JPS6019138A - Image receiving element for thermal transfer - Google Patents

Abstract

PURPOSE:To control fog, to provide high maximum density, and to prevent retransfer by using polycarbonate contg. a plasticizer as the material of an image receiving layer. CONSTITUTION:Polycarbonate contg. a plasticizer is used as the material of an image receiving layer. Polycarbonate has low receptivity to a dye to be transferred, yet by adding a plasticizer such as dibutyl phthalate, sufficiently high transfer density is provided, and retransfer can be controlled. The image receiving layer may be laminated on other support. A superior image receiving element for thermal transfer causing no fog can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an image-receiving element which is placed in a stacked relationship with a heat-developable photosensitive element at least during thermal transfer, and which contains an image-receiving element contained in a photographic constituent layer of the photosensitive element. The present invention relates to an image-receiving element to which a dye released or formed by thermal development from a thermally transferable dye-providing material is thermally transferred. Specifically, it is possible to obtain a sufficiently maximum density while suppressing the occurrence of fog, and to form an image-receiving element for thermal transfer that can suppress so-called back-transfer.

PRIOR ART Color photography using photosensitive silver halide, which has been known for a long time, is superior to other color photography methods in terms of photosensitivity, gradation, image preservation, etc., and is the most widely put into practical use. It has been. However, in this method, wet processing is used for steps such as bleaching, fixing, and washing (l), which requires time and effort.
There are also concerns about pollution to the human body due to treatment chemicals.
In addition, there are many problems such as contamination of workers in the processing room by processing chemicals, and the labor and cost of waste liquid processing.Therefore, there is a method for forming color images that allows dry processing. The development of this product has been requested.

Black and white heat-developable photosensitive materials characterized by heat treatment in the development process have been known for a long time.For example, Japanese Patent Publication No. 43
This is described in No. 4921 and No. 43-4924, which disclose a photosensitive material comprising an organic acid silver salt, a halogenated compound, and a developer. Furthermore, there are many known photosensitive materials such as Kan-Kan-kama and image-sensitive materials to which this black and white heat-developable photosensitive material is applied.

For example, U.S. Pat. No. 3,531,286, U.S. Pat.
No. 1.270, No. 3,764,328, Research
Re5earch Dia
crawlure) (υlower RD), NQl
No. 5108, No. 15127, No. b12044, and No. 16479 are disclosed in U.S. Patent No. 3. ll'IO, No. 731, RDm 1344
3B and Nn ] 4347 etc., those using leuco dye are described in U.S. Patent No. 4.235.957-Q.
,[YDNO14433, same, N+114448, same 1
Company] 5227, No. 1 15776, No. 1813
7 and It, 19419, etc., U.S. Pat.
No. 8, No. 4, I24, '387 +Fjs, and No. 4,123,273 describe a method for thermally whitening heat-developable Ix optical materials.

However, these proposals regarding color heat-developable light-sensitive materials have shown that it is difficult, or even impossible, to whiten or attach simultaneously formed black, white, and silver images. It also requires wet processing. Therefore, these proposals are based on the bright color 1i
It is difficult to obtain 111 mounds, and complicated post-processing is required, so there is no preferable method.

- 10,000, a heat-developable color photosensitive material for obtaining a color image by transferring a diffusible dye released by heat development was disclosed in JP-A-57-
No. 179840, No. 57-186744, No. 57-1
98458++, No. 57-207250, No. 58-4
No. 0551 and No. 58-58543, and patent application No. 57-122590 filed by the present inventors.
No., □, and 1-cho No. 57-229649. These proposals suggest that a dye-donating substance containing a diffusible dye in the same molecule can be
A color image is obtained by releasing a diffusible dye and transferring it to an image-receiving layer, and is referred to herein as a "dye-releasing type."

On the other hand, patent application tlIj57-229 by the present inventors
No. 671, No. 58-33363, No. 58-: U33
(i) The proposal shown in each specification of No. 4 is that a colorless or light-colored dye-donating substance reacts with the oxidation of a color developing agent produced by a heat development reaction of an organic silver salt to form a heat-diffusible dye. , to obtain a color image by transferring it to an image-receiving layer,
In this specification, this is referred to as "r-pigment-forming type."

However, in both the dye-releasing type and the dye-forming type, fog occurs when trying to obtain a sufficiently high maximum density, and when fog is suppressed, only a low maximum density can be obtained, which is still insufficient for practical use. It is.

The present inventors have discovered that the occurrence of the first capri can be suppressed.

And a high enough maximum? We proposed an image-receiving element for thermal transfer having an image-receiving layer containing a vinyl chloride polymer with a high yield. However, if the surface of the image-receiving layer of the image-receiving element for thermal transfer on which an image is formed by transfer comes into contact with other materials, such as paper, plastic film, or the surfaces of the layers of the same image-receiving element for thermal transfer come into contact with each other, When it comes to
It was discovered that the dye forming the image migrates to other materials it comes into contact with, resulting in a phenomenon called "retransfer."

The occurrence of such retransfer not only reduces the m[ of the image, but also contaminates the album, and also causes mutual transfer when the surfaces of the same image receiving element for thermal transfer come into contact with each other, making it undesirable. do not have.

Therefore, it is desired to develop a thermal transfer technique that can obtain a sufficiently high maximum density while suppressing the generation of capri, and can also suppress the occurrence of so-called re-transfer.

As a result of continuing research into this technical problem, the inventors of the present invention have found that in both the dye-releasing type and the dye-forming type, color images are obtained by being transferred and dyed onto the image-receiving layer by thermal diffusion. It has been found that the characteristics of this image-receiving element largely control the quality of the resulting color image.

In addition, it was found that retransfer from the surface of a thermal transfer image-receiving element on which a transferred image is formed does not have a large effect on the structure of the dye that forms the image, or in particular, on the characteristics of the thermal transfer image-receiving element. . Furthermore, it has been found that among the conventionally known image receiving elements for thermal transfer, the five that can obtain high maximum density have a large occurrence of writing transfer.

However, in the technology related to conventionally known dye-releasing type or dye-forming type heat-developable color photographic materials, several solutions have been described for 01'I retransfer regarding thermal transfer image receiving elements that can obtain high maximum density. There is no one.

Purpose of the Invention Therefore, the purpose of the present invention is to suppress the generation of capri and to
An object of the present invention is to provide an image-receiving element for thermal transfer, which provides a high maximum density and improves the occurrence of retransfer.

Structure of the Invention As a result of repeated research by the present inventors, the above purpose was achieved as follows.
It has been found that this can be achieved by using an image-receiving silicon for thermal transfer 4 whose image-receiving layer is made of polycarbonate containing a plasticizer.

The present invention will be explained in more detail below.

The image-receiving layer according to the present invention is characterized in that it is made of polycarbonate containing a plasticizer. In the present invention, the above-mentioned plasticizer is a material that imparts plasticity to ordinary plastics or synthetic rubbers, or increases the plasticity even more. These substances can be used.

To this invention? Examples of plasticizers that can be effectively used include inorganic acid esters, organic acid esters, polyhydric alcohol esters, and epoxylated oils, as detailed below.

Examples of the above inorganic acid esters include phosphoric acid esters, specifically triethyl phosphate, tributyl phosphate, tri-n-octyl phosphate, diphenyl-n-octyl phosphate,
Butyl-2-quinrenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, etc. are alkaline.

Examples of the organic acid esters mentioned above include lower fatty acid esters, such as citric acid esters, specifically tributyl citrate, acetyl tributyl 7-trate, triethyl citrate, acedeltriethyl citrate, and drink. , oral hexyl citrate, acetyl tributyl heptolate, acenal octyl defruntorate, etc.

Examples of organic acid esters belonging to higher fatty acid esters include butyl stearate, oleic methoxyethyl, methyl acetyl ricinoleate, ethyl acetyl ricinoleate, acetyl linol methoxyethyl, and the like. Further, in the present invention, the organic acid ester includes aliphatic and aromatic divalent organic acid esters.

Examples of aliphatic divalent i, r+S m esters include dibutyl adipate, di-2-ethyl-hexyl adipate, di-n-octyl adipate, di-n-ofdersebacate, dibutyl sebacate, di-2-ethyl −
There are hexyl azelate, diisodecyl adipate, etc., and aromatic divalent organic acid ester C is, for example, phthalic acid ester b=, dimethyl phthalate,
Silylable birlphthalate, diethyl phthalate, dibutyl phthalate, dibutyl terephthalate, butylbenzyl phthalate, dibutoxyethyl phthalate.

Diethyl phthalate, dicyclohexyl phthalate, /
-n-heptyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, di-2-ethylhexyl terephthalate, di-2-ethylhexyl inphthalate, di-n-nonyl phthalate, di-n-nonyl isophthalate, Examples include butyl chlorohexyl phthalate, dibutyl tetrataselphthalate, dibutyl isophthalate, capril phthalate, di-2-methoxyethyl phthalate, diisobutyl phthalate, and the like.

Furthermore, among the above-mentioned polyhydric alcohol esters and l, for example, glycol esters are the main ingredients, and specifically, ethyl phthalyl ethyl glymarate, 1, butylphthalyl butyl glycolate, methyl phthalyl ethyl glycolate, etc. In addition, examples include diethylene glycol benzoate, diethylene glycol sichenzoate, and salanine saccharide henzoate. Examples of the epoxidized oils listed in M include epoxidized pig oil,
Glycisyl oleate, aryl 9,10-epoxystearate, 9. io-epoxystearic acid-2-
Examples include ethylhexyl, epoxidized tall oil fatty acid-21-ethylhexyl, and epoxidized tall oil alkyl.

Next, the polycarbonate used in the present invention will be described, but the polycarbonate in the present invention is:
Polyesters of carbonic acid and glycols or dihydric phenols are preferably used in the present invention as the above-mentioned glycols or 2fah phenols (:VJ
, p-xylylene glycol, 2.2-bis(4-oxyphenyl)propane, bis(4-oxophenyl"methane, 1.1-bis(4-oxyphenyl)ethane, 1
,1-bis(4-ox/phenyl9gutane,l,1-bis(4-oxyphenylpisobutane,1,1-bis(
4-oxyphenylaclohegisan, 2,2-bis(
4-:t xy7 enyl dibutane.

In the present invention, the amount of the ufq agent contained in the polycarbonate is -CO
1-40% by weight, preferably 1-40% by weight.

When incorporating a plasticizer into polycarbonate according to the present invention, polycarbonate is mixed with benzene, acetate/
A method in which a plasticizer is added to and mixed with a solvent such as methyl chloride, chloroform, or tetrahydrofuran is preferably used.

In the present invention, the polycarbonate containing a pear agent as described above can be formed into a film or a plate, or can be tilted on a support as described later to form an image-receiving layer of an image-receiving element.

1 with polycarbonate itself that does not contain plasticizers
-1' The ability of the dye to be transferred is small, and it is not effective as an image receiving element for thermal transfer, but by mixing it with a plasticizer as in the present invention, it has a high maximum The degree of transfer is obtained, and the above-mentioned (]J transfer is suppressed.

The image-receiving layer according to the invention may be formed by molding polycarbonate containing bJ plasticizer itself into a film or plate shape as described above, or may be coated or laminated on another support. Good too.

Useful supports include, for example, paper, photographic baryta nails, eye poly paper, condenser paper, polyether sulfone film, polyimide film, cellulose ester film, acetyl cellulose film, polyvinyl acetal film, polyenalene terephthalate film (preferably , Polyenalene terephthalate film glass with a crystallinity of 1' or higher, Kaede, and ceramics.

Uke 1 corps layer of the present invention? The liquid containing the constituent polycarbonate and ljT plasticizer (total + 1 part) was placed on the above-mentioned support (r setting 4), and the Y mixture was tetrahydrofuran, methylene chloride, benzene, methyl ethyl ketone, toluene, In some cases, polycarbonate is prepared by emulsion polymerization, preferably by dispersion in water. Methods used for sieving can be applied, including dipping, dipping, roller, reverse roll, air knife, doctor blade, spray, and extrusion. method, bead method, stretch flow method, curtain method, etc.

On the other hand, in order to laminate a film or sheet mainly composed of polycarbonate containing a plasticizer on the support, a filtration method in which the film or sheet is formed in advance is used.

In addition, when coating or laminating a polycarbonate image-receiving layer containing an o'T plasticizer on a support, coating of the image-receiving layer on the support, itl'i', I L/rrj ~
x, oooP/mJ, preferably 5 j! /m' ~
500 &/lri.

The image-receiving layer according to the present invention may be mixed with other polymers, so-called polymer blending, in order to enhance its physical strength and improve its heat resistance. Polyvinyl butyral, saturated polyester, etc., which have excellent retention properties, may be added. These other polymers are used in up to 50% of the image receiving layer.

The image-receiving layer according to the present invention contains a lubricant (
Adding a slip agent) is effective.

As a lubricant (d, for example, hydrocarbons such as liquid paraffin and low-molecular polyethylene h, aliphatic alcohols such as stearyl alcohol and cetyl alcohol, aliphatic ketones such as stearone and palmitone, fatty acids such as stearic acid and lauric acid) , stearic acid amide, oleic acid amide, methylene ester amide, etc., waxes such as valmitine, polyalcohol esters such as diethylene glycol monooleate, other VC-geared naphthalenes, chlorinated Examples include diphenyl, ):t Shiki IJ#, silicone oil, /recon resin, and finely divided silicic anhydride.

To my father's health class, there is an Emperor 'tK prevention j'L1. It is preferable to contain I (-7〈normal anionic surfactant,
Cationic surfactant MIJ, nonionic surfactant, and amphoteric surfactant are used.

In addition to the above, antioxidants, ultraviolet absorbers, dyes, pigments, etc. can also be added to the image receiving element for Sr transfer of the present invention.

In the thermal transfer image receiving element of the present invention (hereinafter referred to as the image receiving element of the present invention), a white pigment may be added to the support or a white reflective layer may be provided in order to view a reflected image. Examples of white pigments include titanium white, magnesium carbonate, zinc oxide, He barium, silica, talc, clay, and calcium carbonate. Further, in order to provide a light shielding effect to the light layer, a black pigment may be added to the support, or a light shielding layer may be provided. Examples of black pigments include carbon black, manganese dioxide, and graphite. As described above, the image receiving element of the present invention may have one or more photographic constituent features other than the above-mentioned image receiving layer.

The image-receiving element of the present invention may have any conventionally known form with respect to the relationship with the photosensitive element layers used in combination therewith, for example, (11 to 1-1 photographic constituent layers of the photosensitive element; (2) The image receiving element of the present invention is placed in a stacked relationship during thermal development; (2) the image receiving element of the present invention is placed in a stacked relationship during thermal development; The Δ element is in the form of a stacking relationship, P and (3)
Photographic structure of the photosensitive element A light image receiving element is integrally provided on the top of the photosensitive element, and the image receiving element is exposed in a form in which imagewise exposure, thermal W, and imaging are carried out. -f7hi, [1] The image receiving element of the present invention is of a type that is peeled off during thermal transfer, and [II) The image receiving element of the IC body is peeled off after thermal transfer. It may be in any form that cannot be peeled off.

In the case of [■] above, by improving retransfer according to the present invention, the transferred dye on the image-receiving layer is less likely to return to the photosensitive layer or dye-releasing layer, etc., and the image density is stabilized over time. The characteristics are improved.

In the present invention, thermal transfer refers to the process in which the dye is sublimated by heat.
Refers to vaporization, evaporation, melting, or dissolution by means of a solvent, diffusion, and transfer.

The image-receiving element of the present invention can be applied to both the dye-releasing type and dye-forming type photothermographic elements, but due to the moderate polarity of polycarbonate, which is the main component of the image-receiving layer, It shows excellent suitability for thermal transfer and dyeing of azomethine dyes and indoaniline dyes formed by coupling with oxidized developing agents. Preferred examples of such dyes are disclosed in the aforementioned Japanese Patent Application Nos. 57-229671 and 58-33363 by the present inventors.
No. 58-33364.

For the image-receiving element of the present invention, thermal transfer is performed when the photothermographic element is thermally developed or when it is reheated after thermal development. For heating the thermal transfer chamber, all methods applicable to ordinary heat-developable photographic materials can be used. For example, by contacting with a heated block or plate, by contacting with a heated roller or drum, by passing through a high-temperature atmosphere, by using radiation heating, or even in a heat-developable photosensitive element or book. It is also possible to provide an electrically conductive layer in the image-receiving element of the invention and utilize the Joule heat generated by passing current or a strong magnetic field. There are no particular restrictions on the heating pattern, and the heating pattern must be preheated and then heated again, such as heating at a high temperature for a short period of time, or at a low temperature for a long period of time, continuously increasing, cutting, turning, or turning. , and even discontinuous heating is also available in Town 6'F3,
A 1m flight pattern is preferred. Generally, the heating temperature during transfer is 80°C to 2 (1()'C, preferably
The heating time is usually in the range of 1 second to 1 minute, preferably 1 second to 40 seconds.

For thermal transfer using the image receiving/determination device of the present invention, a commercially available thermal transfer machine can be easily used. For example, ``Image forming model 4634'' (manufactured by Nyi Tektronix,
It can be easily applied to any of the Tibero Tuber module 277# (manufactured by 3M Company) and the 1 video hard copy unit KWZ-:<□t' (manufactured by Nippon Mudensha).

The image receiving element for thermal transfer of the present invention can be used not only as an image receiving element for the heat-developable photosensitive V element, but also as a receiver for thermal transfer.
It can also be used as a search element.

Namely, Japanese Patent Application No. 1ld57-217063, No. 1ld57-21
No. 7796, No. 57-217797, No. 57-229
No. 651, JP-A No. 51-15446, JP-A No. 54-682
53, No. 57-160691, etc., it can be used as a thermal transfer image receiving element used in a thermal transfer recording medium or a thermal transfer recording method. That is, for example, by superimposing a thermal transfer ink 7-t and the image-receiving element of the present invention, the dye is transferred onto the image-receiving element of the present invention in response to thermal information from a thermal head, laser, xenon lamp, etc. The color tone 1 of the present invention is contained in the image receiving element.
It exhibits a desirable color tone when brought into contact with, mixed with, or dissolved in 1J conditioning agent. The general art regarding heat sensitive elements is known and may be used in combination with any of these types of heat sensitive elements in the components of the present invention. It is particularly useful as an image receiving element in the system described in Japanese Patent Application No. 57-229651.

The invention will now be illustrated by examples.

Example-1 4-sulfobenzotriazole silver 7:459, Eslec W-201, 8% water bath solution 24a, ossein gelatin 1. Knee 1,! 7, water 110 m, l, meta 7-
Add 25 tall and minute in an alumina ball mill.
A silver salt dispersion was obtained.

To δml of this silver salt dispersion, 0.21% of phthalic acid was added. p, phthalazine 0. +6.9. The following compound x-i is 0.44,9
0.42g of ゜cho N12 present I landlord article IJev-1, 1,
3-dimethyl urea
, water resistant to 10, furthermore, a silver iodide emulsion with an average grain size of 0.04 μm was subtracted from the silver to add 36 m9. A photosensitive element having a photosensitivity of J was obtained.

The dried heat-developable photosensitive element samples were exposed to 30,000 CMS through a step wedge.

On the other hand, as an image-receiving element for thermal transfer, the components shown in Table 1 below were coated on lighter paper (for photography).

Layer the exposed sample on top of the image receptor for private photography and heat it with a heat block iron type heat block with a surface temperature of 150°C (2)
After crimping and heating for a second, it was immediately peeled off.

The maximum reflection density and minimum reflection at 642 nm of the solid wood surface image obtained on the surface of the image-receiving element for thermal transfer, and the minimum reflection all (
Fog), and when the same thermal transfer image-receiving elements on which images have not been transferred are brought into contact face-to-face and left in an atmosphere of 55°C and a relative humidity of ~40%, the retransferred image Maximum reflection once 4・shown in Table 2 below.

(X-1) H (Dev -1) Table -1 Table -2 As is clear from the above table, the image-receiving element sample according to the present invention using an image-receiving layer made of polycarbonate containing a plasticizer has a fog suppressing effect. n1, it can be seen that it shows good maximum density of transfer dye and at the same time has good writing transferability (improved image reception with no occurrence of blurring or re-transfer - J with vines).
.

Example 2 In this example, the following compounds X-2, X-3 and X-4 were used in place of X-1 used in Example 1. ! A sample was prepared in exactly the same manner as in Example 1, and the adductivity of the delirium was tested by treating it in the same manner as in Example 1. No retransfer was observed in the case of a sample containing a plasticizer and having a rough texture.

-2 -3 -4 Example-3 A heat-sensitive transfer element of T or more was prepared.

146 μm transparent polyethylene terephthalate film with 27 μm gelatin subbing.
rt water-soluble polyvinyl butyral (varnish)
201, manufactured by Sekisui Chemical Co., Ltd.], and in the layer, 2. +l X 1O-3nl 017m
``Contained.

Pigment (A) On the other hand, the feeling? As the image-receiving element for jc transfer, art paper (sample-1), l't (with 2.!9/'ni''r of Altron of Example-1 on the surface (sample-2)
9. 7F polycarbonate containing 10% by weight of di-2-ethyl hequinulfthalate on the surface of art paper 2.9/m
A coated sample (Sample-3) was prepared.

The thermal transfer element and the image receiving element for thermal transfer are superimposed on each other, and from the thermal transfer element side, the thermal head V trowel is applied with a constant force of Q, 8w/dot, When the pulse width was applied stepwise from 5 mS to 40 m5t, a magenta stepwise pattern was obtained on the surface of the receiving element.

As a retransfer test, an eye poly-gap was placed on the surface of samples 1 and -3, respectively, and a pressure of 50 (1,9/di) was applied to
Bending force in an atmosphere of 0℃ and 60% relative humidity for 40 days! ＜N゛」L, 7hi.

Table F-3 shows the maximum reflection density obtained on the image-receiving surface at the time of heat transfer and the maximum reflection 0 degrees obtained when retransferred to the Ipoly paper surface in the retransfer test.

Table 3 shows that the image-receiving element for thermal transfer of the present invention; It is an excellent product that can be obtained without causing retransfer.

Effects of the Invention The image-receiving element of the present invention, which uses polycarbonate containing a ggable agent and which has a different receptivity, has a fog of 1 (j 匍) and an excellent transferred dye image with a maximum Q degree. It is an image receiving element for thermal transfer which has an excellent T1 performance, and almost no retransfer is observed.

Deputy 1. Festival J5A Yoshimi

Claims (1)

[Claims] An image-receiving element for thermal transfer characterized by having an image-receiving layer made of polycarbonate containing a plasticizer.