JP2996556B2 - Image forming dyes - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a novel image forming dye, and more particularly, to a novel image forming dye having excellent fastness.

[0002]

BACKGROUND OF THE INVENTION As a method of obtaining a color hard copy,
A color recording technique using ink jet, electrophotography, thermal transfer, and the like is being studied.

[0003] Of these, the thermal transfer method has advantages in that it is easy to operate and maintain, that the apparatus can be reduced in size and cost can be reduced, and that the running cost is low.

In the thermal transfer method, a transfer sheet (also referred to as a thermal transfer material) having a fusible ink layer on a support is heated by a thermal head, and the ink is transferred to a transfer sheet (also referred to as an image receiving material). ), And a transfer sheet having an ink layer containing a heat-diffusible dye (sublimable dye) on a support is heated by a heat-sensitive head, and the heat-diffusible dye is applied to a transfer-receiving sheet. There are two types of thermal diffusion transfer system (sublimation transfer system) that transfers the dye, but the latter thermal diffusion transfer system changes the amount of dye transfer according to the change in thermal energy of the thermal head, and Since the gradation can be controlled, it is advantageous for full color.

In thermal transfer recording, the dye used in the thermal transfer material is important and greatly affects the speed of transfer recording, image quality, image storage stability, and the like.

Therefore, it is necessary that the dye used in the thermal transfer has the following properties. (1) Dyes used in the thermal diffusion transfer method should be easily thermally diffused (sublimated) under thermal recording conditions (head temperature, head heating time). (2) To have a favorable hue in color reproduction. (3) No thermal decomposition at the heating temperature during recording. (4) Good light resistance, heat resistance, moisture resistance, chemical resistance, etc. (5) The molar absorption coefficient is large. (6) The addition to the thermal transfer material is easy. (7) Easy synthesis. Further, in addition to this, it is required that the fixing property of the image is excellent.

Conventionally, magenta dyes for thermal transfer materials have been disclosed in JP-A-59-78896, JP-A-60-30392, JP-A-60-30394,
60-253595, 61-262190, 63-5992, 63-20
Nos. 5288, 64-1591, 64-63194, etc., disclose anthraquinone dyes, azo dyes, azomethine dyes and the like, but in particular heat diffusion, heat resistance, light resistance, etc. A dye that is satisfactory and has good fixability has not yet been found.

Accordingly, the present inventors have conducted various studies on dyes for thermal transfer materials from the above viewpoint, and as a result, the dye represented by the general formula [I] satisfies the above-mentioned conditions. In particular, the present inventors have discovered that they are excellent in heat resistance, moisture resistance, and light resistance, and based on this, the present invention has been completed.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel magenta dye having excellent heat resistance, moisture resistance and light resistance.

[0010]

The above objects of the present invention have been attained by an image forming dye represented by the general formula [I].

[0011]

Embedded image [Wherein, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or a substituted alkyl group, and R ₁ and R ₂ may combine with each other to form a 5- or 6-membered ring.

R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an alkoxy group or a substituted alkoxy group. R ₁ and R ₄ , or R ₂ and R ₆ may be bonded to each other to form a 5- or 6-membered ring. R ₇ and R ₈ each represent a hydrogen atom or a substituent, R ₇
And R ₈ may be fused to each other to form a ring, R ₉ represents a substituent, n represents 1 or 2, and Z represents O or S. Hereinafter, the present invention will be described more specifically.

The dye represented by the general formula [I] can be used for many purposes, for example, thermal transfer recording, color image forming dyes suitable for image media such as ink jet and printing, filter dyes and photographic dyes. It is applied to dyes, antihalation dyes, dyes for textiles and the like.

In the general formula [I], R ₁ and R ₂ are preferably a hydrogen atom, an alkyl group or a substituted alkyl group such as a hydroxyalkyl group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group, an alkylsulfonamidoalkyl group. (The term alkyl group also includes cyclic alkyl groups.) Examples of these groups include methyl, ethyl, propyl, isopropyl, sec-butyl, butyl, isobutyl, tert-butyl, octyl, dodecyl, octadecyl, cyclohexyl, etc. Examples thereof include an alkyl group having a number of 1 to 18, a hydroxyethyl group, a methoxyethyl group, a methoxybutyl group, an ethoxyethyl group, a methoxyethoxyethyl group, and a β-methanesulfonamidoethyl group.

Examples of the 5- or 6-membered ring formed by combining R ₁ and R ₂ with each other include a pyrrolidino group, a piperidino group, a piperazino group, and a morpholino group.

R ₃ , R ₄ , R ₅ and R ₆ may be the same or different and are preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylsulfonamide Examples include an alkyl group and an alkoxy group. Examples thereof include a chlorine atom, a bromine atom, a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a methoxyethyl group, a methanesulfonamidoethyl group, a methoxy group, and an ethoxy group.

As the 5-membered or 6-membered ring formed by bonding R ₁ and R ₄ and R ₂ and R ₆ to each other, for example, the rings shown in the following groups are preferred.

[0018]

Embedded image The substituents represented by R ₇ , R ₈ and R ₉ are not particularly limited, but typically include groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like. Other than halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, sulfonyloxy, aryloxy,
Heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido,
Sulfamoylamino, alkoxycarbonylamino,
Aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxy, hydroxy, mercapto, nitro,
Examples include groups such as sulfonic acid, as well as spiro compound residues and bridged hydrocarbon compound residues.

Among the substituents represented by R ₇ , R ₈ and R ₉ , the alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched. As the aryl group, a phenyl group is preferable. Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group. Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group. Examples of the alkyl component and the aryl component in the alkylthio group and the arylthio group include the above-described alkyl groups and aryl groups. The alkenyl group has 2 to 2 carbon atoms.
32 cycloalkyl groups include those having 3 to 12 carbon atoms,
Particularly, those having 5 to 7 are preferable, and the alkenyl group may be linear or branched. The cycloalkenyl group has 3 carbon atoms.
~ 12, especially 5-7 are preferred.

Examples of the sulfonyl group include an alkylsulfonyl group and an arylsulfonyl group; examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group;
Examples of the phosphonyl group include an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, and an arylphosphonyl group; acyl groups include an alkylcarbonyl group and an arylcarbonyl group; and carbamoyl groups include an alkylcarbamoyl group and an arylcarbamoyl group. A sulfamoyl group such as an alkylsulfamoyl group and an arylsulfamoyl group; an acyloxy group such as an alkylcarbonyloxy group and an arylcarbonyloxy group; a carbamoyloxy group such as an alkylcarbamoyloxy group and an arylcarbamoyloxy group; Examples of the ureido group include an alkylureido group and an arylureido group; examples of the sulfamoylamino group include an alkylsulfamoylamino group and an arylsulfamoylamino group; Are preferably 5- to 7-membered, specifically, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group, etc .; heterocyclic oxy group As 5
Those having a 7 to 7-membered heterocyclic ring are preferred.
4,5,6-tetrahydropyranyl-2-oxy group, 1
-Phenyltetrazol-5-oxy group and the like; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group,
2,4-diphenoxy-1,3,5-triazole-6
A thio group or the like; a siloxy group such as a trimethylsiloxy group, a triethylsiloxy group, or a dimethylbutylsiloxy group; an imide group such as a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, or a glutarimide group; compound spiro [3.3] heptane-1-yl and the like as a residue; bridged hydrocarbon compound residue bicyclo [2.2.1] heptane-1-yl, tricyclo [3.3.1.1 ^{3 , 7} ] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like.

The above-mentioned groups may further have a substituent such as a long-chain hydrocarbon group or a non-diffusible group such as a polymer residue.

Next, the representative compounds of the present invention represented by the general formula [I] will be shown, but the present invention is not limited thereto.

[0023]

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[0024]

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[0025]

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[0026]

Embedded image The dye represented by the general formula [I] is oxidatively coupled to a coupler represented by the following general formula [II] and a paraphenylenediamine-based color developing agent represented by the following general formula [III] in the presence of an oxidizing agent. Can be synthesized.

[0027]

Embedded image Wherein, _{R 7, R 8, R 9} , Z and n are respectively the same as _{R 7, R 8, R 9} , Z and n in the general formula [I] described above. X represents a hydrogen atom or a substituent released by a reaction with an oxidized form of a color developing agent. ]

[0028]

Embedded image _{Wherein, R 1, R 2, R} 3, R 4, R 5 and R ₆ are each synonymous with _{R 1, R 2, R 3} , R 4, R 5 and R ₆ in the general formula [I] . The oxidative coupling reaction preferably proceeds under basic conditions, and the reaction medium may be an organic solvent, an aqueous organic solvent or an aqueous solution. The oxidizing agent may be any one having a potential capable of oxidizing p-phenylenediamine regardless of whether it is organic or inorganic.
Examples of the oxidizing agent include inorganic oxidizing agents such as silver halide, hydrogen peroxide, manganese dioxide, potassium persulfate, and oxygen, and various organic oxidizing agents such as NBS and chloramine T.

The oxidative coupling reaction is described in “T.
he Theory of the Photographic Process ”(4th edition)
(Macmillan, 1977), Leuco dyes are formed by nucleophilic attack of a coupler anion on a reactive species formed by oxidation of phenylenediamine or aminophenol, followed by azomethine dye dyes. It is thought to be.

The dye used in the present invention is, for example, a magenta coupler used in a silver halide color photographic light-sensitive material, wherein a coupler represented by the above general formula [II] is used.
Magenta formed by developing with a color developing solution containing a phenylenediamine-based color developing agent represented by the general formula [III], and coupling the coupler with the developing agent oxidized by exposed silver halide. It is also useful as a photographic dye for obtaining images.

The dyes used in the present invention may be used for photographic purposes as filter dyes, or disclosed in JP-A-58-149048,
Nos. 58-18169, 58-205798, 58-219086 and the like, and are useful as magenta dyes for images in thermal transfer processes, ink jet systems, color electrophotography, printing, etc. Used for thermal transfer recording materials.

In order to improve the stability of the dye used in the present invention to light or heat, a known stabilizer can be used in combination. Examples of such stabilizers include hydroquinone derivatives described in U.S. Pat.Nos. 3,935,016 and 3,982,944, hydroquinone diether derivatives described in U.S. Pat.No. 4,254,216 and JP-A-55-21004, 54-145530, spiroindane derivatives and methylenedioxybenzene derivatives described in UK Patent Publication Nos. 2,077,455 and 2,062,888, U.S. Pat.Nos. 3,764,337, 3,432,3
No. 00, No. 3,574,627, No. 3,573,050, JP-A-51-1
Nos. 52225, 53-20327 and 53-17729, chroman derivatives, spirocumarone derivatives and coumaran derivatives, JP-A-55-6321, UK Patent No. 1,347,556, UK Patent Publication No. 2,066,975 and Tokubosho No. 54-12337, hydroquinone monoether derivatives and p-aminophenol derivatives, JP-B-48-31625 and U.S. Pat.
Bisphenol derivatives described in US Pat. No. 700,455, and metal complexes described in US Pat. No. 4,245,018 and the like can be mentioned.

[0033]

EXAMPLES The present invention will be described specifically with reference to Examples, but the embodiments are not limited thereto. Example 1 Synthesis scheme of exemplified compound (3)

[0034]

Embedded image Synthesis of Intermediate (A) 300 ml of ethanol and 53.1 g of benzaldehyde were added to 63.8 g of p-chloroaniline and stirred at room temperature for 1 hour. Thereafter, the reaction solution was recrystallized as it was to obtain the desired compound (A) (yield 95.9 g, 89%). Synthesis of Intermediate (B) To 50.0 g of the compound (A), 150 ml of toluene and 3 parts of mercaptoacetic acid were added.
5.0 g and 13.2 g of p-toluenesulfonic acid monohydrate were added and the mixture was boiled under reflux for 2 hours. After removing toluene under reduced pressure, 200 ml of ethyl acetate and 200 ml of water were added, and the mixture was washed with water. Thereafter, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, and the residue was recrystallized from methanol to obtain the desired compound (B) (yield 25.6 g, 38%). Synthesis of Intermediate (C) To 5.8 g of compound (B), 40 ml of acetic acid and 14 ml of 35% H ₂ O ₂ were added, and 0.66 g of sodium tungstate dihydrate was further added, followed by heating at 60 ° C. for 1 hour. After adding 50 ml of water to the reaction solution and cooling to room temperature, the precipitated solid was filtered. The residue was recrystallized from acetonitrile to obtain the desired compound (C) (yield 3.9 g, 61%). Synthesis of Exemplified Compound (3) 2.0 g of Compound (C) was dissolved in 70 ml of ethyl acetate, and 5 wt.
70 ml of a 5% aqueous potassium carbonate solution was added. Then, while stirring at room temperature, 4-amino-3-methyl-N-ethyl-N
-(Β-methanesulfonamidoethyl) aniline / 3 /
4.1 g of disulfate monohydrate was added. The reaction solution was charged with silver oxide 3.6
g, and further stirred at room temperature for 2% aqueous hydrogen peroxide.
20 ml was added slowly. After stirring at room temperature for 1 hour as it was, the mixture was filtered, only the ethyl acetate layer of the filtrate was taken out, washed with water, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The residue was purified by silica gel chromatography to obtain the desired Exemplified Compound (3) (yield 2.2 g,
Yield 60%).

The structures of these compounds are represented by NMR, I
R, confirmed by mass spectrum.

Compounds other than the exemplified compound (3) can be synthesized according to the above synthesis examples, starting from the corresponding raw materials. Example 2 A gelatin layer containing a comparative dye (A) dissolved in dioctyl phthalate was applied on a paper support laminated on both sides with polyethylene so as to have a reflection density of about 1.5 to prepare Sample 1. . Next, Samples 2 to 11 were prepared in exactly the same manner as in Sample 1 except that the comparative dye (A) was replaced with the dye shown in Table 1.

Each of the coated samples 1 to 11 was subjected to high temperature and high humidity (60
(C, 80% RH) atmosphere for 20 days, and examined the heat resistance and moisture resistance of the applied dye. Table 1 shows the obtained results. However, the heat and humidity resistance of the applied dye is represented by the percentage of the dye remaining after the heat and humidity test with respect to the initial concentration of 1.5. Note that a KD-7R densitometer (manufactured by Konica Corporation) was used for various measurements.

Each sample was measured with a xenon fade meter for 10 minutes.
After irradiation for 0 hours, the density was measured, and the light resistance of the dye image was examined from the dye remaining rate after the light resistance test with respect to the initial density of 1.5. The results are also shown in Table 1.

[0039]

Embedded image

[0040]

[Table 1] As is clear from the results in Table 1, the dye-coated sample used in the present invention has a higher dye residual ratio, is superior in heat resistance, moisture resistance, and light resistance as compared with the comparative dye-coated sample, and is robust. You can see that there is.

[0041]

The dye of the present invention has high fastness to heat, humidity and light. That is, the dye is a robust dye having good heat resistance, moisture resistance, and light resistance, and is therefore favorably used in thermal transfer recording materials.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI G02B 5/20 101 G03C 1/43 G03C 1/43 1/825 1/825 B41M 5/26 101K (56) References JP 55-1333044 (JP, A) JP-A-55-147558 (JP, A) JP-A-2-69292 (JP, A) JP-A 1-172838 (JP, A) JP-A 4-220644 (JP, A) Kaihei 2-147665 (JP, A) UK Patent 1323455 (GB, A) CHEMICAL ABSTRACT S, 54 [20] (1960), 21050 d. (58) Fields investigated (Int. Cl. ⁷ , DB name) C09B 55 / 00 C09B 23/00 B41M 5/00 B41M 5/38 C09B 57/00 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)

Claims (1)

(57) [Claims] 1. An image forming dye represented by the general formula [I]. Embedded image [Wherein, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or a substituted alkyl group, and R ₁ and R ₂ may combine with each other to form a 5- or 6-membered ring. R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an alkoxy group or a substituted alkoxy group. R ₁ and R ₄ , or R ₂ and R ₆ may be bonded to each other to form a 5- or 6-membered ring. R ₇ and R ₈ each represent a hydrogen atom or a substituent; R ₇ and R ₈ may be fused to each other to form a ring; R ₉ represents a substituent; n represents 1 or 2; Is O
Or S. ]