JPS59156791A - Image-receiving element for thermal transfer - Google Patents

Abstract

PURPOSE:To obtain a developed color image excellent in color reproduction characteristic, by providing an image-receiving layer comprising a color tone adjusting agent. CONSTITUTION:The image-receiving layer comprising a color tone adjusting agent is provided. The color tone adjusting agent is a compound inducing a shift of a maximum absorption wavelength of a coloring matter by at least 2 nm, preferably at least 5 nm, or inducing a change in absorption wave form in the case of dying on a polyethylene terephthalate (degree of crystallinity: 50%) by making contact with, mixing with or dissolving in a coloring matter which is generated from a thermally transferrable coloring matter providing substance incorporated in a thermal transfer element and is transferred to the image-receiving element through thermal diffusion. The shift of the maximum absorption wavelength is preferably a shift to the longer wavelength side. A preferable example of the color tone adjusting agent is a phosphoric acid amide compound or a phenol compound.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an image receiving element for thermal transfer, and more particularly, to a thermal development device used in combination with a thermal development color, & optical element that involves thermal diffusion transfer of a dye. The present invention relates to an image receiving element for a photosensitive material or an image receiving element for a thermal transfer material using a heat source such as a thermal head, and relates to an image receiving element for obtaining an image with adjusted tone. The present invention relates to an image receiving element used in combination with a thermal transfer element, and the term thermal transfer element herein refers to any one of a thermal development photosensitive element in a thermal 3A image-sensitive material, and a final thermal element in a thermal transfer material. There may be.

[Prior art]

When obtaining a color image by the subtractive color method, the three primary colors are yellow, magenta, and cyan. Among these, yellow is a complementary color to blue, and is required to be clear yellow and have a maximum absorption wavelength of 420 to 480 nm. Also,
Magenta is a complementary color to green, and is required to be a clear reddish-purple color with an extremely thick absorption wavelength of 520 to 580 nm. Cyan is a complementary color to red, and is required to be a clear blue-green color with a maximum absorption wavelength of 620 to 720 nm. However, commonly existing dyes are yellow, orange, red, violet, blue, and green, and in order to obtain a color 1III image with excellent color reproducibility using the subtractive color method, the extremely thick absorption wavelengths are set in the yellow, magenta, and cyan regions. Although many designs of dye molecule structures have been carried out in order to allow the dye to migrate, the current situation is that it is complicated and difficult.

On the other hand, as an image receiving element for thermal transfer, JP-A-57-1078
No. 85 and No. 57-137191 propose a product in which a water-dispersed portion of saturated polyester is coated on a paper support.
No. 7250 proposes a thermal dust image sensitive material in which a polyester support serves also as an image receiving layer or an image receiving element.

However, when dyeing a saturated polyester image-receiving layer, the dye migrates to the longer wavelength side compared to when the dye is dyed in an acetate ester solvent. You can't get it.

[Purpose of the invention]

An object of the present invention is to provide an image-receiving element for thermal transfer in which the maximum absorption wavelength of a dye can be shifted or the absorption waveform can be changed.

In other words, colors with excellent color reproducibility are produced by diffusion transfer using ordinary dyes, by moving extremely thick absorption wavelengths to yellow, magenta, or cyan tone regions on the image-receiving element, and/or by changing absorption waveforms. An object of the present invention is to provide an image-receiving element for thermal transfer with which an image can be obtained.

[Structure of the invention]

The above objects of the present invention have been achieved by an image receiving element for thermal transfer having an image receiving layer containing a tone control agent. A color tone adjusting agent is an agent that shifts the maximum absorption wavelength of a dye by contacting, mixing with, or dissolving the dye generated from a heat transferable dye-providing substance contained in a heat transfer element and thermally diffused transferred to an image receiving element. and/or changes the absorption waveform.
%) for the thickest absorption wavelength of the dye,
2 nm or more, preferably 5 nm or more (refers to a dye that moves by 5 nm or more, or refers to a dye in which a shift in the maximum absorption wavelength is not observed but a change in the absorption waveform is observed.The shift in the maximum absorption wavelength is to the short wavelength side. It may be a movement to or to a longer wavelength side, but movement to a longer wavelength side is preferable.

[Example of color tone adjusting agent]

Preferred color tone adjusting agents in the present invention are phosphoric acid amide compounds and phenol compounds.

Specific examples of phosphoric acid amide compounds are shown below.

(P-1) (P-2) (P-3) (P-4) (P-s) (P-6) These compounds are called “annaren der hemi-
(Annalen der chemie)
It is synthesized by the method shown in Volume 326, pages 177-302'°. Also useful are the phosphoric acid amide compounds shown in Belgian Patent No. 891,205.

The phenol compound, which is an example of the color tone adjusting agent used in the present invention, refers to phenols, catechols, and resorcinols, and includes, for example, U.S. Patent No. 2,835,579.
No. 4.12'4.396, British Patent No. 1,001
, No. 947 and No. 1,076,054 are useful.

A specific example is shown below.

(F”-1) (F”-2) (F-3) (F-4) (F-5) (F-6) (F-7) (F-8) (F-9) (F- 10) (j4Hg(nλ) (F-11) (F-12) (F-13) (F-i 4) The image-receiving element of the present invention is one in which a layer containing a tone adjusting agent is provided on a support. Although preferred, it is also possible that the color tone adjusting agent is contained in the support and the support itself serves as the image-receiving layer.

The support used in the present invention may be of any conventionally known type, such as paper, synthetic paper, aluminum foil, 7-cetyl cell p-film, cellulose ester film, polyvinyl acetal film, polyether sulfone film, These include polystyrene film, polycarbonate film, polychloride/vinylidene film, and polyethylene terephthalate film.

In the present invention, the binder for the layer containing the color tone adjusting agent may be any conventionally known binder (including natural or synthetic resins, etc., specifically casein, vegetable protein, gum tragacanth, gum arabic, etc.). starch,
Starch, dextrin, gelatin, glue, alginic acid, agar, polyethylene glycol, polyethylene glycol ester, propylene glycol ester, polyacrylamide, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polyvinyl butyral, methylcellulose, ethylcellulose, hydroxyethylcellulose , hydroxypropyl cellulose, carboxymethyl cellulose, polyvinyl acetate, oil-soluble polyvinyl butyral, acetyl cellulose, polymethyl acrylate, polybutyl hepta acrylate, polybutyl mec hepta acrylate, polystyrene, polyvinyl pyridine, polyethylene terephthalate, and epoxy resins.

Moreover, various additives can be added to the layer containing the color tone adjusting agent. For example, inorganic additives such as titanium white, silica, talc, clay, talc, barium sulfate, calcium carbonate, glass powder, kaolin, and zinc oxide are added to give matte properties, whiteness, smoothness, and gloss. It's okay. Further, other additives may be included for the purpose of improving image fastness or for other purposes.

In the present invention, the method of incorporating the color tone adjusting agent into the image-receiving element is not particularly limited, but may include coating or dipping on the support forming the image-receiving element, a support that also serves as a thermal transfer element, or a thermal transfer element. In the case of an image receiving element integrated with a thermal transfer element, there is a method of coating or dipping the surface of the thermal transfer element as an image receiving layer, and a method of adding a color tone adjusting agent in advance when forming a support. be.

In the case of the former hole, the color tone adjusting agent can be applied in the form of a solution, powder, or emulsion, or can be dipped or applied by a method such as latex impregnation. On the other hand, in the case of the latter method, there are methods in which paper is made using a paper machine using a mixed solution (slurry) in which the color tone adjusting agent of the present invention is added to natural or synthetic pulp along with a paper strength agent, sizing agent, filler, etc., or a method in which a synthetic polymer dope is used to make paper There is a method in which the color tone adjusting agent of the present invention is added to a film and then a film is formed.

The amount of the color tone adjusting agent of the present invention added is 0. OIS'/171
'~100v/i, preferably 0.05r/n?
~507/II.

The image-receiving element of the present invention allows for tone adjustment by shifting the maximum absorption wavelength and/or changing the absorption waveform of any dye produced from a thermally transferable dye-donor material.

The image-receiving element of the present invention can be placed in a stacked relationship with a thermal transfer element during thermal diffusion transfer, and can be any type of thermal transfer element containing a thermally transferable dye-providing substance. However, they can be used in combination, and the thermal transfer element may be of a so-called integrated type or a so-called peelable type.The dyes used here include azo dyes, anthraquinone dyes, and azomethine dyes. , indoaniline dyes, naphthoquinone dyes, nitro dyes, styryl dyes, phthalocyanine dyes, quinophtha p-triphenylmethane dyes, cyanine dyes, etc., but the effect is remarkable in azomethine dyes and indoaniline dyes. .

Azomethine dyes have the following \0=N- bonded chromophore in their molecules, and are generally formed from a compound having an active methylene group and an aromatic amine.

In particular, the oxidative coupling reaction product of an open-chain active methylene compound and a p-phenylenediamine derivative results in a 1-block dye, and the reaction product of a C-1-phenyl-5-pyrazolone derivative results in a magenta dye.

Specific examples of azomethine dyes are shown below.

(Y-1) (Y-2) H2O202H40H (Y-3) 0 0 0 0 115Lj2 U2ti5 (Y-6) 0 H3O-0-0-0-OH3 1 H3O2C21(5 (Y-7) O H5C'; ”ゝC2H3 (Y-8) 0 0 (Y-11) .6 H5O2C2H40H (Y-12) cooH (M-1) (M-2) OL (M-3) (M-4) (M--6 ) CH3 (M-7) (M-8) (M-9) (M-10) (M-1t) t (M-12) t (Mu4-13) (M-14) (M-15) o3H (M-16) refers to enyl)-p-quinoneimine and its derivatives,
Usually by the condensation reaction of p-nitronephenol or quinone chloroimine with dialkylaniline, or by the reaction of nitroso or nitrodialkylaniline with phenol or naphthol in the presence of a reducing agent in an alkaline bath. It is synthesized by oxidative coupling reaction of a mixture of p-phenylenediamine derivative and phenol or naphthol.

Specific examples of indoaniline dyes are shown below.

(C-1) (0-2) (C-4) (0-6) (0-7) C-8) (0-9) 1, 0-7o) 3C-rt) (0-12) H3 (3 (0-13) H3CO (0-14) t t (0-1s) r (0-16) 31j (0-17) (0-18) (C-19) (0-20) 31j (C -21) (0-22) (C-23) (0-24) (0-25) (0-26) (0-27) (0-28) (0-29) (0-30) H3 ( 0-31) (0-32) (0-33) 12H25 (0-34) (0-35) (0-36) (0-37) (0-39,) In the present invention, thermal transfer refers to The dye is diffused by sublimation (not limited to those that evaporate from solid to liquid, but also includes those that evaporate with melting) or by a solvent,
It means to be transcribed.

The image receiving element of the present invention is disclosed in Japanese Patent Application No. 57-217063, Japanese Patent Application No. 57-217796, Japanese Patent Application No. 57-217797, Japanese Patent Application No. 57-217797,
7 229651 and JP-A-51-15+146,
It can be used as a thermal transfer image receiving element used in a thermal transfer recording medium or a thermal transfer recording method, as described in Japanese Patent No. 54-68253 and Japanese Patent No. 57-160691. That is, for example, an ink sheet for thermal transfer and an image receiving element of the present invention are superimposed, and a thermal head, laser,
In response to thermal information from a xenon lamp or the like, the dye transferred onto the image-receiving element of the present invention is brought into contact with, mixed with, or dissolved in the tone adjusting agent of the present invention contained in the image-receiving element,
It shows a preferable color tone. The general art regarding heat sensitive elements is known and the image receiving element of the present invention may be used in combination with any of these types of heat sensitive elements.

Further, the image receiving element of the present invention can be used, for example, in Japanese Patent Application No. 57-12
No. 2596, No. 57-205447, JP-A-57-1
No. 86744, No. 57-179840, No. 57-19
No. 8458, No. 57-207250, Patent Application No. 57-2
No. 29649, No. 57-22.9650, No. 5'7-
It can be applied to a heat-developable photosensitive material or an image-receiving element for a thermal diffusion transfer method as shown in No. 229675.

That is, the heat-diffusible dye released by thermal development after imparting optical information is brought into contact with, mixed with, or dissolved in the tone adjusting agent contained in the image-receiving element of the present invention, and exhibits a preferable color tone. It is. General techniques relating to heat-developable elements and heat-developable photosensitive materials are well known, and the present invention may be used in combination with any of these types of heat-developable elements.

Preferred embodiments of the invention include the following.

(1) An image receiving element for thermal transfer having an image receiving layer containing a phosphoric acid amide compound.

(2) An image receiving element for thermal transfer having an image receiving layer containing a phenolic compound.

(3) A heat-sensitive element or a heat-developable element containing a heat-transferable dye-providing substance capable of releasing a heat-diffusion-transferable 7-dimethine dye or an indoaniline dye, and an image-receiving element that is placed in a stacked relationship at least during thermal transfer. An image receiving element characterized in that it contains at least one color tone adjusting agent selected from a phosphoric acid amide compound and a phenol compound.

〔Example〕

The invention will now be illustrated by examples.

Example-1 Mix 4 degrees of carnauba wax 607 and beeswax, and add 1.8 f of the azomethine dye (Y-4) to this.
, one with the above (M-1) 1.62 added, and one with the above (0-9) 1.55' of the indoaniline dye added, respectively, were coated on capacitor paper.
A thermosensitive cloud dye was created.

On the other hand, phosphoric acid amide compound P-1 was mixed with gelatin and water-soluble polyvinyl butyral (W-201, Tsukisui Kagaku) in 1 part.
The phosphoric acid amide compound P was dispersed in an aqueous solution mixed at a ratio of
-1 is 0.8f/n? An image receiving element of the present invention was prepared as follows.

The heat-sensitive element and this image-receiving element were superimposed, and the applied power was kept constant at 0.8 w/dot using a thermal head, and the pulse width was varied from 5 mS' (approximately 2.8 x 10"J) to 4 ohms (approximately 22"). When applied in steps up to IX1O-3J), a step wedge transfer image of yellow, magenta and cyan was obtained on the image receiving element.

In place of the image receiving element of the present invention, a 100 μm thick polyethylene terephthalate film (crystallinity 50%)
For comparison, the maximum absorption wavelength of the resulting transferred image is shown in Table 1 below.

Table-1 Example-2 The above (p-i
The same operation was carried out using the phenol compound (F-5) instead of ). The results are shown in Table 2 below.

Table 2 (Unit: nm) Example 3 To 7.45 r of 4-sulfobenzotriazole silver, add 1.3 fP of Eslec W-2018% aqueous bath part 4CC1 ossein gelatin, 110cc of water, and 25α of methanol, and add alumina hole. Dispersion was performed using a mill to obtain a silver salt dispersion.

Phthalic acid 021? , 0.16S' of phthalazine, 0.44 of the following compound (MX-1)
f, 0.42f of the following developing agent (Dev -1)? , and water-soluble polyvinyl alcohol (105, Clan) 8
%5CC, water 10CC, and 36111g of silver iodide emulsion with an average grain size of 0.04μ were added, and a photosensitive layer was formed on photographic baryta paper using a wire bar so that the wet film thickness was 55μ. was painted.

The dried thermally developable element was exposed to 30,0000 M8 through a step wedge.

Washi paper was sandwiched between the coated surface of the exposed heat development element and the coated surface of the image-receiving element of Example-1, and they were heated with a pressure iron for 30 seconds using an iron with a surface temperature of 160°C. The heat developing element and image receiving element were separated.

A magenta step wedge negative image with a maximum reflection density of 0.97, a minimum reflection density of 008, and a maximum absorption wavelength of 542 nm was obtained on the surface of the image receiving element.

(MX-1) (Devl) As a result of analyzing the magenta dye formed in the image-receiving element, it was found that it is a 7-dimethine dye (M-1) consisting of oxidative coupling of (MX-1) and (Dev-1). I found out something.

Example 5 In place of the photographic baryta paper in Example 3, a transparent polyimide film (KAPT) with a thickness of 1θOμ coated with polystyrene-butadiene copolymer latex
ON, DuPont! Using A) as a support, Example-
A photosensitive layer was formed by coating under the same conditions as in Example 3. A white reflective layer and an image-receiving layer having the following compositions were provided thereon, and a transparent polyethylene terephthalate film having a thickness of 50 μm was adhered onto the image-receiving layer.

Dark white reflective layer〉 (Units: f/m') Image receiving layer〉 (Units: ?/?7Z') A step wedge was passed through the photosensitive layer side of this sample for 30 minutes. Applying OOOOMS exposure, using a 3M heat developing machine 6-day tube module 277'',
Heating was performed at 140°C for 40 seconds.

A magenta step wedge negative image with a maximum reflection density of 0.78 and a minimum reflection density of 005 was obtained on the image-receiving layer side surface, and its maximum absorption wavelength was 540 nm.

Patent applicant: Agent for Konishiroku Photo Industry Co., Ltd. Patent attorney: Nobuaki Sakaguchi (and one other person) Procedural amendment (voluntary) 1 Ikwa April 12, 1958 Japan Patent Office Kazuo Wakasugi, Director-General 1 Indication of the case 1988 Special Grant I No. 31288 2, Title of the invention! ``I8 Requirement for transcription Purple 3, Relationship with the case of the person making the amendment Patent applicant 4, Agent 〒105 6 Number of inventions increased by the amendment 7, details subject to the amendment;) (Details of the invention A11ll etc.) Explanation ii, j) 8,
Contents of Amendment As shown in the attached sheet, the details of the amendment will be amended as follows.

l On page 3, line 6, "acetate ester" is corrected to "ethyl acetate."

Corrected to be in the squid construction (v-2) on page 14 of 21 Kuzu.

3 Add “00” to the box on page 15 in the formula (Y-5) and correct it.

that's all

Claims (1)

[Claims] An image receiving element for thermal transfer having an image receiving layer containing a tone adjusting agent.