JP2003073358A - New triphenylmethane compound, oil-based ink, water- based ink, image recoding method, triphenylmethane compound dispersion and colored photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new colored compound (triphenylmethane compound) having good hue and fastness to light, heat, humidity, etc., and to provide an oil-based ink, water-based ink, image recording method, dispersion and colored photosensitive composition each using the above compound. SOLUTION: This triphenylmethane compound is shown by the general formula (1) (Ar<1> and Ar<2> are each independently an aryl or heterocyclic group; -Z<1> =, -Z<2> =, and -Z<3> = are each CR= or -N=; R is H, an alkyl, aryl, heterocyclic group, acyl, alkoxy, hydroxy, halogen atom or acylamino; Mt1 is a metal atom; Y and X are each group ionically bindable to Mt1; A<-> is a counteranion; m is the valence of the metal atom, being an integer of 1-4; n is an integer of 1-4, wherein m>=n). The other objective ink, image recording method, triphenylmethane compound dispersion and colored photosensitive composition each using the triphenylmethane compound are provided, respectively.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel triphenylmethane compound, and an oil-based ink, an aqueous ink, an image recording method, a triphenylmethane compound dispersion and a colored photosensitive composition using the compound.

[0002]

2. Description of the Related Art The term "coloring compound" is a general term for colored compounds called dyes, dyes, pigments, stains, etc., and is widely used in various fields. Although the required properties vary depending on the purpose of use of the coloring compound, it is necessary that the hue is good and the formed color image is robust against light, heat, humidity and the like. Various improvements have been made from the past, and there is a demand for an integrated and balanced compound including price. The aqueous ink is generally a composition in which a coloring compound is dispersed or dissolved in an aqueous medium, and the oil-based ink is generally a composition in which a coloring compound is dispersed or dissolved in an oil medium. These water-based inks and oil-based inks are not only used as general paints and dyes,
It is also used as an ink for a recording material for transferring an ink such as an inkjet recording ink, a thermal fusion transfer ink, a thermal sublimation transfer ink. Even if an ink is prepared using a coloring compound with good performance, the original hue cannot be reproduced due to the aggregation of the coloring compound, or it cannot be stabilized in the ink when it is desired to use it as an aggregate of the coloring compound, and it is robust. May be unsatisfactory. Further, since the dispersibility or dissolution stability of the coloring compound in the medium is insufficient, there are drawbacks such that the dye is decolored or discolored or separated from the medium when the ink composition is stored for a long time. In the field of use of inks, for example, inks used in inkjet recording systems include both water-based inks and oil-based inks. In this case, as the composition of the water-based ink, there are a type in which a water-soluble coloring compound is dissolved and a type in which a hardly-soluble coloring compound is dispersed in an aqueous medium. On the other hand, as the composition of the oil-based ink, there are a type in which an oil-soluble coloring compound is dissolved in an oil-based medium, a solid type used by being melted by heat, and a type in which a hardly soluble coloring compound (pigment) is dispersed in the oil-based medium. . Thus, it can be seen that there are various combinations of ink compositions when used in the inkjet recording system. In either case, it is basically necessary to impart hue and fastness, and improvement is required. In addition, a coloring compound, particularly a coloring compound that is hardly soluble in an oil medium, is added to a photosensitive resin composition to form a colored photosensitive composition, which is used on a substrate such as an electrophotographic toner, a printing ink, a color display plate, and a color proof. It is used for forming a multicolor image on a screen, manufacturing a color filter used for a liquid crystal display and the like. Also in this case, a coloring compound having a good balance between hue and fastness is required.

[0003]

SUMMARY OF THE INVENTION The present invention has been made based on the above-mentioned demands, and its object is to provide a novel coloring compound (tri-colorant) which has a good hue and is fast against light, heat, humidity and the like. It is intended to provide a phenylmethane compound), an oil-based ink using the compound, an aqueous ink, an image recording method, a triphenylmethane compound dispersion, and a colored photosensitive composition.

[0004]

The above object of the present invention is to provide the following triphenylmethane compound, oil-based ink, water-based ink, image recording method, triphenylmethane compound dispersion and colored photosensitive composition. Will be resolved. (1) A triphenylmethane compound represented by the following general formula (1).

[0005]

[Chemical 3]

In the general formula (1), Ar ¹ and Ar ² each independently represent an aryl group or a heterocyclic group, and -Z ¹ =, -Z ² =, and -Z ³ = are CR.
= Or -N =, R represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxy group, a hydroxy group, a halogen atom or an acylamino group, Mtl represents a metal atom, and Y represents And X represent a group capable of forming an ionic bond with Mtl, and A ⁻ represents a counter anion. m
Represents the valence of a metal atom and represents an integer of 1 to 4. n is 1
Represents an integer of 4. However, m ≧ n. (2) In the general formula (1), Ar ¹ and Ar ² are
The triphenylmethane compound according to (1) above, which is a 4-substituted aminophenyl group or an indol-3-yl group represented by the following structural formula.

[0007]

[Chemical 4]

In the above structural formula, R ²¹ , R ²² and R ²³ are
Represents a hydrogen atom, an alkyl group or an aryl group, R
²⁴ represents a hydrogen atom, an alkyl group, an aryl group, an acyl group or an alkoxycarbonyl group. (3) An oil-based ink containing the triphenylmethane compound represented by the general formula (1). (4) A water-based ink containing the triphenylmethane compound represented by the general formula (1). (5) An image recording method in which energy is applied to the water-based ink according to (4) above to cause the droplets of the ink to be ejected onto a recording medium, and an image made of the ink is recorded on the recording medium. (6) A triphenylmethane compound dispersion liquid in which the triphenylmethane compound represented by the general formula (1) is dispersed in a liquid. (7) A triphenylmethane compound dispersion liquid containing the triphenylmethane compound represented by the general formula (1), an organic solvent, and a dispersant. (8) The triphenylmethane compound dispersion liquid as described in (7) above, which further contains a binder polymer having an acidic group. (9) A colored photosensitive composition containing the triphenylmethane compound dispersion according to (6) or (7), a polyfunctional monomer having two or more ethylenically unsaturated double bonds, and a photopolymerization initiator. .

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The novel triphenylmethane compound of the present invention is represented by the above general formula (1) and has a good hue and light,
It is a metal chelate dye that is robust against heat and humidity and stable. Therefore, when an image is formed using an oil-based ink, a water-based ink, or a dispersion liquid that uses this dye,
An image having good fastness to light, heat, humidity, etc. can be obtained. In the general formula (1), Ar ¹ and Ar ² each independently represent an aryl group or a heterocyclic group, and -Z ¹ =,
-Z ² =, and -Z ³ = is, CR =, or represents -N =, the R is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxy group, hydroxy group, a halogen atom or Represents an acylamino group, Mtl represents a metal atom, Y and X represent groups capable of forming an ionic bond with Mtl, and A ⁻ represents a counter anion. m represents the valence of a metal atom and represents an integer of 1 to 4. n represents an integer of 1 to 4. However, m ≧ n.

Ar ¹ and A in the general formula (1)
Each r ² independently represents an aryl group or a heterocyclic group, the aryl group is preferably a phenyl group and a naphthyl group, the heterocyclic group is nitrogen as a ring atom,
A 5- to 7-membered ring group containing at least one sulfur or oxygen atom is preferable, and an unsaturated 5-membered ring group containing at least one nitrogen atom as a ring atom is particularly preferable. The 5-membered ring may be condensed. Among them, the aromatic ring or hetero ring shown below is preferable.

[0011]

[Chemical 5]

The above R ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an acyl group, and R ⁴ , R ⁶ , R ⁸ , R ⁹ and R ¹⁰ represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxy group or an acylamino group. Z represents an oxygen atom, a sulfur atom or a nitrogen atom. A plurality of substituents may be substituted on the benzene ring of the ring.

R ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ¹¹ and R
^The alkyl group, aryl group or acyl group represented by ^{12 includes} an alkyl group having 1 to 20 carbon atoms (chain or cyclic), an aryl group having 6 to 12 carbon atoms, and an acyl group having 1 to 20 carbon atoms (carbon group). (Including a formyl group having 1 to 12 carbon atoms) is preferable, and an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an acyl group having 1 to 12 carbon atoms are particularly preferable. Also, R
^The heterocyclic group represented by ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ¹¹ and R ¹² is preferably a 5- to 7-membered ring group containing a nitrogen, sulfur or oxygen atom as a ring atom, Particularly, a 5- or 6-membered ring group containing an oxygen atom as a ring atom is preferable.

The alkyl group, aryl group, acyl group, alkoxy group or acylamino group represented by R ⁴ , R ⁶ , R ⁸ , R ⁹ and R ¹⁰ is an alkyl group having 1 to 12 carbon atoms or 6 carbon atoms. To 12 aryl groups, total 1 to 18 acyl groups, total 1 to 12 alkoxy groups, and total 1 to 18 acylamino groups are preferred, and especially 1 carbon atoms.
~ 8 alkyl groups, C6-10 aryl groups, C1-10 acyl groups, C1-8 alkoxy groups, C1-10 acylamino groups are preferred. The heterocyclic group represented by R ⁴ , R ⁶ , R ⁸ , R ⁹ and R ¹⁰ is preferably a 5- to 7-membered ring group containing a nitrogen, sulfur or oxygen atom as a ring atom, and particularly preferably a ring. An unsaturated 5-membered ring group containing nitrogen, sulfur and oxygen atoms as atoms is preferable.

R ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ¹¹ and R
Specific examples of the alkyl group, aryl group, heterocyclic group and acyl group represented by ¹² include a methyl group, an ethyl group and n.
-Propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n-octyl group, 2 -Ethylhexyl group, n-decyl group, n-dodecyl group, cyclopentyl group, cyclohexyl group, benzyl group, 2-phenethyl group, 1-phenethyl group, dichloromethyl group, trichloromethyl group, trifluoromethyl group,
Examples thereof include a phenyl group, p-tolyl group, tetrahydrofurfuryl group, 2-furylmethyl group, acetyl group, propionyl group, benzoyl group and octanoyl group. Further, specific examples of the alkyl group, aryl group, heterocyclic group, acyl group, alkoxy group or acylamino group represented by R ⁴ , R ⁶ , R ⁸ , R ⁹ and R ¹⁰ include a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group,
n-pentyl group, i-pentyl group, n-hexyl group, n
-Octyl group, 2-ethylhexyl group, n-decyl group,
n-dodecyl group, cyclopentyl group, cyclohexyl group, benzyl group, 2-phenethyl group, 1-phenethyl group, dichloromethyl group, trichloromethyl group, trifluoromethyl group, phenyl group, p-tolyl group, thienyl group, furyl group , Pyrrolyl group, imidazolyl group, thiazolyl group, pyrazolyl group, acetyl group, pivaloyl group, benzoyl group, methoxy group, butoxy group, octyloxy group, hydroxy group, acetylamino group, pivaloylamino group and benzoylamino group. In addition, an alkyl group, an alkoxy group, an aryl group,
A halogen atom or the like may be substituted.

When Ar ¹ or Ar ² contains a benzene ring, the carbon atom of the benzene ring may be substituted with one or more substituents. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, an acylamino group, and a halogen atom. Examples of the alkyl group, the aryl group, an alkoxy group, and an acylamino group include R ⁴ , R ⁶ ,
The same groups as the alkyl group, aryl group, alkoxy group and acylamino group represented by R ⁸ , R ⁹ and R ¹⁰ can be mentioned. Examples of the halogen atom include Cl atom.

As Ar ¹ or Ar ² , a 4-substituted aminophenyl group and an indol-3-yl group represented by the following structural formulas are preferable.

[0018]

[Chemical 6]

R ²¹ , R ²² and R ²³ in the above structural formula represent a hydrogen atom, an alkyl group or an aryl group, and R ²⁴ represents
It represents a hydrogen atom, an alkyl group, an aryl group, an acyl group or an alkoxycarbonyl group. Examples of the alkyl group and aryl group of R ²¹ , R ²² and R ²³ include R ¹ , R ² and
The same groups as the alkyl group and aryl group represented by R ³ , R ⁵ , R ⁷ , R ¹¹ and R ¹² can be mentioned. Also, R
The alkyl group, aryl group and acyl group of ²⁴ are the same as those described above for R.
^An alkyl group represented by ⁴ , R ⁶ , R ⁸ , R ⁹ and R ¹⁰ ;
Examples thereof include those similar to the aryl group and the acyl group.
The alkoxycarbonyl group of R ²⁴ has a total carbon number of 2 to 6
Preferred are, for example, a methoxycarbonyl group,
Examples thereof include an ethoxycarbonyl group and a butoxycarbonyl group. Further, the phenyl group and indole-3-
The carbon atom of the benzene ring of the yl group may have a substituent, and as the substituent, a group capable of substituting on the carbon atom of the benzene ring when Ar ¹ or Ar ² includes a benzene ring is mentioned above. The same can be mentioned as mentioned above. Both Ar ¹ and Ar ² are preferably indol-3-yl groups in order to obtain a red or magenta color tone in the dye, and either Ar ¹ or Ar ² is 4 in order to obtain a blue to cyan color tone. It is preferably a -substituted aminophenyl group.

[0020] In the general formula ^{(1), -Z 1 =,} - Z 2 = and -Z ³ = is, CR =, or represents -N =, the R is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic Represents a group, an acyl group, an alkoxy group, a hydroxy group, a halogen atom or an acylamino group. The alkyl group, the aryl group,
Examples of the acyl group, alkoxy group and acylamino group are the same as the alkyl group, aryl group, acyl group, alkoxy group and acylamino group represented by R ⁴ , R ⁶ , R ⁸ , R ⁹ and R ^{10 above.} Can be mentioned. Examples of the halogen atom include Cl atom. The heterocyclic group is preferably a 5- to 7-membered ring group containing nitrogen, sulfur or oxygen atom as a ring atom, and particularly preferably an unsaturated 5-membered ring group containing nitrogen, sulfur or oxygen atom as a ring atom. preferable.

In the general formula (1), Mtl represents an m-valent metal atom and m represents an integer of 1 to 4, preferably 2 or 3. As the divalent metal, zinc, cobalt,
Examples include nickel and copper, examples of the trivalent metal include iron and aluminum, and examples of the tetravalent metal include titanium.
Of these, zinc, cobalt, nickel and copper are preferable. Further, Mtl may be a ligand, but any ligand may be used as long as it can coordinate with a metal. Y and X are
It represents a group capable of forming an ionic bond with Mtl. Examples of -Y- include those shown below, but the present invention is not limited thereto.

[0022]

[Chemical 7]

Of the two bonds of the above divalent group, the bond shown on the right side bonds to Mtl (for example, in the case of an ester bond, an O-bond). As the divalent groups R ³¹ , R ³² and R ³³ , a hydrogen atom, an alkyl group, an aryl group, a substituted carbonyl group, a substituted sulfonyl group and a heterocyclic group are preferable. The alkyl group or aryl group is preferably an alkyl group having 1 to 16 carbon atoms or an aryl group having 6 to 12 carbon atoms, and particularly preferably an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms. The substituted carbonyl group preferably has 1 to 18 carbon atoms in total, and the substituted sulfonyl group preferably has 1 to 12 carbon atoms. The heterocyclic group is preferably a 5- to 7-membered ring group containing a nitrogen atom, a sulfur atom or an oxygen atom as a ring atom, and particularly preferably an unsaturated 5 to 6-membered ring group containing a nitrogen atom, a sulfur atom or an oxygen atom. Ring groups are preferred. R ³¹ , R ³² and R
Examples of the alkyl group, aryl group, substituted carbonyl group, substituted sulfonyl group, and heterocyclic group represented by ³³ include a methyl group, an ethyl group, a hexyl group, a phenyl group, an acyl group, a phenylacetyl group, a phenoxyacetyl group, and a methylsulfonyl group. Group, tolylsulfonyl group, 2-thienyl group, 2-
A furyl group, a 2-pyridyl group and the like can be mentioned.

X- which is a group capable of forming an ionic bond with Mtl
For R⁴¹-Y-, F-, Cl-, Br-, I-, SC
N-, BF_Four-, PF₆-, SbCl_FiveAnd the like are preferable.
Y has the same meaning as Y in formula (1), and R⁴¹Is the above
R³¹, R³²And R³³Is synonymous with. In addition, the general formula
(X) in (1)_mnX has one bond is (m-
Not only does (N) exist, but X is (m-
n) having one bond (X)_mnInto the category of
It Also, A^-Represents a counter anion, but A in the molecule^-Is n
In addition to the case where individual anions are present, the counter anion is an n-valent polyvalent
It may be a nonion. A^-As R⁴¹-Y^-, F ^-,
Cl^-, Br^-, I^-, SCN^-, BF_Four ^-, PF₆ ^-, SbC
l_Five ^-Anions of X mentioned above as X- (X^-)But
Preferred examples include:

Next, the method for producing the triphenylmethane compound of the present invention will be described. The triphenylmethane compound of the present invention can be produced, for example, by reacting a compound represented by the following structural formula with a metal compound in an organic solvent. In the structural formulas below, Ar ¹ , Ar ² , and −
Z ¹ =, -Z ² =, -Z ³ = and Y are represented by the general formula (1).
Is synonymous with that in. As the metal compound, chlorides, bromides, iodides, acetates, sulfates of zinc, cobalt, nickel, copper, iron, aluminum and the like can be used.

[0026]

[Chemical 8]

The compound represented by the above structural formula can be produced according to the method described in JP-B-64-1856, JP-A-62-270662 and the like. Also, A
When r ¹ and Ar ² are the same, JP-A-7-20
The compound of the above structural formula can be produced by the method described in Japanese Patent No. 6866.

Specific examples of the triphenylmethane compound of the present invention are shown below, but the invention is not limited thereto.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

[0033]

[Table 5]

[0034]

[Table 6]

[0035]

[Table 7]

[0036]

[Table 8]

[0037]

[Chemical 9]

The above-mentioned triphenylmethane compounds include those soluble in an aqueous medium, those sparingly soluble in an aqueous medium, those soluble in an oily medium, and those sparingly soluble in an oily medium,
Although the kind of the substituent does not always determine the solubility in various media, in general, the OH group in the molecule,
At least one hydrophilic group such as —CO ₂ H, —SO ₃ H, —PO ₃ H, quaternary ammonium group, —CO ₂ M _{1 / n} and —SO ₃ M _{1 / n,} preferably 2 to 4 hydrophilic groups. By introducing it, solubility in the aqueous medium can be imparted. When the oily medium is an aromatic hydrocarbon compound such as naphthalene or diphenylethane, the solubility of the triphenylmethane compound in the medium can be improved by including three or more aromatic rings and / or hetero rings in the molecule. Can be given. When the oily medium is an ester compound or an amide compound, solubility in the medium can be imparted by introducing at least one ester group or preferably two or more ester groups or amide groups into the triphenylmethane compound. When making a triphenylmethane compound insoluble or sparingly soluble in an oily medium, a structure combining a protonic group capable of intermolecular hydrogen bonding and its acceptor group, and increasing the planarity of the molecule by intramolecular hydrogen bonding As a structure capable of intramolecular hydrogen bonding capable of controlling the packing structure of crystals, it may be insoluble or sparingly soluble in the medium. Further, it may be made insoluble or sparingly soluble by designing a rake structure or the like by forming a salt with a metal. Further, when the molecular design as described above is not performed, it may be sparingly soluble in an aqueous medium or soluble in an oily medium.

[Aqueous Ink] In the aqueous ink of the present invention, a triphenylmethane compound represented by the general formula (1), particularly a compound which is soluble or slightly soluble in an aqueous medium, is dissolved or dispersed in an aqueous medium. Can be prepared. As the aqueous medium, water or a mixed solvent mainly composed of water and a water-soluble organic solvent is used. Examples of the water-soluble organic solvent include methanol, ethanol,
Alcohols such as propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol,
Polyhydric alcohols such as polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, and thiodiglycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, tri Chi glycol monomethyl ether, triethylene glycol monoethyl ether, glycol derivatives such as ethylene glycol monophenyl ether; ethanolamine, diethanolamine, triethanolamine, N- methyldiethanolamine, N- ethyldiethanolamine, morpholine, N
Amines such as ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine;
Formamide, N, N-dimethylformamide, N, N
-Dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone, etc. A polar solvent; Two or more kinds of the water-soluble organic solvent may be used in combination with water.

The triphenylmethane compound represented by the general formula (1) may be dissolved or dispersed in a mixed solvent of water and the water-soluble organic solvent. When dispersing the compound in a mixed solvent, various dispersers (for example, ball mill, sand mill, attritor, roll mill, agitator mill, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, jet mill, ong mill, etc.). It is preferable to use the compound to atomize it. In addition, after the dye is dissolved in an organic solvent, it can be used by dispersing it in the mixed solvent using an appropriate dispersant or surfactant. Regarding the method for preparing the water-based ink, JP-A-5-148436 and JP-A-5-29531
No. 2, No. 7-97541, No. 7-82515, No. 7
Reference can be made to the method described in, for example, JP-A-118584.

The water-based ink of the present invention can be used not only as a general paint or dye, but also as an ink for inkjet recording.

[Image Recording Method] In the image recording method of the present invention, energy is applied to the water-based ink so that the ink droplets are ejected onto the recording medium to record an image of the ink on the recording medium. To do. An inkjet printer of any type may be used for this image recording method. For example, it may be used for both continuous type and on-demand type inkjet printers. The inkjet head system is not limited, and the inkjet head system can be preferably used in a printer equipped with a head of any system such as a bubble jet (R) system, a thermal jet system, or a system using ultrasonic waves.

Further, for example, a method of ejecting a large number of low density ink called photo ink in a small volume, a method of improving image quality by using a plurality of inks having substantially the same hue but different densities, and a colorless transparent ink are used. It can also be used for many new inkjet recording printers. In particular, the improvement effect is remarkably exhibited when the ink is used as an ink for a printer that ejects a large amount of ink having a high printing speed and a low density and forms an image close to a photograph.

Examples of the recording medium used in the image recording method of the present invention include plain paper, coated paper, and plastic film. It is preferable to use coated paper as the recording medium because the image quality and the image storage durability are improved.

In the image recording method of the present invention, a recording paper containing a mordant may be used as the recording medium.
In particular, it is preferable to use a recording paper containing an immobilized polymer mordant. Examples of polymer mordants are JP-A-48-28325, JP-A-54-74430, and JP-A-54-54430.
-124726, 55-22766, 55-1
No. 42339, No. 55-23850, No. 60-238.
No. 51, No. 60-23852, No. 60-23853
No. 60, No. 60-57836, No. 60-60643, No. 60-118834, No. 60-60643, and No. 60.
-118834, 60-122940, 60-
122941, 60-122942, 60-2
35134, JP-A-1-161236, U.S. Pat. Nos. 2,484,430, 2,548,564, 3,148,061, 3,309,690 and 4,115,124. No. 4,124,386, No. 4,193,800, No. 4,273,853, No. 4,282,305, No. 4,450,224. . In particular, JP-A-1-161236
No. pp. 212-215, it is preferable to use a recording paper containing the polymer mordant. When an image is formed using a recording paper containing the polymer mordant, an image with excellent image quality is obtained and the light resistance of the image is improved.

In the image recording method of the present invention, a recording paper containing an inorganic pigment can be used as the recording medium. The type of inorganic pigment is not particularly limited,
Any inorganic pigment can be used. For example, silica pigment, alumina pigment, titanium dioxide pigment, zinc oxide pigment, zirconium oxide pigment, mica-like iron oxide, lead white, lead oxide pigment, cobalt oxide pigment, strontium chromate, molybdenum pigment, smectite, magnesium oxide pigment, oxidation Calcium pigments, calcium carbonate pigments, mullite, etc. can be mentioned, and one kind or two or more kinds can be used.

In the image recording method of the present invention, recording paper containing various hydrophilic binders can be used as the recording medium. As the hydrophilic binder, it is possible to use any compound such as gelatin or its derivative, polyvinyl alcohol or its derivative, polyalkylene oxide or its derivative, and other superabsorbent polymer. For example, those described in JP-A-1-161236, pages 215 to 222 can be used. In the image recording method of the present invention, it is preferable to use recording paper containing a matting agent as the recording material. As the matting agent, conventionally known ones can be used, but as an example, JP-A 1-1
The thing described in 61236 page 263-264 can be used. In the image recording method of the present invention, recording paper hardened with a hardener can be used. There are no particular restrictions on the type of hardener, and known hardeners such as those described in JP-A-1-161236, page 222 can be used.

Various surfactants can be used in the constituent layers of the recording medium for the purpose of improving coating properties, improving peelability, improving sliding property, and preventing static electricity. Specific examples of the surfactant are disclosed in JP-A-62-173463 and JP-A-62-1.
It is described in various publications such as No. 83457. Further, an organic fluoro compound may be included for the above purpose. As a typical example of the organic fluoro compound, Japanese Patent Publication No. 57-9053
No. 8-17, JP-A Nos. 61-20994 and 62-62.
Examples thereof include fluorine-based surfactants described in each publication such as 135826, oil-based fluorine-based compounds such as fluorine oil, and hydrophobic fluorine-containing compounds such as solid fluorine-containing compound resins such as tetrafluoroethylene resin.

The constituent layers (including the back layer) of the recording medium contain various polymer latices for the purpose of improving the physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, and film cracking prevention. You can Specifically, JP-A-62-245258, JP-A-62-1316648,
Any of the polymer latices described in JP-A Nos. 62-110066 and the like can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or lower) is used for the mordant layer, cracking of the mordant layer can be prevented and curl can be improved, and when a polymer latex having a high glass transition point is used for the back layer. The curl prevention effect can be obtained. In the image recording method of the present invention, the constituent layers may contain an anti-fading agent. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex.
As an example, JP-A-1-161236, page 225-
Those described on page 247 can be used.

The recording medium may contain a fluorescent whitening agent. In particular, it is preferable to incorporate a fluorescent whitening agent in the recording medium or to make it contained in ink or the like and supply it to the recording medium from the outside. In the present invention, the support of the recording medium is not particularly limited, but both sides are polyolefin (for example, polyethylene, polystyrene,
Paper laminated with homopolymers such as polyethylene terephthalate and polybutene, copolymers of any combination of these, and plastic supports (however, white pigments such as titanium oxide and zinc oxide in polyolefin, cobalt blue and ultramarine blue, oxidation) It is also preferable to add a coloring dye such as neodymium).

[Oil-Based Ink] The oil-based ink of the present invention is a medium containing an oil-based medium which is liquid or solid at room temperature as a main component.
It can be prepared by dissolving or dispersing a compound represented by the general formula (1), particularly a soluble or sparingly soluble compound in the oily medium. Examples of the oil medium (organic solvent) that is liquid at room temperature include alcohols such as ethanol, pentanol, heptanol, octanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, and anise alcohol;
Ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether Glycol derivatives such as ethyl ether, ethylene glycol diacetate, ethylene glycol monoethyl ether acetate, propylene glycol diacetate;

Ketones such as benzyl methyl ketone, diacetone alcohol, cyclohexanone; ethers such as butyl phenyl ether, benzyl ethyl ether, hexyl ether; ethyl acetate, amyl acetate, benzyl acetate, phenyl ethyl acetate, phenoxy ethyl acetate,
Ethyl phenylacetate, benzyl propionate, ethyl benzoate, butyl benzoate, ethyl laurate, butyl laurate, isopropyl myristate, isopropyl palmitate, triethyl phosphate, tributyl phosphate, diethyl phthalate, dibutyl phthalate, malonic acid Diethyl, dipropyl malonate, diethyl diethyl malonate,
Diethyl succinate, dibutyl succinate, diethyl glutarate, diethyl adipate, dibutyl adipate, di (2-methoxyethyl) adipate, diethyl sebacate, diethyl maleate, dibutyl maleate, dioctyl maleate, diethyl fumarate, Esters such as dioctyl fumarate and 3-hexenyl cinnamate; hydrocarbon solvents such as petroleum ether, petroleum benzyl, tetralin, delican, 1-amylbenzene, dimethylnaphthalene; acetonitrile, formamide, N, N-dimethylformamide, N , N-dimethylacetamide, dimethyl sulfoxide, sulfolane, propylene carbonate, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-diethyldodecane amide and the like polar solvents; These solvents may be used alone or in combination of two or more.

The compound represented by the general formula (1) may be dissolved in the organic solvent, or may be dispersed in combination with a suitable dispersant. Regarding the method for preparing the oil-based ink, JP-A-3-231975 and JP-A-5-50888
The method described in Japanese Patent Publication No. 3 can be referred to. Furthermore, the vehicle described in paragraph 0013 of JP-A-9-176532 can be used, and the method described in the above-mentioned publication can be used as a method for producing the oil-based ink.

When an oily medium that is solid at room temperature is used as the medium for the oily ink of the present invention, it becomes a so-called solid ink, and the compound of the general formula (1) is solid at room temperature, but is heated by heating. It is prepared by dissolving or dispersing it in a phase change solvent that melts into a liquid state. Examples of the phase change solvent include beeswax, carnauba wax, rice wax, wood wax, jojoba oil, spermaceti wax, candelilla wax, lanolin, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, petrolactam. Natural waxes such as; polyethylene wax, chlorinated hydrocarbons, palmitic acid, stearyl acid, behenic acid, tiglic acid, 2-acetonaphthobehenic acid, 12-hydroxystearic acid, organic acids such as dihydroxystearic acid; dodecanol,
Tetradecanol, hexadecanol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, dodecenol, myricyl alcohol, tetracenol, hexadecenol, eicosenol, docosenol, pinene glycol, hinokiol, butynediol, nonanediol, isophthalyl Alcohol, messerine, hexanediol, decanediol, tetradecanediol, hexadecanediol,
Alcohols such as docosane diol, tetracosane diol, television neol, phenylglycerin, eicosane diol, octane diol, phenyl propylene glycol;

Phenols such as bisphenol A and p-α-cumylphenol; organic acid esters of the above organic acids such as glycerin, ethylene glycol and diethylene glycol; cholesterol stearate, cholesterol palmitate, cholesterol myristate, cholesterol behenate, Cholesterol fatty acid esters such as cholesterol laurate and cholesterol melicinate; saccharose stearate, saccharose palmitate, saccharose behenate, saccharose laurate, saccharose melicinate, lactose stearate, lactose palmitate, lactose behenate, lactate laurate, melicin. Acid fatty acid esters such as lactose; benzoylacetone, diacetobenzene, benzophenone, Kosanon, heptacosanone,
Ketones such as heptatriacontanone, hentriacontanone, stearone, laurone; oleic acid amide,
Lauric acid amide, stearic acid amide, ricinoleic acid amide, palmitic acid amide, tetrahydrofuranic 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-ethylenebisstearic acid amide, N, N-ethylenebisbehenic acid amide, N, N-xylylenebisstearic acid amide, N,
N-butylene bisstearic acid amide, N, N-dioleyl adipamic acid amide, N, N-dioleyl sebacic acid amide, N, N-distearyl sebacic acid amide, N,
N-distearyl terephthalic acid amide, phenacetin,
Amides such as toluamide and acetamide; sulfonamides such as p-toluenesulfonamide, ethylbenzenesulfonamide and butylbenzenesulfonamide;
Is mentioned.

The phase change temperature of the phase change solvent from solid to liquid is preferably 60 to 200 ° C, and 80 to 15
It is more preferably 0 ° C. The solid ink may be prepared by dissolving the compound represented by the general formula (1) in the phase change solvent that has been melted by heating, or may be used in combination with an appropriate dispersant or binder. It may be prepared by dispersing or dissolving. For the preparation method of solid ink,
The methods described in JP-A-5-186723 and JP-A-7-70490 can be referred to. Furthermore, JP-A-9
The vehicle described in paragraph 0013 of JP-A-176532 can be used, and the method described in the above publication can be used as a method for producing the oil-based ink.

As the oily medium which is liquid or solid at room temperature, a medium having a relatively low melting point (softening point) (for example, 70 ° C. or lower) and a medium having a relatively high melting point (120 to 200 ° C.) are used in combination. preferable. When used in combination, the robustness of the image portion of the formed image is improved, and color transfer or the like is less likely to occur even when a plurality of recording sheets on which images are formed are stacked, which is preferable. The oily medium preferably contains a polyamide-based, polyurethane-based, polyester-based, epoxy-based or polyacrylic-based resin compatible with the oily medium used. By using the resin in combination, the film strength of the oil-based ink can be further increased. The resin is preferably contained in an amount of 0.5 to 20 mass% with respect to the total mass of the oil-based ink of the present invention. Further, an additive having an action of improving the fastness of the dye, an antioxidant, a singlet oxygen quencher, an ultraviolet absorber and the like may be allowed to coexist.

The oil-based ink of the present invention can be used as an ink for inkjet recording. In particular, when the oily medium is solid at room temperature, it can be used as an ink composition of a so-called hot melt type (or wax jet type) inkjet recording device. Further, the oil-based ink of the present invention can be used as a recording material ink such as an ink sheet for thermal melt transfer or thermal sublimation transfer by coating or impregnating a substrate such as a cloth or a plastic film. In addition, common paints, dyes,
It can also be used as ballpoint pen ink and marker ink.

In the water-based and oil-based inks of the present invention,
The compound represented by the general formula (1) is preferably contained in an amount of 0.2 to 50% by mass, more preferably 0.5 to 25% by mass.

A dye other than the compound represented by the general formula (1) may be added to the water-based and oil-based inks of the present invention for the purpose of adjusting hue. Further, various additives may be added to the ink of the present invention, if desired.
As the additive, a viscosity modifier, a surface tension modifier, a specific resistance modifier, a film modifier, an ultraviolet absorber, an antioxidant,
Examples include anti-fading agents, anti-mold agents, anti-rust agents, dispersants, and surfactants. When the ink of the present invention is used as an inkjet recording ink, its viscosity is preferably adjusted to 40 cp or less, and its surface tension is 20
It is preferably adjusted to dyn / cm to 100 dyn / cm.

[Triphenylmethane Compound Dispersion] The triphenylmethane dispersion of the present invention (hereinafter sometimes referred to as “pigment dispersion”) is prepared by using the triphenylmethane compound of the present invention in a pigment dispersant. It is dispersed in an organic solvent and preferably contains a binder polymer having an acidic group. Further, as the triphenylmethane compound, among the compounds represented by the general formula (1), those which are hardly soluble in an oil medium (pigment) are used.

The dispersant can be roughly classified into a polymer dispersant and a low molecular weight compound dispersant. Examples of the polymer dispersant include polyacrylic acid salt, sodium maleate olefin copolymer, and terminal carboxyl group-containing polyester. (Japanese Patent Publication No. 54-34009), Tetrakis (2-
Hydroxyalkyl) polyester having an acidic group and / or a basic group having ethylenediamine as a starting material (JP-A-2-245231), macromonomer (oligomer having ethylenically unsaturated group at terminal), monomer having hydroxyl group, Copolymer consisting of four kinds of monomers containing a carboxy group and monomers other than these (JP-A-8-2
No. 59876) is known. Further, as the low molecular compound dispersant, sorbitan fatty acid ester,
Polyoxyethylene alkylamines, alkyldiamines, alkanolamine derivatives (US Pat. No. 35365)
No. 10) and the like, and examples of dispersants in which a pigment mother nucleus is introduced are disclosed in JP-B-5-72943 and JP-A-8-48.
No. 890.

The organic solvent is not particularly limited,
It can be appropriately selected from known ones, for example,
(Poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether and acetic acid esters thereof; ethyl acetate , N-propyl acetate, i-acetic acid
Acetic acid esters such as propyl, n-butyl acetate, i-butyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene; ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone; ethanol, propanol, butanol, Examples thereof include alcohols such as hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin. These may be used alone or in combination of two or more. Among these, alkylene glycol monoalkyl ethers, acetic acid esters thereof, acetic acid esters, methyl ethyl ketone, and the like are preferable.

The content of the triphenylmethane compound in the pigment dispersion is usually about 5 to 80% by mass, preferably 10 to 70% by mass. If the content is less than 5% by mass, the coloring power may not be sufficient,
If it exceeds 0% by mass, the viscosity of the pigment dispersion may increase.

The content of the pigment dispersant in the pigment dispersion is usually 0.1 to 10 relative to 100 parts by weight of the pigment.
About 0 parts by mass is suitable, and 1 to 30 parts by mass is preferable. If the content is less than 0.1 parts by mass, the viscosity of the pigment dispersion may increase, and if it exceeds 100 parts by mass, it is difficult to adjust the chromaticity when producing a color filter or the like. May be.

The content of the organic solvent in the pigment dispersion is
About 10 to 1000 parts by mass is usually suitable for 100 parts by mass of the pigment, and 20 to 500 parts by mass is preferable. If the content is less than 10 parts by mass, the viscosity of the pigment dispersion may increase, and if it exceeds 1000 parts by mass, it may be difficult to secure a space during storage.

(Binder Polymer Having Acidic Group) The pigment dispersion of the present invention preferably contains a binder polymer having an acidic group. The binder polymer having an acidic group is capable of imparting both the dispersion stability of the pigment and the alkali developability when used as a colored photosensitive composition described below. For example, (meth) acrylic acid And a (meth) acrylic acid ester copolymer, a styrene / maleic anhydride copolymer, a reaction product of a styrene / maleic anhydride copolymer and an alcohol, and the like. These may be used alone or in combination of two or more. Among these, excellent in pigment dispersibility, when used as a colored photosensitive composition, polyfunctional monomer, excellent compatibility with the photopolymerization initiator, alkali developer solubility, organic solvent solubility, strength, softening Those having an appropriate temperature and the like are preferable, and specifically, a copolymer of (meth) acrylic acid and (meth) acrylic acid ester is preferable.

The weight average molecular weight of the binder polymer having an acidic group is preferably about 5,000 to 200,000. If the weight average molecular weight is less than 5,000, there may be a problem in forming a coating film when used as a colored photosensitive composition, and if it exceeds 200,000, the viscosity of the colored photosensitive composition becomes high. There is.

The content of the binder polymer having an acidic group in the pigment dispersion is usually about 10 to 200 parts by mass with respect to 100 parts by mass of the triphenylmethane compound (hereinafter sometimes referred to as "pigment"). And preferably 20 to 150 parts by mass. The content is 1
If it is less than 0 parts by mass, the steric repulsion effect may not be obtained, and if it exceeds 200 parts by mass, the viscosity of the dispersion may increase.

The pigment dispersion liquid of the present invention can be prepared, for example, by the following method. 1) A method in which a composition obtained by previously mixing a pigment and a pigment dispersant is added to an organic solvent (or vehicle) and dispersed. 2) A method in which a pigment and a pigment dispersant are separately added and dispersed in an organic solvent (or vehicle). 3) A method in which the pigment and the pigment dispersant are separately dispersed in an organic solvent (or vehicle) in advance, and the resulting dispersions are mixed (in this case, the pigment dispersant may be dispersed only in the organic solvent). 4) A method of dispersing a pigment in an organic solvent (or vehicle) and then adding a pigment dispersant to the obtained dispersion.

The vehicle refers to a portion of a medium in which the pigment is dispersed when the coating material is in a liquid state, and is a liquid component (binder) that binds to the pigment and hardens the coating film.
And a component (the organic solvent) for dissolving and diluting the same.

The disperser used to disperse the pigment is not particularly limited, and examples thereof include known dispersers such as a kneader, roll mill, attritor, super mill, dissolver, homomixer and sand mill.

The pigment dispersion can be used for forming a colored image, and can be used, for example, as a component of a colored photosensitive composition described later. Further, a coating solution containing the pigment dispersion is applied onto a support and dried to form a layer of the pigment dispersion, or a layer of the pigment dispersion formed on a temporary support is applied to the support. To a known positive or negative photosensitive resin composition layer, exposed and developed, and then unexposed to the photosensitive resin composition layer and the pigment dispersion in the same region. It can be performed by a method of removing the liquid layer.

[Colored Photosensitive Composition] The colored photosensitive composition of the present invention comprises at least the above-mentioned triphenylmethane compound dispersion, the above-mentioned binder polymer having an acidic group, and an ethylenically unsaturated double bond. It contains a polyfunctional monomer having two or more and a photopolymerization initiator. Examples of the polyfunctional monomer having two or more ethylenically unsaturated double bonds include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate. . Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) )ether,
Tri (acryloyloxyethyl) isocyanurate,
After addition reaction of ethylene oxide and propylene oxide to polyfunctional alcohol such as tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane and glycerin (meth)
Acrylate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 5
No. 0-6034, urethane acrylates described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 Polyester acrylates and polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, can be mentioned. More preferable examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

As the photopolymerization initiator, US Pat. No. 236766 is used.
Substituted with a vicinal polyketaldonyl compound disclosed in No. 0, an acyloin ether compound described in US Pat. No. 2448828, an α-hydrocarbon described in US Pat. No. 2722512. Aromatic acyloin compounds, polynuclear quinone compounds described in U.S. Pat. Nos. 3,046,127 and 2,951,758, triarylimidazole dimers and p-
Combination of aminoketones, benzothiazole compound and trihalomethyl-s-triazine compound described in JP-B-51-48516, trihalomethyl-s-triazine compound described in U.S. Pat. No. 4,239,850, U.S. Pat. The trihalomethyl oxadiazole compound etc. which are described in the specification are mentioned. Particularly preferred are trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer.

The content of the triphenylmethane compound (pigment) in the colored photosensitive composition is appropriately about 5 to 50% by mass, preferably 10 to 30% by mass, and the content of the monomer is 5%. The content of the photopolymerization initiator is preferably about 0.5 to 20% by mass, and more preferably 2 to 15% by mass. Further, the content of the binder having an acidic group is appropriately about 50 to 95 mass%, preferably
It is 60 to 90 mass%. The colored photosensitive composition of the present invention is used for forming a multicolor image on a substrate such as an electrophotographic toner, a printing ink, a color display plate and a color proof, and a color filter used for a liquid crystal display and the like. It is preferably used.

[0077]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. <Example 1> (Synthesis of triphenylmethane compound (B-1)) (1) Synthesis of phthalide compound represented by the following structural formula (X-1): 30.8 g of ketocarboxylic acid represented by the following structural formula (A)
And 16.3 g of the dialkylaniline derivative represented by the following structural formula (B) were reacted in 30 ml of acetic anhydride at 75 ° C. for 3 hours. Isopropyl alcohol 3 in the reaction mixture
0 ml was added, the internal temperature was cooled to 5 ° C., and the precipitated crystals were collected by filtration. Then, it was recrystallized from isopropyl alcohol and ethyl acetate to obtain 34.1 g of the compound of the chemical formula (X-1). The yield was 75%.

[0078]

[Chemical 10]

(2) Triphenylmethane compound (B-
Synthesis of 1) 4.5 g of the phthalide compound (X-1) obtained in (1) above was dissolved in 50 ml of ethyl acetate, and a solution of 1.36 g of zinc chloride in 50 ml of acetone was added thereto at room temperature. 2 at the same temperature
The mixture was stirred for 4 hours (crystals started to precipitate after 30 minutes). The reaction solution was cooled with ice water, filtered, and dried to obtain 3.2 g of blue-green crystals having metallic luster. When this crystal was measured by FAB-MS (matrix m-nitrobenzyl alcohol), a molecular weight component of 552 was detected. Moreover, when the zinc content in the molecule was examined by an atomic absorption method (AAS flame method), it was confirmed that the ratio of the phthalide compound (X-1) as a raw material to zinc was about 1: 1.

<Example 2> (Synthesis of triphenylmethane compound (B-2)) In Example 1, the amount of zinc chloride was ½ (0.68).
3.1 g of a blue-green crystal having a metallic luster was obtained in the same manner as in Example 1 except that g) was changed and the mixture was stirred at an internal temperature of 60 ° C. for 48 hours.
g was obtained. A molecular weight component of 970 was confirmed by FAB-MS. The ratio of phthalide compound (X-1) to zinc is about 2:
It was 1.

<Example 3> (Synthesis of triphenylmethane compound (B-5)) Example 1 was repeated except that zinc iodide 3.19 g was used in place of zinc chloride 1.36 g. The same reaction was performed to obtain 3.8 g of crystals of the triphenylmethane compound (B-5). A molecular weight component of 643 was confirmed by FAB-MS.

<Example 4> (Synthesis of triphenylmethane compound (B-6)) A triphenylmethane compound was prepared in the same manner as in Example 3, except that the amount of zinc iodide used was halved. 3.1 g of crystals of (B-6) were obtained. 9 by FAB-MS
70 molecular weight components were identified.

<Example 5> (Synthesis of triphenylmethane compound (B-13)) Instead of zinc chloride of Example 1, copper chloride (CuCl ₂ ) 1.
2.9 g of crystals of the triphenylmethane compound (B-13) was obtained in the same manner as in Example 1 except that 34 g was used. F
A molecular weight component of 640 was confirmed by AB-MS.

<Example 6> (Synthesis of triphenylmethane compound (B-14)) In Example 5, except that the amount of copper chloride used was halved.
In the same manner as in Example 5, the triphenylmethane compound (B
2.7 g of crystals of -14) were obtained. 96 by FAB-MS
A molecular weight component of 7 was confirmed. <Example 7> (Aqueous ink) An aqueous ink having the following composition was prepared. Dye (Exemplified Compound B-1) 4 parts by mass (Compound represented by the general formula (1)) Diethylene glycol 9 parts by mass Tetraethylene glycol monobutyl ether 9 parts by mass Glycerin 7 parts by mass Diethanolamine 1 part by mass Water 70 parts by mass or more After stirring the components for 1 hour while heating at 30 to 40 ° C., pressure filtration was performed using a microfilter having an average pore size of 0.8 μm and a diameter of 47 mm to obtain the target ink.

An ink jet printer PM-700C (manufactured by Seiko Epson Corp.) was used to print on the inkjet paper, Super Photo Grade (photoglossy paper) manufactured by Fuji Photo Film, using the ink thus prepared to obtain an image sample.

Using the obtained image sample, hue and light resistance were evaluated. The evaluation results are shown in Table 9 below. (Evaluation of hue) The hue of the image area was visually evaluated. (Evaluation of light resistance) An image sample is referred to as "Atlas C.I.
5 weather meter, irradiate with xenon light (85,000 lux) for 3 days, measure the image density before and after irradiation with xenon using a reflection densitometer (“X-Rite 310TR”), and the dye remains. The rate was calculated. The higher the residual ratio of the dye, the higher the light fastness. The reflection density before irradiation was evaluated at three points of 1, 1.5, and 2.0. At any of the concentrations, the dye residual rate was 80% or more as ◯, 50 to 80% as Δ, and other than that. The case was evaluated as x.

<Examples 8 to 10> (Aqueous ink) An ink was prepared in the same manner as in Example 7 except that the dyes (Exemplary Compound B-1) used in Example 7 were replaced with the dyes shown in Table 9 below. It was produced and evaluated for hue and light resistance in the same manner as in Example 7. The evaluation results are shown in Table 9 below.

<Example 11> (Aqueous ink) An ink was prepared in the same manner as in Example 7 except that 4 parts by mass of the dye (Exemplified Compound B-1) used in Example 7 was replaced with the following dye. Dye (Exemplary Compound B-1) 1.3 parts by mass Dye (compound represented by Structural Formula 1 below) 1.3 parts by mass Dye (compound represented by Structural Formula 2 below) 1.4 parts by mass

[0089]

[Chemical 11]

With respect to the prepared ink, the hue and light resistance were evaluated in the same manner as in Example 7. The evaluation results are shown in Table 9 below.

[0091]

[Table 9]

As shown in Table 9, by using the triphenylmethane compound of the present invention, an ink jet recording ink having good light resistance can be obtained.

<Example 12> (Oil-based ink) 1-methylnaphthalene 35 parts by mass 2,6-dimethylnaphthalene 60 parts by mass Dye (Exemplified Compound B-7) 5 parts by mass The mixture having the above composition is stirred at 60 ° C for 5 hours. Then, the dye was dissolved in an oil medium of 1-methylnaphthalene or 2,6-dimethylnaphthalene to obtain an oil-based ink. This is the hot melt type inkjet printer "JOLT SJ0
1A PS2 "(trade name, product of Hitachi Koki Co., Ltd.) was used to print on electrophotographic paper (product of Xerox Co.). When the image portion of the formed image was visually observed, the image portion was free from bleeding and had an excellent cyan hue. When the image area was rubbed with a hand 10 seconds after the image was recorded, no stain was generated on the background area around the image and the rubbed hand. Further, irradiation with a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.) was performed for 100 hours, but the discoloration and fading of the image was small. Further, even after the ink composition was stored at 60 ° C. for 3 months, the dye and the medium did not separate.

<Example 13> (Oil-based ink) Dibutyl naphthalate 50 parts by mass Naphthalene-2,6-dicarboxylic acid diethyl ester 43 parts by mass Dye (Exemplified compound B-7) 7 parts by mass Using the mixture having the above composition, An oil-based ink was prepared in the same manner as in Example 12. When the obtained oil-based ink was evaluated in the same manner, good results were obtained as in Example 12.

<Example 14> (Oil-based ink) Dibutyl adipate 30 parts by weight Benzyl benzoate 63 parts by weight Dye (Exemplified compound B-7) 7 parts by weight Using the mixture having the above composition, an oil-based ink was prepared in the same manner as in Example 12. Was produced. When the obtained oil-based ink was evaluated in the same manner, good results were obtained as in Example 12.

<Example 15> (Oil-based ink) Benzylbenzoate 40 parts by mass 2-Methylnaphthalene 20 parts by mass Stearic acid amide 35 parts by mass Dye (Exemplified Compound B-7) 5 parts by mass Implemented using the mixture having the above composition. An oil-based ink was prepared in the same manner as in Example 12. When the obtained oil-based ink was evaluated in the same manner, good results were obtained as in Example 12.

<Example 16> (Oil-based ink) Tricresyl phosphate 65 parts by mass Dibutyl adipate 31 parts by mass Dye (Exemplified compound B-7) 4 parts by mass Oilyness similar to Example 12 using the mixture of the above composition. An ink was made. When the obtained oil-based ink was evaluated in the same manner, good results were obtained as in Example 12.

<Example 17> (Oil-based ink) An oil-based ink was prepared in the same manner as in Example 12 except that the dye was changed to the exemplified compound A-7. The obtained hue was cyan, and the same evaluation of the oil-based ink as in Example 12 was obtained.

<Example 18> (Oil-based ink) An oil-based ink was prepared in the same manner as in Example 12 except that the dye was changed to the exemplified compound C-7. The obtained hue was magenta, and the same evaluation of the oil-based ink as in Example 12 was obtained.

<Example 19> (Oil-based ink) An oil-based ink was prepared in the same manner as in Example 12 except that the dye was changed to Exemplified Compound D-7. The obtained hue was green, and the same evaluation of the oil-based ink as in Example 12 was obtained.

<Example 20> (Oil-based ink) Example 12 except that the dye is changed to the exemplified compound B-24.
An oil-based ink was prepared in the same manner as in. The obtained hue was green, and the same evaluation of the oil-based ink as in Example 12 was obtained.

<Example 21> (Oil-based ink) 1-methylnaphthylene 35 parts by mass 2,6-dimethylnaphthalene 55 parts by mass Dye (Exemplified compound C-7) 3 parts by mass Dye (represented by the following structural formula 3) Compound) 3 parts by mass Dye (compound represented by Structural Formula 4 below) 4 parts by mass Using the mixture having the above composition, an oil-based ink (hue: black) was prepared in the same manner as in Example 12. When the same evaluation was performed on the obtained oil-based ink, good results were obtained as in Example 12 (however, the hue of the image area was black).

[0103]

[Chemical 12]

<Example 22> (Oil-based ink) Tricresyl phosphate 60 parts by mass Dibutyl adipate 20 parts by mass Compound 10 represented by the following structural formula 5 10 parts by mass Dye (Exemplified compound B-7) 5 parts by mass Mixture of the above composition An oil-based ink (hue: cyan) was prepared in the same manner as in Example 12. When the obtained oil-based ink was evaluated in the same manner, good results were obtained as in Example 12.

[0105]

[Chemical 13]

<Example 23> (Oil-based ink) Tricresyl phosphate 60 parts by mass Dibutyl adipate 15 parts by mass The compound represented by the structural formula 5 10 parts by mass The compound represented by the following structural formula 6 10 parts by mass Dye (Exemplary Compound B-7) 5 parts by mass Using the mixture having the above composition, an oil-based ink (hue: cyan) was prepared in the same manner as in Example 12. When the obtained oil-based ink was evaluated in the same manner, good results were obtained as in Example 12.

[0107]

[Chemical 14]

<Example 24> (Oil-based ink) Similar to Example 23 except that the compound represented by the structural formula 6 was used in place of the compound represented by the structural formula 6 in Example 23. To produce an oil-based ink (hue: cyan). When the same evaluation was performed on the obtained oil-based ink, the same good result as in Example 23 was obtained.

[0109]

[Chemical 15]

<Example 25> (Pigment dispersion) A blue pigment dispersion having the following composition was prepared. Compound of the present invention (Exemplified compound B-2) 6.4 g Dispersant (ethylenedinitrilotetraethanol) 0.6 g [(HOCH ₂ CH ₂ ) ₂ NCH ₂ CH ₂ N (CH ₂ CH ₂ OH) ₂ ] methacrylic acid / Benzyl methacrylate copolymer 15.8 g (molar ratio 28/72, weight average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution) 1-methoxy-2-propyl acetate 57.2 g

The blue pigment dispersion having the above composition was dispersed in a motor mill M-50 (manufactured by Eiger) using zirconia beads having a diameter of 0.65 mm at a peripheral speed of 9 m / s for 9 hours,
A red pigment dispersion was prepared.

The following evaluations were carried out on the obtained pigment dispersions. (1) Viscosity measurement: With respect to the obtained pigment dispersion liquid, its viscosity was measured using an E-type viscometer to evaluate the degree of thickening. The results are shown in Table 10.

(2) Contrast measurement: The obtained pigment dispersion liquid was applied onto a glass substrate so as to have a thickness of 6 μm to prepare a sample. This sample was placed between two polarizing plates, the amount of transmitted light when the polarization axes were parallel and when the polarization axes were vertical was measured, and the ratio was defined as the contrast (“199
Year 0 7th Color Optical Conference, 512 color display 1
0.4 "size TFT-LCD color filter, Ueki, Koseki, Fukunaga, Yamanaka"). The results are shown in Table 10.
Shown in.

<Examples 26 to 30> Pigment dispersions were prepared in the same manner as in Example 25 except that the compounds shown in Table 10 below were used instead of the compound B-2 in Example 25, and the viscosity and The contrast was measured. The results are shown in Table 10.

[0115]

[Table 10]

<Example 31> (Colored photosensitive composition) The following compositions were mixed to prepare a colored photosensitive composition for producing a color filter. Blue pigment dispersion of Example 25 32.4 g Methacrylic acid / benzyl methacrylate copolymer 9.0 g (molar ratio 28/72, weight average molecular weight 30,000, 30% 1-methoxy-2-propylacetate solution) Pentaerythritol tetraacrylate 5.2 g 4- [p-N, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -5-triazine 0.2 g Hydroquinone monomethyl ether 0.01 g 1-methoxy- 2-propyl acetate 62g

The above mixing was carried out by a motor mill M50 (manufactured by Eiger) using zirconia beads having a diameter of 0.65 mm at a peripheral speed of 9 m / s for 9 hours. The obtained colored photosensitive composition for producing a color filter was applied onto a glass substrate using a spin coater and dried at 100 ° C. for 2 minutes to form a film having a thickness of about 2 μm. Next, under a nitrogen stream, it was exposed with an ultra-high pressure mercury lamp and then developed with a 1% sodium carbonate aqueous solution. The contrast of the obtained colored film was measured in the same manner as in Example 25. The results are shown in Table 11.

<Examples 32 to 36> (Colored photosensitive composition) A color filter was prepared in the same manner as in Example 31 except that the pigment dispersion of Example 31 was replaced with the pigment dispersions of Examples 26 to 30. A colored photosensitive composition for use was prepared, a colored film was similarly prepared, and the contrast was measured. The results are shown in Table 11.

[0119]

[Table 11]

From the results shown in Tables 10 and 11, it can be seen that the pigment dispersion liquid of the present invention has a low viscosity, and a colored photosensitive composition using the pigment dispersion liquid can obtain high contrast. It is speculated that the high contrast is obtained because the pigment particles are dispersed in a finely divided state.

[0121]

The triphenylmethane compound of the present invention is
It is a stable metal chelate dye that has a good hue and is robust against light, heat, humidity, etc. Therefore, when an image is formed using the oil-based ink, the water-based ink, and the dispersion liquid that use this dye, an image having good fastness to light, heat, humidity and the like can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07D 401/14 C07D 403/06 4J039 403/06 C09B 11/26 A C09B 11/26 B C C09D 11/00 C09D 11/00 B41J 3/04 101Y F term (reference) 2C056 EA13 FC01 2H086 BA02 BA53 BA54 BA56 BA59 4C055 AA01 BA02 BA57 BB14 BB15 CA02 CA27 CB02 DA01 GA02 4C063 BC03 BD01 BC34 DD56 040302 BC05 BC07 BC20 BC33 BC44 BC49 BC50 BC51 BC52 BC65 BE01 CA03 CA04 CA06 CA07 GA06 GA24

Claims (9)

[Claims] 1. A triphenylmethane compound represented by the following general formula (1). [Chemical 1] In the general formula (1), Ar ¹ and Ar ² each independently represent an aryl group or a heterocyclic group,
¹ =, - Z ² =, and -Z ³ = is, CR =, or -N
=, R represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxy group, a hydroxy group, a halogen atom or an acylamino group, Mtl represents a metal atom, and Y and X represent Mtl. It represents a group capable of ionic bonding, and A ⁻ represents a counter anion. m represents the valence of a metal atom and represents an integer of 1 to 4. n represents an integer of 1 to 4. However, m ≧ n. 2. The Ar ¹ and Ar ² in the general formula (1) is a 4-substituted aminophenyl group or an indol-3-yl group represented by the following structural formula, wherein The described triphenylmethane compound. [Chemical 2] In the structural formula, R ²¹ , R ²² and R ²³ represent a hydrogen atom, an alkyl group or an aryl group, R ²⁴ represents a hydrogen atom,
It represents an alkyl group, an aryl group, an acyl group or an alkoxycarbonyl group. 3. An oil-based ink containing a triphenylmethane compound represented by the general formula (1). 4. An aqueous ink containing a triphenylmethane compound represented by the general formula (1). 5. An image recording method, wherein energy is applied to the water-based ink according to claim 4 to cause the droplets of the ink to be ejected onto a recording medium to record an image of the ink on the recording medium. 6. A triphenylmethane compound dispersion liquid in which the triphenylmethane compound represented by the general formula (1) is dispersed in a liquid. 7. A triphenylmethane compound dispersion liquid containing the triphenylmethane compound represented by the general formula (1), an organic solvent and a dispersant. 8. The triphenylmethane compound dispersion liquid according to claim 7, which further contains a binder polymer having an acidic group. 9. A colored photosensitive composition containing the triphenylmethane compound dispersion according to claim 6 or 7, a polyfunctional monomer having two or more ethylenically unsaturated double bonds, and a photopolymerization initiator. object.