JP2003221532A - Ink and method for ink jet recording - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink having excellent preservation stability, radiation curability and water, light and ozone resistances and especially suitable for ink jet recording. <P>SOLUTION: This ink comprises a monomer having a polymerizable group and an oil-soluble dye represented by general formula (A-I) (wherein, X<SB>1</SB>s to X<SB>4</SB>s denote each a group selected from -SO-Z, -SO<SB>2</SB>-Z, -SO<SB>2</SB>NR<SB>1</SB>R<SB>2</SB>, -CONR<SB>1</SB>R<SB>2</SB>, -CO<SB>2</SB>R<SB>1</SB>and sulfo group; Z, R<SB>1</SB>and R<SB>2</SB>denote each a substituted or an unsubstituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group, aryl group or heterocyclic group, with the proviso that both R<SB>1</SB>and R<SB>2</SB>are not hydrogen atoms; M denotes a hydrogen atom, a metal element, a metal oxide, a metal hydroxide or a metal halide; Y<SB>1</SB>s to Y<SB>4</SB>s denote each a hydrogen atom or a monovalent substituent; and a<SB>1</SB>to a<SB>4</SB>and b<SB>1</SB>to b<SB>4</SB>denote each the number of X<SB>1</SB>s to X<SB>4</SB>s and Y<SB>1</SB>s to Y<SB>4</SB>s and are each an integer of 0-4, with the proviso that the sum total of a<SB>1</SB>to a<SB>4</SB>is ≥2). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-curable ink containing an oil-soluble dye and a curable ink having excellent image light resistance, and an ink jet recording method using the ink.

[0002]

2. Description of the Related Art Water-based ink-jet inks have poor water resistance when printed on plain paper and are prone to bleeding. Furthermore, when printed on non-water-absorbent recording materials such as plastics, There are drawbacks that images cannot be formed due to bad adhesion of droplets, that the drying of the solvent is extremely slow, it is necessary to dry the printed matter without overlapping the printed matter immediately after printing, and the images are easily blurred. As a material suitable for printing on a non-water-absorbent recording material, Table 2
No. 001-512777 discloses an ultraviolet curable ink using a polyfunctional monomer excellent in adhesiveness to a recording material, but it is slow to dry because of an aqueous dispersion type ink,
It was insufficient to form a full-color image. In order to solve the drying property, a method of using a volatile organic solvent as a solvent of the ink has been carried out, but in order to dry quickly, it is highly flammable such as methyl ethyl ketone and ethanol, and has high volatility. It was necessary to use a solvent. In order to solve these problems, Japanese Unexamined Patent Publication No.
No. 214279 discloses an ink jet ink that is cured and fixed by radiation instead of volatilization of an ink solvent. However, since the pigment dispersion is used as the coloring component, the nozzle is clogged due to the aggregation of the pigment, and it is difficult to eject the ink stably.
On the other hand, when a pigment is used as a colorant, it is difficult to obtain photographic image quality because the transparency is poor and the color tone is insufficient. As a means for solving the problem, an ultraviolet curable ink using a dye as a colorant is disclosed in US Pat. No. 4,303,924, but since the curability is often lowered by the addition of a dye, high energy It is necessary to increase the amount of UV irradiation and the amount of polymerization initiator added, which reduces the storage stability of the ink, discolors the image in the environment of long-term light exposure,
There was a problem that it was easy to fade. Further, when a recording material having inorganic fine particles such as silica gel in the image receiving layer is used, there is a drawback that the image storability is extremely poor against active gases (SO _x , NO _x , ozone, etc.) in the environment. Was.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the various problems in the prior art and achieve the following objects. That is, the present invention, in addition to conventional paper, high-quality printing is possible even on non-water-absorbent recording materials such as plastics and metals, and storage stability of ink, radiation curability, water resistance, An object of the present invention is to provide an inkjet recording ink and an inkjet recording method which are excellent in light resistance and ozone resistance.

[0004]

Means for solving the problems Means for solving the above problems are as follows. That is, (1) a monomer having a polymerizable group and the following general formula (A
And an oil-soluble dye represented by -I).

[0005]

[Chemical 2]

In the general formula (AI): X ₁ , X ₂ , X ₃ and X ₄ are each independently --SO--Z, --SO ₂ --Z,
_{-SO 2 NR 1 R 2, -CONR} 1 R 2, represents a group selected from -CO ₂ R ₁ and a sulfo group. Here, Z is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted Represents a substituted heterocyclic group. R ₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group,
It represents a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, both R ₁ and R ₂ are not hydrogen atoms. M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide or a metal halide. Y ₁ , Y ₂ ,
Y ₃ and Y ₄ each independently represent a hydrogen atom or a monovalent substituent. a _{1 to} a ₄ and b _{1 to} b ₄ are X _{1 to} X ₄ and Y
_It represents the number of _{1 to} Y ₄ , and is independently an integer of 0 to 4. However, the total sum of a _{1 to} a ₄ is 2 or more. (2) The ink according to (1) above, wherein the oil-soluble dye represented by the general formula (AI) is an oil-soluble dye represented by the following general formula (A-II).

[0007]

[Chemical 3]

In the general formula (A-II): X _{11 to} X ₁₄ , Y ₁₁ to
Y ₁₈ and M are each of X _{1 to} X ₄ and Y in the general formula (AI).
_{It has the same} meaning as _{1 to} Y ₄ and M, respectively. a ₁₁ ~a ₁₄ each independently represent a integer of 1 or 2. (3) The ink according to (1) or (2), wherein the monomer is a bifunctional or higher functional monomer. (4) The ink according to any one of (1) to (3), which contains a photopolymerization initiator and is cured by radical polymerization. (5) Oxidation potential of oil-soluble dye is 1.0V (vs. SCE)
The ink according to any one of (1) to (4) above, which is more noble. (6) Storage stabilizer is contained in the ink in an amount of 0.005 to 1% by mass.
The ink according to any one of (1) to (5) above, which further comprises: (7) The ink according to any one of (1) to (6) above, which contains substantially no dispersion medium or solvent other than the monomer. (8) An ink jet recording method, wherein an image is recorded on a recording medium using the ink described in (1) to (7) and curing is performed by radiation.

[0009]

DETAILED DESCRIPTION OF THE INVENTION (Ink) The ink of the present invention is a radiation curable ink, preferably a radiation curable jet ink. The ink is an ink composition containing a monomer having a polymerizable group and an oil-soluble dye having a specific structure, and may contain other components appropriately selected as necessary. Examples of the other components include a drying inhibitor, a penetration enhancer, an antioxidant, a fungicide, and p.
Known additives such as H regulators, surface tension regulators, defoamers, viscosity regulators, dispersants, dispersion stabilizers, rust preventives, chelating agents and the like can be mentioned, and these are described in JP-A-2001-279141. The compounds described in (0217) to (0226) can be used.

In the present invention, α-rays, γ-rays, X-rays, ultraviolet rays, visible rays, electron rays and the like can be used as the radiation for promoting the polymerization of the monomers. Among these, it is preferable to use ultraviolet rays and visible rays from the viewpoint of cost and safety, and it is more preferable to use ultraviolet rays. When ultraviolet rays, visible rays, etc. are used as the radiation, a photopolymerization initiator for initiating the polymerization is also used.
Therefore, the radiation curable ink according to another aspect of the present invention contains a photopolymerization initiator for initiating the polymerization of monomers.

-Oil-soluble dye-The oil-soluble dye used in the present invention is represented by the general formula (AI)
It is preferable to use an oil-soluble dye represented by

In the above general formula (AI), X ₁ ,
X ₂ , X ₃ and X ₄ are each independently -SO-Z,
It represents a group selected from —SO ₂ —Z, —SO ₂ NR ₁ R ₂ and a sulfo group. Z is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted Or represents an unsubstituted heterocyclic group,
In particular, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferable, and among them, a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group is most preferable. X ₁ ,
X ₂ , X ₃ and X ₄ are respectively —SO ₂ —Z and —SO ₂ NR ₁
Preferred is R ₂ .

R ₁ and R ₂ are each independently a hydrogen atom,
Substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted heterocyclic group In particular, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferable, and among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, or a substituted Heterocyclic groups are most preferred. However, both R ₁ and R ₂ are not hydrogen atoms. Specific examples of the above-mentioned substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group and the like include those described below in (Specific examples of substituents).

The heterocyclic group represented by R ₁ , R ₂ and Z is preferably a 5-membered or 6-membered ring, which may be further condensed. Further, it may be an aromatic hetero ring or a non-aromatic hetero ring. Hereinafter, the heterocyclic group represented by R ₁ , R ₂ and Z is exemplified in the form of a heterocycle by omitting the substitution position, but the substitution position is not limited and, for example, in the case of pyridine, Substitutions at the second, third, and fourth positions are possible. (Specific examples of heterocyclic group) pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, Triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole,
Pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. Among them, aromatic heterocyclic groups are preferable, and when the preferable examples are exemplified in the same manner as above, pyridine, pyrazine, pyrimidine, pyridazine, triazine,
Examples thereof include pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole and thiadiazole. They may further have a substituent described below.

Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently
Represents a hydrogen atom or a monovalent substituent. The monovalent substituent represented by Y ₁ , Y ₂ , Y ₃ and Y ₄ includes a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group and a hydroxyl group. Group, nitro group, amino group, alkylamino group,
Alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group , Heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group,
Examples thereof include a heterocyclic thio group, a phosphoryl group, an acyl group, a carboxyl group, and a sulfo group, each of which may further have a substituent.

Among them, Y ₁ , Y ₂ , Y ₃ and Y ₄ are hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido group,
A sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, a carboxyl group, or a sulfo group is preferable, and a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, or a sulfo group is particularly preferable.
Most preferred is a hydrogen atom.

When Z, R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ and Y ₄ are groups capable of further having a substituent, they may further have the following substituents. Good. (Specific examples of substituents) Halogen atom (for example, chlorine atom,
Bromine atom), a linear or branched alkyl group having 1 to 12 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and 2-1 carbon atoms
2 alkenyl groups, C2-C12 linear or branched alkynyl groups, C3-C12 linear or branched cycloalkyl groups, C3-C12 linear or branched cycloalkenyl groups, etc. ( For example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), an aryl group (eg, phenyl, 4-t-butylphenyl, 2,4-diphenyl). -T-amylphenyl), a heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2
-Pyrimidinyl, 2-benzothiazolyl), cyano group,
Hydroxyl group, nitro group, carboxy group, amino group,
Alkyloxy groups (eg methoxy, ethoxy, 2-
Methoxyethoxy, 2-methanesulfonylethoxy),
Aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (for example, acetamide, benzamide, 4 -(3-t-butyl-4-hydroxyphenoxy) butanamide), an alkylamino group (for example, methylamino, butylamino, diethylamino, methylbutylamino), an anilino group (for example, phenylamino, 2-chloroanilino),
Ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoylamino), alkylthio group (eg, methylthio, octylthio, 2-phenoxy) Ethylthio), arylthio groups (eg phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino groups (eg methoxycarbonylamino), sulfonamide groups (eg methane Sulfonamide, benzenesulfonamide, p-toluenesulfonamide), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl),
Sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkyloxycarbonyl Group (for example, methoxycarbonyl, butyloxycarbonyl), heterocyclic oxy group (for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4 -Pivaloylaminophenylazo, 2-
Hydroxy-4-propanoylphenylazo), acyloxy group (eg acetoxy), carbamoyloxy group (eg N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (eg,
Trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (eg, phenoxycarbonylamino), imide group (eg, N-
Succinimide, N-phthalimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-
Pyridylthio), sulfinyl group (for example, 3-phenoxypropylsulfinyl), phosphonyl group (for example,
Phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic group (for example, carboxyl) Group, sulfo group,
And quaternary ammonium groups).

A _{1 to} a ₄ and b _{1 to} b ₄ are X _{1 to} X ₄ and Y ₁ to
It represents the number of Y ₄ and is independently an integer of 0 to 4. In addition, since it is already defined, naturally, a ₁ and b ₁ are
Each is an independent integer of 0 to 4 that satisfies the relationship of a ₁ + b ₁ = 4. However, the total sum of a _{1 to} a ₄ is 2 or more and 16 or less. Particularly preferred is that a ₁ is 1 or 2,
Most preferred is a combination in which b ₁ is 3 or 2, in which a ₁ is 1 and b ₁ is 3.

The respective combinations of a ₂ and b ₂ , a ₃ and b ₃ , a ₄ and b ₄ have the same relationship as in the case of a ₁ and b ₁ , and the preferred combinations are also the same.

M is a hydrogen atom, a metal element, a metal oxide,
Represents a metal hydroxide or metal halide.

Preferable M includes, in addition to hydrogen atoms, metal atoms such as Li, Na, K, Mg, Ti, Zr, V, Nb, Ta and C.
r, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, P
t, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, S
n, Pb, Sb, Bi, etc., as oxides, VO, GeO, etc., as hydroxides, Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) _2, etc.,
As halides, AlCl, SiCl ₂ , VCl, VCl ₂ , VOCl,
FeCl, GaCl, ZrCl and the like can be mentioned. Especially, C
u, Ni, Zn, Al and the like are preferable, and Cu is most preferable.

In addition, Pc is connected via L (divalent linking group).
(Phthalocyanine ring) is a dimer (for example, Pc-ML
-M-Pc) or a trimer may be formed, and Ms at that time may be the same or different.

The divalent linking group represented by L is an oxy group-
O-, thio group -S-, a carbonyl group -CO-, a sulfonyl group -SO ₂ -, -NH- imino group, or a methylene group -CH ₂ - are preferred.

Particularly preferred combinations as the oil-soluble dye represented by formula (AI) are as follows.

X _{1 to} X ₄ are independently --SO _2-
Particularly preferred is Z or —SO ₂ NR ₁ R ₂ .
Z is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, among which a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group is preferable. Most preferred are groups. R ₁ and R ₂ are each independently a hydrogen atom,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferable, and among them, a hydrogen atom, a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group is most preferable. .
Y _{1 to} Y ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, a carboxyl group. A group and a sulfo group are preferable, and particularly a hydrogen atom, a halogen atom, a cyano group, a carboxyl group,
Alternatively, a sulfo group is preferable, and the case where all are hydrogen atoms is most preferable. It is preferable that a _{1 to} a ₄ are each independently 1 or 2, and particularly preferably 1. It is preferable that b _{1 to} b ₄ are each independently 3 or 2, and particularly preferably 3. M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide or a halide, and Cu, Ni, Zn and Al are particularly preferable, and Cu is particularly preferable. In addition, the general formula (A-
The oil-soluble dye represented by I) preferably contains an ionic hydrophilic group, more preferably one having at least 4 ionic hydrophilic groups in one molecule of the oil-soluble dye, and particularly, an ionic hydrophilic group. It is preferable that the functional group is a sulfo group,
Among them, those having at least 4 or more sulfo groups are most preferable.

Regarding the preferred combination of groups of the compound represented by formula (AI), the compound in which at least one of various groups is the above-mentioned preferred group is preferable, and more various groups are the above-mentioned preferred groups. Compounds that are groups are more preferred, and compounds in which all groups are the above preferred groups are most preferred.

Among the oil-soluble dyes represented by the general formula (AI), the oil-soluble dye having the structure represented by the following general formula (A-II) is more preferable. Hereinafter, the general formula (A-II) of the present invention will be described.
The oil-soluble dye represented by will be described in detail.

In the above general formula (A-II), X _{11 to} X
₁₄ , Y _{11 to} Y ₁₈ are each X _{1 to} X ₄ in the general formula (AI),
It has the same meaning as Y _{1 to} Y ₄ , respectively, and the preferred examples are also the same. Further, M has the same meaning as M in formula (I), and preferred examples are also the same.

In the general formula (A-II), a _{11 to} a ₁₄ each independently represents an integer of 1 or 2, and 4 is particularly preferable.
≦ a ₁₁ + a ₁₂ + a ₁₃ + a ₁₄ ≦ 6, of which a ₁₁ = a ₁₂ = a ₁₃ = a ₁₄ = 1 is particularly preferable.
It is time for

Among the oil-soluble dyes represented by formula (A-II), particularly preferable combinations of substituents are as follows.

X _{11 to} X ₁₄ are each independently --SO ₂
-Z or -SO ₂ NR ₁ R ₂ it is particularly preferred. Z is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, among which a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group is preferable. Most preferred are groups. R ₁ and R ₂ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom or a substituted alkyl group. Most preferred are substituted aryl groups, or substituted heterocyclic groups. However, R ₁ and R ₂ are not both hydrogen atoms. Y ₁₁ ~
Y ₁₈ is preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, a carboxyl group or a sulfo group. , Especially hydrogen atom, halogen atom,
A cyano group, a carboxyl group or a sulfo group is preferable,
Most preferred is a hydrogen atom. It is preferable that a _{11 to} a ₁₄ are each independently 1 or 2, and it is particularly preferable that all are 1. M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide or a metal halide,
Cu, Ni, Zn and Al are preferable, and Cu is most preferable. When the oil-soluble dye represented by formula (A-II) contains an ionic hydrophilic group, one having at least 4 ionic hydrophilic groups in one molecule of the oil-soluble dye is more preferable. The ionic hydrophilic group as a substituent includes a sulfo group, a phosphono group, a carboxyl group and a quaternary ammonium group. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion which forms a salt include an alkali metal ion (eg, sodium ion, potassium ion) and an organic cation (eg, tetramethylguanidinium ion). Is included. Of these, a sulfo group and a carboxyl group are preferable. Furthermore, it is most preferable that the ionic hydrophilic group is a sulfo group.

With respect to the preferable combination of groups of the compound represented by formula (A-II), the compound in which at least one of various groups is the above-mentioned preferable group is preferable, and more various groups are the above-mentioned preferable groups. Compounds that are groups are more preferred, and compounds in which all groups are the above preferred groups are most preferred.

Further, at least one electron-withdrawing group such as a sulfinyl group, a sulfonyl group, or a sulfamoyl group may be introduced into each benzene ring of phthalocyanine so that the sum of σp values is 1.6 or more. preferable.

The Hammett's substituent constant σp value will be briefly described. Hammett's rule is 193 to quantitatively discuss the effect of a substituent on the reaction or equilibrium of a benzene derivative.
5 years L. P. The rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include σp values and σm values, and these values can be found in many general textbooks. A. Dean edition, "Lange '
s Handbook of Chemistry ", 12th Edition, 1979 (McGrow-Hill) and" The Area of Chemistry "Special Issue, No. 122, pp. 96-103, 19
Detailed in 1979 (Nankodo).

The oil-soluble dye used in the present invention contains oxygen as a polymerization initiator or a monomer radical (including a growth radical of an oligomer or a polymer) in order to prevent a polymerization inhibition or a polymerization termination action in the presence of air from occurring easily. In order to reduce the reactivity with oxygen radicals (oxy radicals and the like) generated by the action, it is desirable to introduce an electron withdrawing group into the phthalocyanine skeleton to make the oxidation potential noble. By making the oxidation potential noble, not only the curability of the ink is improved, but also the reactivity with ozone, which is an electrophile, is lowered, so that the ozone resistance is simultaneously improved. Oxidation potential is 1.05
It is desirable to be more noble than V (vs SCE). The more preferable the oxidation potential is, the more preferable the oxidation potential is 1.1 V.
More preferred is (vs SCE),
Most preferred are those nobler than 1.2 V (vs SCE). The oxidation potential value (Eox) can be easily measured by those skilled in the art. For this method, see P. Del
Ahay “New Instrumental Met”
hods in Electrochemistry ”
(1954 Interscience Public
published by shers) and A. J. Bard et al., "Elect
“Rochemical Methods” (published by John Wiley & Sons in 1980), Aki Fujishima et al. “Electrochemical measurement method” (1984 published by Gihodo Publishing Co.)
It is described in.

Specifically, the oxidation potential of the test sample was 1 × 10 ⁻⁴ to 1 × 10 ^{− in} a solvent such as dimethylformamide or acetonitrile containing a supporting electrolyte such as sodium perchlorate or tetrapropylammonium perchlorate. Dissolve ⁶ mol / liter and measure as a value for SCE (saturated calomel electrode) using cyclic voltammetry or direct current polarography. Although this value may deviate by about several tens of mil volts due to the influence of the liquid-potential difference and the liquid resistance of the sample solution, the reproducibility of the potential can be guaranteed by inserting a standard sample (for example, hydroquinone). In addition, in order to uniquely define the potential, in the present invention,
The value (vs SCE) measured by direct current polarography in dimethylformamide containing 0.1 moldm ^-3 tetrapropylammonium perchlorate as a supporting electrolyte (the concentration of the dye was 0.001 moldm ^-3 ) was defined as the oxidation potential of the dye. To do.

The value of Eox represents the ease with which electrons are transferred from the sample to the electrode. The larger the value (the higher the oxidation potential is), the more difficult it is for electrons to transfer from the sample to the electrodes. In other words,
Indicates that it is difficult to oxidize. In relation to the structure of the compound, the oxidation potential becomes more noble by introducing the electron-withdrawing group, and the oxidation potential becomes less by introducing the electron-donating group. Therefore, if the Hammett's substituent constant σp value, which is a measure of the electron withdrawing property or electron donating property of a substituent, is used, it is possible to introduce a substituent having a large σp value such as a sulfinyl group, a sulfonyl group, or a sulfamoyl group. It can be said that the oxidation potential can be made more noble. Specific examples of the oil-soluble dyes represented by the general formulas (AI) and (A-II) (exemplified compounds AI-1 to AI-3 and AII-1)
~ AII-28) are shown below, but the oil-soluble dye used in the present invention is not limited to the following examples.

[0038]

[Chemical 4]

[0039]

[Chemical 5]

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

The content of the oil-soluble dye in the ink is
0.05 to 15 mass% is preferable, and 0.1 to 10 mass%
Is more preferable, and 0.2 to 6 mass% is particularly preferable. Further, the ink composition of the present invention, in order to adjust the color tone to obtain a full-color image with the oil-soluble dye,
Other oil-soluble dyes may be used in combination. Examples of dyes that can be used in combination include the following dyes.

As the oil-soluble dye, there is disclosed in JP-A-2001-27.
The yellow dyes, magenta dyes, and / or cyan dyes described in paragraph numbers (0144) to (0147) of No. 9141 can be used.

The following dyes formed by the reaction of yellow, magenta and cyan couplers with an oxidized product of an aromatic primary amine developing agent can be used. As the yellow coupler, magenta coupler and cyan coupler, the respective couplers described in paragraph numbers (0159) to (0162) of JP 2001-279141 A can be used.

—Monomer Having Polymerizable Group— As the monomer having a polymerizable group used in the present invention, a polymerizable double bond which solidifies upon application of energy such as ultraviolet rays, heat, or electron beams (hereinafter referred to as “polymerizable group”) A compound having a group). As the monomer, it is essential to use a compound having two or more functional groups (hereinafter referred to as a polyfunctional monomer), and a monofunctional compound for controlling viscosity, controlling crosslink density, and controlling physical properties after curing (strength, adhesiveness, etc.). (Hereinafter,
A monofunctional monomer) may be used together. Examples of the polymerizable group include an acryloyl group, a methacryloyl group, an allyl group, a vinyl group, and an internal double bond group (maleic acid, etc.), among which an acryloyl group and a methacryloyl group are preferable because they can be cured with low energy. ,
The acryloyl group is particularly preferred. The polyfunctional monomer is a vinyl group-containing aromatic compound, an acrylate that is an ester of a divalent or higher alcohol and acrylic acid or methacrylic acid, and an amide of a divalent or higher amine and an acrylic acid or methacrylic acid. Acrylamide, polyester acrylate obtained by introducing acrylic acid or methacrylic acid into polycaprolactone or ester obtained by bonding polybasic acid and dihydric alcohol, acrylic acid or methacrylic acid by ether obtained by bonding alkylene oxide and polyhydric alcohol Introduced polyether acrylate, epoxy acrylate obtained by introducing acrylic acid or methacrylic acid into an epoxy resin, or by reacting a divalent or higher alcohol with an epoxy-containing monomer, and a urethane acrylate having a urethane bond. Rate, amino resin acrylate, acrylic resin acrylate, alkyd resin acrylate, spirane resin acrylate, silicone resin acrylate, a reaction product of an unsaturated polyester and the photopolymerizable monomer, and a reaction product of waxes and the polymerizable monomer. The acrylate, polyester acrylate, polyether acrylate, epoxy acrylate, urethane acrylate, acrylic resin acrylate, silicone resin acrylate, a reaction product of an unsaturated polyester and the photopolymerizable monomer is preferable, acrylate, polyester acrylate, polyether acrylate, Epoxy acrylate and urethane acrylate are particularly preferable. Examples of the polyfunctional monomer include divinylbenzene, 1,3-butanediol diacrylate, 1,6
-Hexanediol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, 1,6-acryloylaminohexane, hydroxypivalate neopentyl glycol diacrylate, dibasic acid and dihydric alcohol Molecular weight 500
To 30,000 polyester having a (meth) acryloyl group at the molecular chain end, polyester acrylate, polyethylene glycol diacrylate, bisphenol (A
Alternatively, S, F) skeleton-containing molecular weight 450 to 300
00 epoxy acrylate, a phenol novolac resin skeleton-containing molecular weight of 600 to 30000, a reaction product of a polyvalent isocyanate having a molecular weight of 350 to 30000 and a (meth) acrylic acid monomer having a hydroxyl group, and a urethane bond in the molecule. And a urethane modified product having As the monofunctional monomer, a substituted or unsubstituted (meth) acrylate, a substituted or unsubstituted styrene, a substituted or unsubstituted acrylamide, a vinyl group-containing monomer (vinyl ester, vinyl ether, N-vinylamide, etc.), ( (Meth) acrylic acid and the like, and substituted or unsubstituted (meth) acrylate, substituted or unsubstituted acrylamide, vinyl esters and vinyl ethers are preferable, and substituted or unsubstituted (meth) acrylate, substituted or unsubstituted Acrylamide is particularly preferred. Examples of the monofunctional monomer include hydroxyethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate,
2-acryloyloxyethyl phosphate, allyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylacrylamide, N, N-diethylaminopropylacrylamide, N-butoxymethylacrylamide, acryloylmorpholine, 2-hydroxyethyl vinyl ether, N -Vinylformamide,
Examples thereof include N-vinylacetamide, 2-cyclohexylcarbamoyloxyethyl acrylate, an acrylate containing a polybutyl acrylate moiety in the ester, and an acrylate containing a polydimethylsiloxane moiety in the ester. The content of the monomer in the ink is
Usually, the range of 50 to 99.6 mass% is preferable, but 70 to
99.0 mass% is more preferable, 80-99.0 mass%
Is more preferable. The monomer may be any one as long as the effects of the present invention can be obtained, but it is more preferable to select from those having high safety. Highly safe monomers are those with low PII (skin irritation) values,
The PII is preferably 3.0 or less, more preferably 2.0 or less, further preferably 1.0 or less, and particularly preferably 0.5 or less. —Photopolymerization Initiator and Sensitizer— The photopolymerization initiator is not particularly limited as long as radicals generated by light and other active species react with the polymerizable double bond in the monomer. As the photopolymerization initiator, acetophenone derivative, benzophenone derivative, benzyl derivative, benzoin derivative, benzoin ether derivative, benzyldialkylketal derivative, thioxanthone derivative, acylphosphine oxide derivative, metal complex, p-dialkylaminobenzoic acid, azo compound, peroxide Compounds and the like are generally known, and acetophenone derivatives, benzyl derivatives, benzoin ether derivatives,
A benzyldialkylketal derivative, a thioxanthone derivative and an acylphosphine oxide derivative are preferable, and an acetophenone derivative, a benzoin ether derivative, a benzyldialkylketal derivative and an acylphosphine oxide derivative are particularly preferable. Examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone and p.
-Dimethylaminopropiophenone, benzophenone,
p, p'-dichlorobenzophenone, p, p'-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin-n-propyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1-hydroxy- Cyclohexyl phenyl ketone, tetramethyl thiuram monosulfide, thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,2-dimethylpropioyldiphenylphosphine oxide, 2-methyl-2-
Ethylhexanoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxy) Benzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,3,6-
Trimethylbenzoyl-diphenylphosphine oxide, bis (2,3,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethoxybenzoyl-diphenylphosphine oxide,
2,4,6-Trichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylnaphthylphosphonate, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-
3- (1H-pyrrol-1-yl) -finyl) titanium, p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid, azobisisobutyronitrile, 1,1′-
Azobis (1-acetoxy-1-phenylethane), benzoin peroxide, di-tert-butyl peroxide and the like can be mentioned. Furthermore, examples of the photopolymerization initiator include those described in "UV Curing System" (published by Sogo Gijutsu Center Co., Ltd .: 1989) by Kiyomi Kato on pages 65 to 148. You can These photopolymerization initiators can be used alone or in combination of two or more, and may be used in combination with a sensitizer. Further, it is preferable that the photopolymerization initiator does not cause thermal decomposition up to 70 ° C. The use of an initiator that causes thermal decomposition at 70 ° C. or lower is not preferable because it causes a problem in product storage. The amount of these photopolymerization initiators used in the ink is not particularly limited, but is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and 3 to 10% by mass.
Is particularly preferable. If the amount is less than 0.5% by mass, the composition may not be cured or the curing time may be slow, and if it exceeds 20% by mass, precipitation or separation may occur after dissolution with time, and performance such as strength and scratch resistance of the ink after curing may be deteriorated. It is not preferable because it exists.
Although the sensitizer is not activated by irradiation with light alone, it is more effective when used together with the photopolymerization initiator than when used alone, and amines are generally used. The reason why the curing rate is increased by adding amines is because first, hydrogen is supplied to the photopolymerization initiator by the hydrogen abstraction action, and secondly, the generated radicals are bonded to oxygen molecules in the atmosphere to cause reactivity. However, the amine has a function of trapping oxygen dissolved in the composition. Examples of the sensitizer include amine compounds (aliphatic amine, amine containing aromatic group, piperidine, reaction product of epoxy resin and amine, triethanolamine triacrylate, etc.), urea compound (allyl thiourea, o
-Tolylthiourea), sulfur compounds (sodium diethyldithiophosphate, soluble salts of aromatic sulfinic acid, etc.), nitrile compounds (N, N-diethyl-p)
-Aminobenzonitrile etc.), phosphorus compounds (tri-n
-Butylphosphine, sodium diethyldithiophosphide, etc.), nitrogen compounds (Michler's ketone, N-nitrisohydroxylamine derivatives, oxazolidine compounds, tetrahydro-1,3-oxazine compounds, condensates of formaldehyde or acetaldehyde and diamine), chlorine compounds (Carbon tetrachloride, hexachloroethane, etc.) and the like. The amount of sensitizer used in the ink is
It is usually 0 to 10% by mass, preferably 0.1 to 10% by mass, and particularly preferably 0.2 to 5% by mass. The selection and combination of the photoinitiator and the sensitizer, and the compounding ratio may be appropriately selected depending on the ultraviolet curing monomer used and the apparatus used. A low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a xenon lamp, a chemical lamp, etc. can be used as a light source for irradiating ultraviolet rays or visible light.

-Other components-Other components may be appropriately selected depending on the purpose within a range not impairing the effects of the present invention. Examples of the other components include known additives such as solvents and polymers, surface tension adjusting agents, storage stabilizers, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, and pH adjusting agents. .

The solvent can be used for the polarity of ink, viscosity, surface tension, improvement of solubility of oil-soluble dye, adjustment of conductivity and adjustment of printing performance. Examples of the solvent include water, a low boiling point organic solvent, and a high boiling point organic solvent. The low boiling point organic solvent is an organic solvent having a boiling point of 100 ° C. or lower. The low boiling point organic solvent is preferably not used in consideration of environmental pollution, but when used, it is preferable to use one having high safety. A highly safe solvent is a solvent having a high controlled concentration (an index shown in the work environment evaluation standard), preferably 100 ppm or more.
00 ppm or more is more preferable. Examples thereof include alcohols, ketones, esters, ethers, hydrocarbons and the like, and specific examples include methanol, 2-butanol, acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran and the like. The high boiling point organic solvent is an organic solvent having a boiling point higher than 100 ° C. The high boiling point organic solvent preferably has a boiling point of 150 ° C. or higher, 17
It is more preferably 0 ° C. or higher. Examples thereof include polyhydric alcohols, esters of aliphatic carboxylic acids, phosphoric acid esters, hydrocarbons, and the like. Specifically, diethylene glycol, trimethylolpropane, dibutyl phthalate, and 2-ethylhexyl benzoate. , Alkylnaphthalene and the like. These can be either liquid or solid at room temperature depending on the purpose. The solvent may be used alone or in combination of two or more. The amount used in the ink is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and particularly preferably substantially not contained. The term “substantially free from” means that the material used is contained as an impurity other than the main component, that is, not intentionally added. The polymer can be used for adjusting the polarity and viscosity of the ink, improving the solubility of the oil-soluble dye, adjusting the adhesion of the cured ink to the recording material, and adjusting the light resistance. The polymer may be dissolved in the ink or may be a fine dispersion, but from the viewpoint of the storage stability of the ink and the ejection performance, it is preferable that the polymer be dissolved. When the polymer is dissolved in the ink, it is preferable that the polymer has high compatibility with a dye or a monomer, and the weight average molecular weight is preferably 50,000 or less, more preferably 20,000 or less, from the viewpoint that the viscosity of the ink is less likely to increase. Is particularly preferable. Examples thereof include vinyl polymers, polyurethanes, polyesters, and the like. Specifically, polybutyl acrylate, poly (isobutyl methacrylate-
Hydroxyethyl acrylate) (copolymerization mass ratio 95:
5), poly (isopropyl acrylate-tetrahydrofurfuryl acrylate) (copolymerization mass ratio 70:30), poly (butyl methacrylate-N-methoxymethyl acrylamide) (copolymerization mass ratio 80:20), polybutyl acrylate-polydimethyl Examples thereof include a siloxane block copolymer (copolymerization mass ratio 90:10). In the case of the fine dispersion of the polymer, it is essential that the polymer is not substantially dissolved in the monomer, and it is more preferable that the polymer does not swell or does not swell. The particle size of the dispersion in the ink is preferably 1 μm or less, more preferably 0.5 μm or less, particularly preferably 0.1 μm or less. Examples thereof include vinyl polymer fine particles, polyurethane fine particles, polyester fine particles, urethane-vinyl composite particles, and the like. Specifically, poly (acrylonitrile-ethyl acrylate-ethylene glycol dimethacrylate) (copolymerization mass ratio 60: 37: 3 ), Poly (styrene-butadiene) (copolymerization mass ratio 50:50) and the like. The polymers may be used alone or in combination of two or more, and the amount used in the ink is 0 to 40% by mass.
Is preferable, 0-30 mass% is more preferable, and 0-20
Mass% is particularly preferred. The storage stabilizer suppresses undesired polymerization during storage, and is used as a storage stabilizer. Examples include quaternary ammonium salts, hydroxyamines, cyclic amides, nitriles, substituted ureas, heterocyclic compounds, organic acids, hydroquinone, hydroquinone monoethers, organic phosphines, copper compounds, and the like. Specifically, benzyltrimethylammonium chloride, diethylhydroxylamine, benzothiazole, 4-amino-2,2,6,6-tetramethylpiperidine, citric acid, hydroquinone monobutyl ether,
Examples include copper naphthenate. The usage amount is 0.005
1 mass% is preferable, 0.01-0.5 mass% is still more preferable, and 0.01-0.2 mass% is especially preferable. Surface tension adjuster, ultraviolet absorber, antioxidant, anti-fading agent,
As the pH adjuster, those described in JP 2001-181549 A may be used. It is essential that the conductive salts be dissolved in the ink, and examples thereof include potassium thiocyanate, lithium nitrate, ammonium thiocyanate, and dimethylamine hydrochloride. Although the preferable physical properties of the ink depend on the printing device, generally, the viscosity is preferably 5 to 100 mPa · s, more preferably 10 to 80 mPa · s. The surface tension is preferably 20 to 60 mN / m, more preferably 30 to 50 mN / m. (Inkjet recording method) In the inkjet recording method of the present invention, recording is performed using the inkjet recording ink, but the ink nozzles and the like used at that time are not particularly limited and may be appropriately selected according to the purpose. You can The ink jet recording method is described in JP 2001
The thing described in the paragraph number (0247) of 279141 can be used.

The ink jet recording ink of the present invention comprises
It can be suitably printed on a known recording material. For example, plain paper, resin-coated paper, ink-jet dedicated paper, film, electrophotographic common paper, cloth, glass, metal, ceramics and the like can be mentioned. Regarding the recording material, Japanese Patent Application Laid-Open No. 2001-2001
The materials described in paragraph numbers (0228) to (0246) of Japanese Patent No. 1815549 and Japanese Patent Laid-Open No. 2001-279141 can be used.

[0051]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “parts” and “%” represent “parts by mass” and “mass%” unless otherwise specified. (Example 1) <Preparation of ink 01> Oil-soluble dye (AII-17) 2.5 in a mixture of 49 parts of pentaerythritol tetraacrylate, 25 parts of hexamethylene-1,6-diacrylate and 15 parts of N-vinylformamide. Parts, fluorinated nonionic surfactant 1.2 parts, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide 4 parts, 1-hydroxy-cyclohexylphenylketone 1 part, triethanolamine 2.3 parts, hydroquinone monobutyl ether 0.
02 parts were added and dissolved, and filtered with a 0.45 μm filter to prepare an inkjet recording ink. <Preparation of Ink 02> Pentaerythritol tetraacrylate 39 parts, Dipentaerythritol tetraacrylate 24 parts, Ethylene glycol diacrylate 9 parts, Diethylaminoethyl acrylate 5 parts, N
-Vinylformamide 7 parts, pentaerythritol
2.5 parts of oil-soluble dye (AII-17) in a mixture of 5 parts,
Fluorine-based nonionic surfactant 1.2 parts, bis (2,6
-Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (2 parts), 1-hydroxy-cyclohexylphenyl ketone (5 parts) and hydroquinone monobutyl ether (0.02 parts) were added and dissolved,
An ink jet recording ink was prepared by filtering through a 45 μm filter. <Preparation of Ink 03> A mixture of 40 parts of ditrimethylolpropane tetraacrylate, 34 parts of pentaerythritol tetraacrylate and 9 parts of tetrahydrofurfuryl acrylate is used as an oil-soluble dye (AII-17) .2.
5 parts, polybutyl methacrylate (number average molecular weight 120
00) 5 parts, fluorinated nonionic surfactant 1.2
Part, bis (2,6-dimethoxybenzoyl) -2,4
4-Trimethylpentylphosphine oxide 3
Part, 1-hydroxy-cyclohexyl phenyl ketone
2 parts, diethanolamine 2 parts, potassium thiocyanate 1.3 parts, hydroquinone monobutyl ether
0.02 part was added and dissolved, and filtered with a 0.45 μm filter to prepare an ink for inkjet recording. <Preparation of Inks 04 to 09> Ink preparations of Inks 04 to 09 were prepared in the same manner as the preparation of Ink 02 except that the oil-soluble dye (AII-17) was replaced in the preparation of Ink 02. did. <Preparation of Inks 10 to 15> Ink preparations of Inks 10 to 15 were prepared in the same manner as Preparation of Ink 03 except that the addition amount of hydroquinone monobutyl ether was changed.

An image was recorded on a PET film using the produced ink for inkjet recording, and then an exposure treatment was carried out with a metal halide lamp at 200 mJ / cm ² .
The following evaluations were performed on the ink and the obtained recording sample. The results are shown in Table 5.

<Storage Stability> After the ink was stored at 60 ° C. for 30 days, the state of the ink and the filterability of the 0.45 μm filter were evaluated. A (good) when there is no change in the ink and good filterability of the filter, B (acceptable) when there is no change of the ink and bad filterability of the filter, and C (bad) when the ink is gelled or the viscosity increases. ), <Curability> evaluated in three stages, the recorded image was observed, A (good) without stickiness, B (acceptable) with a little stickiness but not enough to stain the contact, stickiness. The item marked with "C" was rated as C (poor) and evaluated in three levels. <Color Tone> The recorded image was observed, A (good) and B (bad) were judged, and evaluated in two stages. <Water resistance> The PET film on which the image is formed is immersed in water for 1 minute and naturally dried at room temperature to cause bleeding and peeling.
The color tone was observed. Evaluation was made in two stages, with A showing that there was no bleeding or peeling and no change in color tone, and B showing any change in color tone.

<Light resistance> The PET film having the image formed thereon was irradiated with xenon light (85000 lx) for 3 days using a weather meter (Atlas CI65).
Reflection densitometer (X-Rite3)
10TR) and evaluated as the residual dye rate. The case where the residual rate of the dye was 80% or more was evaluated as A, and the case where the residual rate of the dye was less than 80% was evaluated as B.

[0055]

[Table 5]

[0056]

[Chemical 6]

As is clear from the results shown in Table 5, the ink using the oil-soluble dye of the present invention has an excellent color tone, and the ink 10 containing no storage stabilizer does not have storage stability and contains a storage stabilizer. The ink 15 having a large amount has excellent storage stability but poor curability. The inkjet recording ink of the present invention has excellent storage stability and curability, and has no liquid absorbability.
Even when an image was recorded on the ET, the color tone, water resistance, and light resistance were excellent. (Example 2) Except that an image was recorded by changing the recording material.
Recording samples were prepared and evaluated in the same manner as in Example 1. Example 1 except for the oxidation potential and ozone resistance
Evaluation was carried out in the same manner as. <Ozone resistance> Regarding ozone resistance, the ozone concentration is 1.
The concentration before and after the sample was stored for 5 days under the condition of 0 ppm was measured by X-rite 310, and the dye residual rate was obtained and evaluated. A when the residual dye ratio is 90% or more, 70% or more 9
Less than 0% was evaluated as B and less than 70% was evaluated as C. <Oxidation potential> The oxidation potential is measured in a constant amount (converted into a molecular weight) of a dye in N, N-dimethylformamide containing 0.1 moldm ⁻³ tetrapropylammonium perchlorate as a supporting electrolyte (of the dye). The concentration is 0.001 mol
It was measured by direct current polarography at dm ^-3 ). In a polarographic apparatus, a carbon (GC) electrode was used as a working electrode and a rotating platinum electrode was used as a counter electrode, and the oxidation wave obtained by sweeping to the oxidation side (noble side) was linearly approximated to obtain its peak value. The midpoint of the intersection between the intersection and the residual current value was taken as the oxidation potential value (vsSCE). The measurement results of the phthalocyanine compound used in the examples and the comparative compound are shown in Table 6 below.

[0058]

[Table 6]

As is clear from the results shown in Table 6, good images can be formed on both conventional paper and recording materials having no liquid absorption, and the curability, color tone, water resistance, light resistance and ozone resistance are excellent. Was there. (Example 3) A four-color ink set was prepared in the following manner to record a full-color image, and the same evaluation as in Example 1 was carried out. As a result, any of curability, color tone, water resistance and light resistance was obtained. Was also excellent. <Yellow Ink> A mixture of 40 parts of ditrimethylolpropane tetraacrylate, 34 parts of pentaerythritol tetraacrylate and 9 parts of tetrahydrofurfuryl acrylate, 2.7 parts of an oil-soluble dye (Y-1), and polybutyl methacrylate (number average molecular weight of 8000). 5
Parts, fluorinated nonionic surfactant 1.2 parts, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide 4 parts, 1-hydroxy-cyclohexylphenylketone 2 parts, diethanolamine 2 parts , 0.01 part of hydroquinone monobutyl ether was added and dissolved, and filtered through a 0.45 μm filter to prepare an ink for inkjet recording. <Magenta Ink> Preparation of the yellow ink except that 2.0 parts of the oil-soluble dye (M-1) was used in place of 2.7 parts of the oil-soluble dye (Y-1) in the preparation of the yellow ink. A cyan ink for inkjet recording was prepared in the same manner as in. <Cyan ink> In preparing the yellow ink,
A cyan ink for inkjet recording was prepared in the same manner as in the preparation of the yellow ink, except that 3.8 parts of the oil-soluble dye (AII-17) was used instead of 2.7 parts of the oil-soluble dye (Y-1). did. <Black Ink> In the preparation of the yellow ink, 1.0 part of the oil-soluble dye (M-1) and oil-soluble dye (II-17) were used instead of 2.7 parts of the oil-soluble dye (Y-1).
A black ink for inkjet recording was prepared in the same manner as in the preparation of the yellow ink except that 1.9 parts and 1.4 parts of the oil-soluble dye (Y-1) were used.

[0060]

[Chemical 7]

[0061]

According to the present invention, a good image can be formed not only when a recording material having excellent ink storage stability and liquid absorbability but also a recording material having no liquid absorbability is used. It is possible to provide an inkjet recording ink and an inkjet recording method which are excellent in curability, color tone, water resistance, light resistance, and ozone resistance.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2C056 EA13 FC01 HA44                 2H086 BA05 BA56 BA59                 4J039 AD21 BC50 BC59 BE02 BE07                       GA24

Claims (2)

[Claims] 1. An ink containing a monomer having a polymerizable group and an oil-soluble dye represented by the following general formula (AI). [Chemical 1] In formula (AI): X ₁ , X ₂ , X ₃ and X ₄ are each independently —SO—Z, —SO ₂ —Z, —SO ₂ NR ₁
It represents a group selected from R ₂ , —CONR ₁ R ₂ , —CO ₂ R ₁ and a sulfo group. Here, Z is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted Represents a substituted heterocyclic group. R
₁ and R ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted Represents an aryl group or a substituted or unsubstituted heterocyclic group.
However, both R ₁ and R ₂ are not hydrogen atoms.
M represents a hydrogen atom, a metal element, a metal oxide, a metal hydroxide or a metal halide. Y ₁ , Y ₂ , Y ₃ and Y ₄ each independently represent a hydrogen atom or a monovalent substituent. _{a 1 ~a 4, b 1 ~b} 4 represents the number of _{X 1 ~X 4, Y 1 ~Y} 4, each independently, an integer of 0-4. However, the total sum of a _{1 to} a ₄ is 2 or more and 16 or less. 2. An ink jet recording comprising: a step of recording an image on a recording material using the ink according to claim 1; and a step of curing the image-recorded recording material by radiation. Method.