JP2011073172A - Sublimation thermal transfer recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sublimation thermal transfer recording medium capable of recording a good transfer image without having rolling wrinkles when rolled or causing wrinkling of a printed image or unevenness of a printed image even if a rolled medium is used for thermal transfer printing. <P>SOLUTION: The sublimation thermal transfer recording medium comprises a heat resistant resin layer provided on one side of a base and a sublimation dye layer provided on the other side via an anchor layer, the sublimation dye layer being made of component materials having a sublimation dye contained in a resin binder. The ratio of the linear coefficient of expansion of the anchor layer to the linear coefficient of expansion of the base (linear coefficient of expansion of the anchor layer/linear coefficient of expansion of the base) is 0.5 to 1.5. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a sublimation thermal transfer recording medium used for thermal transfer recording of a desired image by a thermal transfer recording method, and in particular, when used in a wound form, a wrinkle is not generated and a wound form is used. Thus, the present invention relates to a sublimable thermal transfer recording medium which can record a good transfer image without causing printing wrinkles or printing unevenness even when thermal transfer recording is performed.

  A sublimation thermal transfer recording medium is a so-called ink ribbon that is used as a recording material for a sublimation thermal transfer printer, and has a heat-resistant resin layer (backcoat layer) on one side of a substrate and the other. Each of the surfaces is provided with a sublimable dye layer.

  At present, the sublimation thermal transfer recording method using such a sublimation thermal transfer recording medium has been rapidly promoted to improve the functions of printers used for transfer recording, and various images can be easily formed. Widely used for thermal transfer recording on cards such as certificates, bank cards, and amusement output.

  Under such circumstances, in such a sublimation thermal transfer recording system, there is an increasing demand to improve the durability of the printed matter obtained, and the number of pixels to be printed is increased and the speed of the printer is increased. Therefore, there has been a strong demand for higher sensitivity that can cope with image quality and ensuring good color reproducibility in high-speed printing.

  On the other hand, in such a sublimation thermal transfer recording method, it occurs due to winding wrinkles that have occurred when the thermal transfer recording medium is wound up, or due to insufficient heat-resistant lubricity in the heat-resistant resin layer. In many cases, printing defects due to printing wrinkles occur, and development of a technique for preventing such printing defects from occurring is strongly demanded.

  Under such circumstances, for example, in Patent Document 1, an azodicarbonamide is used in order to prevent the occurrence of winding wrinkles in the manufacturing process of the thermal transfer recording medium and to prevent printing defects due to winding wrinkles. A technique has been proposed in which the above powder is dispersed in the resin constituting the anchor layer.

  Further, in Patent Document 2, by forming a heat-resistant resin layer from a mixture of a silicone-modified cellulose resin and hydrophobic silica, printing wrinkles due to insufficient heat-resistant slip of the heat-resistant resin layer, and printing defects resulting therefrom Is to prevent the occurrence of.

  However, in any of the methods, in the winding work in the manufacturing process of the sublimation thermal transfer recording medium, for example, in the work for winding the wide sublimation thermal transfer recording medium as a narrow sublimation thermal transfer recording medium while hanging on a slitter. As a result of the ribbon deformation due to the winding tension, a lot of winding wrinkles occurred, and defective printing occurred in transfer recording using the sublimation thermal transfer recording medium wound in such a state.

JP-A-2-229087 Japanese Patent Laid-Open No. 9-277728

  The present invention is intended to solve the above-mentioned problems in sublimation thermal transfer recording media. In the manufacturing process of sublimation thermal transfer recording media, for example, a wide sublimation thermal transfer recording medium is used as a slitter. When winding as a narrow sublimation thermal transfer recording medium, it is no longer wrinkled due to ribbon deformation due to the winding tension of the slitter. An object of the present invention is to provide a sublimation thermal transfer recording medium in which printing defects due to winding wrinkles do not occur even if it is performed.

  In view of the above situation, the invention according to claim 1 is a constituent material in which a heat-resistant resin layer is included in one surface of a substrate and a sublimable dye is included in a resin binder on the other surface. A sublimable thermal transfer recording medium having a sublimable dye layer comprising at least an anchor layer interposed between the anchor layer and the base material. The material has a linear expansion coefficient of 0.5 to 1.5, and is a sublimable thermal transfer recording medium.

  The invention according to claim 2 is the sublimation thermal transfer recording medium according to claim 1, wherein the anchor layer is a polymer compound obtained by a urethane reaction between an OH group of a binder resin and an NCO group of a curing agent. And the ratio of NCO group to OH group (NCO group / OH group) is 0.5 to 1.5.

  Furthermore, the invention described in claim 3 is the sublimation thermal transfer recording medium according to claim 1 or 2, wherein at least sublimation dye layers exhibiting cyan, magenta, and yellow hues are provided in the surface order. At least one of the layers is provided on the base material via an anchor layer.

  Since the sublimation thermal transfer recording medium of the present invention does not generate wrinkles due to ribbon deformation due to winding tension when it is wound, thermal transfer recording was performed using the wound one. However, it is possible to prevent poor printing due to winding wrinkles and perform good sublimation thermal transfer recording.

It is explanatory drawing which shows the general | schematic cross-section structure of the sublimation thermal transfer recording medium of this invention.

The sublimable thermal transfer recording medium of the present invention will be described below with reference to the drawings.
The sublimation thermal transfer recording medium of the present invention generally has a heat-resistant resin layer (2) on one side of a substrate (1) and a sublimation dye on the other side as shown in FIG. The sublimable dye layers (4), (5) and (6) made of a constituent material containing a resin binder are provided via an anchor layer (3).

  The sublimable dye layers (4), (5), and (6) provided in the surface order on the anchor layer (3) exhibit hues of yellow, magenta, and cyan, respectively. This sublimation thermal transfer recording medium is provided with the sublimation dye layers (4), (5) and (6) exhibiting three kinds of hues in the surface order, but the sublimation thermal transfer recording medium of the present invention is like this. The sublimation dye layer exhibiting black or other hues may be further provided in the surface order.

The base material (1) is required to have heat resistance and strength that is not softened and deformed by heat pressure during thermal transfer recording.
For example, synthetic resin film made of polyethylene terephthalate, polyethylene naphthalate, polypropylene, cellophane, acetate, polycarbonate, polysulfone, polyimide, polyvinyl alcohol, aromatic polyamide, aramid, polystyrene, paper such as condenser paper, paraffin paper, Furthermore, a laminate in which these are laminated is used. Of these, a polyethylene terephthalate film is preferably used in consideration of physical properties, workability, cost, and the like. The thickness may be about 2 to 50 μm in consideration of operability, workability, etc., but is preferably about 2 to 12 μm in consideration of handling properties such as transfer suitability and workability. .

  On the other hand, the heat-resistant resin layer (2) is a sublimation dye layer (to be described later) in order to prevent thermal contraction of the base material (1) and breakage due to friction with the thermal head due to heat applied from the thermal head. 4), (5), provided on the surface opposite to the surface on which (6) is provided.

  Examples of the binder constituting the heat resistant resin layer (2) include cellulose resins, polyester resins, acrylic resins, vinyl resins, polyurethane resins, polyether resins, polycarbonate resins, and acetal resins. It is done. And the thickness should just be about 0.1 micrometer-2.5 micrometers, but it is more preferable if it is about 0.5 micrometer-1.5 micrometers. The glass transition temperature (Tg) of the above resin is preferably 40 ° C. or higher.

  Further, the heat resistant resin layer (2) may contain a lubricant for the purpose of improving the lubricity. Specifically, natural waxes such as animal waxes and plant waxes, synthetic hydrocarbon waxes, aliphatic alcohols and acid waxes, fatty acid esters and glycerite waxes, synthetic ketone waxes, amine and amide waxes, chlorine Synthetic waxes such as activated hydrocarbon waxes and alpha-olefin waxes, higher fatty acid esters such as butyl stearate and ethyl oleate, higher fatty acids such as sodium stearate, zinc stearate, calcium stearate, potassium stearate and magnesium stearate Surfactants such as metal salts, long-chain alkyl phosphate esters, polyoxyalkylene alkyl aryl ether phosphate esters, or phosphate esters such as polyoxyalkylene alkyl ether phosphate esters. By including such a lubricant, the coefficient of dynamic friction between the heat-resistant resin layer and the thermal head can be reduced, so that deformation of the substrate due to friction with the thermal head can be prevented.

Moreover, you may make it use together a hardening | curing agent with the binder as mentioned above for the purpose of improving heat resistance to the constituent material of a heat resistant resin layer (2). Examples of the curing agent used for such a purpose include polyisocyanate, which may be used in combination with acrylic, urethane, and polyester polyol resins, cellulose resins, and acetal resins.
The amount of polyisocyanate used may be about 0.8 or more in terms of the NCO / OH ratio, but more preferably about 0.8 to 1.3.

  Furthermore, the heat resistant resin layer (2) may contain fine particles. By incorporating fine particles, irregularities are formed on the surface and the contact area with the thermal head is reduced, so that the slipperiness with respect to the thermal head during printing is improved.

  The fine particles to be contained may be either organic fine particles or inorganic fine particles, but those that are not deformed by heat from the thermal head are preferable. Specific examples include silica particles, magnesium oxide, zinc oxide, calcium carbonate, magnesium carbonate, talc, kaolin, clay, silicone particles, polyethylene particles, polypropylene particles, polystyrene particles, polymethyl methacrylate resin particles, polyurethane resin particles, and the like. be able to. These fine particles may be used alone or in combination of two or more. And it is preferable to make the content rate into about 0.01-0.1 weight ratio with respect to a heat resistant resin layer.

  On the other hand, the anchor layer (3) winds up the sublimation thermal transfer recording medium in the process of manufacturing the sublimation thermal transfer recording medium. Even in difficult operations, there is no generation of winding wrinkles due to ribbon deformation due to the winding tension of the slitter. Therefore, even if transfer recording is performed using a wound form, printing defects caused by winding wrinkles This layer is provided to prevent the occurrence of

  Examples of the binder constituting the anchor layer include polyester resin, polyester urethane resin, polyethylene glycol resin, acrylic resin, polycarbonate diol resin, and epoxy resin.

  The anchor layer (3) has a ratio of the linear expansion coefficient of the base material (1) to 0.5 to 1.5. When the ratio of the linear expansion coefficient between the anchor layer (3) and the base material (1) is smaller than 0.5, the flexibility of the sublimable thermal transfer recording medium is lowered, resulting in poor printing. On the other hand, when the ratio is larger than 1.5, winding wrinkles occur when winding the sublimation thermal transfer recording medium, resulting in poor printing. Moreover, the thickness should just be about 0.1 micrometer-3.0 micrometers, but it is more preferable if it is about 0.5 micrometer-1.5 micrometers.

Moreover, you may make it use a hardening | curing agent with the above-mentioned binder as a constituent material of an anchor layer (3) for the purpose of improving winding wrinkle tolerance and heat adhesiveness. By containing a curing agent, it is possible to more reliably retain the adhesiveness when heated with the substrate and the sublimable dye layer, and to more reliably prevent ribbon deformation due to tension during winding. become.
For example, when the anchor layer is composed mainly of a polymer compound obtained by a urethane reaction between the OH group of the resin binder and the NCO group of the curing agent, the anchor layer is composed of an NCO group and an OH group. The ratio (NCO group / OH group) is preferably 0.5 to 1.5.

  On the other hand, as the sublimable dye in the sublimable dye layers (4), (5) and (6), a sublimable disperse dye is mainly preferably used. For example, diarylmethane, triarylmethane, thiazole, methine, azomethane, xanthene, axazine, thiazine, azine, acridine, azo, spirodipyran, isorinospiropyran, fluorane, rhodamine It is a sublimable disperse dye such as a dactam or anthraquinone.

  More specifically, examples of the yellow component include C.I. I. Solvent Yellow 14, 16, 29, 30, 33, 56, 93 etc., C.I. I. Disperse Yellow 7, 33, 60, 141, 201, 231 and the like include C.I. I. Solvent Red 18, 19, 27, 143, 182, C.I. I. Disperse thread 60, 73, 135, 167, C.I. I. Disperse Violet 13, 26, 31, 56, etc. include C.I. I. Solvent Blue 11, 36, 63, 105, C.I. I. Disperse blue 24, 72, 154, 354, etc. are mentioned, but it is not necessarily limited to these. These sublimable dyes may be used alone or in combination.

The resin binder containing such a sublimable dye includes vinyl resins such as polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, polyvinyl acetal, and polyvinyl butyral, ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and cellulose acetate. Excellent heat resistance, sublimation dye transfer properties, etc., cellulose resins such as cellulose acetate butyrate and cellulose acetate propionate, polyester resins, phenoxy resins, styrene-acrylonitrile copolymer resins, polycarbonate resins, polyacrylamide resins, etc. Resins can be mentioned.
Although the glass transition point of these resin binders should just be about 60 degreeC or more, it is more preferable if it is 110 degreeC or more. The weight ratio between the sublimable dye and the binder may be about 0.1 to 3.0, but more preferably about 0.5 to 1.5.

  The sublimable dye layers (4), (5) and (6) having such a structure may contain a lubricant. Examples of the lubricant include various oils and surfactants such as silicones, fluorines, and phosphates. Of these, silicone-based or fluorine-based oils and surfactants are preferably used.

More specifically, the silicone type includes straight silicone oils such as dimethyl silicone and methylphenyl silicone, amino modification, epoxy modification, carbinol modification, mercapto modification, carboxyl modification, methacryl modification, polyether modification, phenol modification. Reactive modified silicone oil such as one-end reactive / heterofunctional group modified, polyether modified, aralkyl modified, fluoroalkyl modified, long chain alkyl modified, higher fatty acid ester modified, phenyl modified etc. nonreactive modified silicone oil, etc. Is mentioned.
Moreover, as a fluorine-type thing, surfactant containing a fluoroalkyl group or a perfluoroalkyl group is mentioned.
Such a lubricant is preferably contained in the sublimable dye layer at a weight ratio of about 0.001 to 0.05.

  Furthermore, as a constituent material of the sublimable dye layers (4), (5), (6), a curing agent may be used together with the resin binder described above for the purpose of improving heat resistance. Specific examples of such curing agents include polyisocyanates, which may be used in combination with acrylic, urethane, and polyester polyol resins, cellulose resins, and acetal resins. The curing agent is preferably contained in the sublimable dye layer at a weight ratio of about 0.01 to 1.

  EXAMPLES Hereinafter, although an Example is described in detail, this invention is not limited to these Examples.

[Example 1]
A polyester film having a thickness of 4.5 μm was used as a base material, and a heat-resistant resin layer forming ink having the following composition was applied to one surface thereof by a gravure coating method so that the dry thickness was 1.1 μm. A resin layer was provided. Subsequently, an anchor layer was provided on the other surface of the base material by a gravure coating method so that an ink for forming an anchor layer having the following composition had a dry thickness of 0.8 μm. Further, a sublimation dye layer exhibiting yellow, magenta, and cyan hues on the anchor layer using a sublimation thermal transfer formation yellow ink, a sublimation thermal transfer formation magenta ink, and a sublimation thermal transfer formation cyan ink having the following composition: (Dry thickness 0.8 μm) were provided in the surface order to obtain a sublimable thermal transfer recording medium according to Example 1. The ratio of the coefficient of linear expansion between the anchor layer and the substrate was 1.0.

<Heat resistant resin layer forming ink>
Acrylic polyol resin 15.0 parts Zinc stearate 1.5 parts Polyoxyalkylene alkyl ether 1.5 parts Talc 1.0 parts 2,6-tolylene diisocyanate 5.0 parts Toluene 50.0 parts Methyl ethyl ketone 20.0 parts Acetic acid 6.0 parts of ethyl <yellow ink for forming a sublimation thermal transfer layer>
C. I. Solvent Yellow 93 0.6 part C.I. I. Solvent Yellow 16 3.6 parts Polyvinyl butyral resin 3.2 parts Organically modified polysiloxane 0.1 part 2,6-tolylene diisocyanate 0.7 part Methyl ethyl ketone 60.5 parts Toluene 30.3 parts <For sublimation thermal transfer layer formation Magenta ink>
C. I. Disperse thread 60 6.7 parts C.I. I. Disperse Violet 26 1.3 parts C.I. I. Solvent Blue 36 0.4 parts Polyvinyl butyral resin 5.2 parts Organically modified polysiloxane 0.1 part 2,6-tolylene diisocyanate 0.9 part Methyl ethyl ketone 55.3 parts Toluene 27.6 parts Cyclohexanone 2.5 parts <Sublimation Cyan Ink for Conductive Thermal Transfer Layer Formation>
C. I. Solvent Blue 36 5.9 parts C.I. I. Solvent Blue 63 1.5 parts Polyvinyl butyral resin 5.2 parts Organically modified polysiloxane 0.2 parts 2,6-tolylene diisocyanate 0.8 parts Methyl ethyl ketone 55.9 parts Toluene 27.9 parts Cyclohexanone 2.6 parts <Anchor Layer forming ink>
Acrylic resin 30.0 parts Ethyl acetate 35.0 parts Toluene 35.0 parts

[Example 2]
Example 2 was carried out in the same manner as in Example 1 except that an anchor layer forming ink having the following composition in which the resin binder was changed to an epoxy resin was used, and the ratio of the linear expansion coefficient between the anchor layer and the substrate was 0.50. A sublimation thermal transfer recording medium was obtained.

<Ink for forming anchor layer>
Epoxy resin 30.0 parts Xylene 70.0 parts

[Example 3]
Example 1 was used in the same manner as in Example 1 except that an anchor layer forming ink having the following composition in which the resin binder was changed to polycarbonate diol resin was used, and the ratio of the linear expansion coefficient of the anchor layer to the base material was set to 1.50. 3 was obtained.

<Ink for forming anchor layer>
Polycarbonate diol resin 30.0 parts Ethyl acetate 35.0 parts Butyl acetate 35.0 parts

[Example 4]
The resin binder is an acrylic resin, and 2,6-polyisocyanate is added, and an anchor layer forming ink having the following composition in which the NCO / OH ratio of 2,6-polyisocyanate and acrylic resin is 0.5 is used. A sublimation thermal transfer recording medium according to Example 4 was obtained in the same manner as in Example 1 except that the ratio of the linear expansion coefficient between the anchor layer and the substrate was 1.0.

<Ink for forming anchor layer>
Acrylic resin 28.1 parts 2,6-Tolylene diisocyanate 1.9 parts Ethyl acetate 35.0 parts Toluene 35.0 parts Hydroxyl value of acrylic resin 17.5 KOHmg / g
NCO content of 2,6-tolylene diisocyanate 13.0%

[Example 5]
The ratio of the linear expansion coefficient of the anchor layer to the base material was determined using an anchor layer forming ink having the following composition in which the resin binder was an acrylic resin and the NCO / OH ratio of 2,6-polyisocyanate and the acrylic resin was 1.5. A sublimable thermal transfer recording medium according to Example 5 was obtained in the same manner as in Example except that the value was 1.0.

<Ink for forming anchor layer>
Acrylic resin 24.9 parts 2,6-Tolylene diisocyanate 5.1 parts Ethyl acetate 35.0 parts Toluene 35.0 parts Hydroxyl value of acrylic resin 17.5 KOHmg / g
NCO content of 2,6-tolylene diisocyanate 13.0%

[Comparative Example 1]
The resin binder was changed to a phenol resin, and an anchor layer forming ink having the following composition in which the NCO / OH ratio of 2,6-polyisocyanate and phenol resin was 1.0 was used. The sublimation thermal transfer recording medium according to Comparative Example 1 was obtained in the same manner as in Example 1 except that the ratio was 0.42.

<Ink for forming anchor layer>
Phenolic resin 26.7 parts 2,6-Tolylene diisocyanate 3.3 parts Isopropyl alcohol 35.0 parts Ethanol 35.0 parts Hydroxyl value of phenolic resin 20 KOHmg / g
NCO content of 2,6-tolylene diisocyanate 13.0%

[Comparative Example 2]
The resin binder is changed to polyvinyl acetal resin, and an anchor layer forming ink having the following composition in which the NCO / OH ratio of 2,6-polyisocyanate and polyvinyl acetal resin is 1.0 is used. A sublimation thermal transfer recording medium according to Comparative Example 2 was obtained in the same manner as in Example 1 except that the ratio of expansion coefficients was 1.8.

<Ink for forming anchor layer>
Polyvinyl acetal resin 26.7 parts 2,6-tolylene diisocyanate 3.3 parts Methyl ethyl ketone 35.0 parts Toluene 35.0 parts Hydroxyl value of polyvinyl acetal resin 23.5 KOHmg / g
NCO content of 2,6-tolylene diisocyanate 13.0%

  Next, using the sublimation thermal transfer recording media according to Examples and Comparative Examples, printing evaluation was performed under the following conditions. For printing, a transfer medium prepared as described below was used. The results of the print evaluation are shown in Table 1.

<Preparation of transfer object>
Sublimation on one surface of a substrate to be transferred (foamed polyester film: thickness 188 μm) by a gravure coating method using a sublimation heat transfer image-receiving layer forming ink having the following composition so that the dry thickness becomes 5.0 μm. An image receiving layer for thermal transfer was provided, and a transfer material for sublimation thermal transfer recording was produced.

<Sublimation thermal transfer image-receiving layer forming ink>
Vinyl chloride-vinyl acetate-vinyl alcohol copolymer 20.0 parts Silicone oil 0.5 part Toluene 40.0 parts Methyl ethyl ketone 39.5 parts

[Sublimation evaluation and print evaluation of sublimation thermal transfer recording media]
Each sublimation thermal transfer recording medium was subjected to a slitter, and the presence or absence of winding wrinkles due to ribbon deformation due to winding tension when winding the narrow sublimation thermal transfer recording medium was visually observed to evaluate the scroll.

  Evaluation of defective printing at the time of printing was visually performed on a printed matter on which a color patch to which heat energy can be applied stepwise and a landscape photograph were printed. When printing wrinkles or printing unevenness was confirmed in the printed material after printing, it was determined that the printing was defective.

  The sublimation thermal transfer recording medium of the present invention has excellent heat adhesion performance, no wrinkles generated due to ribbon deformation due to the winding tension of the slitter, and no printing defects due to printing wrinkles or uneven printing. It was. On the other hand, the sublimation thermal transfer recording medium according to Comparative Example 1 has a low ratio of the linear expansion coefficient between the anchor layer and the base material and lacks flexibility, so that winding wrinkles occur and printing defects occur. It was. Further, in the sublimation thermal transfer recording medium according to Comparative Example 2, since the ratio of the linear expansion coefficient between the anchor layer and the base material was high, the base material was stretched and winding wrinkles and poor printing occurred. In addition, evaluation is evaluated by ○ ×. ○ means that no defect has occurred, and x means that a defect has occurred.

・ Base material ・ Heat resistant resin layer ・ Anchor layer ・ Yellow sublimation dye layer ・ Magenta sublimation dye layer ・ Cyan sublimation dye layer

Claims (3)

  A sublimation in which a heat-resistant resin layer is provided on one side of the substrate and a sublimation dye layer made of a constituent material containing a sublimation dye in a resin binder is provided on the other side via an anchor layer. The ratio of the coefficient of linear expansion of the anchor layer to the coefficient of linear expansion of the substrate (the coefficient of linear expansion of the anchor layer / the coefficient of linear expansion of the substrate) is 0.5 to 1.5. A sublimation thermal transfer recording medium characterized.   The anchor layer is mainly composed of a polymer compound obtained by a urethane reaction between the OH group of the binder resin and the NCO group of the curing agent, and the ratio of NCO group to OH group (NCO group / OH group) is 0. The sublimable thermal transfer recording medium according to claim 1, which is from 0.5 to 1.5.   2. A sublimable dye layer exhibiting cyan, magenta, and yellow hues is provided at least in a surface sequence, and at least one of the layers is provided on a substrate via an anchor layer. Or the sublimation thermal transfer recording medium of 2.

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