JPH04282293A - Heat dyestuff sublimation transfer acceptance material - Google Patents

Abstract

PURPOSE: To provide an excellent dyeable polyester dye acceptive layer. CONSTITUTION: A dye image acceptive material for use by a thermal dye sublimation transfer comprises a dye image acceptive layer containing a copolyester containing one or more diols and a condensed residue of one or more dicarboxylic acids on a support. At least one of the diol and/or the dicarboxylic acid contains a linear alkyl or alkylene group having 5 or more carbon atoms in a main chain, and 6 or more carbon atoms in a side chain.

Description

Description: This invention relates to dye image-receiving materials for use by thermal dye sublimation transfer. Thermal dye sublimation transfer, also referred to as thermal dye diffusion transfer, involves bringing a dye-donor element provided with a dye image containing a sublimable dye with thermal transferability into contact with a dye image-receiving element to transfer pattern information. selective heating in accordance with the signal with a thermal printing head provided with a number of juxtaposed heat generating registers, thereby transferring dye from the selectively heated zones of the dye-donor element to the dye image-receiving element; forming a pattern, the shape and density of which follows the pattern and intensity of the heat applied to the dye-donor material. Dye image receiving materials for use by thermal dye sublimation transfer usually contain a support such as paper or a transparent film coated with a dye image receiving layer into which the dye can diffuse more easily. An adhesive layer may be provided between the support and the receiving layer. The dye image-receiving layer can contain as binder, for example polycarbonate, polyurethane, polyester, polyamide, polyvinyl chloride, polystyrene-co-acrylonitrile, polycaprolactone or mixtures thereof. Commonly used binders are (co)polyesters obtained by (co)polycondensation between one or more dicarboxylic acids and one or more diols. Preferably at least one of the dicarboxylic acids and/or diols contains aromatic moieties such that the glass transition temperature of the (co)polyester is at least 0°C, preferably at least 20°C. [0006] Such a polyester receptive layer is, for example, EP2
89161, EP275319, EP261505, E
P368318, JP86/3796 and JP89/2
69589. JP 89/269589 describes polyester image-receiving layers using malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid and adipic acid as examples of dicarboxylic acid condensation residues. Examples of diols mentioned for incorporation into the polyester receiving layer include ethylene glycol and neopentyl glycol. In the polyester image-receiving layers of the prior art, the dyeability is not always good enough and when images with high densities are desired, correspondingly excessive heat contents are required during printing. This inevitably increases the energy load on the thermal head, which causes the thermal head drive voltage to become disadvantageously high. Furthermore, when the donor and receiver materials are peeled off after thermal transfer, the donor layer adheres to the receiver layer and is thus peeled off so that it is transferred onto it, whereby both sheets are separated. It will never be fit for use. Therefore, in order to improve the anti-blocking properties of the image-receiving layer, release agents are generally incorporated into or into the surface coating on the image-receiving layer of the prior art. It is an object of the present invention to provide a polyester dye image-receiving layer with excellent dyeability. Another object of the present invention is to provide a polyester dye image-receiving layer having improved strippability without the need for incorporating a separate stripping agent in the image-receiving layer or in a layer above the image-receiving layer. be. Other objects of the invention will become apparent from the description below. According to the invention there is provided a dye image receiving element for use by thermal dye sublimation transfer, said dye image receiving element comprising a condensation of one or more diols and one or more dicarboxylic acids. a support having thereon a dye image-receiving layer containing a (co)polyester containing residues, wherein at least one of said diol and/or said dicarboxylic acid contains not more than 5 carbon atoms in the main chain. , characterized by containing in the side chain a long-chain alkyl or alkylene group having at least 6 carbon atoms. Preferably the long side chain groups contain at least 10 carbon atoms. The long chain alkyl or alkylene groups of the side chains may be branched or unbranched. Also, two or more long chain alkyl or alkylene pendant groups may be contained in the diols or dicarboxylic acids of the invention on the same or different carbon atoms of the main chain. Long chain alkyl or alkylene pendant groups include aromatic moieties, alicyclic moieties, heteroatoms (such as -O-, -NH
-, -O-CO-, -NH-CO-) can be bonded into the main chain via a bonding group such as -, -O-CO-, -NH-CO-. Examples of short chain diols of the invention containing long chain alkyl or alkylene side groups include 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-hexadecane. Diol, 1,4-octadecanediol, N,N-di-(n-decyl)amino-2,3-propanediol, glycerin monostearate, glycerin monooleate, glycerin monoricinoleate, glycerin monolaurate, Contains glycerin monocaprylate, pentaerythritol distearate and pentadecyl resorcinol. Among these 1 and 2
-dodecanediol, 1,2-hexadecanediol,
Particularly preferred are glycerin monostearate, glycerin monooleate, pentaerythritol distearate and pentadecyl resorcinol. Examples of short chain dicarboxylic acids of the invention containing long chain alkyl or alkylene side groups include tetradecylmalonic acid, hexadecylmalonic acid, octadecylmalonic acid, diheptylmalonic acid, octylsuccinic acid, decylsuccinic acid. , dodecylsuccinic acid, tetradecylsuccinic acid, hexadecylsuccinic acid, octadecylsuccinic acid, octenylsuccinic acid, iso-octenylsuccinic acid, decenylsuccinic acid, dodecenylsuccinic acid, tetradecenylsuccinic acid, hexadecenylsuccinic acid, octadecylsuccinic acid Nylsuccinic acid, docosylsuccinic acid, docosenylsuccinic acid, tetrapropenylsuccinic acid, triacontenylsuccinic acid, polyisobutenylsuccinic acid, 1-dodecylglutaric acid, 1-tetradecylglutaric acid, 1-hexadecylglutaric acid and 1- Contains decyladipic acid. Among these, hexadecylmalonic acid, octadecylmalonic acid, hexadecylsuccinic acid, octadecylsuccinic acid, and docosenylsuccinic acid are particularly preferred. The (co)polyesters of the present invention contain aromatic and aliphatic dicarboxylic acids and diols and contain one or more short chain diols or dicarboxylic acids of the present invention containing long chain alkyl or alkylene side groups. It can be obtained by condensing the above diol with one or more dicarboxylic acids. The condensation can also be carried out using derivatives of dicarboxylic acids in the form of the corresponding esters and/or derivatives of diols in the form of the corresponding epoxides or the corresponding acetates. Preferably at least one fused residue contains an aromatic moiety. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, sulfoisophthalic acid, orthophthalic acid, t-butyl isophthalic acid, 4,4'-oxybisbenzoic acid, 2,5-, 2,6- or 2 , 7-naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, dipicolinic acid and 2,2-bis(p-carboxyphenyl)propane. Examples of aromatic diols include bisphenol A
, ethoxylated bisphenol A (e.g. Dianol 22, commercially available by Akzo), propoxylated bisphenol A (e.g. Dianol 33, commercially available by Akzo), p-xylylene glycol, 5-sulforesorcin sodium. Examples of aliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid, and 1,4-cyclohexanedicarboxylic acid. Examples of aliphatic diols include ethylene glycol, diethylene glycol, triethylene glycol,
Neopentyl glycol, 1,4-butanediol, 1
, 2-propanediol, 1,3-propanediol,
Contains 1,2-hexanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, and 2,2'-bis(4-hydroxy-cyclohexyl)propane. Apart from the diols and dicarboxylic acids mentioned above, small amounts of long-chain diols and/or dicarboxylic acids and/or hydroxy-carboxylic acids can be introduced into the polyester to further enhance the dyeability. Examples of the long chain diols include 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,1
2-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, 1
, 17-heptadecanediol, 1,12-octadecanediol, 1,18-octadecanediol, 1,2
-Epoxyoctadecanediol, 1,19-nonadecanediol, 1,20-eicosandiol, 1,21
- including heneicosane diol, 1,22-docosane diol, 1,25-pentacosane diol, 9-octadecene-1,12-diol and dimer aliphatic alcohol. Examples of the long chain dicarboxylic acids include sebacic acid, azelaic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, heptadecanedicarboxylic acid, octadecanedicarboxylic acid, nonadecane. Dicarboxylic acids, eicosandicarboxylic acid, docosandicarboxylic acid, dimeric fatty acids and derivatives such as PRIPOL10
08/1009 (aromatic, cycloaliphatic and aliphatic C36
CAS Registration No. 1, which is a mixture of dimeric fatty acid isomers.
68783-41-5) and PRIPLAST300
8 (CAS Registration No. 68956-10-5, which is the dimethyl ester of the dimer acid), PRIPOL10
04 (C44 dimer fatty acids) (all of these are U
marketed by nichema), EMPOL
(Quantum C, a C36 aliphatic dimer acid)
commercially available) and UN
IDYME 14 (commercially available from Union Camp). Examples of said hydroxy-carboxylic acids containing long-chain alkyl or alkylene groups include methyl-n-hexylglycolic acid, 2,3-dihydroxynonanoic acid, 11-hydroxyundecanoic acid, 2-hydroxy-4
, 6,6-trimethylheptanoic acid, 16-hydroxyhexadecanoic acid, 12-hydroxystearic acid, 12-
Hydroxy-9-octadecenoic acid, ricinoleic acid, 1
Contains 2,13-epoxy-9-octadecenoic acid and anacardic acid. The polyester resins used according to the invention can be produced by polycondensation reactions known to those skilled in the art. In the case of polyesters containing one or more double bonds, inhibitors can be added to avoid crosslinking and/or side reactions. The short-chain diols or dicarboxylic acids of the present invention containing long-chain alkyl or alkylene side groups contain from 1 to 60 mol %, preferably from 5 to 25 mol %, more preferably from 5 to 25 mol % of the respective total diol dicarboxylic acid content. Preferably, it is incorporated into the polyester in an amount of 5 to 10 mol %. Preferably, the molecular weight of the polyester binder according to the invention is between about 1,000 and 10,000. The molecular weight can be increased by adding small amounts (for example about 0.1 mol %) of trifunctional or tetrafunctional products such as compounds corresponding to the structural formula below during the polycondensation reaction. Preferably COO-, SO3-, O-
or solubilizing groups such as polyethylene oxide chains (
co) in the polyester via one of the dicarboxylic acids (e.g. sulfoisophthalic acid, sulfoterephthalic acid, sulfoorthophthalic acid) or diols [e.g.
Tegomer DS3117 corresponding to the following formula (a) or the following formula (b) both commercially available from chmidt
Tegomer D3403], which then has the advantage of facilitating the aqueous application of the image-receiving layer to the support. Examples of such enabling groups are described in EP 368318 and JP 86/3796. ##STR2## Preferred (co)polyesters of the present invention are shown in Table 1 below, but the present invention is not limited thereto. [Table 1] [Table 2] [0039] Display TPA, IPA, SIPA, EG, D
IA22, CHDM, MPG, TEGODS, TEGO
D, MAL, HSA and LCA represent components from which polyester units are derived, and these designations are as follows. TPA Terephthalic acid IPA Isophthalic acid SI
PA 5-sulfoisophthalic acid sodium salt EG Ethylene glycol DIA22 Dianol22 (epoxidized bisphenol) marketed by Akzo CHDM Cyclohexane dimethanol NPG Neopentyl glycol TEGODS Goldschmid
Tegomer DS3117 TEGOD Goldschmidt, commercially available from
Tegomer D3403 MAL Maleic Acid Dimethyl Ester HSA 12-Hydroxystearic Acid LCA Short chain diols or dicarboxylic acids of the invention with long chain alkyl or alkylene side groups. An example is shown below. 1,2OD 1,2-octanediol DODD 1,2-dodecanediol HDD 1,2-hexadecanediol GMS Glycerin monostearate GMO Glycerin monooleate HDMAL Hexadecyl malonic acid OSUC Octenyl succinic acid TPSUC Tetrapropenyl succinic acid ODSUC Octadecyl succinic acid IODSUC Isooctadecyl succinic acid DOCSUC Docosenyl succinic acid [
[0041] The values in the above table represent the respective total diols,
It indicates the amount of diol or dicarboxylic acid groups in the (co)polyester composition in mole % with respect to the dicarboxylic acid content. [0042] The polyester resin of the present invention can be used as one of the supports.
It is preferable to coat in an amount of 0.5 to 100 g/m2, more preferably 1 to 10 g/m2. Mixtures of the (co)polyester resins of the invention can be used in the invention, and also mixtures of these resins with other known dye-receiving resins. For example, in combination with the (co)polyester resin of the present invention, the following synthetic resins (a) to (e) can be used alone or in a mixture of two or more. (a) Those having an ester bond: polyester resin, polyacrylate resin, polycarbonate resin, polyvinyl acetate resin, styrene-acrylate resin, vinyltoluene-acrylate resin, etc. (b) Those having urethane bonds: polyurethane resins, etc. (c) Those having an amide bond: polyamide resin. (d) Those having a urea bond: urea resin, etc. (e) Those having highly polar bonds: polycaprolactone resin, polystyrene resin, polyvinyl chloride resin, polyacrylonitrile resin, cellulose derivative resin. Examples of such resins are eg EP 133011
, EP133012, EP144247, EP2270
94, EP 228066. For example, the receiving layer can be composed of a resin mixture of a (co)polyester according to the invention and a conventional (co)polyester resin. When the (co)polyester resin of the present invention is used in combination with other resins, the amount of the other resin will depend on the (co)polyester of the present invention used; It is preferably 0 to 100 parts by weight per 100 parts by weight of polyester resin. High-boiling organic solvents or thermal solvents or plasticizers can be included in the image-receiving layer as diffusion promoters for dyes or as substances capable of accepting or dissolving dyes. Useful examples of such high boiling point organic solvents and thermal solvents include, for example, JP62/174754, JP62/245253.
, JP61/209444, JP61/200538,
JP62/8145, JP62/9348, JP62/
30247, JP62/136646. [0050] For the purpose of improving the whiteness of the receiving layer in order to improve the sharpness of the transferred image, or providing writing properties on the receiving surface and preventing retransfer of the transferred image, the receiving layer may be added. White pigments can be added. As the white pigment, titanium oxide, zinc oxide, kaolin, clay, calcium carbonate, finely powdered silica, etc. can be used, and these are as described above.
Can be used as a mixture of more than one species. In order to further enhance the light resistance of the transferred image, one or more additives such as ultraviolet absorbers, light stabilizers and antioxidants may be added, if necessary. The amounts of these ultraviolet absorbers and light stabilizers are 0.05 parts by weight each for 100 parts by weight of the resin constituting the receptor layer.
~10 parts by weight and preferably 0.5 to 3 parts by weight. The dye-receiving material of the invention may contain a stripping agent to improve its stripping properties to the donor material. As a release agent, solid wax such as polyethylene wax,
Amide waxes, and Teflon powders; fluorine-based and phosphate ester-based surfactants; and paraffin-based, silicone-based and fluorine-based oils, silicone oils, preferably reactive silicone oils and silicone-containing copolymers such as polysiloxane-polyether copolymers. preferable. [0053] Also, on at least a part of the surface of the image-receiving layer,
A coating of a dispersion or solution of the release agent in a suitable solvent can be applied, followed by drying and other steps to provide the release agent. The thickness of the release layer is preferably 0.01 to 5 μm, particularly 0.005 to 2 μm. The formation of the image-receiving layer can be carried out not only by known coating or printing methods, but also by first coating the receptor layer composition obtained by dissolving or dispersing suitable materials on another temporary support, and then applying the composition thereto. It can also be carried out by transferring it from a substrate onto a permanent support. Supports for the receptor sheet include transparent films or sheets of various plastics such as polyethylene terephthalate, polyolefin, polyvinyl chloride, polystyrene, polycarbonate, polyether sulfone, polyimide, cellulose ester, or polyvinyl alcohol co-acetal. can be used. The support can also be paper (top paper, art paper, cellulose fiber paper), baryta-coated paper, polyolefin-coated paper, such as double polyethylene-coated paper, synthetic paper (polyolefin-based, polystyrene-based), or white polyester, such as white pigmented paper. It can also be reflective, such as polyester. Laminated products in any combination of the above may also be used. Representative examples of laminates include laminates of sululose fiber paper and synthetic paper, and laminates of cellulose fiber paper and plastic film or sheet. As another example of a laminate, a plastic film using synthetic paper instead of cellulose fiber paper can be used. Furthermore, laminates of cellulose fiber paper, plastic film and synthetic paper can also be used. The support sheet serves to support the dye-receiving layer, and it is desirable that the support sheet have sufficient mechanical strength to handle the dye-receiving sheet as it is heated during thermal transfer recording. The support can be omitted when the dye-receiving layer alone has the necessary mechanical strength. The dye-receiving layer of the present invention preferably has an overall thickness of 0.5 to 50 μm, preferably 2.5 to 10 μm when the dye-receiving layer is provided on a support sheet. More preferred, or when the support sheet is omitted, it is preferred to have a thickness of 3 to 120 μm. The image-receiving layer may be a single layer or two or more such layers may be provided on the support. Further, the receiving layer may be formed on both sides of the support. European patent application no. 96200930.7.
erso) When printing on a transparent support, this results in an increase in the density of the transferred image. The image-receiving material of the invention can also have one or more intermediate layers between the support and the image-receiving layer. Depending on the material from which they are formed, interlayers can function as buffer layers, porous layers or dye diffusion prevention layers, or can fulfill two or more of these functions, and they also have special applications. In some cases, it also serves the purpose of an adhesive. Materials constituting the intermediate layer include, for example, urethane resin, acrylic resin, ethylene resin, butadiene rubber,
Or it can contain an epoxy resin. Preferably, the thickness of the intermediate layer is about 2-20 μm. The dye diffusion prevention layer is a layer that prevents dye from diffusing into the support. The binders used to form these layers can be water-soluble or organic solvent-soluble, but water-soluble binders are preferred, with gelatin being most preferred. The porous layer is a layer that prevents the heat applied during thermal transfer from diffusing from the image-receiving layer to the support in order to ensure that the applied heat is used efficiently. be. For example, silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate,
The fine powder made of aluminum silicate, synthetic zeolite, zinc oxide, lithopone, titanium oxide, or alumina can be used in the image-receiving layer, buffer layer, porous layer, diffusion prevention layer, and adhesive layer that constitute the thermal transfer image-receiving material of the present invention. etc. can be contained in. The image-receiving material of the invention can also have an antistatic treatment applied to its front or back side. Such an antistatic treatment can be carried out, for example, by incorporating an antistatic agent into the antistatic layer applied to the image-receiving layer or into the image-receiving layer that is on the front side. The same process can be done on the back side as well. Such treatment allows the image-receiving sheets to slide smoothly over each other, and also has the effect of preventing dust from adhering to the image-receiving sheets. Furthermore, the image-receiving sheet can have a slipping layer provided on the back side of the sheet support. Materials for the slip layer may include methacrylate resins such as methyl methacrylate, or corresponding acrylate resins, vinyl resins such as vinyl chloride-vinyl acetate copolymers. [0068] The receiver material can have detection marks provided on one side, preferably on the back side, so that the receiver material can be set correctly in the desired position during transfer, so that the image is always formed in the correct desired position. Dye-donor elements for use by thermal dye sublimation transfer in combination with the receiving elements of the invention usually include a very thin support, such as a polyester support, on one side of which is a dye layer containing the printing dye. covered with. An adhesive layer or subbing layer is usually provided between the support and the dye layer. The opposite side is usually coated with a lubricious layer that provides a lubricious surface for the thermal printing head to pass through without suffering from wear. The dye layer can be a monochromatic layer, or it can contain successive repeating areas, such as dyes of different shades of cyan, magenta, yellow and optionally black. When using dye-donor elements containing dyes of three or more primary colors, multicolor images can be obtained by performing dye transfer processing steps for each color sequentially. The dye layer of such a thermal dye sublimation transfer donor element is applied to the support by adding the dye, polymeric binder vehicle, and other optional ingredients to a suitable solvent or solvent mixture and dissolving or dispersing the ingredients. To form a coating composition, the support may initially be provided with an adhesive layer or a subbing layer and dried. The dye layer thus formed has a density of about 0.2 to 5
．． It has a thickness of 0 μm, preferably 0.4 to 2.0 μm, and a dye to binder ratio of 9:1 to 1:3, preferably 2:1 to 1:2 by weight. The following can be used as polymer binders: cellulose derivatives such as ethylcellulose, hydroxyethylcellulose, ethylhydroxycellulose, ethylhydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, nitrocellulose, cellulose acetate formate, cellulose acetate hydrogen phalate. , cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate pentanoate, cellulose acetate benzoate, cellulose triacetate; vinyl resins and derivatives such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral,
Copolyvinyl butyral-vinylacetal-vinyl alcohol, polyvinylpyrrolidone, polyvinylacetoacetal, polyacrylamide; polymers and copolymers derived from acrylates and acrylate derivatives such as polyacrylic acid, polymethyl methacrylate, and styrene-acrylate copolymers ; polyester resins; polycarbonates; organosilicones such as polysiloxanes; polyphenylene oxides; gum arabic. Preferably cellulose acetate butyrate or copolystyrene-acrylonitrile is used as binder for the dye layer. Any dye may be used in the dye image-receiving layer of the receiving sheet provided that it can be readily transferred to the dye image-receiving layer of the receiving sheet by the action of heat. Typical and specific examples of dyes for use in thermal dye sublimation transfer include eg EP 400 706, EP 20
9990, EP209991, EP216483, EP
218397, EP227095, EP227096,
EP229374, EP235939, EP24773
7, EP257577, EP257580, EP258
856, EP279330, EP279467, EP2
85665, US4743582, US4753922
, US4753923, US4757046, US47
69360, US4771035, JP84/7889
4, JP84/78895, JP84/78896, J
P84/227490, JP84/227948, JP
85/27594, JP85/30391, JP85/
229787, JP85/229789, JP85/2
29790, JP85/229791, JP85/22
9792, JP85/229793, JP85/229
795, JP86/41596, JP86/26849
3, JP86/268494, JP86/268495
and JP86/284489. Particularly preferred dyes or dye mixtures for use in the primary dye-donor element include: 00
77 For yellow, a mixture of dyes corresponding to the following formula in the ratio from 1:10 to 10:1; for magenta from 1:10 A mixture of dyes corresponding to the following formula in a ratio of 10:1; A mixture of the corresponding dyes; For black, a mixture of a magenta dye corresponding to the following formula (1), a cyan dye corresponding to the following formula (2), and a yellow dye corresponding to the following formula (3) is used. [Chemical 12] [Chemical 13] [Chemical 13] [Chemical 14] [Chemical 14] Preferred binders for use in the primary color dye layer include those containing 0 to 100% of any of the constituent components. co-styrene-acrylonitrile and co-styrene-acrylonitrile in a range of ratios
There is a mixture of acrylonitrile-butadiene. The preferred binder/dye ratio is 5:1 to 1:5. The coating layer can also contain other components such as curing agents, preservatives, organic or inorganic fine particles, dispersants, antistatic agents, antifoaming agents, viscosity control agents, and the like. These and other ingredients are EP133011, EP133012, EP1110
04 and EP279467. As a support for the dye-donor element, it is dimensionally stable and can withstand temperatures up to and including 400° C. for periods of 20 milliseconds or less, and for such short periods of time, typically Any material can be used, provided it is thin enough to conduct heat applied on one side through the dye on the other side, for transfer to the receiver sheet within 1 to 10 milliseconds. can. Such materials include polyesters such as polyethylene terephthalate, polyamides, polyacrylates, polycarbonates, cellulose esters, fluorinated polymers, polyethers, polyacetals, polyolefins, polyimides, glassine paper and condenser paper. Preferred is polyethylene terephthalate. Generally the support has a thickness of 2 to 30 μm. The support may also optionally be coated with an adhesive layer or a subbing layer. The dye layer of the dye-donor element may be coated onto the support or printed thereon by a printing process such as a gravure process. A hydrophilic colloidal polymer is present in the dye-donor element between the support and the dye layer to improve dye transfer density by preventing misdirection of dye towards the support. A dye barrier layer containing . The dye barrier layer can contain any hydrophilic material useful for the intended purpose. Generally good results are
Gelatin, polyacrylamide, polyisopropylacrylamide, butyl methacrylate grafted gelatin, ethyl methacrylate grafted gelatin, ethyl acrylate grafted gelatin, cellulose monoacetate, methyl cellulose, polyvinyl alcohol, polyethylene imine, polyacrylic acid, mixtures of polyvinyl alcohol and polyvinyl acetate , obtained using a mixture of polyvinyl alcohol and polyacrylic acid or a mixture of cellulose monoacetate and polyacrylic acid. Suitable dye barrier layers are e.g. EP 227091 and E
P228065. Certain hydrophilic polymers, such as those described in EP 227091,
It also has adequate adhesion to the support and dye layer, thus eliminating the need for separate adhesive and subbing layers. These special hydrophilic polymers used in single layer form in the donor element therefore perform a dual function and are therefore referred to herein as dye barrier/subbing layers. Preferably the opposite side of the dye-donor element can be coated with a slippery layer to prevent the printing head from sticking to the dye-donor element. Such lubricious layers may contain lubricious materials such as surfactants, liquid lubricants, with or without polymeric binders.
Contains solid lubricants or mixtures thereof. Surfactants can be any known to those skilled in the art, such as carboxylates, sulfonates, phosphates, aliphatic amine salts,
Aliphatic quaternary ammonium salt, polyoxyethylene alkyl ether, polyethylene glycol fatty acid ester,
It can be a fluoroalkyl C2-C20 fatty acid. Examples of liquid lubricants include silicone oils, synthetic oils, saturated hydrocarbons and glycols. Examples of solid lubricants include various higher alcohols such as stearyl alcohol, fatty acids and fatty acid esters; suitable lubricant layers include, for example EP1.
38483, EP227090, US4567113,
It is described in US4572860, US4717711. Preferably, the slipping layer contains a styrene-acrylonitrile copolymer or a styrene-acrylonitrile-butadiene copolymer as a binder, and a polysiloxane-polyether copolymer or polytetrafluoroethylene or a mixture thereof as a lubricant. (mixture) of 0.1
Contains in an amount of ~10% by weight. The dye layer of the dye-donor element can also contain a release agent to assist in separating the dye-donor element from the dye-receiving element after transfer. The release agent can also be applied in the form of a separate layer on at least part of the dye layer. Solid waxes, fluorine- or phosphate-containing surfactants and silicone oils are used as release agents. Suitable release agents include, for example, EP
133012, JP85/19138, EP22709
It is described in 2. The dye-receiving material according to the invention is used for forming dye transfer images. Such methods involve placing the dye layer of the donor element in face-to-face relationship with the dye-receiving layer of the receiver sheet and imagewise heating the donor element from the back side. Dye transfer is achieved by heating at a temperature of 400° C. for about a few milliseconds. When this method is applied only to a single color,
A monochromatic dye transfer image is obtained. Multicolor images can be obtained by using donor elements containing dyes of three or more primary colors and sequentially performing the processing steps described above for each color. The sandwich of donor material and receiver sheet is formed on three occasions during the period of time that heat is applied by the thermal printing head. The material is pulled apart after the first dye has been transferred. A second dye-donor element (or another area of the donor element with a different dye area) is then brought into register with the dye-receiver element and the process is repeated. A third color and optionally more colors can be obtained in the same manner. To achieve perfect registration when performing this method for more than one color, and to detect that a color is present in the printed portion of the donor material, a detection mark is usually placed on one side of the donor material. Give. Detection can be performed by measuring the light reflected from or transmitted through the detection mark, typically using an optically detectable mark that can be detected with a light source or a light sensor. Marks in the form of light-absorbing or light-reflecting coatings are formed at predetermined locations on the donor element, for example by gravure printing. The detection mark can contain an infrared absorbing compound such as carbon black. The detection mark may also contain one of the image dyes used for imaging, the detection of which is in the visible range. [0103] In addition to thermal heads, laser light, infrared flash or heated pens can be used as heat sources to provide thermal energy. Thermal printing heads that can be used to transfer dye from the dye-donor elements of this invention to receiver sheets are commercially available. When using laser light, the dye layer or another layer of dye material must contain a compound, such as carbon black, that absorbs the light emitted by the laser and converts it into heat. Alternatively, the support for the dye-donor element can be an electrically resistive ribbon, for example consisting of a multilayer structure of carbon-filled polycarbonate coated with a thin aluminum film. Current is injected into the resistive ribbon electrically targeting the printhead electrode causing highly localized heating of the ribbon beneath the compliant electrode. In this case the heat is generated directly in the resistive ribbon, and the fact that it is therefore the ribbon that gets hot means that each element of the thermal head gains heat before the head can be moved to the next printing position. Using resistive ribbon/electrode head technology offers unique advantages in printing speed compared to thermal head technology, which must be cooled. The following examples illustrate the invention in further detail, but include:
It is not limited to this. Example 1: Polyester synthetic resin N
o. 4 0.450 mol terephthalic acid dimethyl ester, 0.400 mol isophthalic acid dimethyl ester, 0.150 mol 5-sulfoisophthalic acid dimethyl ester sodium salt and 1.7 mol ethylene glycol and 0.3 mol A mixture of moles of 1,2-dodecanediol, 0.0002 moles of zinc acetate and 0.0001 moles of antimony(III) oxide was melted in a reactor under a nitrogen atmosphere and stirred at 200°C. Esterification started rapidly and methanol was distilled off. The temperature was raised to 255° C. over a period of 60-90 minutes and the theoretical amount of methanol was distilled off. The reaction product was heated at 255-280°C for 60-12°C until the desired degree of polymerization was obtained.
Condensation was carried out under reduced pressure for 0 minutes. Excess ethylene glycol was distilled off during the condensation reaction. The condensation yield was 100%. Other polyesters of the present invention, such as those shown in Table 1, can be made in the manner described above. Example 2: Preparation of an image-receiving element A 10% by weight aqueous polyester dispersion is applied to a support material (polyethylene coated paper) at a wet thickness of 20 μm by bar coating and
It was dried at 0°C and further dried at 90°C for 30 minutes. Image-receiving materials containing the polyester resins shown in Table 2 below were made in this manner. Example 3: Evaluation of image-receiving material A commercially available Mitsubishi Material type CK100S was used as the dye-donor material. The dye-receiving material obtained was printed in combination with a dye-donor element on a Mitsubishi video printer type CP100 so as to form a black image by superimposing the yellow, magenta and cyan images. Separate the receiver sheet from the dye-donor material and measure the color density of the black image recorded on the receiver sheet using Macb.
Measured using an eth RD919 densitometer. This experiment was repeated for each of the polyester resins shown in Table 2. As a result, a black colored record having the color density shown in Table 2 was obtained. [0116] These results show that high densities can be obtained using the polyester image-receiving layer of the present invention. Furthermore, the anti-blocking properties of the image-receiving layer are improved without the use of release compounds in the receiving layer or the top layer. Example 4: Comparative Experimental Example The following comparative polyester image-receiving material (made as in Example 2) was evaluated in the same manner as in Example 3. [0120]
Table 3 No.
TPA IPA SIPA E
G DIOL C 1
53 40
7 100 0
C 2 50 40
10 60
NPG=40C3
50 40 10
40 NPG=60
C 4 53
40 7 40
MPD=60C5
53 40
7 47.5 EPD=5
2.5 C 6 55.5
33.5 11
40CHDM=60C
7 53 40
7 62
TCDDM=35 C 8 5
0 40 10
60 TEG=40
C 9 50 4
0 10 80
1,2HD=20 In Table 3, the following abbreviations were used. NPG neopentyl glycol MPD 2-methyl-2,4
-Pentanediol EPD 2,2-diethyl-1
, 3-propanediol 1,2HD 1,2-hexanediol CHDM cyclohexanedimethanol TCDDM tricyclodecanedimethanol TEG triethylene glycol The results are shown in Table 4. These results show that significantly lower concentrations can be obtained using polyesters containing short chain diols with no side groups or short chain side groups. Additionally, it was necessary to incorporate a release agent into the layer to prevent adhesion of the donor material to the receiver material.

Claims (8)

[Claims] 1. Thermal dye sublimation comprising a support having thereon a dye image-receiving layer containing a (co)polyester containing condensed residues of one or more diols and one or more dicarboxylic acids. In the dye image-receiving element for use by transfer, at least one of said diol and/or said dicarboxylic acid contains not more than 5 carbon atoms in the main chain and at least 6 carbon atoms in the side chain. A dye image-receiving material characterized in that it contains a long-chain alkyl or alkylene group. 2. Dye image-receiving element according to claim 1, characterized in that the long-chain alkyl or alkylene radicals have at least 10 carbon atoms. 3. A dye image-receiving material according to claim 1, wherein the long-chain alkyl or alkylene group is branched. 4. The diol is selected from the group consisting of 1,2-dodecanediol, 1,2-hexadecanediol, glycerin monostearate, glycerin monooleate, pentaerythritol distearate, and pentadecylresorcinol. Claims 1-
3. The dye image-receiving material according to any one of Item 3. 5. The dicarboxylic acid is selected from the group consisting of hexadecylmalonic acid, octadecylalonic acid, hexadecylsuccinic acid, octadecylsuccinic acid and docosenylsuccinic acid. Dye image-receiving material. 6. Any one of claims 1 to 5, characterized in that the (co)polyester contains condensed residues of one or more aromatic dicarboxylic acids and one or more aliphatic diols. A dye image-receiving material according to item 1. 7. The aromatic dicarboxylic acid is one or more dicarboxylic acids selected from the group consisting of terephthalic acid, isophthalic acid and 5-sulfophthalic acid, and the aliphatic diol is ethylene glycol. 7. A dye image-receiving material according to claim 6. 8. Dye image-receiving element according to claim 1, characterized in that the (co)polyester contains solubilizing groups.