JP2623181B2 - Thermal dye sublimation transfer receiving material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to a dye image receiving material for use by thermal dye sublimation transfer.

In thermal dye sublimation transfer, also called thermal dye diffusion transfer, a dye-donor element provided with a dye image containing a sublimable dye having thermal transferability is brought into contact with a dye image-receiving element to obtain pattern information. In accordance with the signal, selective heating is provided by a thermal print head provided with a number of juxtaposed heat generating registers, whereby dye is transferred from the selectively heated zone of the dye-donor element to the dye image-receiving element, and The shape and density of the pattern depends on the pattern and intensity of the heat applied to the dye-donor element.

Dye image receiving materials for use by thermal dye sublimation transfer usually include a support, such as paper or a transparent film, coated with a dye image receiving layer so that the dye can diffuse more easily. An adhesive layer may be provided between the support and the receiving layer.

[0004] The dye image receiving layer can contain as binder, for example, polycarbonate, polyurethane, polyester, polyamide, polyvinyl chloride, polystyrene-co-acrylonitrile, polycaprolactone or mixtures thereof.

[0005] 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 an aromatic moiety such that the (co) polyester has a glass transition point of at least 0 ° C, preferably at least 20 ° C.

[0006] Such polyester receiving layers are, for example, EP2
89161, EP275319, EP261505, E
P368318, JP86 / 3796 and JP89 / 2
69589.

JP 89/269589 describes a polyester image receiving layer using malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid and adipic acid as examples of dicarboxylic acid condensation residues.

[0008] Examples of diols described for incorporation into the polyester receiving layer include ethylene glycol and neopentyl glycol.

In prior art polyester image receiving layers, the dyeability is not always good enough, and when an image having a high density is desired, a correspondingly excessive heat content is required during printing. This inevitably increases the energy load on the thermal head, which disadvantageously increases the thermal head drive voltage.

Furthermore, when the donor element and the receiving element are peeled off after performing the thermal transfer, the donor layer adheres to the receiving layer and is therefore peeled off so as to be transferred thereon, whereby both sheets are separated. Will never fit for use. Thus, to improve the anti-stick properties of the image receiving layer, release agents are generally incorporated into the prior art image receiving layer or into the surface coating on this image receiving layer.

It is an object of the present invention to provide an excellent dyeable polyester dye image receiving layer.

Another object of the present invention is to provide a polyester dye image-receiving layer having improved releasability without having to separately incorporate a release agent in the image-receiving layer or a layer above the image-receiving layer. is there. Other objects of the present invention will become clear from the following description.

According to the present 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. , A long-chain alkyl or alkylene group having at least 6 carbon atoms in the side chain.

[0014] Preferably, the long chain side groups contain at least 10 carbon atoms.

[0015] 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 side groups may be included in the diols or dicarboxylic acids of the present invention on the same carbon atom of the main chain or on different carbon atoms.

The long-chain alkyl or alkylene side group may be an aromatic moiety, an alicyclic moiety, a hetero atom (for example, --O--, --NH
—, —O—CO—, —NH—CO—), and can be bonded to the main chain through a bonding group.

Examples of short-chain diols of the present 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, Includes glycerin monocaprylate, pentaerythritol distearate and pentadecylresorcin. Among them 1, 2
-Dodecanediol, 1,2-hexadecanediol,
Glycerin monostearate, glycerin monooleate, pentaerythritol distearate and pentadecylresorcin are particularly preferred.

Examples of short-chain dicarboxylic acids of the present 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,
Hexadecenyl succinic acid, octadecenyl succinic acid, docosyl succinic acid, docosenyl succinic acid, tetrapropenyl succinic acid, triacontenyl succinic acid, polyisobutenyl succinic acid, 1-dodecyl glutaric acid, 1-tetradecyl glutaric acid , 1-hexadecylglutaric acid and 1-
Contains decyl adipic acid. Among these, hexadecylmalonic acid, octadecylmalonic acid, hexadecylsuccinic acid,
Octadecyl succinic acid and docosenyl succinic acid are particularly preferred.

The (co) polyester of the present invention comprises one or more of the short-chain diols or dicarboxylic acids of the present invention containing aromatic and aliphatic dicarboxylic acids and diols and 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 the dicarboxylic acids in the form of the corresponding esters and / or 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-butylisophthalic 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 (eg, Dianol 22 marketed by Akzo), and propoxylated bisphenol A (eg, Dianol marketed by Akzo).
33), p-xylylene glycol, sodium 5-sulforesorcin.

Examples of the aliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid and 1,4-cyclohexanedicarboxylic acid.

Examples of the aliphatic diol include ethylene glycol, diethylene glycol, triethylene glycol,
Neopentyl glycol, 1,4-butanediol,
1,2-propanediol, 1,3-propanediol, 1,2-hexanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,4-
Includes cyclohexanediol, 2,2'-bis (4-hydroxy-cyclohexyl) propane.

Apart from the aforementioned diols and dicarboxylic acids, 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 diol 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,
2-epoxyoctadecanediol, 1,19-nonadecanediol, 1,20-eicosandiol, 1,2
Includes 1-heneicosanediol, 1,22-docosanediol, 1,25-pentacosanediol, 9-octadecene-1,12-diol and dimer fatty alcohols.

Examples of the long-chain dicarboxylic acids include sebacic acid, azelaic acid, decane dicarboxylic acid, undecane dicarboxylic acid, dodecane dicarboxylic acid, tridecane dicarboxylic acid, tetradecane dicarboxylic acid, heptadecane dicarboxylic acid, octadecane dicarboxylic acid, nonadecane Dicarboxylic acids, eicosanedicarboxylic acids, docosandicarboxylic acids, dimer fatty acids and derivatives such as PRIPOL1008
/ 1009 (aromatic, CAS registration No. 6878 is a mixture of cycloaliphatic and aliphatic C ₃₆ dimer fatty acid isomers
3-41-5) and PRIPLAST3008 (CAS registration No. 68957-, which is the dimethyl ester of the dimer acid)
10-5), marketed by PRIPOL1004 (C ₄₄ is a dimer fatty acid) (all Unichema), Quantum Ch is EMPOL (C ₃₆ aliphatic dimeric acid
emicals) and UNIDYME 14
(Commercially available from Union Camp).

Examples of the hydroxy-carboxylic acids containing a long-chain alkyl or alkylene group 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,
Includes 12,13-epoxy-9-octadecenoic acid, anacardic acid.

The polyester resin used according to the present invention can be prepared by a condensation polymerization reaction 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 according to the invention containing long-chain alkyl or alkylene side groups are present in an amount of from 1 to 60 mol%, preferably from 5 to 25 mol%, more preferably from 5 mol% of the respective total diol dicarboxylic acid content. It is preferred to introduce 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 1000 and 10,000. The molecular weight can be increased during the polycondensation reaction by adding a small amount (eg, about 0.1 mol%) of a trifunctional or tetrafunctional product, for example, a compound corresponding to the structural formula below.

[0032]

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[0033] Preferably _{^{COO -, SO 3 -, O}} - or such soluble groups of the polyethylene oxide chains, the (co) in the polyester, the dicarboxylic acids (e.g. sulfoisophthalic acid, sulfoterephthalic acid, sulfo ortho phthalic acid) Via one or via a diol [eg Tegomer D corresponding to the following formula (a), which is commercially available together from Goldschmidt:
S3117 or Tegomer D34 corresponding to the following formula (b)
03], thus providing an advantage that the image-receiving layer can be easily made water-soluble on the support. Examples of such enabling groups are described in EP 368318 and JP
86/3796.

[0034]

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[0035]

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Preferred (co) polyesters of the present invention are shown in Table 1 below, but the present invention is not limited thereto.

[0037]

[Table 1]

[0038]

[Table 2]

Display TPA, IPA, SIPA, EG, D
IA22, CHDM, MPG, TEGODS, TEGO
D, MAL, HSA and LCA represent the components from which the units of the polyester are derived, and their designations are as follows.

TPA Terephthalic acid IPA Isophthalic acid SIPA 5-Sulfoisophthalic acid sodium salt EG Ethylene glycol DIA22 Dianol 2 marketed by Akzo
2 (epoxylated bisphenol) CHDM cyclohexane dimethanol NPG neopentyl glycol TEGODS Te commercially available from Goldschmidt
gomer DS3117 Tego commercially available from TEGOD Goldschmidt
gomer D3403 MAL Maleic acid dimethyl ester HSA 12-Hydroxystearic acid LCA The short-chain diols or dicarboxylic acids of the present invention having long-chain alkyl or alkylene side groups. Examples are shown below. 1,2OD 1,2-octanediol DODD 1,2-dodecanediol HDD 1,2-hexadecanediol GMS glycerin monostearate GMO glycerin monooleate HDALAL hexadecylmalonic acid OSUC octenyl succinic acid TPSUC tetrapropenyl succinic acid ODSUC octadecyl succinic acid IODSUC isooctadecyl succinic acid DOCSUC docosenyl succinic acid

The numerical values in the above table indicate the amount of the diol or dicarboxylic acid group in the (co) polyester composition in mol% with respect to each of the total diol and dicarboxylic acid contents.

The polyester resin of the present invention comprises a support
preferably 1 to 10 g / m ² is more preferable to coat in an amount of 0.5~100g for m ^2.

In the present invention, mixtures of the (co) polyester resins of the present invention can be used, and mixtures of these resins with other known dye-receiving resins can also be used.

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 and the like. (B) Those having a urethane bond: polyurethane resin and the like. (C) Those having an amide bond: polyamide resin. (D) Those having a urea bond: urea resin and the like. (E) Those having a highly polar bond: polycaprolactone resin, polystyrene resin, polyvinyl chloride resin, polyacrylonitrile resin, cellulose derivative resin.

Examples of such resins are, for example, EP 13301
1, EP133302, EP144247, EP227
094, EP 228066.

For example, the receiving layer can be composed of a resin mixture of the (co) polyester according to the present invention and a conventional (co) polyester resin.

When the (co) polyester resin of the present invention is used in combination with another resin, the amount of the other resin is determined by the (co) polyester of the present invention to be used. The amount is preferably 0 to 100 parts by weight based on 100 parts by weight of the polyester resin.

A high boiling organic solvent or a thermal solvent or a plasticizer can be contained in the image receiving layer as a diffusion accelerator for the dye or as a substance capable of receiving or dissolving the dye. Useful examples of such high boiling organic solvents and thermal solvents include:
For example, JP62 / 174754, JP62 / 24525
3, JP61 / 209444, JP61 / 20053
8, JP62 / 8145, JP62 / 9348, JP6
2/30247, JP62 / 136646.

For the purpose of improving the whiteness of the receiving layer in order to improve the sharpness of the transferred image, or providing writeability to the receiving surface and preventing retransfer of the transferred image, White pigments can be added. As the white pigment, titanium oxide, zinc oxide, kaolin, clay, calcium carbonate, fine powder silica, and the like can be used, and these can be used as a mixture of two or more as described above.

In order to further enhance the light fastness of the transferred image, one or more of additives such as an ultraviolet absorber, a light stabilizer and an antioxidant can be added as required. The amounts of these ultraviolet absorbers and light stabilizers are each 0.0
It is preferably 5 to 10 parts by weight and 0.5 to 3 parts by weight.

The dye-receiving element of the present invention can contain a release agent to improve the releasability of the donor element. As the release agent, solid wax such as polyethylene wax,
Amide waxes and Teflon powders; fluorinated and phosphate ester based surfactants; and paraffinic, silicone and fluorinated oils, silicone oils, preferably reactive silicone oils and silicone containing copolymers such as polysiloxane-polyether copolymers. preferable.

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 provided, 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 preferably 0.005 to 2 μm.

The image-receiving layer is formed not only by a known coating or printing method, but also by first coating a receiving layer composition obtained by dissolving or dispersing an appropriate material on another temporary support, It can also be carried out by transferring it onto a permanent support.

As the support for the receptor sheet, a transparent film or sheet 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. Can be used. The support may also be paper (superior 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 It can also be reflective, such as polyester.

Also, laminated products of any combination described above can be used. Representative examples of the laminate include a laminate of a cellulose fiber paper and a synthetic paper and a laminate of a cellulose fiber paper and a plastic film or sheet. As another example of the laminate, a plastic film using synthetic paper instead of cellulose fiber paper can be used. Further, a laminate of cellulose fiber paper, plastic film and synthetic paper can also be used.

The support sheet acts to support the dye-receiving layer, and it is desirable that the support sheet have sufficient mechanical strength to handle the dye-receiving sheet that is heated for the duration of thermal transfer recording. When the dye receiving layer alone has the required mechanical strength, the support can be omitted.

The dye receiving layer of the present invention preferably has a total thickness of 0.5 to 50 μm when the dye receiving layer is provided on the support sheet, and preferably has a thickness of 2.5 to 10 μm. More preferably, or when the support sheet is omitted, it preferably has a thickness of 3 to 120 μm.

The image receiving layer can be a single layer, or two or more such layers can be provided on a support.

The receiving layer may be formed on both sides of the support. In the case of a transparent support printed recto-verso on both receiving layers as described in European Patent Application No. 962009930.7, this results in an increase in the density of the transferred image.

The image receiving material of the present 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, the intermediate layer can function as a buffer layer, a porous layer, or a dye diffusion barrier, or can perform more than one of these functions, and they may also have special applications. Some also serve the purpose of an adhesive.

The material constituting the intermediate layer is, for example, urethane resin, acrylic resin, ethylene resin, butadiene rubber,
Or, it may include an epoxy resin. Preferably, the thickness of the intermediate layer is about 2 to 20 μm.

The dye diffusion preventing layer is a layer for preventing the dye from diffusing into the support. The binder used to form these layers can be water-soluble or organic solvent-soluble, but water-soluble binders are preferred, especially gelatin.

The porous layer is a layer that prevents the heat applied during thermal transfer from diffusing from the image receiving layer to the support to ensure that the heat applied is used efficiently. is there.

For example, silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate,
The fine powder consisting of aluminum silicate, synthetic zeolite, zinc oxide, lithopone, titanium oxide or alumina is used as the image receiving layer, buffer layer, porous layer, diffusion preventing layer and adhesive layer constituting the thermal transfer image receiving material of the present invention. And the like.

The image receiving material of the present invention can have an antistatic treatment applied to the front or back surface. Such an antistatic treatment can be performed, for example, by mixing an antistatic agent into the antistatic layer provided on the image receiving layer or into the image receiving layer on the front surface. The same process can be performed on the backside. By such processing, mutual sliding between the image receiving sheets can be performed smoothly, and there is also an effect of preventing dust from adhering to the image receiving sheets.

Further, the image receiving sheet may have a lubricating layer provided on the back surface of the sheet support. Materials for the lubricating layer may include methacrylate resins such as methyl methacrylate, or the corresponding acrylate resins, vinyl resins such as vinyl chloride-vinyl acetate copolymer.

The receiving material can have detection marks provided on one surface, preferably on the back, so that the receiving material can be set correctly at the desired position during the transfer, so that the image can always be formed at the correct desired position.

Dye-donor elements for use by thermal dye sublimation transfer in combination with the receiving element of the present invention usually comprise a very thin support, such as a polyester support, on one side of which is a dye layer containing a printing dye. It is covered with. Usually, an adhesive layer or an undercoat layer is provided between the support and the dye layer.
The opposite side is usually coated with a lubricating layer that provides a lubricated surface to allow the thermal print head to pass without suffering from wear.

The dye layer can be a monochromatic layer, or it can comprise successive repeating areas of different dyes, for example cyan, magenta, yellow and optionally black hue. When a dye-donor element containing three or more primary color dyes is used, a multicolor image can be obtained by sequentially performing a dye transfer step for each color.

The dye layer of such a thermal dye sublimation transfer donor element can be applied to a support by dissolving or dispersing the components in a suitable solvent or solvent mixture, adding the dye, polymer binder medium, and other optional components. The support may be first provided with an adhesive layer or subbing layer, and dried.

The dye layer thus formed is about 0.2 to
It has a thickness of 5.0 μm, preferably 0.4-2.0 μm, and the dye to binder ratio is 9: 1 to 1: 3, preferably 2: 1 to 1: 2 by weight.

The following polymer binders can be used: cellulose derivatives such as ethylcellulose, hydroxyethylcellulose, ethylhydroxycellulose, ethylhydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, nitrocellulose, cellulose acetate formate, cellulose acetate hydrogen phthalate 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-vinyl acetal- Vinyl alcohol, polyvinyl alcohol Polymers and copolymers derived from acrylates and acrylate derivatives, such as polyacrylic acid, polymethyl methacrylate, and styrene-acrylate copolymers; polyester resins; polycarbonates; Siloxane; polyphenylene oxide; arabic gum. Preferably, cellulose acetate butyrate or copolystyrene-acrylonitrile is used as binder in the dye layer.

Any dye can be used in such a dye layer if it can be easily transferred to the dye image receiving layer of the receiving sheet by the action of heat.

Representative and specific examples of dyes for use in thermal dye sublimation transfer are, for example, EP400706, EP20
9990, EP2099991, EP216483, EP
218397, EP227095, EP227096,
EP229374, EP235939, EP24773
7, EP257577, EP257580, EP258
856, EP279330, EP279467, EP2
85665, US4744352, US475392
2, US4753923, US4757046, US4
679360, US47701035, JP84 / 788
94, JP84 / 78895, JP84 / 78896,
JP84 / 227490, JP84 / 227948, J
P85 / 27594, JP85 / 30391, JP85
/ 229787, JP85 / 229789, JP85 /
229790, JP85 / 229791, JP85 / 2
29792, JP85 / 229793, JP85 / 22
9795, JP86 / 41596, JP86 / 2684
93, JP86 / 268494, JP86 / 26849
5 and JP86 / 284489.

Particularly preferred dyes or dye mixtures for use in primary color dye-donor elements include the following:

For yellow, a mixture of dyes corresponding to the following formula in a ratio of 1:10 to 10: 1:

[0078]

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[0079]

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For magenta, a mixture of dyes corresponding to the following formula in a ratio of 1:10 to 10: 1:

[0081]

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[0082]

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For magenta, a mixture of dyes corresponding to the following formula in a ratio of 1:10 to 10: 1:

[0084]

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[0085]

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For cyan, a mixture of dyes corresponding to the following formula in a ratio of 1:10 to 10: 1:

[0087]

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[0088]

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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);

[0090]

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[0091]

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[0092]

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Preferred binders for use in the primary color dye layer include co-styrene-acrylonitrile and co-styrene-containing any of the constituents in a ratio ranging from 0 to 100%.
There is a mixture of acrylonitrile-butadiene. The preferred binder / dye ratio is from 5: 1 to 1: 5.

The coating layer may also contain other components such as a curing agent, a preservative, organic or inorganic fine particles, a dispersant, an antistatic agent, an antifoaming agent, a viscosity controlling agent and the like. These and other components are described in EP133011, EP133012, EP111
004 and EP 279467 are more fully described.

As a support for the dye-donor element, it is dimensionally stable, capable of withstanding temperatures up to 400 ° C. for up to 20 milliseconds, and for such short periods of time, typically Use any material that is thin enough to transfer the heat applied to one side through the dye on the other side to transfer to the receiver sheet within 1-10 milliseconds it 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 be coated with an adhesive or subbing layer if desired.

The dye layer of the dye-donor element may be coated on a support or printed thereon by a printing method such as a gravure method.

To improve dye transfer density by preventing the transfer of dye in the wrong direction toward the support, a hydrophilic colloid polymer is incorporated into the dye-donor element between the support and the dye layer. May be used. The dye barrier layer can contain any hydrophilic material that is 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, methylcellulose, polyvinyl alcohol, polyethylene imine, polyacrylic acid, a mixture of polyvinyl alcohol and polyvinyl acetate And a mixture of polyvinyl alcohol and polyacrylic acid or a mixture of cellulose monoacetate and polyacrylic acid.
Suitable dye barrier layers are, for example, EP227091 and E
P228065. Certain hydrophilic polymers, such as those described in EP227091,
It also has adequate adhesion to the support and the dye layer, thus obviating the need for separate adhesive and subbing layers. These particular hydrophilic polymers used in the donor element in the form of a single layer 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 slip layer to prevent the print head from sticking to the dye-donor element. Such a lubricating layer may be a lubricating material such as a surfactant, a liquid lubricant, with or without a polymeric binder.
Contains solid lubricants or mixtures thereof. Surfactants can be any known to those skilled in the art, such as carboxylate, sulfonate, phosphate, aliphatic amine salts,
Aliphatic quaternary ammonium salt, polyoxyethylene alkyl ether, polyethylene glycol fatty acid ester,
It can be a fluoroalkyl C ₂ -C ₂₀ fatty acids. 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.
8483, EP227090, US4567113, U
S4572860, US4717711. Preferably, the lubricating layer is made of styrene-acrylonitrile copolymer or styrene-acrylonitrile-
A butadiene copolymer is contained, and a polysiloxane-polyether copolymer or polytetrafluoroethylene or a mixture thereof is used as a lubricant in an amount of 0.1 to 0.1% of a binder (mixture).
It is contained in an amount of 10% by weight.

The dye layer of the dye-donor element can also contain a release agent to help separate the dye-donor element from the dye-receiving element after transfer. The release agent can also be applied in a separate layer over at least a portion of the dye layer. Solid waxes, fluorine or phosphate containing surfactants and silicone oils are used as release agents. Suitable release agents are, for example, EP
133012, JP85 / 19138, EP22709
2.

The dye-receiving element according to the present invention is used for forming a dye transfer image. Such methods include 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 from behind the donor element. Dye transfer is achieved by heating at a temperature of 400 ° C. for about several milliseconds.

When this method is performed for only a single color,
A monochromatic dye transfer image is obtained. Multicolor images can be obtained by using a donor element containing three or more primary color dyes and sequentially performing the processing steps described above for each color. The above sandwich of donor element and receiver sheet is formed in three cases during the time when heat is supplied by the thermal printing head. The material is separated after the first dye has been transferred. The second dye-donor element (or another area of the donor element with a different dye area) is then brought in register with the dye-receiving element and the process is repeated. The third color and, if desired, further colors are obtained in the same way.

In order 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 element, a detection mark is usually placed on one side of the donor element. Give. Generally, using an optically detectable mark that can be detected by a light source or light sensor, detection can be performed by measuring the light reflected from or transmitted through the detection mark. Marks in the form of a light-absorbing or light-reflective coating are formed at predetermined locations on the donor element by, for example, gravure printing.
The detection mark can contain an infrared absorbing compound such as carbon black. The detection mark can also contain one of the image dyes used for imaging, the detection being in the visible range.

In addition to a thermal head, a laser light, infrared flash or heating pen can be used as a heat source to supply thermal energy. Thermal printing heads that can be used to transfer dye from the dye-donor element of the invention to a receiver sheet are commercially available. If laser light is used, the dye layer or another layer of the dye material must contain a compound that absorbs the light emitted by the laser and converts it to heat, for example, carbon black.

Alternatively, the support of the dye-donor element can be an electrical resistance ribbon consisting of a multilayer structure of, for example, a carbon-filled polycarbonate coated with a thin aluminum film. Electrical current is injected into the resistive ribbon for electrical purposes at the printhead electrode, which produces a highly localized heating of the ribbon below the compliant electrode. The fact that the heat is generated directly in the resistive ribbon in this case, and thus the ribbon that gets hot, is the fact that each element of the thermal head gets heat and can move the head to the next printing position. The use of resistive ribbon / electrode head technology offers an inherent advantage in printing speed as compared to thermal head technology that must be cooled.

The following examples illustrate the invention in more detail.
It is not limited to this.

Example 1: Synthesis of polyester Resin No. 4

0.450 mol of dimethyl terephthalate, 0.400 mol of dimethyl isophthalate, 0.150 mol of dimethyl 5-sulfoisophthalate, 1.7 mol of ethylene glycol and 0.3 mol Of a mixture of 1,2-dodecanediol in a reactor was prepared by melting 0.0002 mol of zinc acetate and 0.0001 mol of antimony (III) oxide in a reactor under a nitrogen atmosphere, followed by stirring at 200 ° C.

Esterification started rapidly and methanol was distilled off. The temperature was raised to 255 ° C. over a period of 60 to 90 minutes and the theoretical amount of methanol was distilled off. The reaction product is reacted at 255-280 ° C for 60-1 until the desired degree of polymerization is obtained.
Condensed under reduced pressure for 20 minutes. Excess ethylene glycol was distilled off during the condensation reaction. The condensation yield was 100%.

Other polyesters of the invention, as shown in Table 1, can be made in the manner described above.

Example 2: Preparation of an image-receiving material A 10% by weight aqueous polyester dispersion is applied to a support material (polyethylene-coated paper) with a bar coat at a wet thickness of 20 μm, dried at 40 ° C. and further dried at 90 ° C. For 30 minutes.

Image receiving materials containing the polyester resins shown in Table 2 below were prepared in this manner.

Example 3 Evaluation of Image Receiving Material As a dye-donor material, commercially available Mitsubishi Material Type CK100S was used.

The resulting dye-receiving element was printed on a Mitsubishi Video Printer Type CP100 in combination with a dye-donor element to form a black image by superimposing the yellow, magenta and cyan images.

The receiver sheet was separated from the dye-donor element and the color density of the black image recorded on the receiver sheet was determined by Macbet.
h Measured with a RD919 densitometer.

This experiment was repeated for each of the polyester resins shown in Table 2. As a result, a black coloring record having the color density shown in Table 2 was obtained.

[0116]

[Table 3]

These results show that high densities can be obtained using the polyester image receiving layer of the present invention.

Further, the anti-adhesion of the image receiving layer is improved without using a release compound in the receiving layer or the uppermost layer.

Example 4: Comparative Experimental Example The following comparative polyester image-receiving material (prepared in the same manner as in Example 2) was evaluated in the same manner as in Example 3.

Table 3 No. TPA IPA SIPA EG DIOL C 1 53 40 7 100 0 C 2 50 40 10 60 NPG = 40 C 3 50 40 10 40 NPG = 60 C 4 53 40 7 40 MPD = 60 C 5 53 40 7 47.5 EPD = 52.5 C 6 55.5 33.5 11 40 CHDM = 60 C 7 53 40 7 62 TCDDM = 35 C 8 50 40 10 60 TEG = 40 C 9 50 40 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

Table 4 shows the results.

[0123]

These results show that much lower concentrations can be obtained with polyesters containing short-chain diols without side groups or with short side groups.

Further, it was necessary to incorporate a release agent into the layer in order to prevent adhesion of the donor element to the receiving element.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Rolf Wehrmann De-4150 Krefeld, Scheibstraße 81 (56) References JP-A-63-74691 (JP, A) JP-A-2- 274591 (JP, A) JP-A-3-173690 (JP, A) JP-A-4-263991 (JP, A)

Claims (8)

(57) [Claims] (1) containing a condensed residue of one or more diols and one or more dicarboxylic acids
In a dye image receiving material for use by thermal dye sublimation transfer including a support having thereon a dye image receiving layer containing a polyester, at least one of the diol and / or the dicarboxylic acid is not more than 5 in a main chain. A dye image-receiving material, characterized by containing a long-chain alkyl or alkylene group having at least 6 carbon atoms in the side chain. 2. A dye image receiving element according to claim 1, wherein the long chain alkyl or alkylene side group has at least 10 carbon atoms. 3. A dye image receiving material according to claim 1, wherein the side chain alkyl or alkylene side group is separated. 4. The method of claim 1, wherein 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 the above items. The method according to claim 5, wherein the dicarboxylic acid, hexadecyl malonic acid, octadecyl Ma Ron acid, hexadecyl succinic acid,
5. The dye image receiving material according to claim 1, wherein the dye image receiving material is selected from the group consisting of octadecylsuccinic acid and docosenylsuccinic acid. 6. The polyester according to claim 1, wherein the (co) polyester contains a condensed residue of one or more aromatic dicarboxylic acids and one or more aliphatic diols. Or a dye image receiving material according to item 1. 7. The aromatic dicarboxylic acid is terephthalic acid,
Is one or more dicarboxylic acids selected from the group consisting of isophthalic acid and 5-sulfoisophthalic acid,
7. The dye image receiving material according to claim 6, wherein the aliphatic diol is ethylene glycol. 8. The dye image receiving material according to claim 1, wherein the (co) polyester contains a solubilizing group.