Thermal transfer dyesheet

Abstract: A dyesheet is provided for thermal transfer printing, comprising a base sheet having a thermal transfer dye layer on one surface, and on the other a heat resistant backcoat comprising a crosslinked reaction product of radically polymerising a compound having a plurality of polymerisable unsaturated groups per molecule, wherein the backcoat is formulated to minimise scratching of the print during printing. The formulation comprises a) a compound having a single radically polymerisable unsaturated group which is copolymerised with the compound having a plurality of polymerisable unsaturated groups per molecule, and b) a multivalent metal salt of a long chain alkyl or alkyphenyl phosphate ester as slip agent. These two factors (a & b) work together, and if either is omitted, relief from scratching does not generally occur.

Description: The invention relates to dyesheets for thermal transfer printing, which are suitable for forming printed images on receiver sheets by thermal transfer of dyes using such heating means as thermal heads; and in particular to reducing scratching defects in such prints. Thermal transfer printing is a process for printing and generating images by transferring thermally transferable dyes from a dyesheet to a receiver. The dyesheet comprises a base sheet coated on one side with a dyecoat containing one or more thermally transferable dyes, and printing is effected while the dyecoat is held against the surface of the receiver, by heating selected areas of the dyesheet so as to transfer the dyes from those selected areas to corresponding areas of the receiver, thereby generating images according to the areas selected. Thermal transfer printing using a thermal head with a plurality of tiny heaters to heat the selected areas, has been gaining widespread attention in recent years mainly because of its ease of operation in which the areas to be heated can be selected by electronic control of the heaters, eg according to a video or computer-generated signal; and because of the clear, high resolution images which can be obtained in this manner. The base sheet of a thermal transfer dyesheet is generally a thermoplastic film, orientated polyester film usually being selected because of its superior surface smoothness and good handling characteristics. The thermoplastic materials used in such films, however, may lead to a number of problems. For example, for high resolution printing at high speed, it is necessary to provide the thermal stimulus from the heaters in pulses of very short duration to enable all the rows to be printed sequentially within an acceptably short time, but this in turn requires higher temperatures in the printer head in order to provide sufficient thermal energy to transfer sufficient dye in the time allowed. Typically such temperatures are well in excess of the melting or softening temperatures of the thermoplastic base sheet. One effect of such high temperatures can be localised adhesion between the dyesheet and the printer head, the so-called "sticking" effect, with a result that the dyesheet is unable to be moved smoothly through the printer. Printing may be accompanied by a series of clicks as the sheets become stuck to, then freed from, the apparatus, this becoming a chatter-like noise at higher frequencies. In severe cases the base sheet can lose its integrity, and the dyesheet become torn. In the past, these problems have been addressed by providing the dyesheet with one or more protective backcoats of various heat-resistant, highly crosslinked, polymers. By "backcoats" in this context we mean coatings applied either directly or indirectly on the base sheet surface remote from that to which the dyecoat is applied. Thus it is to the backcoat side to which heat is applied by the thermal head during printing. In addition to providing a heat-resistant layer to combat sticking, backcoats may also be formulated to improve slip and handling properties. A wide variety of highly crosslinked polymer compositions have been proposed for heat-resistant backcoats over many years past. Particularly effective of such compositions in respect of their overall balance of properties, being those described in EP-A-314,348. Such compositions are based on organic resins having a plurality of pendant or terminal acrylic groups per molecule available for crosslinking, especially those having 4-8 such groups, these being cross-linked after application to the base film surface, so as to form a strong heat-resistant layer. These polyfunctional resins were used in combination with linear organic polymers, which did not copolymerise with them during crosslinking but which had an important effect on the physical properties of the coating. Various slip agents, antistatic agents and small solid particles were also included in the coating composition to contribute to the handling and slip properties of the backcoat. A problem that can often be seen on thermal transfer prints is the so called "scratching" defect, in which the printed image has streaks in the direction of travel of the receiver sheet through the printer, thus degrading the quality of the image. We have now found that this problem can be reduced, and usually even eliminated altogether, by modifying the backcoat of the dyesheet, despite this coating never coming into contact with the receiver. We achieve this by incorporating two cooperating features into the backcoat composition, by a) copolymerising a compound having a single radically polymerisable unsaturated group, with the polyfunctional compound providing the cross linking, and b) selecting as slip agent a multivalent metal salt of a long chain alkyl or alkylphenyl phosphate ester. These two features work together, and if either is omitted, relief from scratching does not generally occur. Accordingly, the present invention provides a dyesheet for thermal transfer printing, which comprises a base sheet having a thermal transfer dye layer on one surface and a heat resistant backcoat on the other, wherein the backcoat comprises the reaction product of radically copolymerising in a layer of coating composition, the following constituents: a ) at least one organic compound having a plurality of radically polymerisable unsaturated groups per molecule, and b ) at least one organic compound having a single radically polymerisable unsaturated group per molecule, wherein the proportion of constituent a is between 5% and 95% by weight of the radically polymerisable compounds; the backcoat also containing as slip agent from 0.5% to 30% by weight of the radically polymerisable compounds, of c ) a metallic salt of a phosphate ester, which is expressed by the following general formula (A) or (B): in which R is an alkyl group of C₈₋₃₀ or an alkylphenyl group, m is an integral number of 2 or 3, and M a metal atom. When the radically polymerisable groups have been copolymerised, the polyfunctional materials provide the backcoat with improving hardness and thermal properties as the number of unsaturated groups per molecule increases, thereby increasingly avoiding sticking. Although polyfunctional compounds with more than about a unsaturated groups per molecule lead to coatings having very good thermal properties, this may be at the expense of flexibility and scratching, but ve find such deleterious affects to be less prevalent when using the higher functionality compounds with the monofunctional comonomers of the present invention, than when using a linear polymer as described hereinabove. However, we still prefer to restrict the bulk (at least 95% by weight) of our polyfunctional constituent a to compounds with only 2-8, preferably 2-6, radically polymerisable unsaturated groups per molecule. Examples of polyfunctional compounds having just two radically polymerisable unsaturated groups per molecule and suitable for use as or as part of constituent a of this composition, include 1,6-hexandiol di(meth)acrylate (the designation "(meth)" being used herein to indicate that the methyl group is optional, i.e. referring here to both 1,6-hexandiol dimethacrylate and 1,6-hexandiol diacrylate), ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethyleneglycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. Examples of compounds having three or more radically polymerisable groups and suitable for use as or as part of constituent a include trimethylol propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerithritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Other Examples include compounds having three or more radically polymerisable groups corresponding to the di-functional compounds above, including esters of (meth)acrylic acid with polyester polyols and polyether polyols which are obtainable from a polybasic acid and a polyfunctional alcohol, urethane (meth)acrylates obtained through a reaction of a polyisocyanate and an acrylate having a hydroxy group, and epoxy acrylates obtained through a reaction of an epoxy compound with acrylic acid, an acrylate having a hydroxy group or an acrylate having a carboxyl group. Examples of monofunctional compounds suitable for use in constituent b i.e. compounds having a single radically polymerisable unsaturated group per molecule, include such aliphatic (meth)acrylates as 2-ethylhexyl (meth)acrylate and lauryl (meth)acrylate, such alicyclic (meth)acrylates as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentadienyl (meth)acrylate, such alkoxyalkylene glycol (meth)acrylates as methoxydiethylene glycol acrylate, and ethoxydiethylene glycol acrylate, such aromatic (meth)acrylates as phenyl acrylate, and benzyl acrylate, and such (meth)acrylates of aliphatic alcohols as 2-hydroxyethyl (meth)acrylate, and 2-hydroxyethyl di(meth)acrylate. Of these, compounds having at least one alicyclic group per molecule are particularly favoured because of their low shrinkage characteristics and because they give coatings with good heat resistance. We also find that they can provide a surprising degree of resistance to migration of the dye from dyecoat to backcoat during storage. The proportion of constituent a in the total weight of radically polymerisable compounds, is more than 5% and less than 95% by weight, with constituent b varying correspondingly from less than 95% to more than 5% by weight. Less than 5% by weight of constituent a can result in problems during manufacture from inferior curing and coating characteristics (due to low solution viscosity), and resulting in backcoats having reduced heat resistance characteristics, compared with those containing relatively greater amounts of constituent a . However, if the proportion of constituent a exceeds 95% by weight, scratching increasingly results. Generally we prefer to weight this balance of properties in favour of thermal stability, by having an excess of constituent a over constituent b . Our preferred composition has the polymerisable constituents a and b in the proportions of a 50-90% and b correspondingly 50-10% by weight, depending on the specific balance of properties desired. Examples of constituent c i.e. of the metallic salts of phosphate esters expressed by the general formula (A) and/or (B), include zinc stearyl phosphate, zinc lauryl phosphate, zinc myristyl phosphate, zinc nonyl phosphate, zinc nonylphenyl phosphate, zinc octylphenyl phosphate, calcium stearyl phosphate, magnesium stearyl phosphate, barium stearyl phosphate, aluminium stearyl phosphate, aluminium lauryl phosphate, aluminium tridecyl phosphate, aluminium nonyl phosphate and aluminium nonylphenyl phosphate. Any alkyl chains within the specified C₈₋₃₀ may be used to obtain good slip effect, but to avoid plasticisation we generally prefer to use a slip agent of higher rather than lower Tg. Thus particularly preferred are alkyl chains of at least twelve carbon atoms, giving our preferred alkyl groups a range of C₁₂₋₃₀. The quantity of the slip agent constituent c in the composition lies within the range 0.5-30% by weight, especially 1-20%, of the total amount of the radically polymerisable compounds of constituents a and b . If the proportion drops below 0.5% by weight, the coating will not overcome poor slip characteristics, and problems such as scratching and poor travelling characteristics of the thermal transfer dyesheet over the thermal head may increasingly occur. The upper limit is one of compromise depending on the materials used. As the proportion reaches 10% by weight, very good slip properties can be obtained, but dye sheet stability may thereafter increasingly become a problem with some materials, particularly as the proportion approaches 30%, when other problems such as sticking of the metal salt of the phosphate ester to the thermal print head. In order to make such a heat-resistant backcoat of the above mentioned radically-polymerisable compounds and metallic salts of phosphate esters, a coating composition containing them is applied as a layer onto the base sheet, any solvent removed by drying, and then the resultant layer cured by heating or by irradiating with electromagnetic radiation. In addition. to the above mentioned radically-polymerisable compounds, this coating solution may include, as necessary, solvents and radical polymerisation initiators. Suitable solvents include alcohols, ketones, esters, aromatic hydrocarbons, and halogenated hydrocarbons. The quantity of solvent required is that which provides a solution viscosity having good coating characteristics. Examples of suitable radical polymerisation initiators, include benzophenone, benzoin, such benzoin ethers as benzoin methyl ether and benzoin ethyl ether, such benzyl ketals as benzyl dimethyl ketal, such acetophenones as diethoxyacetophenone and 2-hydroxy-2-methylpropiophenone, such thioxanthones as 2-chloro-thioxanthones and isopropyl-thioxanthone, such anthraquinones as 2-ethyl-anthraquinone and methylanthraquinone (the above normally being in the presence of an appropriate amine, eg Quantacure ITX (a thioxanthone) in the presence of Quanacure EPD (an aromatic amine) ("Quantacure" is a trade mark of Ward Blenkinsop), such azo compounds as azobisisobutyronitrile, such organic peroxides as benzoyl peroxide, lauryl peroxide, di-t-butyl peroxide, and cumyl peroxide. Other examples of commercially available systems include Igacure 907 and Uvecryl P101 ("Igacure" and "Uvecryl" are trade marks of Ciba Geigy and UCB respectively. The quantity of these radical polymerisation initiators used in the polymerisation is 0.01-15% by weight of the aforementioned radically polymerisable compounds. Various other additives may also beneficially be added to the coating solution. These may include, for example, such stabilising agents as polymerisation inhibitors and oxidation inhibitors. Inorganic fine powers (preferable less than 5 µm in diameter), antistatic agents and surfactants, may also be included in the coating composition to give the backcoat good handling properties. The backcoats of EP-A-314,348 referred to above contained, as essential constituents, linear organic polymers such as (meth)acrylic polymers, polyesters and polycarbonates. In the present compositions, these are not essential, their role being taken over to some extent by the monofunctional constituent b . Nevertheless, we find that generally we do still prefer to add small quantities of such polymers, more effectively to reduce shrinkage of the backcoat when curing, and to modify the physical properties of the cured coating. Thus for particularly preferred dyesheets of the present invention, in addition to constituents a, b, and c, the backcoat also contains the following further constituent: d ) at least one linear organic polymer in amount within the range 1-20% by weight of the total amount of the radically polymerisable compounds of constituents a and b . Various coating methods may be employed, including, for example, roll coating, gravure coating, screen coating and fountain coating. After removal of any solvent, the coating can be cured by heating or by irradiating with electromagnetic radiation, such as ultraviolet light, electron beams and gamma rays, as appropriate. Typical curing conditions are heating at 50-150°C for 0.5-10 minutes (in the case of thermal curing), or exposure to radiation for 1-60 s from an ultraviolet lamp of 80 W/cm power output, positioned about 15 cm from the coating surface (in case of ultraviolet light curing). In-line UV curing may utilise a higher powered lamp, eg up to 120 W/cm power output, focused on the coating as it passes the lamp in about 0.1-10 ms. The coating is preferably applied with a thickness such that after drying and curing the backcoat thickness is 0.1-5 µm, preferably 0.5-3 µm, and will depend on the concentration of the coating composition. The backcoat of the invention will benefit dyesheets with a variety of base sheets, including polyester film, polyamide film, polyimide film, polycarbonate film, polysulfone film, cellophane film and polypropylene film, as examples. Orientated polyester film is most preferred, in view of its mechanical strength, dimensional stability and heat resistance,. The thickness of the base sheet is suitably 1-30 µm, and preferably 2-15 µm. The dyecoat is similarly formed by coating the base sheet with an ink prepared by dissolving or dispersing a thermal transfer dye and a binder resin to form a coating composition, then removing any volatile liquids and curing the resin. Any dye capable of bring thermally transferred in the manner described above, may be selected as required. Known thermally transferable dyes come from a variety of dye classes, e.g. from such nonionic dyes as azo dyes, anthraquinone dyes, azomethine dyes, methine dyes, indoaniline dyes, naphthoquinone dyes, quinophthalone dyes and nitro dyes. The dyecoat binder can be selected from such known polymers as polycarbonate, polyvinylbutyral, and cellulose polymers, such as methyl cellulose, ethyl cellulose, and ethyl hydroxyethyl cellulose, for example, and mixtures thereof. The ink may include dispersing agents, antistatic agents, antifoaming agents, and oxidation inhibitors, and can be coated onto the base sheet as described for formation of the backcoat, or may overlie a cross-linked dye-barrier layer, eg as described in EP-A-314,349. The thickness of the dyecoat is suitably 0.1-5 µm, preferably 0.5-3 µm. Printing and/or generation of images through the use of a thermal transfer printing dyesheet of the invention, is carried out by placing the dyecoat against a receiver sheet, and heating from the back surface of the dyesheet by means of a thermal head heated in accordance with electric signals delivered to the head. The invention is now illustrated by specific examples of dyesheets, prepared according to the invention as described in Examples 1-6 below, reference also being made to other dyesheets prepared for comparative purposes in the Comparative Examples A-D, that follow them. Each backcoat was then assessed by the following qualitative and semi-quantitative tests: 1) Sticking - the dyesheet was placed with its dyecoat against a receiver sheet and transfer printing commenced using a Kyocera KMT 85 thermal head, having 6 dot/mm of heating element density. Printing was carried out one row at a time in normal manner, with the two sheets incrementally moved through the printer after each row was printed. Electric power of 0.32 W/dot was applied for 10 ms to each heater so as to heat the backcoat, and thereby cause transfer of the dye over an area 5 cm long and 8 cm wide. Following printing, assessment of the extent of adhesion between the thermal head and the dyesheet by melting, was made by microscopic inspection of the thermal head. 2) Scratching - thermal transfer was performed as described above, and the number of visible streaks in the direction of travel of the receiver sheet through the printer, was counted. 3) Dye migration - to evaluate dye migration, a portion of dyesheet 10 cm long and 5 cm wide was placed with its dyecoat against the backcoat of a further similar portion, and these were pressed together with a pressure of 10 g/cm². While maintaining this pressure, they were stored in an oven at 60°C for 3 days, and the colour density of the dye that had migrated into the backcoat was measured using a reflection-type densitometer (Sakura Densitometer PDA 65). The results of all these tests on dyesheets according to the invention and on comparative dyesheets, are respectively given in Tables 1 and 2 below. Example 1 Preparation of Thermal Transfer Dyesheet 1 A coating composition for providing a heat-resistant backcoat was prepared as a homogenous dispersion, from the following constituents, where the quantities are parts by weight, and the functionality refers to the number of radically-polymerisable unsaturations per molecule: Coating composition for preparing backcoat 1: The dispersion was coated onto one surface of 6 µm thick polyester film using a standard No 3 wire-bar. After removal of the solvent in a draught of warm air, the coating was irradiated with ultraviolet light for 10 seconds using an 80 W/cm ultraviolet irradiation apparatus (UVC-2534, manufactured by Ushio) held 15 cm from the coating surface, thereby to produce a heat resistant slipping layer of 1 µm thickness. A coating composition for providing a dyecoat was then prepared as a solution from the following materials Dyecoat coating composition This coating composition A was applied onto the front surface of the base film backcoated as above, i.e. onto that surface of the base film remote from the backcoat, using a No 10 wire-bar. The solvent was then removed to leave a dyecoat of 1.0 µm thickness, thereby completing the thermal transfer printing dyesheet 1. Preparation of Receiver Sheet A coating composition for forming a receiver layer was prepared as a solution from the following materials: Receiver coating composition polyester resin 80 parts amino-silicone 20 parts epoxy-silicone 15 parts 1,4-diazobicycloctane 5 parts methyl ethyl ketone 80 parts Using a Melinex 990 polyester film of 100 µm thickness "Melinex" is trade mark of ICI) as a base sheet, the above coating composition B was applied to the polyester film by means of a wire bar No. 36. After removal of the solvent, a receiver layer of about 5 µm thickness was obtained. This base sheet having a single coating of receiver layer was used as Receiver Sheet C in the following evaluations. The dyesheet and the receiver sheet prepared as above, were placed together so that the dyecoat was positioned against the receiver layer, and an area printed using the Kyocera thermal head. No sticking between the thermal head and the dyesheet was detected, the latter running smoothly through the printer without producing any wrinkling. No scratching was detected in the formed image. Dye migration was evaluated as described above. A very low reflection density of 0.09 was recorded. Examples 2 to 12 A series of eleven further dyesheets (Dyesheets 2 to 12 respectively) was prepared in the manner of Example 1, but with alternative backcoats according to the invention. The coating compositions used different mixtures of polymerisable compounds and additives, but the same quantity of the same photoinitiators, photosensitisers and solvent as were used in Example 1. The coating compositions were as follows: Backcoat coating composition 2 Backcoat coating composition 3 Backoat coating composition 4 Backcoat coating composition 5 Backcoat coating composition 6 Backcoat coating composition 7 Backcoat coating composition 8 Backcoat coating composition 9 Backcoat coating composition 10 Backcoat coating composition 11 Backcoat coating composition 12 Dyesheets 2 to 12 were each prepared from the above dispersion of like number. The appropriate dispersion was coated onto one surface of 6 µm thick polyester base film, the solvent removed and the coating cured using the same procedure as described in Example 1, thereby to provide the base film with a heat resistant backcoat. The dyesheet was then completed by the provision of a dyecoat using the same composition as that used in Example 1. Sticking, scratching and dye migration were evaluated for each dyesheet by using fresh portions of the same receiver sheet, and employing the same methods, as described in Example 1. The results are given in Table 1. Comparative Examples A to E A series of further dyesheets (A, B, C, D and E respectively) was prepared in the manner of Example 1, but with alternative backcoats outside the present invention. In composition A there is present no mono-functional constituent b two polyfunctional compounds being used, one being hexa-functional and the other having di-functionality. In composition B, two polymerisable constituents are again used, but these are both alicyclic mono-functional compounds b . In both cases, the same quantity of the same photoinitiators, photosensitisers were used as in Example 1, although smaller amounts of solvent were used in order to provide a composition having similarly good coating properties. In comparative example C, two polyfunctional compounds a were again used without any monofunctional alicyclic compounds b , but the solvent level has been raised towards that used in Example 1. In comparative example D, both polymerisable constituents a and b were used, but to show the importance of the slip agents selected for the backcoats of the invention, a different but related slip agent was used. Similarly, comparative example E corresponds with Example 2, except that calcium stearate is used as slip agent (c), instead of calcium stearyl phosphate. The coating compositions were as follows: Backcoat coating composition (A) Backcoat coating composition (B) Backcoat coating composition (C) Backcoat coating composition (D) Backcoat coating composition E Dyesheets A, B, C, D and E were each prepared from the above dispersions identified by like letter codes. The appropriate dispersion was coated onto one surface of 6 µm thick polyester base film, the solvent removed and the coating cured using the same procedure as described in Example 1, thereby to provide the base film with a heat resistant backcoat. The dyesheet was then completed by the provision of a dyecoat, again using the same composition as that used in Example 1. Sticking, scratching and dye migration were evaluated for each dyesheet by using fresh portions of the same receiver sheet, and employing the same methods, as described in Example 1. The results are given in Table 2. These results demonstrate the useful balance of properties we have found when using the backcoats of the present invention. By applying a coating composition based on the specified radically polymerisable constituents a and b and containing the selected slip agent, curing of the composition provided crosslinked heat resistant backcoats according to the invention, for which no sticking and/or scratching during printing was observed when the dyesheets wart moved across a thermal head and further, no contamination was produced on the thermal head. Moreover, where low levels of dye migrate to the backcoat, it is possible to preserve such dye sheets for relative long periods before use.

Claims: A dyesheet for thermal transfer printing, which comprises a base sheet having a thermal transfer dye layer on one surface and a heat-resistant backcoat on the other, wherein the backcoat comprises the reaction product of radically copolymerising in a layer of coating composition, the following constituents: a ) at least one organic compound having a plurality of radically-polymerisable unsaturated groups per molecule, and b ) at least one organic compound having a single radically polymerizable unsaturated group per molecule, wherein the proportion of constituent a is between 5% and 95% by weight of the radically polymerisable compounds; the backcoat also containing as slip agent from 0.5% to 30% by weight of the radically polymerisable compounds of c ) a metallic salt of a phosphate ester, which is expressed by the following general formula (A) or (B): in which R is an alkyl group of C₈₋₃₀ or an alkylphenyl group, m is an integral number of 2 or 3, and M is a metal atom. A dyesheet as claimed in claim 1, characterised in that constituent b comprises at least one compound selected from aliphatic (meth)acrylates, alicyclic (meth)acrylates, alkoxyalkylene glycol (meth)acrylates, aromatic (meth)acrylates, and (meth)acrylates of aliphatic alcohols. A dyesheet as claimed in claim 2, characterised in that constituent b comprises a compound having at least one alicyclic group per molecule. A dyesheet as claimed in any one of the preceding claims, characterised in that the composition has the polymerisable constituents a and b in the proportions of a 50-90% and b correspondingly 50-10% by weight. A dyesheet as claimed in any one of the preceding claims, characterised in that the quantity of slip agent constituent c in the composition lies within the range 1-20% by weight of the total amount of the radically-polymerisable compounds of constituents a and b . A dyesheet as claimed in any one of the preceding claims, characterised in that in addition to constituents a, b, and c, the backcoat also contains the following further constituent: d ) at least one linear organic polymer in amount within the range 1-20% by weight of the total amount of the radically polymerisable compounds of constituents a and b .

Inventors: HANN RICHARD ANTHONY, PACK BARRY, SAKATA KAZUHIKO, SMITH WARREN THOMAS, HANN, RICHARD ANTHONY, PACK, BARRY, SAKATA, KAZUHIKO, SMITH, WARREN THOMAS
Applicants: ICI PLC, IMPERIAL CHEMICAL INDUSTRIES PLC
Application year: 1991
Main classification: B41M5
IPC codes: B41M5