle dispersion; and the dye fine particle dispersion and the polymer And a third step of preparing a colored fine particle dispersion by mixing with the fine particle dispersion. A fourth example of this method is a first step of preparing a dye fine particle dispersion by preparing a dye solution in which the oil-soluble dye is dissolved in an organic solvent, and mixing the dye solution and a liquid containing at least water. And a second step of preparing a polymer solution in which an oil-soluble polymer is dissolved in an organic solvent, and a third step of preparing a colored fine particle dispersion by mixing the dye fine particle dispersion and the polymer solution. . A fifth example of this method includes a step of directly preparing a colored fine particle dispersion by mixing the oil-soluble dye and the oil-soluble polymer with a liquid containing at least water.

  The amount of the oil-soluble polymer used in the colored fine particle dispersion is preferably 10 to 1000 parts by mass, more preferably 50 to 600 parts by mass with respect to 100 parts by mass of the oil-soluble dye. If the amount of the polymer used is less than 10 parts by mass, fine and stable dispersion tends to be difficult, and if it exceeds 1000 parts by mass, the proportion of the oil-soluble dye in the colored fine particle dispersion decreases, and the colored fine particle dispersed When the liquid is used as a water-based ink, there is a tendency that there is no margin in the formulation design.

  There is no restriction | limiting in particular as an organic solvent used when manufacturing the said colored fine particle dispersion, It can select suitably based on the solubility of the said oil-soluble dye or the said oil-soluble polymer. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, and cyclohexanone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, chloroform. Chlorinated solvents such as methylene chloride, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, ethylene glycol monomethyl ether, Examples thereof include glycol solvents such as ethylene glycol dimethyl ether. The said organic solvent may be used individually by 1 type, may use 2 or more types together, and may be a mixed solvent with water.

  The amount of the organic solvent used is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 10 to 2000 parts by mass, and 100 to 1000 parts by mass with respect to 100 parts by mass of the oil-soluble polymer. Part is more preferred. When the amount of the organic solvent used is 10 parts by mass or less, fine and stable dispersion of the colored fine particles tends to be difficult. When the amount exceeds 2000 parts by mass, solvent removal and concentration for removing the organic solvent are performed. The process becomes indispensable and complicated, and there is a tendency that there is no margin in the formulation design.

  The organic solvent is removed from the viewpoint of the stability of the colored fine particle dispersion when the solubility of the organic solvent in water is 10% or less, or when the vapor pressure of the organic solvent is higher than water. preferable. The removal of the organic solvent can be performed at 10 ° C to 100 ° C under normal pressure to reduced pressure conditions, preferably 40 ° C to 100 ° C under normal pressure conditions, or 10 ° C to 50 ° C under reduced pressure conditions. .

  The colored fine particle dispersion may contain an additive appropriately selected according to the purpose. Examples of the additive include a neutralizer, a dispersant, a dispersion stabilizer, and a high-boiling organic solvent described later.

  As the neutralizing agent, when the oil-soluble polymer has an unneutralized ionic group, it is used for adjusting the pH of the colored fine particle dispersion, adjusting the self-emulsifying property, and imparting dispersion stability. can do. The neutralizing agent may be added at the time of taking out as a polymer before preparing a dispersion, or may be added after any step of dispersing or after the completion of dispersion. As the neutralizing agent, for an anionic group, an organic base (for example, triethanolamine, diethanolamine, N-methyldiethanolamine, dimethylethanolamine, etc.), an inorganic alkali (for an alkali metal hydroxide, for example, water Examples of carbonates such as sodium oxide, lithium hydroxide, and potassium hydroxide include sodium carbonate and sodium hydrogen carbonate) and ammonia. Examples of the cationic group include organic acids (for example, oxalic acid, formic acid, acetic acid, methanesulfonic acid, paratoluenesulfonic acid, etc.), inorganic acids (for example, hydrochloric acid, phosphoric acid, sulfuric acid), and the like. From the viewpoint of improving the dispersion stability in the colored fine particle dispersion, the neutralizing agent is preferably added so as to have a pH of 4.5 to 10.0, and is preferably added so as to have a pH of 6.0 to 10.0. More preferred.

  The dispersant and the dispersion stabilizer may be added to any of the polymer latex, the oil-soluble polymer solution, the dye solution, a solution containing at least water, and the like, and an oil-soluble polymer and / or dye fine particle dispersion is prepared. It is preferable to add to the solution containing the oil-soluble polymer, dye solution and water in the previous step. Examples of the dispersant and the dispersion stabilizer include cation, anion, and nonionic surfactants, water-soluble or water-dispersible low molecular compounds, and oligomers. As addition amount of the said dispersing agent and the said dispersion stabilizer, 0-100 mass% of the sum total of an oil-soluble dye and an oil-soluble polymer is preferable, and 0-20 mass% is more preferable.

  The high-boiling organic solvent is preferably 1 to 1000% by mass, more preferably 10 to 400% by mass of the oil-soluble dye. The said high boiling point organic solvent may be used individually by 1 type, and may use 2 or more types together.

  The content of the colored fine particles in the colored fine particle dispersion is preferably 1 to 45% by mass, and more preferably 2 to 30% by mass. The content can be appropriately adjusted by dilution, evaporation, ultrafiltration or the like. The average particle diameter of the colored fine particles is preferably 1 to 500 nm, more preferably 3 to 300 nm. The particle size distribution is not particularly limited, but may be a wide particle size distribution or a monodispersed particle size distribution. The particle size and particle size distribution can be adjusted by means such as centrifugation and filtration.

(Dye dispersion)
The pigment dispersion is obtained by dispersing the oil-soluble pigment dissolved in a high boiling point organic solvent in an aqueous medium. The boiling point of the high-boiling organic solvent needs to be 150 ° C. or higher, and preferably 170 ° C. or higher. The dielectric constant of the high boiling point organic solvent needs to be 3 to 12, and 4 to 10 is preferable. Here, the dielectric constant represents the relative dielectric constant with respect to the vacuum at 25 ° C.

  The high-boiling organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in U.S. Pat. No. 2,322,027. Phosphate esters, fatty acids High boiling organic solvents such as esters, phthalates, benzoates, phenols and amides are preferred.

  By using the high-boiling organic solvent, the solubility of the dye in the polymer is improved, the color tone becomes better, and the effect of improving the dispersion stability is also obtained.

  As the high-boiling organic solvent, compounds represented by the following formulas [S-1] to [S-9] are particularly preferable.

In the formula [S-1], R ₃₀ , R ₃₁ and R ₃₂ each independently represents an aliphatic group or an aryl group. A, b and c each independently represents 0 or 1;

In the formula [S-2], R ₃₃ and R ₃₄ each independently represents an aliphatic group or an aryl group. R ₃₅ represents a halogen atom (F, Cl, Br, I and the same shall apply hereinafter), an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group. d represents an integer of 0 to 3. When d is plural, the plural R ₃₅ may be the same or different.

In the formula [S-3], Ar represents an aryl group. e represents an integer of 1 to 6; R ₃₆ represents an e-valent hydrocarbon group or a hydrocarbon group bonded to each other by an ether bond.

In the above formula [S-4], R ₃₇ represents an aliphatic group. f represents an integer of 1 to 6. R ₃₈ represents an f-valent hydrocarbon group or a hydrocarbon group bonded to each other through an ether bond.

In said Formula [S-5], g represents the integer of 2-6. R ₃₉ represents a g-valent hydrocarbon group (excluding an aryl group). R ₅₀ represents an aliphatic group or an aryl group.

In the above formula [S-6], R ₅₁ , R ₅₂ and R ₅₃ each independently represent a hydrogen atom, an aliphatic group or an aryl group. X ₀ is -CO- or -SO ₂ - represents a. R ₅₁ and R ₅₂ or R ₅₂ and R ₅₃ may be bonded to each other to form a ring.

In the formula [S-7], R ₅₄ represents an aliphatic group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group, or a cyano group. R ₅₅ represents a halogen atom, an aliphatic group, an aryl group, an alkoxy group or an aryloxy group. h represents an integer of 0 to 3. When h is two or more, plural R ₅₅ may be the same or may be different.

In the formula [S-8], R ₅₆ and R ₅₇ each independently represents an aliphatic group or an aryl group. R ₅₈ represents a halogen atom, an aliphatic group, an aryl group, an alkoxy group or an aryloxy group. i represents an integer of 0 to 4. When i is plural, plural R ₅₈ may be the same or different.

In said formula [S-9], _R59 and _R60 represent an aliphatic group or an aryl group. j represents 1 or 2;

In the formulas [S-1] to [S-9], when R _{30 to} R ₃₅ , R ₃₇ and R _{50 to} R ₆₀ are an aliphatic group or a group containing an aliphatic group, the aliphatic group is The chain may be linear, branched or cyclic, may contain an unsaturated bond, and may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a hydroxyl group, an acyloxy group, and an epoxy group.

In the above formulas [S-1] to [S-9], R _{30 to} R ₃₅ , R ₃₇ and R _{50 to} R ₆₀ are cyclic aliphatic groups, that is, cycloalkyl groups, or groups containing cycloalkyl groups. In this case, the cycloalkyl group may contain an unsaturated bond in a 3- to 8-membered ring, and may have a substituent or a bridging group. Examples of the substituent include a halogen atom, an aliphatic group, a hydroxyl group, an acyl group, an aryl group, an alkoxy group, an epoxy group, and an alkyl group. Examples of the cross-linking group include a methylene group and an ethylene group. And isopropylidene group.

In the above formulas [S-1] to [S-9], when R _{30 to} R ₃₅ , R ₃₇ and R _{50 to} R ₆₀ are an aryl group or a group containing an aryl group, the aryl group is a halogen atom, It may be substituted with a substituent such as an aliphatic group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group.

In the formula [S-3], the formula [S-4] and the formula [S-5], when R ₃₆ , R ₃₈ or R ₃₉ is a hydrocarbon group, the hydrocarbon group has a cyclic structure ( (For example, a benzene ring, a cyclopentane ring, a cyclohexane ring) or an unsaturated bond may be included, and it may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an acyloxy group, an aryl group, an alkoxy group, an aryloxy group, and an epoxy group.

Next, a particularly preferable high boiling point organic solvent in the present invention will be described.
In the formula [S-1], R ₃₀ , R ₃₁ and R ₃₂ are aliphatic groups having 3 to 24 (preferably 4 to 18) carbon atoms (hereinafter abbreviated as C number) (for example, n-butyl group, 2 -Ethylhexyl group, 3,3,5-trimethylhexyl group, n-dodecyl group, n-octadecyl group, benzyl group, oleyl group, 2-chloroethyl group, 2,3-dichloropropyl group, 2-butoxyethyl group, 2 -Phenoxyethyl group, cyclopentyl group, cyclohexyl group, 4-t-butylcyclohexyl group, 4-methylcyclohexyl group) or an aryl group having 6 to 24 carbon atoms (preferably 6 to 18) (for example, phenyl group, cresyl group, p -Nonylphenyl group, xycle group, cumenyl group, p-methoxyphenyl group, p-methoxycarbonylphenyl group). a, b and c are each independently 0 or 1, preferably all 1.

In the formula [S-2], R ₃₃ and R ₃₄ are aliphatic groups having 4 to 24 carbon atoms (preferably 4 to 18) (for example, the same group as the alkyl group mentioned for R ₃₀ , an ethoxycarbonylmethyl group, 1,1-diethylpropyl group, 2-ethyl-1-methylhexyl group, cyclohexylmethyl group, 1-ethyl-1,5-dimethylhexyl group, 3,5,5-trimethylcyclohexyl group, 1-methylcyclohexyl group) Or an aryl group having 6 to 24 carbon atoms (preferably 6 to 18) (for example, the aryl group, 4-t-butylphenyl group, 4-t-octylphenyl group, 1,3,5-trimethyl described above for R ₃₀ ) Phenyl group, 2,4, -di-t-butylphenyl group, 2,4, -di-t-pentylphenyl group). R35 is a halogen atom (preferably Cl), an alkyl group having 1 to 18 carbon atoms (for example, methyl group, isopropyl group, t-butyl group, n-dodecyl group), an alkoxy group having 1 to 18 carbon atoms (for example, methoxy group, n-butoxy group, n-octyloxy group, methoxyethoxy group, benzyloxy group), C 6-18 aryloxy group (for example, phenoxy group, p-tolyloxy group, 4-methoxyphenoxy group, 4-t-butyl) A phenoxy group), an alkoxycarbonyl group having 2 to 19 carbon atoms (for example, a methoxycarbonyl group, an n-butoxycarbonyl group, a 2-ethylhexyloxycarbonyl group) or an aryloxycarbonyl group having 6 to 25 carbon atoms. d is 0 or 1.

In the formula [S-3], Ar represents an aryl group having 6 to 24 carbon atoms (preferably 6 to 18) (for example, phenyl group, 4-chlorophenyl group, 4-methoxyphenyl group, 1-naphthyl group, 4-n -Butoxyphenyl group, 1,3,5-trimethylphenyl group), b is an integer of 1 to 4 (preferably 1 to 3), and R ₃₆ is an e-valent C number of 2 to 24 (preferably 2). To 18) hydrocarbon group (for example, the alkyl group, cycloalkyl group, aryl group, — (CH ₂ ) ₂ — and the following groups mentioned for R ₃₃ ),

Alternatively, a hydrocarbon group (for example, —CH ₂ CH ₂ OCH ₂ CH ₂ —, —CH ₂ CH ₂ (OCH ₂ ) bonded to each other by an ether bond having 4 to 24 (preferably 4 to 18) carbon atoms having an e valence. CH ₂ ) ₃ —, —CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ —, and the following groups).

In the above formula [S-4], R ₃₇ is an aliphatic group having 3 to 24 carbon atoms (preferably 3 to 17) (eg, n-propyl group, 1-hydroxyethyl group, 1-ethylpentyl group, n-undecyl group). Group, pentadecyl group, 8,9-epoxyheptadecyl group, cyclopropyl group, cyclohexyl group, 4-methylcyclohexyl group), f is an integer of 1 to 4 (preferably 1 to 3), R ₃₈ is f-valent C 2-24 (preferably 2-18) hydrocarbon group or c-valent hydrocarbon group 4-24 (preferably 4-18) ether group linked to each other (for example, R is a group) which listed for _36.

In the formula [S-5], g is 2 to 4 (preferably 2 or 3), and R ₃₉ is a g-valent hydrocarbon group (for example, —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₇ —, and the following groups).

R ₅₀ represents an aliphatic group having 4 to 24 carbon atoms (preferably 4 to 18) or an aryl group having 6 to 24 carbon atoms (preferably 6 to 18) (for example, the aliphatic groups and aryl groups mentioned above for R ₃₃ ). ).

In the formula [S-6], R ₅₁ represents an aliphatic group having 3 to 20 carbon atoms (for example, n-propyl group, 1-ethylpentyl group, n-undecyl group, n-pentadecyl group, 2,4-didecyl group). -T-pentylphenoxymethyl group, 4-t-octylphenoxymethyl group, 3- (2,4-di-t-butylphenoxy) propyl group, 1- (2,4-di-t-butylphenoxy) propyl group, A cyclohexyl group, a 4-methylcyclohexyl group) or an aryl group having 6 to 24 carbon atoms (preferably 6 to 18) (for example, the aryl groups mentioned above for Ar). R ₅₂ and R ₅₃ are aliphatic groups having 3 to 24 carbon atoms (preferably 3 to 18) (for example, isopropyl group, n-butyl group, n-hexyl group, 2-ethylhexyl group, n-dodecyl group, cyclopentyl group, A cyclopropyl group) or an aryl group having 6 to 18 carbon atoms (preferably 6 to 15) (for example, phenyl group, 1-naphthyl group, p-tolyl group). R ₅₂ and R ₅₃ may be bonded to each other to form a pyrrolidine ring, piperidine ring or morpholine ring together with N, or R ₅₁ and R ₅₂ may be bonded to each other to form a pyrrolidone ring. X represents —CO— or —SO ₂ —, preferably —CO—.

In the above formula [S-7], R ₅₄ represents an aliphatic group having 3 to 24 carbon atoms (preferably 3 to 18) (for example, isopropyl group, t-butyl group, t-pentyl group, t-hexyl group, t-hexyl group). Octyl group, 2-butyl group, 2-hexyl group, 2-octyl group, 2-dodecyl group, 2-hexadecyl group, t-pentadecyl group, cyclopentyl group, cyclohexyl group), C 5-24 (preferably 5-5) 17) an alkoxycarbonyl group (for example, n-butoxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-dodecyloxycarbonyl group) C 3-24 (preferably 3-18) alkylsulfonyl group (for example, n-butylsulfonyl) Group, n-dodecylsulfonyl group), arylsulfonyl group having 6 to 30 carbon atoms (preferably 6 to 24) (for example, p-tolylsulfonyl group) p- dodecyl phenylsulfonyl group, a p- hexadecyloxy phenylsulfonyl group), an aryl group (e.g. phenyl group having a C number of 6 to 32 (preferably 6 to 24), p- tolyl) or a cyano group.

R ₅₅ is a halogen atom (preferably Cl), (the alkyl group described for example wherein R ₅₄₎ alkyl group having a C number of 3 to 24 (preferably 3 to 18), a cycloalkyl group having a C number of 5 to 17 (e.g., cyclopentyl Group, cyclohexyl group), C 6-32 (preferably 6-24) aryl group (for example, phenyl group, p-tolyl group) C 1-24 (preferably 1-18) alkoxy group (for example, methoxy group) N-butoxy group, 2-ethylhexyloxy group, benzyloxy group, n-dodecyloxy group, n-hexadecyloxy group) or C6-C32 (preferably 6-24) aryloxy group (for example, phenoxy group) , Pt-butylphenoxy group, pt-octylphenoxy group, m-pentadecylphenoxy group, p-dodecyloxyphenoxy group) h is an integer of 1 to 2.

In the formula [S-8], R ₅₆ and R ₅₇ are as defined above R ₅₂ and R _53, R ₅₈ are as defined above R _55.

In the formula [S-9], R ₅₉ and R ₆₀ are the same as R ₃₀ , R ₃₁ and R ₃₂ . j represents 1 or 2, and 1 is preferable.

  Specific examples of the high boiling point organic solvent (S-1 to 23 as the compound represented by [S-1], S-24 to 39 as the compound represented by [S-2], S-40 to 44 as the compound represented by [S-3], S-45 to 50 as the compound represented by [S-4], and the compound represented by [S-5] S-51 to 58, S-59 to 67 as the compound represented by [S-6], S-68 to 75 as the compound represented by [S-7], and [S-8 S-76 to 79 as a compound represented by the above formula, and a compound represented by the above [S-9]).

  These high boiling point organic solvents may be used alone or in combination of two or more. For example, combined use of tricresyl phosphate and dibutyl phthalate, trioctyl phosphate and di (2- Ethylhexyl) sebacate, and dibutylphthalate and poly (Nt-butylacrylamide).

  Examples of other compounds of the high-boiling organic solvent and the synthesis method thereof include, for example, U.S. Pat. Nos. 2,322,027, 2,533,514, 2,772,163, and second. , 835,579, 3,594,171, 3,676,137, 3,689,271, 3,700,454, 3,748,141 3,764,336, 3,765,897, 3,912,515, 3,936,303, 4,004,928, 4, No. 080,209, No. 4,127,413, No. 4,193,802, No. 4,207,393, No. 4,220,711, No. 4,239,851, 4,278,757, 4,353,979, 4,363,873 4,430,421, 4,430,422, 4,464,464, 4,483,918, 4,540,657, 4,684 No. 4,606, No. 4,728,599, No. 4,745,049, No. 4,935,321, No. 5,013,639, European Patent No. 276,319A, No. No. 286,253A, No. 289,820A, No. 309,158A, No. 309,159A, No. 309,160A, No. 509,311A, No. 510,576A, East German Patent No. No. 147,009, No. 157,147, No. 159,573, No. 225,240A, British Patent No. 2,091,124A, JP-A-48-47335, No. 50-26530, 51-25133, 51 26036, 51-27921, 51-27922, 51-149028, 52-46816, 53-1520, 53-1521, 53-15127, 53-146622 54-91325, 54-106228, 54-118246, 55-59464, 56-64333, 56-81836, 59-204041, 61-84441, 62-118345, 62-247364, 63-167357, 63-214744, 63-301941, 64-9452, 64-9454, 64-68745, JP-A-1 -101543, 1-102454, 2-792, 2-42239, 2-43541, 4-29 No. 237, No. 4-30165, No. 4-232946, No. 4-346338 and the like.

  In the present invention, a low boiling organic solvent can be used in combination with the high boiling organic solvent. The low-boiling organic solvent is an organic solvent having a boiling point of 150 ° C. or lower (usually about 30 ° C. or higher) at normal pressure. For example, esters (eg ethyl acetate, butyl acetate, ethyl propionate, β-ethoxyethyl acetate, methyl Cellosolve acetate), alcohols (eg isopropyl alcohol, n-butyl alcohol, secondary butyl alcohol), ketones (eg methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone), amides (eg dimethylformamide, N-methylpyrrolidone), ethers ( Preferable examples include tetrahydrofuran and dioxane.

  The emulsified dispersion is obtained by mixing an oil phase in which the oil-soluble dye is dissolved in the high-boiling organic solvent, or in some cases, a mixed solvent of the high-boiling organic solvent and the low-boiling organic solvent, in an aqueous phase using the aqueous medium. To form fine oil droplets (dispersed particles) of the oil phase. For the formation of fine oil droplets (dispersed particles) of the oil phase, a method of adding the oil phase to the water phase is common, but the water phase is dropped into the oil phase. A so-called phase inversion emulsification method can also be preferably used.

  When emulsifying and dispersing, either or both of the aqueous phase and the oil phase require additives such as surfactants, wetting agents, dye stabilizers, emulsion stabilizers, preservatives, and antifungal agents described below. It can be added depending on.

  The fine particles containing a coloring material preferably have a polymer core and a polymer shell containing the coloring material. The polymer core mainly contains a coloring material and contributes to maintaining its fastness and color tone. On the other hand, the polymer shell contributes to increasing the stability of the fine particle-containing ink suspension as an ink suspension, further promoting the fixing of the coloring material on the medium, preventing aggregation, and improving the image quality. It also contributes to the fastness and color tone of the color material.

  In the present invention, the color material-containing fine particles preferably have a polymer core and a polymer shell containing the color material. The color material content (concentration) in the shell is preferably 0.8 or less, and more preferably 0.5 or less, of the color material content (concentration) in the core not subjected to core / shell formation.

  The color material content (concentration) can be measured with a mass spectrometer such as TOF-SIMS. In TOF-SIMS, the total amount of ions having a mass number of 1 to 1000 is first measured on the surface of each fine particle, and the color material content can be determined from the total amount of ions derived from the dye. The color material content ratios of the shell and the core / core not formed into shells are compared. Since TOF-SIMS can perform elemental analysis of several nanometers in the depth direction from the surface, core / shell fine particles as in the present invention can be analyzed.

  In the present invention, since the surface area per unit volume of the color material-containing fine particles used for the polymer emulsion type water-based ink is very large when the volume average particle diameter is 5 nm or less, the effect of encapsulating the color material in the core-shell polymer Becomes smaller. On the other hand, particles larger than 500 nm tend to clog the head, and sedimentation in the ink tends to occur, resulting in deterioration of stagnation stability. The particle diameter is preferably 5 nm or less and 400 nm or less, and more preferably 10 nm or more and 300 nm or less.

  The volume average particle diameter is obtained by converting a circle-converted average particle diameter obtained from an average value of a projected area (determined for at least 100 particles) of a transmission electron microscope (TEM) photograph into a sphere. The coefficient of variation can be obtained by determining the volume average particle size and its standard deviation and dividing the standard deviation by the volume average particle size. Alternatively, the coefficient of variation can be obtained using a dynamic light scattering method. For example, it can be obtained using a laser particle size analysis system manufactured by Otsuka Electronics or a Zetasizer manufactured by Malvern.

  The variation coefficient of the particle diameter is a value obtained by dividing the standard deviation of the particle diameter by the particle diameter, and the larger this value, the wider the distribution of the particle diameter. When the variation coefficient of the volume average particle size is 80% or more, the particle size distribution becomes very wide, the thickness of the core shell tends to be non-uniform, and the surface physical properties between the particles are likely to vary. Variations in surface physical properties tend to cause particle aggregation and easily cause clogging of the inkjet head. In addition, the aggregation of the particles easily causes light scattering of the color material on the medium, and also causes a decrease in image quality. The variation coefficient is more preferably 50% or less, and further preferably 30% or less.

  In the present invention, the amount of polymer used for the shell is preferably 5% by mass or more and 95% by mass or less of the total polymer amount. When the amount is less than 5% by mass, the thickness of the shell is insufficient, and a part of the core containing a large amount of coloring material tends to appear on the particle surface. Moreover, when there are too many polymers of a shell, it will be easy to raise | generate the coloring material protection capability of a core. More preferably, it is 10 mass% or more and 90 mass% or less.

  The total amount of the coloring material is preferably 20% by mass to 1000% by mass with respect to the total polymer amount. If the amount of the color material is too small compared to the polymer, the image density after ejection will not increase, and if the amount of the color material is too large, the protective ability of the polymer cannot be sufficiently obtained.

  For the core / shell in the present invention, a polymer core containing a coloring material is first prepared, and then a method of providing a polymer shell and a method of simultaneously providing a core shell are conceivable.

(When a shell is provided after the fine particle core is manufactured)
The coloring material-containing polymer to be the core can be prepared by various methods. For example, a method in which an oil-soluble dye is dissolved in a monomer and emulsified in water, and then the dye is encapsulated in the polymer by polymerization, a method in which the polymer and a coloring material are dissolved in an organic solvent, and the organic solvent is removed after emulsification in water. There is a technique in which porous polymer fine particles are added to a dye solution to adsorb and impregnate the dye into the fine particles. As a method of providing a polymer shell, a method of adding a water-soluble polymer dispersant to an aqueous suspension of a core polymer and adsorbing it, a method of gradually dropping a monomer and depositing it on the core surface simultaneously with polymerization, or an organic There is a method in which a polymer dissolved in a solvent is gradually dropped and adsorbed on the core surface simultaneously with precipitation.

  Alternatively, the pigment can be kneaded with the polymer, and then dispersed in an aqueous system to produce a polymer-coated pigment core, and further shelled by the above method.

(Method of providing a core and shell simultaneously when forming fine particles)
The core polymer and coloring material are dissolved or dispersed in the monomer that becomes the shell after polymerization, and the suspension is polymerized after suspension in water, or emulsion polymerization is performed while gradually dropping the liquid into water containing activator micelles. There is a method to go. The monomer may be a core and the polymer may be a shell. Alternatively, there is a technique in which a coloring material is dissolved or dispersed in a monomer mixed solution that can become a core and a shell after polymerization, and suspension polymerization or emulsion polymerization is performed.

(Evaluation of core shell)
It is important to evaluate whether it is actually a core shell. In the present invention, since the individual particle diameter is as very small as 200 nm or less, the analysis method is limited from the viewpoint of resolution. TEM, TOF-SIMS, etc. can be applied as an analysis method that meets such a purpose. When observing fine particles that have been core-shelled by TEM, the dispersion can be applied on a carbon support film, dried and observed. In the observation image of TEM, since the difference in contrast may be small only with the type of polymer that is an organic substance, in order to evaluate whether or not the core shell is formed, the fine particles are treated with osmium tetroxide, ruthenium tetroxide, chlorosulfonic acid / It is preferable to dye using uranyl acetate, silver sulfide or the like. Dye the fine particles only of the core, observe the TEM, and compare with the one provided with a shell. Further, after mixing the fine particles provided with the shell and the fine particles not provided with the dye, the particles are dyed, and it is confirmed whether or not the proportion of the fine particles having different dyeing degree matches the presence or absence of the shell.

  In a mass spectrometer such as TOF-SIMS, it is confirmed that the amount of color material in the vicinity of the surface is reduced by providing a shell on the particle surface as compared with the case of only the core. When there is an element not contained in the polymer of the core shell in the color material, it can be confirmed whether or not a shell having a small color material content is provided using the element as a probe.

  That is, the color material content (concentration) is determined by measuring the total amount of ions having a mass number of 1 to 1,000 on the surface of each fine particle by TOF-SIMS. It can be determined from the ratio to the total amount of ions derived from elements not contained. By comparing the color material content of each of the shell and the core not subjected to core / shell formation by this method, the content (concentration) of each pigment can be measured. Since TOF-SIMS can perform elemental analysis of several nanometers in the depth direction from the surface, core / shell fine particles as in the present invention can be analyzed.

  In the absence of such elements, the colorant content in the shell can be compared with that without the shell using a suitable dye.

  In addition, the core-shell formation can be observed more clearly by embedding the core-shell particles in an epoxy resin, preparing an ultrathin section with a microtome, and performing staining. As described above, when there is an element that can be a probe in a polymer or a color material, the composition of the core shell and the distribution amount of the color material to the core and shell can be estimated by TOF-SIMS or TEM.

  To obtain the required particle size, it is important to optimize the formulation and select an appropriate emulsification method. Although the formulation varies depending on the colorant and polymer used, it is an aqueous dispersion (suspension). Therefore, the polymer constituting the shell is generally required to have higher hydrophilicity than the polymer constituting the core. Further, the color material contained in the polymer constituting the shell is preferably less than the polymer constituting the core as described above, and the color material is also required to be less hydrophilic than the polymer constituting the shell. . The hydrophilicity and hydrophobicity can be estimated using, for example, the solubility parameter (SP). As for the solubility parameter, its value, measurement and calculation method can be referred to the description from page 675 of POLYMER HANDBOOK 4th edition (John Wiley & Sons, Inc.).

  In addition, the polymer used in the core / shell has a number average molecular weight of 500 to 100,000, particularly 1,000 to 30,000, which indicates film-forming properties after printing, durability and suspension formability. From the point of view, it is preferable.

  Although various kinds of Tg can be used for the polymer, it is preferable to use at least one polymer having a Tg of 10 ° C. or more.

  In the present invention, all generally known polymers can be used, but particularly preferred polymers are polymers containing an acetal group as a main functional group, a polymer containing a carbonate group, and a polymer containing a hydroxyl group. And a polymer having an ester group. The above polymer may have a substituent, and the substituent may have a linear, branched, or cyclic structure. Various polymers having the above functional groups are commercially available, but can also be synthesized by a conventional method. These copolymers can also be obtained, for example, by introducing an epoxy group into one polymer molecule and then performing polycondensation with another polymer or graft polymerization using light or radiation.

  Examples of the surfactant include fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate salt, alkyl naphthalene sulfonate salt, dialkyl sulfosuccinate salt, alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxyethylene alkyl Anionic surfactants such as sulfate salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid Nonionic surfactants such as esters and oxyethyleneoxypropylene block copolymers, and acetylene-based polyoxyethylene oxide surfactants S RFYNOLS (Air Products & Chemicals), amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide, and the like (37) to (38) of JP-A-59-157636 Page, Research Disclosure No. The thing of 308119 (1989) is also mentioned suitably.

  In the present invention, a water-soluble polymer can be added together with these surfactants for the purpose of stabilization immediately after emulsification. Suitable examples of the water-soluble polymer include polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, polyacrylic acid, polyacrylamide and copolymers thereof, and natural water-soluble polymers such as polysaccharides, casein, and gelatin. Can be mentioned.

  When the oil-soluble dye is dispersed into the water-based ink by the emulsification dispersion, it is particularly important to control the particle size. In order to increase color purity and density when an image is formed by the ink jet recording method, it is essential to reduce the average particle size of the dispersed particles in the dye dispersion, and the volume average particle size is preferably 100 nm or less. ˜50 nm is more preferable.

  It was also found that the presence of coarse particles also plays a very important role in printing performance. That is, it was found that the coarse particles clog the nozzles of the head, or even if they are not clogged, the ink droplets are not ejected and the ink jetting is misaligned, which has a significant effect on the printing performance. In order to prevent this, it is preferable to suppress 10 or less particles of 5 μm or more to 1000 or less particles of 1 μm or more in 1 μl of ink when ink is used.

  As a method for removing these coarse particles, a known centrifugal separation method, microfiltration method, or the like can be used. These separation means may be performed immediately after the emulsification dispersion, or may be performed immediately after filling the ink dispersion after adding various additives such as a wetting agent and a surfactant to the emulsification dispersion. As an effective means for reducing the average particle size of dispersed particles in the dye dispersion and eliminating coarse particles, an emulsifying and dispersing apparatus that performs mechanical stirring can be suitably used.

  As the emulsifying and dispersing apparatus, a known apparatus such as a simple stirrer or impeller stirring system, in-line stirring system, a mill system such as a colloid mill, or an ultrasonic system can be used. Among them, a high-pressure homogenizer is particularly preferable.

  The high-pressure homogenizer has a detailed mechanism described in US Pat. No. 4,533,254, JP-A-6-47264, etc., but as a commercially available apparatus, a Gorin homogenizer (APV GAULIN INC. ), A microfluidizer (MICROFLUIDEX INC.), An optimizer (Sugino Machine Co., Ltd.), and the like.

  In addition, a high-pressure homogenizer equipped with a mechanism for atomizing in an ultrahigh-pressure jet stream as described in US Pat. No. 5,720,551 in recent years is particularly effective for the emulsification dispersion of the present invention. DeBEE2000 (BEE INTERNATIONAL LTD.) Is an example of an emulsifying and dispersing apparatus using this ultra-high pressure jet stream.

  The pressure when emulsifying and dispersing using the high-pressure emulsifying dispersion device is preferably 50 MPa or more (500 bar or more), more preferably 60 MPa or more (600 bar or more), and further preferably 180 MPa or more (1800 bar or more). In the present invention, at the time of the emulsification dispersion, for example, it is particularly preferable to use two or more types of emulsifiers together by a method such as emulsification with a stirring emulsifier and then passing through a high-pressure homogenizer. It is also preferable to once emulsify and disperse with these emulsifiers, add additives such as wetting agents and surfactants, and then pass through the high-pressure homogenizer again while filling the ink-jet ink into the cartridge.

  In the emulsification dispersion, when the low-boiling organic solvent is included in addition to the high-boiling organic solvent, it is preferable to substantially remove the low-boiling solvent from the viewpoint of stability and safety and health of the emulsion. . As a method for substantially removing the low-boiling solvent, various known methods such as an evaporation method, a vacuum evaporation method, and an ultrafiltration method can be employed depending on the kind of the low-boiling organic solvent. . The step of removing the low-boiling organic solvent is preferably performed as soon as possible immediately after emulsification.

  The colored composition of the present invention can be used in various fields, and can be suitably used as an ink composition such as a water-based ink for writing, a water-based printing ink, and an information recording ink. The present invention described below In particular, the ink-jet aqueous ink can be suitably used.

(Water-based ink for inkjet)
The water-based inkjet ink of the present invention comprises the colored composition of the present invention, and may further contain other components appropriately selected as necessary. Examples of the other components include a drying inhibitor, a penetration accelerator, an ultraviolet absorber, an antioxidant, an antifungal agent, a pH adjuster, a surface tension adjuster, an antifoaming agent, a viscosity adjuster, a dispersant, and a dispersion. Well-known additives, such as a stabilizer, a rust preventive agent, a chelating agent, are mentioned.

  The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink at the ink ejection port of the nozzle used in the ink jet recording method. The anti-drying agent is preferably a water-soluble organic solvent having a vapor pressure lower than that of water. Specific examples of the drying inhibitor include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithioglycol, 2-methyl-1,3-propanediol, 1,2,3-hexatriol, and acetylene glycol. Derivatives, polyhydric alcohols typified by glycerin, trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether, 2-pyrrolidone N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, 3-sulfolene, diacetone alcohol Le, polyfunctional compounds such as diethanolamine, etc. urea derivatives Ageraru. Of these, polyhydric alcohols such as glycerin diethylene glycol are more preferred. These may be used alone or in combination of two or more. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50 parts by mass.

  Examples of the penetration enhancer include alcohols such as ethanol, isopropanol, butanol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and the above-described surfactant for emulsifying dispersion. Nonionic surfactants listed as agents are listed. These are sufficiently effective if added in an amount of 10 to 30% by mass in the ink jet ink, and are added within a range that does not cause printing bleeding or paper loss (print-through).

  The ultraviolet absorber is used for the purpose of improving the storability of images. For example, JP-A Nos. 58-185677, 61-190537, JP-A-2-782, and JP-A-5-97075. Benzotriazole compounds described in JP-A-9-34057, etc., benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194383, US Pat. No. 3,214,463, etc. Compounds, cinnamic acid compounds described in JP-B-48-30492, JP-A-56-21141, JP-A-10-88106, etc., JP-A-4-298503, JP-A-8-53427, Triazine compounds and research discs described in JP-A-8-239368, JP-A-10-182621, JP-A-8-501291, etc. Disclosure No. Examples thereof include compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, and so-called fluorescent brighteners.

  The antioxidant is used for the purpose of improving the storability of an image, and examples thereof include various organic and metal complex antifading agents. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. . Examples of the metal complex-based antifading agent include nickel complexes and zinc complexes. No. 17643, Nos. VII to I, J; 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. Preferred examples include the compounds described in the patent cited in No. 15162 and the compounds represented by the general formulas and compound examples of the representative compounds described on pages 127 to 137 of JP-A-62-215272.

  Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. . These are preferably used in the ink in an amount of 0.02 to 1.00% by mass.

  Examples of the pH adjuster include alkali metal hydroxides such as lithium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and sodium hydrogen carbonate, inorganic substances such as potassium acetate, sodium silicate, and disodium phosphate. Examples include bases, organic bases such as N-methyldiethanolamine and triethanolamine.

  Examples of the surface tension adjusting agent include nonionic, cationic or anionic surfactants. For example, the surfactant used for the above emulsification dispersion can be used, and the surfactant used here preferably has a solubility in water at 25 ° C. of 0.5% or more.

  Preferred examples of the dispersant and the dispersion stabilizer include the above-mentioned cation, anion, and nonionic surfactants. Examples of the antifoaming agent include fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like.

  The pH of the inkjet ink is preferably 6 to 10 and more preferably 7 to 10 in terms of improving storage stability. The surface tension of the inkjet ink is preferably 20 to 60 mN / m, and more preferably 25 to 45 mN / m. The viscosity of the inkjet ink is preferably 30 mPa · s or less, and more preferably 20 mPa · s or less. The inkjet ink of the present invention is suitably used for the following inkjet recording method of the present invention.

  The colorant-containing polymer fine particles having the core / shell form of the present invention are preferably blended in an amount of 0.5 to 50% by mass in the polymer emulsion type water-based ink of the present invention as a polymer amount, and 0.5 to 30% % Is more preferable. If the blending amount of the polymer is less than 0.5% by mass, the color material cannot be protected sufficiently. If it exceeds 50% by mass, the storage stability of the suspension ink may be reduced, or the tip of the nozzle may The printer head may be clogged due to ink thickening or suspension aggregation caused by ink evaporation, so it is preferably within the above range.

  On the other hand, the colorant is preferably blended in the ink in an amount of 1 to 30% by mass, more preferably 1.5 to 25% by mass. If the blending amount of the coloring material is less than 1% by mass, the printing density is insufficient, and if it exceeds 30% by mass, the suspension stability with time decreases and the particle size tends to increase due to aggregation. It is preferable to be within the range.

  The ink of the present invention comprises a polymer suspension in which water is used as a medium and the above-described coloring material is encapsulated. The suspension includes various conventionally known additives, for example, wetting agents such as polyhydric alcohols, dispersants, and silicone-based inks. An antifoaming agent such as chloromethylphenol, and / or a chelating agent such as EDTA, or an oxygen absorber such as sulfite may be contained.

  Here, as the wetting agent, for example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, diethylene glycol diethyl ether, diethylene glycol mono n-butyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl Polyhydric alcohols such as ether, ethylene glycol monobutyl ether, methyl carbitol, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, diethyl carbitol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether And its ethers, acetates, N Can be used methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, triethanolamine, formamide, nitrogen-containing compounds such as dimethyl formamide, dimethyl monkey sulfoxide one or two or more kinds. Although there is no restriction | limiting in particular in the compounding quantity of these wetting agents, Preferably 0.1-50 mass% can be mix | blended in the said ink, More preferably, 0.1-30 mass% can be mix | blended.

  Further, the dispersant is not particularly limited. However, when the HLB value is 8 to 18, an effect as a dispersant is exhibited, and an increase in suspension particle diameter is suppressed. preferable.

  A commercial item can also be used as a dispersing agent. Examples of such commercially available products include the dispersant Demol SNB, MS, N, SSL, ST, and P (trade names) manufactured by Kao Corporation.

  Although there is no restriction | limiting in particular in the compounding quantity of a dispersing agent, It is preferable to mix | blend 0.01-10 mass% in the ink of this invention. When the compounding amount of the compound is less than 0.01% by mass, it is difficult to reduce the particle size of the suspension. When the compounding amount exceeds 10% by mass, the particle size of the suspension increases or the suspension stability decreases, resulting in gelation. Since there exists a possibility, it is preferable to set it as the said range.

  Moreover, as said antifoamer, a commercial item can be used without a restriction | limiting in particular. Examples of such commercially available products include KF96, 66, 69, KS68, 604, 607A, 602, 603, KM73, 73A, 73E, 72, 72A, 72C, 72F, 82F, 70, 71, manufactured by Shin-Etsu Silicone. 75, 80, 83A, 85, 89, 90, 68-1F, 68-2F (trade name) and the like. Although there is no restriction | limiting in particular in the compounding quantity of these compounds, It is preferable to mix | blend 0.001-2 mass% in the polymer emulsion type water-based ink of this invention. If the compounding amount of the compound is less than 0.001% by mass, bubbles are likely to be generated at the time of preparing the ink, and it is difficult to remove small bubbles in the ink. During printing, repellency may occur in the ink and the print quality may be deteriorated.

  Next, the method for producing the ink of the present invention will be described. The ink of the present invention can be produced by various emulsification methods. Various methods can be used as the emulsification method. Examples thereof are summarized in the description on page 86 of “Advances in Functional Emulsifier / Emulsification Technology and Application Development CMC”. In the present invention, it is particularly preferable to use an emulsifying and dispersing apparatus using ultrasonic waves, high-speed rotational shearing, and high pressure.

  In the emulsification dispersion using ultrasonic waves, two types of so-called batch type and continuous type can be used. The batch method is suitable for producing a relatively small amount of sample, and the continuous method is suitable for producing a large amount of sample. In the continuous type, for example, a device such as UH-600SR (manufactured by SMT Co., Ltd.) can be used. In the case of such a continuous system, the ultrasonic wave irradiation time can be obtained by the volume of the dispersion chamber / flow velocity × the number of circulations. In the case where there are a plurality of ultrasonic irradiation apparatuses, the total irradiation time is obtained. The irradiation time of ultrasonic waves is practically 10000 seconds or less. Further, if it is necessary for 10000 seconds or more, the load on the process is large, and in practice, it is necessary to shorten the emulsification dispersion time by reselecting the emulsifier. Therefore, more than 10,000 seconds are not necessary. More preferably, it is 10 seconds or more and 2000 seconds or less.

  As an emulsifying and dispersing device by high-speed rotational shearing, it is described in Disper Mixer as described in pages 255 to 256 of "Functional emulsifier / emulsification technology and application development CMC", or page 251. Such a homomixer and an ultramixer as described on page 256 can be used. These types can be properly used depending on the liquid viscosity at the time of emulsification dispersion. In the emulsification disperser using these high-speed rotary shears, the rotational speed of the stirring blade is important. In the case of an apparatus having a stator, the clearance between the stirring blade and the stator is usually about 0.5 mm and cannot be made extremely narrow, so the shearing force mainly depends on the peripheral speed of the stirring blade. If the peripheral speed is 5 m / S or more and 150 m / S or less, it can be used for emulsification and dispersion of the present invention. This is because when the peripheral speed is low, it is often impossible to reduce the particle size even if the emulsification time is extended, and in order to achieve 150 m / S, it is necessary to extremely improve the performance of the motor. More preferably, it is 20-100 m / s.

For emulsification and dispersion by high pressure, LAB2000 (manufactured by SMT) can be used, but the emulsification and dispersion ability depends on the pressure applied to the sample. The pressure is preferably in the range of 10 ⁴ kPa to ⁵ × 10 ⁵ kPa. Moreover, it can emulsify and disperse | distribute several times as needed, and can obtain the target particle size. If the pressure is too low, the desired particle size cannot be achieved in many cases by carrying out emulsification and dispersion many times, and in order to make the pressure 5 × 10 ⁵ kPa, the apparatus is heavily loaded and is not practical. . More preferably, it is the range of 5 * 10 < ⁴ > kPa-2 * 10 < ⁵ > kPa.

  These emulsifying / dispersing devices may be used alone or in combination as necessary. Colloid mills, flow jet mixers, etc. alone cannot achieve the object of the present invention, but by combining with the apparatus of the present invention, it is possible to enhance the effects of the present invention, such as enabling emulsification and dispersion in a short time. is there.

  The ink of the present invention can be produced by so-called phase inversion emulsification in addition to using the above-described apparatus. Here, in the phase inversion emulsification, the polymer is dissolved in an organic solvent such as an ester or a ketone together with the dye, a neutralizing agent is added as necessary to ionize carboxyl groups in the polymer, and then the aqueous phase is After the addition, the organic solvent is distilled off and the phase is changed to an aqueous system. After the phase inversion is completed, the ester and ketone solvents are removed by heating the system under reduced pressure, and a predetermined amount of water is removed to provide a water-based ink for inkjet recording according to the present invention having a desired concentration. Is obtained.

  These emulsifying / dispersing devices may be used alone or in combination as necessary. Colloid mills, flow jet mixers, etc. alone cannot achieve the object of the present invention, but by combining with the apparatus of the present invention, it is possible to enhance the effects of the present invention, such as enabling emulsification and dispersion in a short time. is there.

  When forming an image by ejecting the water-based ink for ink-jet recording of the present invention, the ink-jet head to be used may be an on-demand system or a continuous system. Also, as a discharge method, an electro-mechanical conversion method (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a shared wall type, etc.), an electro-thermal conversion method (for example, thermal ink jet) Any ejection method such as a mold, a bubble jet (registered trademark) mold, or the like may be used.

  In the image forming method using the water-based ink for ink-jet recording of the present invention, for example, the ink is ejected as droplets from the ink-jet head based on the digital signal by a printer loaded with the water-based ink for ink-jet recording and attached to the ink receptor. By doing so, for example, an inkjet print in which an inkjet recording image is formed on an inkjet image recording medium is obtained.

  As the inkjet image recording medium, for example, any of plain paper, coated paper, cast coated paper, glossy paper, glossy film, and OHP film can be used, and for example, a so-called void layer in which a porous layer is formed, for example. It is preferable if the recording medium has It is not particularly limited to the material or shape of the support described above, and for example, it may have a three-dimensional structure other than those formed in a sheet shape.

  The polymer emulsion type water-based ink of the present invention can be used as ink for writing instruments such as general fountain pens, ballpoint pens, sign pens, etc., in addition to ink for ink jet recording. The suspension of the present invention can be dried to obtain a fine powder. The obtained powder can be used for toner for electrophotography.

(Image receiving material)
The image receiving material is not particularly limited, and is a known recording material, that is, plain paper, resin-coated paper, for example, JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7. -276789, 9-323475, JP-A-62-238783, JP-A-10-153789, JP-A-10-217473, JP-A-10-235995, JP-A-10-337947, Examples thereof include ink-jet exclusive paper, film, electrophotographic co-paper, cloth, glass, metal, ceramics, and the like described in JP-A-10-217597 and JP-A-10-337947.

  In the present invention, among the image receiving materials, a recording paper and a recording film having an image receiving layer on a support are particularly preferable.

The support is composed of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP, and CGP, and waste paper pulp such as DIP. , Binders, sizing agents, fixing agents, cationic agents, paper strength enhancing agents, and other additives mixed together and manufactured with various devices such as long net paper machines and circular net paper machines can be used. In addition to these, synthetic paper, plastic film sheets, and the like may be used. The thickness of the support is about 10 to 250 μm, and the basis weight is preferably 10 to 250 g / m ² .

  The support may be provided with the image-receiving layer as it is, or may further be provided with a backcoat layer, and after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, the image-receiving layer and A backcoat layer may be provided. The support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar.

  Among the supports, paper and plastic film laminated on both sides with polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used. It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a tinting dye (eg, cobalt blue, ultramarine blue, neodymium oxide) to the polyolefin.

  The image receiving layer is provided on the support and contains a pigment and an aqueous binder. The pigment is preferably a white pigment, and examples of the white pigment include calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, Preferable examples include inorganic pigments such as lithopone, zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins, and melamine resins. Among these white pigments, inorganic pigments are preferable, porous inorganic pigments are more preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, any of anhydrous silicic acid obtained by a dry production method and hydrous silicic acid obtained by a wet production method can be used, and it is particularly preferable to use hydrous silicic acid.

  Examples of the aqueous binder include water-soluble polymers such as polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives. Examples thereof include water dispersible polymers such as styrene butadiene latex and acrylic emulsion. These aqueous binders may be used alone or in combination of two or more. Among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are preferable in terms of adhesion to the pigment and peel resistance of the image receiving layer.

  In addition to the pigment and the aqueous binder, the image receiving layer may contain a mordant, a water resistance agent, a light resistance improver, a surfactant, and other additives.

  The mordant is preferably immobilized. For that purpose, a polymer mordant is preferably used. About the polymer mordant, JP-A-48-28325, JP-A-54-74430, JP-A-54-124726, JP-A-55-22766, JP-A-55-142339, JP-A-60-23850, JP-A-60-23851, 60-23852, 60-23853, 60-57836, 60-60643, 60-118834, 60-122940, 60-122941, 60-122942, 60 -235134, JP-A-1-161236, U.S. Pat. Nos. 2,484,430, 2,548,564, 3,148,061, and 3,309,690. 4,115,124, 4,124,386, 4,193,800, 4,273,853, 4,282,3 No. 5, is described in the specification of the same No. 4,450,224. An image receiving material containing a polymer mordant described in JP-A-1-161236, pages 212 to 215 is particularly preferred. When the polymer mordant described in the publication is used, an image with excellent image quality is obtained, and the light resistance of the image is improved.

  The water-proofing agent is effective for making the image water-resistant, and a cationic resin is particularly preferable. Examples of the cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, colloidal silica, and the like. Among these, polyamide polyamine epichlorohydrin is particularly preferable. The content of these cationic resins is preferably 1 to 15% by mass, particularly 3 to 10% by mass, based on the total solid content of the image receiving layer.

  Examples of the light resistance improver include zinc sulfate, zinc oxide, hindered amine-based antioxidants, and benzotriazole-based ultraviolet absorbers such as benzophenone. Among these, zinc sulfate is particularly preferable.

  The surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent. The surfactant is described in JP-A Nos. 62-173463 and 62-183457. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compounds include fluorine surfactants, oily fluorine compounds (eg, fluorine oil), and solid fluorine compound resins (eg, tetrafluoroethylene resin). The organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-2994, and JP-A-62-135826.

  Examples of the other additives include pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent whitening agents, preservatives, pH adjusting agents, matting agents, and hardening agents. The image receiving layer may be a single layer or two or more layers.

  The thickness of the image receiving layer is preferably 10 to 50 μm, and more preferably 20 to 40 μm.

  The image-receiving material can be provided with a backcoat layer. Examples of components that can be added to the backcoat layer include white pigments, aqueous binders, and other additives.

  Examples of the white pigment contained in the backcoat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and silicic acid. White inorganic pigments such as aluminum, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide And organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin and melamine resin.

  Examples of the aqueous binder contained in the backcoat layer include styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxy Examples thereof include water-soluble polymers such as methyl cellulose, hydroxyethyl cellulose, and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion.

  Examples of other components contained in the back coat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water resistant agent.

  A polymer latex may be added to the constituent layers (including the back coat layer) in the image receiving material. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. The polymer latex is described in JP-A Nos. 62-245258, 62-1316648, and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Further, when a polymer latex having a high glass transition temperature is added to the back coat layer, curling of the layer can be prevented.

  The inkjet recording method is not particularly limited, and is a known method, for example, a charge control method for ejecting ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) using vibration pressure of a piezo element, Either an acoustic ink jet method that converts an electrical signal into an acoustic beam, irradiates the ink and ejects the ink by using radiation pressure, or a thermal ink jet method that heats the ink to form bubbles and uses the generated pressure. There may be. The inkjet recording method includes a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent. A method using ink is included.

〔Color filter〕
The color filter of the present invention is characterized by containing the compound according to the present invention.

  As a color filter forming method, a pattern is first formed with a photoresist and then dyed, or disclosed in JP-A-4-163552, JP-A-4-128703, JP-A-4-175653, and the like. As described above, there is a method of forming a pattern with a photoresist added with a colorant.

  The color filter of the present invention can be formed by any of the above methods, but as a preferable method, the methods described in JP-A-4-175533 and JP-A-6-35182, that is, thermosetting. A positive resist composition comprising a resin, a quinonediazide compound, a crosslinking agent, a colorant and a solvent is applied onto a substrate, then exposed through a mask, and the exposed portion is developed to form a positive resist pattern. A method of exposing the positive resist pattern on the entire surface and then curing the exposed positive resist pattern can be mentioned. In addition, a black matrix is formed according to a conventional method. G. B primary color system or Y.C. M.M. A method for obtaining a C complementary color filter can be mentioned.

  As for the thermosetting resin, quinonediazide compound, crosslinking agent, and solvent used in this case, and those used, those described in the above-mentioned published patent publications can be preferably used.

  When the compound according to the present invention is used for a color filter, when dispersing the compound according to the present invention in a transparent resin, various dispersing means such as a two-roll mill, a three-roll mill, a sand mill, and a kneader can be used.

  In the present invention, as a resin varnish for dispersing a compound to form a colored composition, a varnish used in a conventionally known colored composition for a color filter is used. As the dispersion medium, a solvent suitable for the resin varnish or an aqueous medium is used. Further, conventionally known additives such as a dispersion aid, a smoothing agent and an adhesion agent are added and used as necessary. As the resin varnish, a photosensitive resin varnish and a non-photosensitive resin varnish are used. Examples of the photosensitive resin varnish are photosensitive resin varnishes used for ultraviolet curable inks, electron beam curable inks, etc., and non-photosensitive resin varnishes include, for example, relief printing inks, planographic inks, intaglio gravure inks, Any of varnishes used for printing inks such as stencil screen inks, varnishes used for electrodeposition coating, varnishes used for developers of electronic printing and electrostatic printing, and varnishes used for thermal transfer ribbons can be used.

  Examples of the photosensitive resin varnish include a photosensitive cyclized rubber resin, a photosensitive phenol resin, a photosensitive polymethacrylate resin, a photosensitive polyamide resin, a photosensitive polyimide resin, and an unsaturated polyester resin. Examples of the varnish include a polyester acrylate resin, a polyepoxy acrylate resin, a polyurethane acrylate resin, a polyether acrylate resin, and a polyol acrylate resin, and a varnish to which a monomer is added as a reactive diluent. The photosensitive coloring composition according to the present invention can be obtained by adding a photopolymerization initiator such as benzoin ether or benzophenone to the compound according to the present invention and the above varnish, and carrying out brickwork by a conventionally known method. Moreover, it can replace with said photoinitiator and can use it as a thermopolymerizable coloring composition using a thermal polymerization initiator. When forming a color filter pattern using the above photosensitive coloring composition, spin coating the photosensitive coloring composition on a transparent substrate, coating the entire surface using a low-speed rotary coater, roll coater, knife coater, etc. Or performing full printing by various printing methods or partial printing slightly larger than the pattern, and after pre-drying, the photomask is brought into close contact, and exposure is performed using an ultrahigh pressure mercury lamp to print the pattern. Next, development and washing are carried out, and post-baking is carried out as necessary to form a color filter pattern.

  Examples of non-photosensitive resin varnishes include cellulose acetate resins, nitrocellulose resins, styrene (co) polymers, polyvinyl butyral resins, amino alkyd resins, polyester resins, amino resin modified polyester resins Resin, polyurethane resin, acrylic polyol urethane resin, soluble polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, casein, hydroxyethyl cellulose, styrene-maleic acid ester copolymer water-soluble Water-soluble salts of (meth) acrylic acid ester (co) polymers, water-soluble amino alkyd resins, water-soluble amino polyester resins, water-soluble polyamide resins, etc., used alone or in combination Is done. When forming a color filter pattern using the above-mentioned non-photosensitive coloring composition, the non-photosensitive coloring composition, for example, the above-described various printing methods using a printing ink for color filters is used on a transparent substrate. A method of printing a colored pattern directly on a substrate, a method of forming a colored pattern on a substrate by electrodeposition coating using an aqueous electrodeposition coating composition for color filters, an electronic printing method or an electrostatic printing method, or Examples thereof include a method in which a colored pattern is once formed on a transferable substrate by the above-described method and then transferred to a color filter substrate. Then, according to a conventional method, baking is performed as necessary, polishing for smoothing the surface, or top coating for protecting the surface is performed. In addition, a black matrix can be formed according to a conventional method to obtain an RGB color filter.

  In addition, by incorporating a photocurable monomer, a photopolymerization initiator, or the like into the ink jet ink described above, an RGB filter pattern is produced using an ink jet printer head and cured by, for example, UV light irradiation. The color filter can also be formed directly.

  In addition, the copper chelate dye of the present invention can be used, for example, in an optical recording medium, an electrophotographic color toner, an optical sensor, and the like.

[Optical recording medium]
The copper chelate dye of the present invention can be contained in the recording layer of the optical recording medium.

  The substrate constituting the optical recording medium is required to be substantially transparent (transmittance of 80% or more) in the wavelength region (350 to 900 nm) of laser light used for recording and reproduction. Examples of the material constituting the substrate include polymethyl methacrylate resin, acrylic resin, polycarbonate resin, epoxy resin, polysulfone resin, transparent resin such as methylpentene polymer, and glass. In addition, the oxygen barrier film may be formed on the outer surface, inner surface, inner / outer peripheral surface of the substrate as necessary. Further, it is preferable that a tracking groove is formed on the substrate on which the recording layer is formed.

  In the recording layer using the compound according to the present invention, the extinction coefficient k in the wavelength region of the laser beam becomes preferable as the recording layer of the optical recording medium, and is suitable for light absorption suitable for recording and reproduction. Combined with reflectivity. Here, when the extinction coefficient k of the recording layer in the wavelength region of the laser beam is excessive, the reflectance is lowered, and reproduction by reflected light cannot be performed sufficiently satisfactorily. When the extinction coefficient k is too small, it becomes difficult to perform recording with a normal recording power. The extinction coefficient k is preferably 0.01 to 0.1. On the other hand, the refractive index n (real part of the complex refractive index) of the recording layer in the wavelength region of the laser light is preferably 1.8 to 4.0.

  The recording layer constituting the optical recording medium may contain other types of dye compounds, various resins, surfactants, antistatic agents, dispersants, antioxidants, crosslinking agents, and the like.

  The recording layer may be formed on one surface of the substrate, or may be formed on both surfaces of the substrate.

  The method for forming the recording layer on the substrate is not particularly limited, for example, spin coating method, dip coating method, spray coating method, blade coating method, roller coating method, bead coating method, Meyer coating method, Various methods such as a curtain coating method can be applied. Examples of the solvent used for forming the recording layer include ketone solvents such as cyclohexanone, ester solvents such as butyl acetate, ether solvents such as ethyl cellosolve, alcohol solvents, aromatic solvents such as toluene, and halogenated compounds. Examples include alkyl solvents.

  A reflective layer may be formed on the recording layer. The reflective layer can be formed by means such as vapor deposition or sputtering using a metal having high reflectivity such as Au, Al—Mg alloy, Al—Ni alloy, Ag, Pt, and Cu.

On the reflective layer, a protective film made of, for example, an ultraviolet curable resin may be formed. In addition, an adhesive layer may be provided between the recording layer and the reflective layer to bring them into close contact.

Example 1
<Solution spectral absorption waveform>
The pigment | dye (MD-38) of this invention was melt | dissolved in ethyl acetate, and the spectral absorption waveform was measured. The waveform is shown in FIG. The waveform shows a very sharp waveform with a small half-value width, and it can be seen that it is a pigment with high color purity. Comparative dye 1 was measured in the same manner, but it was found that the solubility was low (DMF solution) and the half width was larger than the dye of the present invention. It is listed in Table 3 together with other dyes of the present invention.

Example 2
(Preparation of ink for inkjet recording 1)
An ink composition IJ-1 having the following composition was prepared according to a conventional method using the coloring matter (MD-1) represented by the general formula (1) of the present invention. Further, ink compositions IJ-C1 and C2 having the same composition as the ink composition IJ-1 were prepared except that C1 (copper phthalocyanine compound) and C2 having the following structures were used as cyan dyes in the same mass%. Ink compositions IJ-2 to IJ-21 were prepared in the same manner except that the coloring matter of the present invention was changed as shown in Table 4.

(Composition of ink composition IJ-1)
Dye of the present invention: MD-1 1.4% by mass
Diethylene glycol 19% by mass
9% by mass of triethylene glycol monobutyl ether
Surfactant Surfynol 465 (produced by Air Products and Chemicals Inc.) 0.6% by mass
Ion-exchanged water 70% by mass

(Preparation of ink for inkjet recording 2)
<Preparation of colored fine particle dispersion (A-1)>
As an oil-soluble polymer, polyvinyl butyral (BL-S manufactured by Sekisui Chemical Co., Ltd., average polymerization degree 350) 15 g, dye (MD-1) represented by the general formula (1) of the present invention: 10 g and ethyl acetate: 150 g The flask was placed in a separable flask, and the inside of the flask was substituted with N _2, followed by stirring to completely dissolve the polymer and the dye. Subsequently, 150 g of an aqueous solution further containing 3 g of sodium lauryl sulfate was dropped and stirred, and then emulsified for 300 seconds using an ultrasonic disperser (UH-150 type, manufactured by SMT Co., Ltd.). Thereafter, ethyl acetate was removed under reduced pressure to prepare a colored fine particle dispersion. Hereinafter, this is abbreviated as colored fine particle dispersion (A-1).

  Each of the colored fine particle dispersions (A-1) prepared as described above was weighed in an amount of 2% by mass as a finished ink content, and 15% ethylene glycol, 15% glycerin, and Surfinol 465 (day (Manufactured by Shinsei Kogyo Co., Ltd.) 0.3%, the remainder being pure water, and further filtered through a 2 μm membrane filter to remove dust and coarse particles to obtain an ink composition IJ-22. IJ-23 to 25 were obtained in exactly the same manner except that MD-1 was replaced with the dye shown in Table 4.

  Each ink was printed on Konica Photojet paper Photolique QP glossy paper (manufactured by Konica Corporation) using a commercially available Epson inkjet printer (PM800), and the color tone, light resistance, ozone resistance, water resistance and The heat and humidity resistance was evaluated by the following method.

《Color tone》
For each coated sample, a four-stage evaluation was performed by visual evaluation with 10 monitors. ○ It is desirable to be above.

◎: Vivid and clear color ○: Vivid color △: Dull color ×: Dirty color << Light resistance >>
The reflection spectral density at the maximum absorption wavelength in the visible region from an unexposed sample after 120 hours exposure with a xenon fade meter (70,000 Lux) on a sample with an initial reflection density of 1.0 in each image. The reduction rate was evaluated and the dye residual rate was calculated.

Light resistance (%) = (maximum absorption wavelength concentration of exposed sample / maximum absorption wavelength concentration of unexposed sample) × 100
It was determined according to the following evaluation criteria based on the following evaluation criteria. ○ If it is above, there is no practical problem.

◎: Light resistance is 95% or more ○: Light resistance is 90% or more and less than 95% △: Light resistance is 80% or more and less than 90% ×: Light resistance is less than 80% << Ozone resistance >>
In a sample with an initial reflection density of 1.0 for each image, the sample was left in a box set at an ozone gas concentration of 0.5 ± 0.1 ppm, room temperature, and in a dark place for 7 days. The ozone resistance was calculated and evaluated in three stages.

A: Dye remaining ratio is 80% or more B: Dye remaining ratio is 70% or more and less than 80% C: Dye remaining ratio is less than 70% << Water resistance >>
With a micropipette, water was dropped on each of the obtained prints, and after 1 minute, it was rubbed with a finger to determine visually whether or not the print was disturbed.

◎: Substantially no change is observed ○: Image can be identified even if it is disturbed (acceptable level)
×: The image is disturbed so that it cannot be identified.
A sample having an initial reflection density of 1.0 for each image was stored under conditions of 50 ° C. and 80% RH for 14 days, and the dye residual ratio was calculated and evaluated in the same manner as light resistance. The image density was measured using a reflection densitometer (X-Rite 310TR). In addition, the color change was observed visually. The evaluation results are shown in Table 4 below.

○: Dye remaining ratio is 90 to 95%
Δ: Dye remaining ratio is less than 80 to 90% ×: Dye remaining ratio is less than 80% and the color appears to be cloudy visually.

  As shown in Table 4, it can be said that the ink-jet ink produced using the copper chelate dye of the present invention and the colored fine particle dispersion is excellent in color tone, light resistance, ozone resistance, water resistance and heat and humidity resistance.

Example 3
<Color filter>
In order to obtain an RGB color filter, a red (R) mosaic pattern, a green (G) mosaic pattern, and a blue (B) mosaic pattern were formed on a glass plate by the following method. Using the components shown below, photosensitive coating agents for red (R), green (G) and blue (B) color filters were prepared. The used photosensitive polyimide resin varnish is a photosensitive polyimide resin varnish containing a photosensitizer.

(Components of photosensitive coating agent for color filters)
R-1:
Dye of the present invention: MD-1 10 parts Photosensitive polyimide resin varnish 50 parts N-methyl-2-pyrrolidone 40 parts G-1:
Color material G-1 10 parts Photosensitive polyimide resin varnish 50 parts N-methyl-2-pyrrolidone 40 parts B-1:
Color material B-1 10 parts Photosensitive polyimide resin varnish 50 parts N-methyl-2-pyrrolidone 40 parts A glass plate treated with a silane coupling agent is set on a spin coater, and the red color filter of the above R-1 The photosensitive coating agent was spin-coated at 300 rpm for 5 seconds and then at 2000 rpm for 5 seconds. Next, prebaking was performed at 80 ° C. for 15 minutes, a photomask having a mosaic pattern was brought into close contact, and exposure was performed using an ultrahigh pressure mercury lamp at a light amount of 900 mJ / cm ² .

  Next, development and washing were performed with a dedicated developer and a dedicated rinse, and a red mosaic pattern was formed on the glass plate. Subsequently, the green mosaic pattern and the blue mosaic pattern were applied and baked in accordance with the above-described method using the above-described G-1 green and B-1 blue color filter photosensitive coating agents, A black matrix was formed according to a conventional method to obtain an RGB color filter: CF-1.

  Similarly, RGB color filters CF-2 to CF-6 and comparison filters CF-C3 and C4 were prepared in the same manner except that MD-1 of R-1 was changed to the dye shown in Table 5.

  The color tone, heat resistance, and light resistance of the obtained filter were evaluated by the following methods.

《Color tone》
Each filter was evaluated in four stages by visual evaluation using 10 monitors. ○ It is desirable to be above.

◎: Vivid and clear color ○: Vivid color △: Dull color ×: Dirty color << Heat resistance >>
The glass substrate with the undercoat layer on which the pattern image was formed was heated with a hot plate at 200 ° C. for 1 hour so as to be in contact with the substrate surface, and then using a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.) The change in chromaticity, that is, the ΔEab value was measured. A smaller ΔEab value indicates better heat resistance.

《Light resistance》
The glass substrate with the undercoat layer on which the pattern image was formed was irradiated with a xenon lamp at 70,000 lux for 5 days, and then the chromaticity change, that is, the ΔEab value was measured. A smaller ΔEab value indicates better light resistance.

  The color filter obtained above had excellent spectral characteristics, had excellent properties such as light resistance and heat resistance, and had excellent properties as a color filter for liquid crystal color displays.

The spectral absorption spectrum of metal chelate pigment | dye MD-38 of this invention is shown.

Claims (10)

A copper chelate dye represented by the following general formula (1).
General formula (1)
Cu ²⁺ [(X ₁ ) _l (X ₂ ) _m (X ₃ ) _n ] · (W ₁ ) _s
[Wherein, X ₁ , X ₂ and X ₃ each independently represent a monodentate or bidentate ligand, which may be the same or different, and at least one of them represents the following general formula (2) . l, m, n, and s each represent an integer of 0 to 2, l + m + n> 1, and (W ₁ ) _s represents a counter ion necessary to neutralize the charge. ]

[Wherein Q represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and Q may be condensed or may have a substituent. Z ₂ represents an atomic group necessary for forming a 4- to 6-membered ring. L _1, represents a L _2, L _3, L ₄ and L ₅ methine group having each independently unsubstituted or substituted. n1 represents an integer of 0 to 4, and n2 is 0 or 1. Y ₂ represents an oxygen atom or ═NR ₃ —, R and R _{1 to} R ₃ each represent a substituent, at least one has a chelatable group, and R ₂ and R ₃ are bonded to form a 5-membered ring. May be formed. ] In the general formula (2), according to claim 1, wherein the copper chelate dye, wherein the ring formed by Z ₂ is represented by the following general formula (3).

[Wherein Y ₁ represents an oxygen atom, a sulfur atom or ═C (CN) R ₁₃ . R ₁₃ represents a cyano group, a carboxylic acid group, a carboxylic acid ester group or a carbonamido group, and is bonded to L ₃ by * and Z ₁ by **. ] In the general formula (2), Y ₂ represents ═NR ₃ —, and the condensed ring structure formed by combining R ₂ and R ₃ is represented by the following general formula (4-1) or (4-2). The copper chelate dye according to claim 1 or 2, wherein:

[Wherein, R _{41 to} R ₄₃ each represent a substituent, at least one of which has a chelatable group, and is bonded to Z ₂ at the * moiety. ] In Formula (4-1) or (4-2), one of the claims 1 to 3, characterized in that the chelating groups of R ₄₁ to R ₄₃ represents is represented by the following general formula (5) The copper chelate dye according to claim 1.

[Wherein W represents ═N— or ═C (OR ₇₁ ) —, Z ₃ represents an atomic group necessary for forming a 5- or 6-membered ring, and may have a substituent, R ₇₁ represents a substituent, and is bonded to Z ₁ by *. ] In the general formula (1), any one of claims 1 to 4, at least one ligand represented by X _1, X ₂ or X _3, characterized by being represented by the following general formula (6) The copper chelate dye according to item 1.

[Wherein E ₁ and E ₂ represent an electron-withdrawing group having a Hammett substituent constant (σp) of 0.1 or more and 0.9 or less, R ₆₁ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, Represents an aryloxy group and an amino group, and may have a substituent. ] A coloring composition comprising the copper chelate dye according to any one of claims 1 to 5. A colored fine particle dispersion comprising the copper chelate dye according to claim 1 and a thermoplastic resin or a high-boiling solvent. An ink-jet ink comprising the colored composition according to claim 6 or the colored fine particle dispersion according to claim 7. An ink jet recording method comprising performing recording using the ink jet ink according to claim 8. A color filter comprising the copper chelate dye according to claim 1.

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