JPS59182785A - Image receiving element for heat transfer material - Google Patents

Abstract

PURPOSE:To provide an image receiving element of a heat transfer material which is obtained with an improved stability of a pigment image formed under the irradiation of light by arranging a compound having a specified composition formula to be contained in a support. CONSTITUTION:One or more kind of compounds of the formulas I , II and III(R1, R1', R3, R3' and R5 are each H, fatty, arromatic, heterocyclic compound or the like; R2, R4, R4', R6 and R7 each H, halogen univalent organic group; land q 1-4; and m, n and p 1-3) are contained into an image receiving element (e.g. paper and synthetic resin film) to be stacked on a heat transfer element containing a heat transferring pigment donor in the heat transfer preferably at a rate of 10-100mol% per 1mol of image pigment at the maximum density to obtain an desired image receiving element.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image receiving element for thermal transfer, and more particularly to an image receiving element for a heat developable photographic material used in combination with a heat developable color photosensitive element involving thermal diffusion transfer of dyes. , or an image receiving element for a thermal transfer material used in combination with a color thermal element that uses a heat source such as a thermal head, and is capable of holding the formed color dye image robustly against light and heat. Regarding image receiving elements. The present invention relates to an image receiving element used in combination with a thermal transfer element, and the thermal transfer element herein may be either a photosensitive element in a heat-developable photographic material or a heat-sensitive element in a heat-sensitive transfer material.

[Prior art]

A method in which the development step for obtaining a color image is performed by dry heat treatment has many advantages over conventional wet methods in terms of processing time, concerns about pollution, cost, and the like. Dry heat treatment methods can be broadly divided into two types.
Another technique is to use heat-sensitive transfer materials.

The basic structure of a heat-developable photographic material consists of a photosensitive element and an image-receiving element. ), if necessary, a photosensitive layer containing silver halide, a binder, and additives and other photographic constituent layers are coated on the support, and the image receiving element is a thermal transfer layer contained in the photosensitive element. The image-receiving element does not have an image-receiving layer capable of forming a dye image by thermal diffusion transfer of a heat-transferable dye released or formed by heat development from a dye-providing substance, and if necessary, the image-receiving element has a support. .

On the other hand, the basic structure of a heat-sensitive transfer material is composed of a heat-sensitive element and an image-receiving element, and the light-sensitive element basically has sublimation,
A heat-sensitive ink layer or other constituent layer containing a heat-transferable dye-providing substance such as vaporizable or melt-transferable is not coated on the support, and the image-receiving element is formed from a heat-transferable dye-providing substance contained in the heat-sensitive element. The image-receiving element has an image-receiving layer capable of forming a dye image by thermal diffusion transfer of a heat-transferable dye released or formed by heating), and if necessary, the image-receiving element has a support.

The relationship between the thermal transfer element and the image-receiving element in thermal transfer materials using these thermal diffusion transfer methods is at least the same as the relationship shown in Figure 1. There are configurations in which both elements are separated after thermal transfer, and there are configurations in which both elements are peeled off after thermal transfer, and there are configurations in which they are integrated, and each is used depending on the purpose. .

In the technique described above, which utilizes thermal diffusion to obtain a color dye image on an image-receiving element, when the image-forming dye is exposed to light during storage, electricity is present in the image-receiving element. They are placed in an atmosphere that is extremely reactive with trace amounts of heavy metals and oxygen.

As a result, the intended dye may be oxidized or converted into another compound, resulting in serious drawbacks such as color staining and a decrease in D degree.

[Purpose of the invention]

As a result of intensive research to eliminate the above drawbacks, the inventors of the present invention found that
An improved image receiving element for color thermal diffusion transfer has been discovered.

An object of the present invention is to provide an image-receiving element that allows a dye image formed in a color thermal diffusion transfer system to exist stably under light irradiation.

[Structure of the invention C]

The above object of the present invention is to provide an image receiving element which is placed in a stacked relationship at least during thermal transfer with respect to a thermal transfer element containing a thermally transferable dye-providing substance, wherein the image receiving element has the following general formula (+), (if). This is achieved by an image-receiving element in a thermal transfer material, characterized in that it contains at least one of the compounds represented by t or I.

General formula (1) General formula (2) In the formula, R1, R1', R3, R3' and R5 each represent a frozen candy atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group, and R2゜R11, R ball',
R6 and R7 each represent a frozen candy atom, a ---rogen atom, or a --valent organic group, t and q each represent an integer of 1 to 4, and m, n and p each represent an integer of 1 to 3. When the dimensions l, m, n, p and q are each 2 or more, R2, R11, R11', R6 and R7 may be the same or different.

More specifically, the above R1 and R1'.

Examples of the aliphatic group represented by R3, R3' and R5 include alkyl groups, alkenyl groups, cycloalkyl groups, etc. The alkyl groups include straight chain or branched groups having 1 to 20 carbon atoms, and alkenyl groups. As for carbon number 2-2
It is preferable that the cycloalkyl group has 0 straight chain branches, and that the cycloalkyl group is 5- to 7-membered.

Further, the aromatic groups represented by R1, R1', R3, R3' and R5 include phenyl group, naphthyl group, etc., and the heterocyclic groups represented by the five groups such as R1 are as follows:
Contains a 5- to 6-membered nitrogen atom, oxygen atom or sulfur atom, such as furyl, pyranyl, tetrahydropyranyl, imidazolyl, pyrrolyl, pyrimidyl, pyrazinyl, triazinyl, chenyl, quinolyl, ogisazolyl or pyridyl. Can be mentioned.

The acyl groups represented by R1, R1', R3, R3' and R5 include alkylcarbonyl groups and arylcarbonyl groups having 1 to 20 carbon atoms, such as acetyl, pivaloyl, oleyl, lauroyl, benzoyl, etc. be. Examples of the sulfonyl group represented by the five members such as R1 include an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group TLJ), methanesulfonyl, butanesulfonyl, benzenesulfonyl, badruenesulfonyl, and the like.

Next, the monovalent organic group represented by R2#R", R'L', R6 and R shown above is represented by the general formula (D, (II)
-z or l means a group that can be substituted on the benzene ring, such as an alkyl group having 1 to 20 carbon atoms, an alkyloxy group, an alkylthio group, a phenyl group, a phenoxy group, an acyl group,
It represents an acylamide group, a sulfonamide group, an alkylamide group, an alkoxycarbonyl group, etc.

Next, the general formula (I), (n) used in the present invention
Specific examples of the compound represented by 'E or (2) (hereinafter referred to as the compound of the present invention) will be exemplified, but the invention is not limited thereto.

[Examples of compounds of the present invention]

H H CBHB (ln-4 0H CJ CH3 -7 (b)-1cH3 CH3 ([1)-2 (of-3 (If) -4 ([D-5 ([)-1 (1)-2 ( 1)-3 (2)-4 (110-5 (lit)-6 H (2)-8 0H (IID-9) These compounds of the present invention can be used for example in I'i Japanese Patent Publication No. 45-14
No. 034, No. 49-8338, No. 49-20977, No. 52-35633, No. 52-147434, No. 53-17729, No. 53-20327, No. 5
No. 4-48538, No. 55-89836, Mukai 47-4
Multiple synthesis can be carried out by the methods described in Publications No. 738 and No. 54-48538.

The compounds of the present invention may be used alone or in combination of two or more.

The amount of the compound of the present invention to be used is not limited, but it is 10 to 1000 mol, preferably 10 to 100 mol, per 1 mol of the maximum density image dye.

The method for incorporating the compound of the present invention into an image-receiving element is not particularly limited, but includes [A] a method of coating or dipping on a support forming an image-receiving element, or a support that also serves as a thermal transfer element;
Alternatively, in the case of an image-receiving element integrated with a thermal transfer element, there is a method of coating or dipping the image-receiving layer on the surface of the thermal transfer element, or (B) the compound of the present invention is added in advance when forming a support. There are ways to keep it.

In the former case [A], the compound of the present invention is added to an appropriate organic 1Wi
The image receiving element is immersed in a solution fermented with acetone, methanol, ethanol, ethyl acetate, dimethylformamide, dibutyl phthalate, tricresyl phosphate, etc., or these liquids are applied to the support or image receiving layer. It can be added by Alternatively, it can be added without a solvent or by dispersing it using a suitable organic solvent when producing the image-receiving layer. On the other hand, in the case of the latter CB, there are methods of making paper using a paper machine using a mixed solution (slurry) in which the compound of the present invention is added to natural or synthetic valves together with paper strength agents, sizing agents, fillers, etc., or a method of making paper using a synthetic polymer dope. There is a method of adding the compound of the present invention and forming it into a film to obtain the image receiving element of the present invention.

Uke 18 that can be used in the present invention! Paper and synthetic polymers (films) can be used as carbon atoms. Synthetic polymers (
Films] include, for example, polyacrylates (e.g. polymethyl acrylate, polyacrylate ether), polyacrylonitrile, Acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polyacetal, chlorinated polyether , polyvinyritine chloride, polyvinyl chloride, polyvinyl carbazole, polystyrene, styrene-butadiene copolymer, polyacetate cellulose, polyacetals (e.g. polyvinyl butyral, polyvirol formal), polytetrafluoroethylene, polychlorotrifluoroethylene, polyethylene , chlorinated polyethylene, polycarbonate,
Polyvinyl acetate, polyvinyl alcohol, polypropylene, polyvinylpyrrolidone, polyacrylates (f!
1 is polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyimpropyl methacrylate, poly-t-butyl methacrylate,
Examples include polycyclohexyl methacrylate, polyenalene glycol dimethacrylate, poly-2-cyano-ether dimethacrylate, etc.), polyesters (eg, polyethylene terephthalate, etc.), polyamide, polyimide, polysulfone, and the like.

These synthetic polymers may be used alone or as a mixture, or as a copolymer.

Particularly preferred image receiving elements include polyvinylidene chloride,
Polyvinyl chloride, polycarbonate, polyacetate cellulose such as polyethylene tere-7-thaleate, triacetate, diacetate, heptamethylene diamine and terephthalic acid, fluorene dipropylamine and adipic acid, hexamethylene diamine and diphenic acid, hexamethylene diamine and inphthalic acid Polyesters synthesized from polyamides synthesized from diethyl glycol tocyphenylcarboxylic acid, and ethylene glycol and bis-p-carboxyphenoxybutane are mentioned.

Further, the image receiving element of the present invention is disclosed in Japanese Patent Application No. 57-1225, for example.
No. 96, No. 57-205447, JP-A-57-186
No. 744, No. 57-179840, No. 57-1984
No. 58, Mukai No. 57-207250, Patent Application No. 57-229
No. 649, No. 57-229650, No. 57-2296
It can be applied to a heat-developable photographic material such as that shown in No. 75 or an image-receiving element for a heat-diffusion transfer method. That is, the heat-diffusible dye released or formed by thermal development after imparting optical information is transferred to the image-receiving element of the present invention. The general art relating to heat developable elements and heat developable photographic materials is well known and may be used in combination with any of these types of heat developable elements in the present invention.

The image receiving element of the present invention is disclosed in Japanese Patent Application No. 57-217063.
Thermal transfer recording media or It can be used as an image receiving element for thermal transfer used in a thermal transfer recording method. That is, for example, an ink sheet for thermal transfer and the 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 7 transferred onto the image-receiving element of the present invention is brought into contact with, mixed with, or dissolved in the color tone adjusting agent of the present invention contained in the image-receiving element, and exhibits a preferred color tone. It is something. The general art regarding heat-sensitive elements is well known, and "unexploded" receiver elements may be used in combination with these types of heat-sensitive elements.

In the present invention, thermal transfer refers to a process in which the dye is sublimated by heat (not limited to those that vaporize from solid to liquid, but also includes those that vaporize with melting) or diffused by a solvent and transferred. means.

Furthermore, when the image receiving element of the present invention is used for a heat-sensitive transfer material, the heat-sensitive element can be used with a thermal head composed of a printed resistor, a thin film resistor, a semiconductor resistor, etc., or a heat source such as a laser or a xenon lamp. In addition to the method of developing color and recording an image, etc., (2), there is a method of obtaining an image, etc. from a heat-sensitive element by a heat source controlled according to image information from another system. Of course, it can also be applied to a heat-sensitive transfer method in which dye is transferred to an image receiving element.

Various cooling agents can be added to the image receiving element of the present invention. For example, titanium white, silica, talc, clay, talc,
Barium sulfate, calcium carbonate, glass powder, kaolin,
Inorganic additives such as curved lead oxide may also be added. Further, it may contain an ultraviolet absorber, an antioxidant, a quenching substance, etc. for the purpose of improving image fastness or for other purposes.

The image-receiving element of the present invention is capable of transferring a dye produced from a thermally transferable dye-providing substance, and the image-receiving element of the present invention is at least in contact with the thermal transfer element during thermal diffusion transfer. It can be used in combination with any type of thermal transfer element that contains a thermally transferable dye-providing substance. , so-called peel-off type may be used. Dyes used here include azo dyes, anth-7 quinone color complexes, azomethine dyes, indoaniline dyes, naphthoquinone dyes, nitro dyes, steryl dyes, phthalocyanine dyes, quinophthalone triphenylmec/dyes, cyanine dyes, etc. However, the effect is remarkable for azomethine dyes and indoaniline dyes.

Azomethine dyes have a chromophore with the following /C=N- bond 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 is
;+, The reaction product of the 1-phenyl-5-vinylon derivative becomes a magenta dye.

Indoaniline dye is N-(p-aminophenyl)
-p-quinoneimine and its derivatives, usually p-
- by the condensation reaction of nitrosophenols or quinone chloroimines with dialkylanilines, or by the reaction of phenols or naphthols with nitrones or nitrodialkylanilines in the presence of a reducing agent in alkaline broth, and also p-phenylenediamine derivatives. It is synthesized by oxidative camping reaction of a mixture of and phenol or 7-tol.

Various types of heat-transferable dye-providing substances are known that provide (release or form) heat-transferable dyes during thermal development or heat-sensitive transfer. See Patent Application (B) 1 Title of Invention: Image receiving element for thermal transfer. ], but the thermal transfer element combined with the image receiving element of the present invention may contain any type of thermal transferable dye-providing T.
! ! /J quality may be included. For example, U.S. Patent Nos. 3,531.286 and 3,761.27.
No. 0, No. 3,764,328 1 Research D
isclosureNl 15108, isclosureNl1151
27, Mukai N112044 and Mukai N[116479, etc. are disclosed in U.S. Pat.
No. 1, Re5earch Disclosure F4a
U.S. Patent No. 4.235.957 uses leuco dyes for 13443 and N[114347, etc.
No., Re5earch Disclosure Na
l 4433, same N[114448, same Na15227
, same 15776, same N[L 18137 and same 1
9419 etc., regarding the application of silver dye bleaching method, as well as U.S. Patent Nos. 4,124,398 and 4.12.
No. 4゜387 and No. 4,123,273 respectively describe the heat development effect f and the heat source white blade method for removing dyes.
The present invention can be applied to any of these.

When the thermal transfer element combined with the image-receiving element of the present invention is a heat-developable F element, it is limited to a conventionally known configuration, for example, without substantially adding a developer (reducing agent) to the photosensitive element. may be contained in the image-receiving element of the present invention.Furthermore, these photosensitive elements may contain organic silver salts, developers (reducing agents), dye-providing substances, binders, silver halides, additives (tone adjusters,
In addition to the photosensitive layer containing (development modifier, chemical sensitizer, physical (spectral) sensitizer, antifoggant, filter dye, anti-tulsion dye, dye release aid, etc.), intermediate layer, protective layer, underlayer, etc. It may also have photographic constituent layers such as a pulling layer or a barrier layer. Further, when the present invention is applied to a heat-developable photographic material, it may have a reflective layer.

Even when the thermal transfer element combined with the image-receiving element of the present invention is a heat-sensitive element, the heat-sensitive element may contain various additives.

As mentioned above, the image receiving element of the present invention may consist of only an image receiving layer coated or placed on a thermal transfer element, or may have a structure of an image receiving element having an image receiving layer and a support. be.

〔Example〕

Preferred examples of the present invention are shown below, but the present invention is not limited to these examples.

Example-1 A heat-developable photographic material was prepared as follows.

9.20 g of 4-sulfobenzotriazole silver, 24 g of water-soluble polyvinyl butyral 25 aqueous solution (Sekisui Chemical Co., Ltd., Eslec W-201), 116 g of water, 70 g of methanol
The mixture was ground and dispersed in an alumina ball mill to obtain a silver salt dispersion.

To this silver salt dispersion 25-0.21 g of 7-talic acid and 0.16 g of 7-talazine were added.
93g, 0.57g of the described developer (B), 5-1 hydroxyl polyvinyl butyl 2-5 aqueous solution, 10-1 water, and a silver iodide gelatin emulsion with an average particle size of 0.04μ converted into silver. A photosensitive element was obtained by applying the photosensitive layer onto photographic baryta paper using a wire bar to a wet film thickness of 55 μm.

Thermal transferable dye-providing substance (A) Developer (B) cH3 The dried photosensitive element was passed through a step wedge for 30 minutes. OOOCMS exposure was given.

-For the image-receiving element, first apply cellulose diacetate (degree of acetylation: about 60%) to 1.4°g/rr on Ipoly paper.
The entire image-receiving layer was obtained by coating and drying. Next, using the compounds of the present invention shown in Table 1 below, 10% of each of these compounds was added.
g, respectively, 5 g of dibutyl phthalate and 2 g of ethyl acetate.
00td and heated to 60° C. to completely dissolve the compound of the present invention, and the image receiving element coated with the image receiving layer of cellulose diacetate was immersed in the solution containing the compound of the present invention. The image-receiving element of the present invention was prepared by impregnating the image-receiving element and drying it.

The photosensitive layer surface of the exposed photosensitive element and the image-receiving layer surface of the image-receiving element were brought into close contact and heated under pressure for 30 seconds with an iron having a surface temperature of 150° C., and then both elements were peeled off. The image receiving layer has a maximum reflection density of 0.60. A clear step wedge negative image with a minimum reflection density of 0.08 was obtained.

A light resistance test was conducted on each of the image receiving elements obtained by the above treatment. In the table, the light resistance is expressed as a percentage of each image obtained by irradiating each image with a 6000 W xenon lamp for 48 hours, and the illuminance on the image surface being 6000 lux], and the residual rate at an initial density of 0.5 after irradiation.

As is clear from the same table, it can be seen that the image receiving element containing the compound of the present invention has excellent light resistance.

Margin below Table 1 Example-2 A thermal transfer material was made as follows.

First, the following composition was applied to a polyethylene terephthalate film base having a thickness of ζ6μ using a wire bar so as to have a wet film thickness of 59.4μ, and dried to form an ink layer.

Subsequently, the following composition was coated on the ink layer described in -11 to a wet film thickness of 27.4 μm, and dried to form a heat-fusible layer. :Obtained.

- For the force, receiver, and element, the following composition was heated and melted at 300° C., and the resultant film was formed into a 100 μm film.

/boriethelene terephthalate) 100g Next, a thermal transfer test will be explained. ffU, the ink layer of the heat-sensitive element and the image-receiving element are stacked facing each other;
The color patch was thermally diffused and transferred by heating from the heat-sensitive element support side with a thermal head via a heating element. The obtained transferred image was irradiated with 6000W xenon light for 48 hours (illuminance on the image surface was 6000 lux), and the optical density (Do before irradiation, after irradiation]) was adjusted to λmax before and after irradiation. Measure and Dz/Dox 100 (@
The total residual rate was determined and the light resistance was tested. These results are shown in Table 2.

As is clear from the same table, it can be seen that the image receiving element containing the compound of the present invention has excellent light resistance.

Margin below Table 2 ■ In this case, (1)-2 is Q, 5 mmol.

(ff)-1ft 0.5 mmol was added.

Example I made the Netsukon statue photographic fee as follows.

In Example-1, a bolysterene-butadiene copolymer latex undercoat was added to the photographic baryta paper sheet.
r: 100 μ thick transparent polyimide film (K
A photosensitive layer was formed by coating under the same conditions as in Example 1 using APTON (manufactured by Teyupon) as a support. A white reflective layer and an image-receiving layer having the following compositions were provided thereon, and a 50 μm thick Xunmei polyethylene terephthalate film K1 was placed on the image-receiving layer.

<White reflective layer> (Unit: 2 g/rr?) Image receiving layer> (Unit: g/i) (S-LEC BX-1. Sekisui Chemical) 30. Give OOOCMS exposure, 3M im
Heating was performed at 150° C. for 30 seconds using a m-image m-Taveron bar module 277″′.

On the surface of the image-receiving layer, a negative image of a zelkova-colored step wedge with a maximum reflection density of 0.67 and a minimum reflection density of 0.06 was obtained.

The same light resistance test as in Example 1 is shown in Table 3.

As is clear from the table, it can be seen that the image-receiving layer containing the compound of the present invention exhibits excellent light resistance.

Below is the margin Table 3 ■ In this case, (1 no 2 is 0.25 g/rr?, ω
0.25g/i of total weight was obtained.

Patent Applicant: Konishi Roku Photo Industry Co., Ltd. Agent, Patent Attorney: Nobuo Sakaguchi Showa Procedural Amendment (Self-Effective May 1980) Mr. Kazuo Wakasugi, Commissioner of the Patent Office Name of the invention Image-receiving element in thermal transfer material 3 Person making the amendment! Relationship with the matter Applicant name (127) Roku Konishi Photo Industry Co., Ltd. 4 Agent 105 6 Number of inventions increased by amendment 7 Subject of amendment Specification (Claims and Detailed Description of the Invention) 8
Contents of the amendment The following amendments are made to the specification of J1- No. 1 (Japanese Patent Application No. 58-30883).

1. The scope of the claims is supplemented as indicated in the following.

For a thermal transfer element containing a thermally transferable acute donor substance, at least in an image receiving element that is placed in a stacked relationship during thermal transfer, the image receiving element has the following general formula (D, (l)
) or ■, an image-receiving element in a thermal transfer material, characterized by containing at least one compound represented by general formula (1) general formula 〇11) [wherein R1, R1', R3, R] ' and R5 are valley Q
Represents a frozen candy atom, aliphatic group, aromatic group, heterocyclic group, acyl group or sulfonyl group, R2゜R'l, R'l
',R63;? and R7 each represent a hydrogen atom, a halogen atom, or a monovalent organic group, and l and q each represent 1 to 4.
m, n and p each represent an integer of 1 to 3. Also, 7, m, n, p and q are each 2
In the above case, R2, R11, RIL', R6 and R7 may each be h- or different. ] The following margin is 2 or 15 The true structural formula f', in) -8 is corrected.

3 In the 2nd line to the closing line from the bottom of the same page, [you may also use 2
The phrase ``more than that'' has been corrected to ``with two imitations.''

that's all

Claims (1)

[Scope of Claims] An image-receiving element that is placed in a stacked relationship at least during thermal transfer with respect to a thermal transfer element containing a thermally transferable dye-providing substance, wherein the image-receiving element has the following general formula (1), (if).
An image-receiving element in a thermal transfer material, characterized in that it contains at least one of the compounds represented by (2). General formula (1) General formula C) [In the formula, R1, R1', R5, R3' and R5 each represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group, and R2゜Ru, R11
, R6 and R7 each represent a hydrogen atom, a -.rogen atom or a monovalent organic group, l and q each represent an integer of 1 to 4, and m, n and p each represent an integer of 1 to 3. Further, when t, m, n, p and q are each 2 or more, R2, R'1, R11', R6 and R7 may be different in each direction. ] Below margin