JPS6164492A - Formation of color image - Google Patents

Abstract

PURPOSE:To form a multicolor image not generating the blotting or re- sublimation of a transferred dye and having good color reproducibility, by imagewise applying heat energy to a transfer material, wherein a thermal transfer dye is contained on a support, from the side of a support to apply the transfer mordanting of the dye to an image receiving sheet containing a mordant. CONSTITUTION:A transfer material 1 is usually prepared by applying a hydrophilic colloid layer containing a thermal transfer dye to a support 2. The thermal transfer dye desirably has at least one mordant group and, because said dye is used so as to be mordanted by a mordant, it is pref. that pKa is 7 or less. When the transfer material 1 is passed between rollers containing water to be impregnated with water and opposed to an image receiving sheet 4 so as to provide a predetermined interval therebetween in face-to-face relation to perform printing by a thermal head 5, a magenta image 9 comprising a dye D-5 is obtained on the image receiving sheet 4. This dye D-5 shows a release type absorption spectrum.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to a new method for forming color images in which thermal energy is applied imagewise rather than uniformly. The present invention relates to a multicolor image forming method for reproducing image electrical signals as a so-called hard copy.

(Prior Art) Conventionally, methods for converting coded electrical signals into visible images include thermal recording, thermal recording, thermal transfer,
Various recording methods are known, such as an electric heat-sensitive recording method, an inkjet recording method, a discharge breakdown method, an electric field recording method, an electrostatic recording method, an electrophotographic recording method, and a silver salt photographic recording method. Regarding these, for example, IEICE Technical Research Reports IEr1-Lehiro, IEr0-4U, and IEr1-j.

Same r3-6, Journal of the Institute of Electronics and Communication Engineers, 4 p.
724 (/ritl) etc.

Currently, there is a thermal transfer method that has a relatively simple device configuration and can be applied to color facsimile and the like. Unlike the heat development method, which uniformly heats the photosensitive material, this method controls the heat source according to the image information to transfer all of the dye. Two methods are known: a method in which the dye is transferred together with a thermal solvent with a low heat capacity (melt transfer type) and a method in which a sublimable dye is transferred (sublimation transfer type). Deterioration of sharpness due to color bleeding,
There are problems such as a decrease in image density due to re-sublimation. Tokukai Akira! Turf No. 1123 describes an attempt to improve the fixing properties of transferred images by increasing the transfer rate.
There are a limited number of dyes that can be used, and it is difficult to select dyes with good hue, so they are insufficient for color reproduction. Further, the polyvalent metal ions contained in the dye sheet are highly colored, and this coloring remains on the white background even after transfer, which is not preferable.

(Object of the Invention) The first object of the present invention is to provide a color image forming method that does not cause bleeding or re-sublimation of transferred dyes. λth
The purpose of the present invention is to provide a method for forming multicolor images with good color reproduction. A third object of the present invention is to provide a method for forming a color image with a clear white background.

(Structure of the Invention) As a result of intensive research, the present inventor has determined that thermal energy is applied imagewise from the side of the support to a transfer material containing at least a heat transferable dye on a support, preferably in the presence of a base generating substance. ,mordant? It has been found that the above object can be achieved by transferring and mordanting the dye to a dye-containing dye sheet.

The transfer material used in the present invention is usually formed by coating a support with a hydrophilic colloid layer containing a heat transferable dye.

In order to add a heat transferable dye to a hydrophilic colloid aqueous solution, it is preferable to dissolve it in water or an organic solvent (acetone, alcohol, dimethylformamide, etc.) and then disperse it in the hydrophilic colloid aqueous solution. There is no particular restriction on the amount added, but jxlo ~3×10−
2 mol/m2 is suitable, preferably a/x10'
~≦×lO mol/rlL.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, z
A wide variety of synthetic hydrophilic polymeric materials can be used, such as monopolymers or copolymers of remethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

In a preferred embodiment of the present invention, the heat transferable dye used is represented by general formula (I).

t(O-D-N=N-A r (I) (however, DH is a carbocyclic or heterocyclic aromatic ring, and OH and -N=, =N-[substitution positions that can be conjugated with each other) (Ar is a carbocyclic or heterocyclic aromatic ring.) The heat transferable dye used in the present invention preferably has at least one mordant group.

The mordant group in the heat convertible dye of the present invention is a dissociable group, and has the ability to be mordanted by a mordant in a dissociated state. In a preferred embodiment, the p K of the mordant group
a n is 7 or less (preferably t, j or less, more preferably t, o-i, o).

In the above formula (I), at least one mordant group is preferably an OH group substituted with D defined in the formula. Other mordant groups include phenolic OH groups, carboxyl groups,
Sulfo group, phosphate group, i-do group, hydroxamic acid group, (
A (substituted) sulfamoyl group, (substituted) sulfamoylamino group, etc. may be included in the D portion or the Ar portion.

The D part and the Ar part are an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an aryl group, an acylamino group, an acyl group, a cyano group, a hydroxyl group, an alkylsulfonylamino group, an arylsulfonylamino group. , alkylsulfonyl group, hydroxyalkyl group, cyanoargyl group, alco-cow dicarbonyl alkyl group, alco-cow dialkyl group, aryloxyalkyl group, nitro group, halokene, aryloxyalkyl group, amino group, substituted amino group, alkylthio group, arylthio The alkyl group and aryl group moiety in these substituents may be further substituted with a substituent selected from the group consisting of a halogen atom, a hydroxyl group, a cyano group, an acyl group, an acylamino group, an alkoxy group, and a carbamoyl group. It may be substituted with an i, u-substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, cal f xyl group, alkylsulfonylamino group, arylsulfonylamine group or ureido group.

In addition, the D part and the -Ar part [, OH group (including alcoholic and phenolic), imide group, quaternary ammonium group, carbamoyl group, substituted carbamoyl group, sulfamoyl S, substituted sulfamoyl group, sulfamoylamino may be substituted with a hydrophilic group such as a substituted sulfamoylamino group, a ureido group, a substituted ureido group, an alkoxy group, a hydroxyalkoxy group, or an alkoxyalkoxy group.

Examples of the carbocyclic aromatic ring represented by D include a benzene ring and a naphthalene ring. Examples of the heterocyclic aromatic ring represented by D include a pyrazole ring and the like.

In a preferred embodiment of the invention, it is the case that in formula (I), DK[ is replaced by 1. OE(, which represents at least one mordant group. In this case, of course, the above-mentioned mordant groups and/or a substituent and/or a hydrophilic group.In this case, the transferred dye exhibits a so-called dissociated type visible absorption waveform, which is sharper and more colored than that of a non-dissociated type. In order to use the present invention as a Victorian color image forming method, which is preferable in terms of reproduction, it is necessary to prepare each of the three primary colors (yellow, magenta, and cyan).

The heat-transferable dye of the present invention which mainly gives yellow images is preferably represented by the following general formula (II).

(M)m Specific examples of heat transferable dyes ([) that are effective in the present invention include:
The following are listed: A-/-CNH A-2-CN Co0CR3 A-J -CN J-CH3 A-Hiro-CN 4cmC1-13 Compound number Q M B-/ -CN 2-QC) 13B-J
-CN Ko CH3 B-J -CN J-CH3B-Hiroshi
-CN 蓼-CH5B-z -CONH
C)13 HB-1-CF3)I B-7-CNI (Examples of compounds containing formula (II)K include:

The expression (■) and the expression (X■
), U.S. Patent U, 0/J.

Described in column 433, column/Q, 1tA-Aμ line 7
The dyes listed in Table 1 and Table 11a of A/7430 are representative.

The heat-transferable dye of the present invention which mainly provides magenta images is preferably represented by the following general formula (III).

H Examples of heat transferable dyes (III) effective in the present invention include:
The following can be mentioned.

020H C-/-CH3I C-λ -C2H5H C-J-CI-i (CI-13)2H C-≠ -C2H5C2H3 C-r -C3H7-(n) -CaH2-
in) C-1-(CH2)4- C-7-C6H5H C-4-C)13 -C)13C-ta -C
4H9-(n) -C4Hg(n)C-i o
-CH2CH20C)13)102NH2 D-/ -C1-13)1 D-λ -C2)i5)LD-J
-C)i(CH3)2t(D-μ -C
(C)13)5)i])-j-C2
)15 -C2H5D 4 -C3H7-
(n) C5H7-(b)D-7-(CH2
)4-1)-4-C6H5)I-2 D-i.

D-／／ Tokukai Akira! 11-/J Hirojo No. formula (III) and (
IV) Pigment expressed by JP-A-Shoj! -μ311 is a dye represented by the formula (M), JP-A-Shoj≠-4jOJIA
Dyes represented by the formula (■) and formula (IX) in JP-A No. 332, dyes represented by the formula (■) and formula (■) in JP-A No. 332, JP-A No. The dye represented by the formula (■) in Hirogo and US Patent 3. Rijl, Hiroshi No. 76 (Column 3 ~ It table ■ and Column 37 ~ See table ■,
and Column 4c/-4'--Table V and Table ■) are also effective as encompassed by formula (I[) of the present invention.

The heat transferable dye of the present invention which primarily provides cyan images is preferably represented by the following general formula (IV).

(Z3).

0H O2 H -j H E-Hiroshi As a specific example of the dye contained in the formula (IV), JP-A-Sho≠
The dye represented by the formula (M) and Matage (V) of Tarko No. 1.33, the dye represented by the formula (VI) of JP-A-10-10 Tata No. 21, and the dye represented by Y'1 (V), Kaisho 13-≠041
Dye represented by the formula (■) of No. 02, JP-A-Shoj≦-7i
oti No. (V) formula 18O2Haj is -SO2NH2
You can use dyes that have been changed to .

Since the heat transferable dye of the present invention is used as a mordant in a mordant, it is preferable that the pKa is 7 or less.

Preferably Otsu! Below, more preferably 6.0 or less, i, o or more is suitable for the purpose of improving fixing performance. In this case, the completely dissociated form (anion) of the heat transferable dye
It is thought that it is electrostatically bonded to a mordant (mostly a cationic substance) as a dye.Also, since it is possible to overprint two colors of dye, a highly saturated image can be obtained.
There is a reproduction of black.

To overprint two or more color dyes, for example, a cyan transfer image is formed on an image-receiving sheet using a transfer material containing the heat transferable dye of the present invention that provides a cyan image, and then a transfer material of the present invention that provides a magenta image is formed on the image receiving sheet. A magenta transfer image @! is placed on the same image-receiving sheet as above using a transfer material containing thermally transferable dye T-!
By completely forming a multicolor image, it is possible to fully form a multicolor image.Supports used in the present invention include, of course, so-called paper,
Particularly preferred are paper and plastic sheets, although plastic sheets and metal sheets can also be used.

The paper used as a support in the present invention is a broad concept that includes not only commonly used paper but also special papers such as art paper and synthetic paper, but from the viewpoint of dimensional stability, art paper and Synthetic paper is preferred.

The plastic sheet used as a support in the present invention is a concept that includes a so-called plastic film, and any known general-purpose or special purpose plastic material can be used as such, but Polyester and cellulose triacetate materials are particularly preferred from the standpoint of strength, dimensional stability, and cost.

To apply thermal energy to the transfer material image-wise, a method of heating with a thermal head or a method of generating heat by irradiating with a laser beam such as a helium-neon laser-1 carbon dioxide laser f+ or a YAG laser can also be applied.

The base generating substance of the present invention is preferably a base or a base precursor. The base generating substance can be used in either the transfer material or the image receiving shift, and may also be supplied from the outside during thermal transfer.

When included in the transfer material (C), it is particularly advantageous to use a base precursor as the base generator.

Examples of preferred base generating substances include, as inorganic bases, alkali metal or alkaline earth metal hydroxides, λ straddle tertiary phosphates, borates, carbonates, quinolates, and metaborates. ; ammonium hydroxide; hydroxide of high-grade alkyl ammonium; hydroxide of other metals, etc.; examples of organic bases include aliphatic amines (trial amines, hydroxylamines, aliphatic polyamines); ), aromatic amines (N-alkyl-substituted aromatic amines, he-hydroxylalkyl-substituted aromatic amines and bis(p-(sialylamino)phenyl)methanes), heterocyclic amines, amidines, cyclic amidines guanidines, cyclic guanidines, and U.S. Pat.

uio, tag number describes betaine tetramethylammonium iodide and diaobutane dihydrochloride, and U.S. Pat. In the present invention, those having a pKa value of r or more are particularly useful.

Examples of base precursors include salts of organic acids and bases that decompose by decarboxylation upon heating, compounds that decompose through Rossen rearrangement, Beckmann rearrangement, etc. and release amines, and those that cause some kind of reaction upon heating to release all of the base. used.

Preferred base precursors include the aforementioned organic base precursors. Salts with thermally decomposable organic acids such as, for example, trichloroacetic acid, lfluoroacetic acid, propiolic acid, cyanoacetic acid, sulfonylacetic acid, acetoacetic acid, etc., US Patent No. U, 01! , and salts with cocarboxylic rupoxamide described in Hiro Pt.

Preferred specific examples of base precursors are shown below. Examples of metal oxides whose acid moieties are thought to decarboxylate and release bases include the following:

Examples of trichloroacetic acid derivatives include guanidine trichloroacetic acid, bilysine trichloroacetic acid, morpholine trichloroacetic acid, p-toluidine trichloroacetic acid, λpicoline trichloroacetic acid, and the like.

Other British Patent No. R, R≠J, U.S. Patent No. 3, 2
No. 20,1146, Tokukai Sho! 0-22. The base precursor described in No. tλj etc. can be used.

Other than trichloroacetic acid, U.S. Patent No. ≠,
ore, 4! US Patent No. ψ, o6o.

Examples include α-sulfonia acetate as-form as described in IAλ0, and salts of propiolic acid derivatives and bases as described in Japanese Patent Application No. Shojl-36,700. As a base component,
In addition to organic bases, salts using alkali metals and alkaline earth metals are also effective, so special request! It is described in r-4ri and jri-7.

Precursors other than those mentioned above include hydroxamic carbamates described in Japanese Patent Applications No. 11-IJ and rtO that utilize Rossen rearrangement, and Japanese Patent Applications No. 11-IJ and rtO that generate nitrile.
The aldoxime carbamates described in Hiroshi No. 1 and the like are effective.

Also, Research Disclosure magazine / 77th anniversary! Monthly issue/! Amine imides described in No. 774, JP-A-ShojO-ko λ, ≦4! The aldoneamides described in the above publication are preferably used because they decompose at high temperatures to produce bases.

The above bases or base precursors can of course be used not only for promoting dye release (but also for other purposes, such as adjusting the pH value).

The image-receiving sheet includes a mordant. Various mordants can be used in the present invention, and a useful mordant can be selected depending on the physical properties of the dye, transfer conditions, other components contained in the photographic material, etc. The mordant used in the present invention is a high molecular weight polymer mordant.

The polymer mordants used in the present invention include polymers containing secondary and tertiary amino groups, polymers having nitrogen-containing heterocyclic moieties, polymers containing these ≠ class cation groups, and having a molecular weight of 1,000 to 20o, ooo, Especially / 0.0
00-jO,000.

For example, U.S. Pat.

pea, No. 430, same! ,/Hiroshi, oi/issue, same 3.7
Vinyl pyridine polymers and vinyl pyridinicum cationic polymers 1 disclosed in Yot, r/≠ specification etc.: ffi Patent J, A-27, 4P Hiro No., same! , 11P
, No. 05P4, same g, iar.

Polymer mordants capable of crosslinking with gelatin, etc., disclosed in U.S. Pat. rr, No. 711, same, 7/
, r! No. Ko, No. 2.7F1,043, JP-A-Sho J-4C
-//j4ko, the same j'lA-/lAj! Aqueous solya mordants disclosed in US Pat. , 9
A reactive mordant capable of covalently bonding with the dye disclosed in the specification etc. of No. 74 (JP-A-Sho!Hiro/J7JJJ); and US time h3.70? -490, same J, 7rr
, rjj No. 3, A4J, l/-1'2
No. 3. Miyako It, No. 704, No. 3,117. O
6l, No. 3, 27/, / Kou 7, No. 3, 27/
, /≠ issue, JP-A No. 10-7/332, same as 3-30
JJt issue, same! Kono J1J Koro No. J-3-7, 2
No. 7 and No. 13-102QL.

Other U.S. Pat. No. 2,671,3/6, λ.

Mention may also be made of the mordants described in No. 112, Ij4.

Among these mordants, those that migrate from the mordant layer to other layers within the photosensitive material layer are preferred.For example, those that crosslink with the matrix such as gelatin, water-insoluble mordants, and aqueous sol (or Latex dispersion) type mordants can be preferably used.

Particularly preferred polymer mordants are shown below.

(1) Groups that have a 4' ammonium salt and can be covalently bonded to gelatin (for example, aldehyde groups, chloroalkanoyl groups, chloroalkanoyl groups, vinylsulfonyl groups,
pyridinium propionyl group, vinyl carbonyl group, alkylsulfonyl group, etc.) For example, (2) a copolymer consisting of a repeating unit of a monomer represented by the following general formula and a repeating unit of another ethylenically unsaturated monomer. and a crosslinking agent (e.g. hahisalkanesulfonate, hisarenesulfonate).

R, R1: H, alkyl group group, aryl group, or R3-R5 at least two combined complete heterocycle formation You may.

X: Anion (The above alkyl group and aryl group include substituted ones.) (3) Polymer X represented by the following general formula: about 0.2 to about! Molch y: about O to about 2θ mol% 2: about 10 to about 2? Molch A: Monomer having at least λ ethylenically unsaturated bond B: Copolymerizable ethylenically unsaturated monomer'Q
:N, P R1, R2, R3" Alkyl group, cyclic hydrocarbon group, or a small number of R1-R3 (two of them may be combined to form a ring. (These groups or rings may not be substituted. [Also acceptable.] (4) Copolymer X consisting of (a), (b) and (cl): hydrogen atom, alkyl group or halogen atom (the alkyl group may be substituted) (b) acrylic ester ( C) Acrylic nitrile (5) represented by the following general formula (water-insoluble polymer having 9 repeating units 1/3 or more R, R2, R3: each represents an alkyl group, R1
-The total number of carbon atoms in R3 is /-2 or more. (The argyl group may be substituted.) As the gelatin used for the anion infection layer, various known gelatins can be used.For example, gelatin produced by different gelatin production methods such as lime-treated gelatin and acid-treated gelatin. Or, or
It is also possible to use gelatin obtained by chemically modifying the obtained gelatin such as phthalation or sulfonylation. Further, if necessary, KH1 desalting treatment can be performed before use.

A person skilled in the art can easily determine the mixing ratio of the polymer mordant and gelatin of the present invention and the application fH1 of the polymer mordant, depending on the amount of dye to be mordanted, the type and composition of the polymer mordant, and the image forming process to be used. However, the mordant/gelatin ratio is 20710-10720 (weight ratio), mordant 11 cloth tflO, j-1, iil /rn2
It is preferable to use it in

The image receiving sheet may have a white reflective layer.

For example, a layer of titanium dioxide dispersed in gelatin can be provided over a mordant layer on a transparent support. The titanium dioxide layer forms a white opaque layer, and a reflective color image can be obtained by viewing the transferred color image from the transparent support side.A typical image-receiving sheet for diffusion transfer uses a polymer containing ammonium salt. A transfer solvent can be used for transferring a dye to an image receiving sheet from a dye transfer material obtained by mixing it with gelatin and coating it on a support. A basic aqueous solution containing 1 cr of a transfer solvent, water, and a potassium hydroxide, a potassium hydroxide, and an inorganic alkali metal salt is used. Also, methanol, N, N
- Low boiling point solvents such as dimethylformamide, acetone, and cynobutyl ketone, and mixed solutions of these low boiling point solvents and water or basic aqueous solutions are used. In the present invention, water is preferred (7).The transfer solvent may be used by moistening the image receiving sheet with a gold solvent, or may be incorporated into the material as crystal water or microcapsules. Good. Water is particularly preferred.

Example 1 10 ml/part of a solution of the dye of the present invention in MDMF and 1/part of Mcllvine solution at various pHs were mixed and
The absorbance Dn of the dye at λmax was measured at C. (
pKa was determined from a plot of DoDn)/(Dn-D-) vs, p)i. However, D.

is the absorbance of the undissociated dye and D- is the absorbance of the dye anion.

pKa of dye B-/ pKa 4L, AIA # B-217, pKa of Tata dye B-t. Hiro #13-4 1 J', 3j1B-7t
u, or 'D-/l 3.2゜I D-213,2bu#1)-J I J, Jr'D-≠
I J,tA? #1)-jlJ,I
EXAMPLE 2 As an image-receiving sheet, a polyvinylbenzyl-N,N,N-trihexylammonium chloride C mordant) was applied to a polyethylene terephthalate support.

All samples were prepared using Ogl Atsushi, Gelatin J, and Ofi/m2.

As a transfer material, the above-mentioned dye D-jtDMFI of the present invention is used.
A solution was prepared in which C was dissolved and dispersed in gelatin, mixed with a methanol solution of guanidine trichloroacetic acid, and then coated on a polyethylene terephthalate support. This transfer material was passed through a roller containing water to become hydrated. Thereafter, when the transfer material and the image receiving sheet fO0Jrnrn were placed face to face with each other and printed using a thermal head, a magenta image of the dye D-r was obtained on the image receiving sheet. The color image is the dissociated (anion) absorption spectrum (2m3Xj j 3n rn) 'c
Indicated. Since it was mordanted with a dye anion in the mordant, it was a magenta image with improved fixability and good hue.

[Brief explanation of drawings]

FIG. 1 is an enlarged sectional view for explaining the multicolor image forming method of the present invention. In the figure, 1 is a transfer material, 2 is a support, 3 is a layer containing a thermally transferable dye and a base generating substance, 4 is an image receiving sheet, 5 is a thermal head, and 6 is a heating resistor. Reference numeral 7 represents a layer containing a mordant, 8 represents a support, and 9 represents a dye image transferred and mordanted. Patent applicant: Fuji Photo Film Co., Ltd. 5
4d

Claims (4)

[Claims] (1) Image-wise applying thermal energy to a transfer material containing at least a thermally transferable dye on a support from the side of the support;
A color image forming method comprising forming a dye image by transferring and mordanting the dye onto an image receiving sheet containing a mordant. (2) The color image forming method according to claim 1, wherein the heat transferable dye is a heat transferable dye having at least one mordant group. (3) The color image forming method according to claim 2, wherein the mordant group has a pKa of 7 or less. (4) Image-wise thermal energy is applied to a transfer material containing at least a thermally transferable dye on a support from the side of the support in the presence of a base generating substance to transfer and mordant the dye onto an image receiving sheet containing a mordant. 2. A color image forming method according to claim 1, wherein the image is formed by: