JP2012196840A - Thermal transfer recording medium, and printed material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermal transfer recording medium and printed material, by which an image with small elongation, no breakage, and less image defect, can be provided in self-serve high speed printing when printing on a transfer-object body having a water-based image receiving layer.SOLUTION: The thermal transfer recording medium includes a heat-resistant slippery layer 4 formed on one surface of a base material 1, and an undercoat layer 2 and a dye layer 3 sequentially formed on the other surface of the base material 1. The undercoat layer 2 is formed of at least a water-soluble polymer, and vinyl pyrrolidone-vinyl caprolactam copolymer. The heat-resistant slippery layer 4 contains at least a filler formed of inorganic material and having Mohs hardness 3 or less, and two or more types of lubricants having different melting points. A ratio of a total amount of lubricants having different melting points with respect to the heat-resistant slippery layer 4 is 5-25%.

Description

  The present invention relates to a thermal transfer recording medium for use in a thermal transfer type printer, and more particularly to a thermal transfer recording medium with less image defects due to small elongation of the thermal transfer recording medium during high-speed printing. It is.

  In general, a thermal transfer recording medium is an ink ribbon used in a thermal transfer printer, called a thermal ribbon, and has a dye layer on one side of the substrate and a heat resistant slide on the other side of the substrate. Provided with a sex layer. Here, the dye layer is an ink layer, and transfers the ink to the transfer target side by the sublimation transfer method or the melt transfer method by the heat generated in the thermal head of the printer.

  At present, the thermal transfer system is widely used for self-printing of digital cameras, cards such as identification cards, amusement output, etc. because various images can be easily formed in full color along with the enhancement of printer functions. . Along with the diversification of such applications, there is a demand for downsizing, cost reduction, and speedup. In recent years, various printers capable of printing at higher speeds than before have been developed and spread to the market. High-speed printing is a performance required for reducing the waiting time when the user prints at the store.

  The heat-sensitive transfer recording medium on the side in contact with the thermal head is provided with a heat-resistant slipping layer for the purpose of preventing seizure of the thermal head and the heat-sensitive transfer recording medium and imparting slidability between the thermal head and the ink sheet. . Image sticking causes breakage of the thermal transfer recording medium during printing. On the other hand, if slipperiness is insufficient, image defects may occur due to deformation of the thermal transfer recording medium or printing wrinkles during printing. Since the thermal head of the printer comes into contact with the heat resistant slipping layer at a higher temperature and higher speed by high speed printing, further improvement in the performance of the heat resistant slipping layer is required. For example, Patent Document 1 discloses that a phosphate ester surfactant is added to the heat resistant slipping layer in order to improve slipperiness.

  The inventor provides a heat-sensitive slipping layer on one surface of a substrate, and an undercoat layer and a dye layer on the other surface of the substrate in this order. , By containing at least a water-soluble polymer and a vinylpyrrolidone-vinylcaprolactam copolymer, the transfer sensitivity during high-speed printing is high, that is, the amount of dye used in the dye layer can be reduced, and at high temperatures and high humidity. Even after storage, abnormal transfer in printing can be prevented, and image quality defects occurring in high density areas, that is, hue fluctuation occurs due to the image receiving layer of the transfer target being fused to the thermal transfer recording medium, and as a result They have discovered a technique that can reduce the phenomenon of so-called “shine” in which the surface of a printed material is partially matted.

  However, the transfer sensitivity at the time of high-speed printing becomes high and the amount of dye used in the dye layer can be reduced, which leads to a reduction in the thickness of the dye layer, that is, the heat resistance of the thermal transfer recording medium. Accordingly, when an undercoat layer containing a water-soluble polymer and a vinylpyrrolidone-vinylcaprolactam copolymer is provided between the substrate and the dye layer, the heat resistant slipping layer is required to have further improved performance. .

  In addition, there are two types of image receiving layers in the transfer target to which the ink of the thermal transfer recording medium is transferred: an image receiving layer formed with an aqueous coating solution and an image receiving layer formed with a solvent based coating solution. The transferred object having the image receiving layer formed in the liquid has no influence on the human body and the environment, and the formed image has a higher gloss feeling than the transferred object having the image receiving layer formed by the solvent-based coating liquid. Can be granted. However, the dye used in the thermal transfer recording medium has a strong tendency to be oil-soluble, and was formed with a solvent-based coating solution when printing on a transfer medium having an image receiving layer formed with an aqueous coating solution. Since it is more difficult for the dye to be dyed on the transferred body than when printing on the transferred body having an image receiving layer, it is necessary to give a larger energy to obtain a sufficient density. Therefore, when printing is performed on a transfer target having an image receiving layer formed with an aqueous coating solution, particularly high heat resistance is required for the thermal transfer recording medium.

JP-A-8-90942

  By the way, in the case of self-service where the user prints at the store, the printer often prints again after waiting for more than 10 minutes, so even if the printing is started again after waiting, the stretch or print There is a need for an improvement that enables image defects to be more effectively suppressed by deformation such as wrinkles.

  However, in the technique using the phosphate ester surfactant described in Patent Document 1, the thermal transfer recording medium may increase in elongation when the printer waits for 10 minutes or more after printing and starts printing again. As a result, there is a risk that image defects may occur due to deformation of the printing wrinkles or the like. In addition, there is a problem in image uniformity due to uneven heat conduction.

  SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and is capable of self-service high-speed printing even when printing on a transfer medium having an image receiving layer formed with an aqueous coating liquid that needs to be heated more. The present invention aims to provide a heat-sensitive transfer recording medium and printed matter that have a small elongation, no breakage, and few image defects.

  The invention according to claim 1 is a thermal transfer recording medium in which a heat-resistant slipping layer is provided on one surface of a substrate, and an undercoat layer and a dye layer are provided in this order on the other surface of the substrate. The pulling layer includes at least a water-soluble polymer and a vinylpyrrolidone-vinylcaprolactam copolymer, and the heat-resistant slipping layer includes at least a lubricant having a melting point different from that of a filler made of an inorganic material having a Mohs hardness of 3 or less. It is the structure characterized by including the seed | species or more and the total amount of the said lubricant with respect to this heat-resistant slipping layer being 5-25 mass%.

  According to a second aspect of the present invention, the melting point of at least one of the lubricants in the heat-resistant slip layer in the thermal transfer recording medium of the first aspect is 50 ° C to 140 ° C. This is a characteristic configuration.

  The invention according to claim 3 is the thermal transfer recording medium according to claim 1 or 2, wherein at least one of the lubricants in the heat-resistant slip layer has a melting point of less than 20 ° C. The configuration is as follows.

  According to a fourth aspect of the present invention, in the thermal transfer recording medium according to any one of the first to third aspects, a difference in melting point between any two of the lubricants contained in the heat resistant slipping layer. However, it is the structure characterized by being 40 degreeC or more.

  The invention according to claim 5 is the thermal transfer recording medium according to any one of claims 1 to 4, wherein the water-soluble polymer contained in the undercoat layer is polyvinyl alcohol. The configuration is as follows.

  According to a sixth aspect of the present invention, the thermal transfer recording medium according to any one of the first to fifth aspects is used, and information is printed on a transfer medium having an image receiving layer formed with an aqueous coating solution. It is a printed matter characterized by this.

  According to the present invention, it is possible to provide a heat-sensitive transfer recording medium and a printed matter having a heat-resistant slipping layer that can give an image with small elongation, no breakage, and few image defects even in high-speed printing. it can.

1 is a cross-sectional view showing a thermal transfer recording medium according to an embodiment of the present invention.

  Hereinafter, the thermal transfer recording medium and the printed material according to the embodiment of the present invention will be described in detail.

  FIG. 1 shows a thermal transfer recording medium 5 according to an embodiment of the present invention, and an undercoat layer 2 is provided on one surface of a substrate 1. On the undercoat layer 2, there is provided a dye layer 3 that is separately applied to a yellow dye layer 3Y, a magenta dye layer 3M, and a cyan dye layer 3C. A heat-resistant slip layer 4 is provided on the other surface of the substrate 1.

  The substrate 1 is required to have heat resistance and strength not to be softened and deformed by heat pressure in thermal transfer. For example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, cellophane, acetate, polycarbonate, polysulfone, polyimide, polyvinyl alcohol, aromatic polyamide , Synthetic resin films such as aramid and polystyrene, and papers such as condenser paper and paraffin paper can be used singly or in combination, among others, physical properties, workability, cost, etc. In consideration, a polyethylene terephthalate film is preferable. In addition, the thickness is in the range of 2 to 50 μm in consideration of operability and workability, but in consideration of handling properties such as transfer suitability and workability, the thickness is about 2 to 9 μm. preferable.

  The heat-resistant slip layer 4 contains 5 to 25% of a filler having a Mohs hardness of 3 or less and at least two lubricants having different melting points relative to the heat-resistant slip layer. When the amount of the lubricant is less than 5%, the printing wrinkles are remarkably deteriorated. Conversely, if the amount of lubricant exceeds 25%, there is a problem that the stability of the coating liquid is lost.

  Examples of the binder resin that can be used for the heat resistant slipping layer 4 include polyvinyl butyral resin, polyvinyl acetoacetal resin, polyester resin, vinyl chloride-vinyl acetate copolymer, polyether resin, polybutadiene resin, acrylic polyol, polyurethane acrylate, Examples include polyester acrylate, polyether acrylate, epoxy acrylate, nitrocellulose resin, cellulose acetate resin, polyamide resin, polyimide resin, polyamideimide resin, and polycarbonate resin.

  Examples of the curing agent include isocyanates such as tolylene diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, and derivatives thereof, but are not particularly limited.

  The heat resistant slipping layer 4 contains a filler having a Mohs hardness of 3 or less. Examples of the filler include calcium carbonate (Mohs hardness 3), mica (Mohs hardness 2.8), gypsum (Mohs hardness 2), talc (Mohs hardness 1), and the most preferable filler is talc. If the Mohs hardness exceeds 3, it is not desirable because it tends to damage the thermal head. Further, the filler having a Mohs hardness of 3 or less needs to be an inorganic material in order to improve the heat resistance of the heat resistant slipping layer 4.

  The content of the filler having a Mohs hardness of 3 or less in the heat-resistant slip layer 4 is preferably 2 to 30% by mass, more preferably 3 to 20% by mass. This is because if the content is less than 2% by mass, the cleaning effect of the thermal head is insufficient, and if it is more than 30% by mass, it is necessary to pay attention to the decrease in coating strength as a heat-resistant slipping layer.

  The average particle diameter of the filler having a Mohs hardness of 3 or less in the heat-resistant slip layer 4 is preferably 4.0 μm or less, and more preferably 0.3 to 3.0 μm. When the average particle diameter exceeds 4.0 μm, image defects tend to deteriorate. Moreover, the possibility of affecting the durability of the thermal head cannot be denied, and if it is too fine, the particles are likely to re-aggregate and the uniformity of the particles themselves may be reduced.

  The filler having a Mohs hardness of 3 or less contained in the heat-resistant slip layer 4 is preferably surface-treated with a silane coupling agent. By treating the surface with a silane coupling agent, the dispersion stability of the filler can be improved, the compatibility with the binder resin can be improved, and the filler is coated with the silane coupling agent This is because the durability of the thermal head can be further improved by forming irregularities on the surface of the heat resistant slipping layer.

  The silane coupling agent is represented by the general formula XSiY3, where X is an organic functional group that reacts with an organic material, and includes a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, an amino group, and a ureido. Group, chloropropyl group, mercapto group, sulfide group, isocyanate group and the like. On the other hand, Y is a hydrolyzing group that reacts with an inorganic material, and examples thereof include a chloro group, a methoxy group, an ethoxy group, an alkoxy group, and an acetoxy group, but are not particularly limited.

  The thickness of the heat-resistant slip layer 4 is not particularly limited, but is preferably 0.3 to 2.5 μm, and more preferably 0.5 to 1.5 μm. When the thickness of the heat-resistant slipping layer is smaller than 0.3 μm, the heat resistance from the thermal head is inferior, and the risk of sticking or breaking at the time of printing increases. On the other hand, when the thickness is larger than 2.5 μm, heat from the thermal head is not sufficiently transmitted to the thermal transfer layer, and there is a high risk that a printed matter with a desired density cannot be obtained.

  The heat-resistant slip layer 4 needs to contain at least two kinds of lubricants for the purpose of improving slipperiness. Examples of lubricants include 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, amines and amides. Waxes, synthetic waxes such as chlorinated hydrocarbon waxes and alpha-olefin waxes, higher fatty acid esters such as butyl stearate and ethyl oleate, sodium stearate, zinc stearate, calcium stearate, potassium stearate, magnesium stearate Surface activity of phosphates such as higher fatty acid metal salts such as long chain alkyl phosphates, polyoxyalkylene alkylaryl ether phosphates, or polyoxyalkylene alkyl ether phosphates Such as it is possible to increase the agent.

  At least two kinds of lubricants contained in the heat resistant slipping layer 4 need to have different melting points. As an effect of the lubricant, there is an effect that the lubricant is melted by heat applied by the thermal head, the slip is improved, and the load applied to the thermal transfer recording medium by the contact of the thermal head is reduced. At that time, if there is no stable slipperiness at any temperature from low temperature to high temperature, it is impossible to prevent the occurrence of printing wrinkles. As a lubricant that provides slipperiness at a low temperature, the melting point is preferably less than 20 ° C, and particularly preferably less than 15 ° C. Moreover, as a lubricant which provides slipperiness at high temperatures, the melting point is preferably in the range of 50 ° C to 140 ° C, more preferably in the range of 60 ° C to 130 ° C. Furthermore, the melting point difference between the two lubricants is preferably 40 ° C. or higher, more preferably 50 ° C. or higher. When the melting point of the lubricant is within these ranges, it is possible to reduce the occurrence of printing wrinkles and obtain a printed material with few image defects.

  The undercoat layer 2 includes at least a water-soluble polymer and a vinylpyrrolidone-vinylcaprolactam copolymer, and is a coating solution for forming an undercoat layer by blending the water-soluble polymer and the vinylpyrrolidone-vinylcaprolactam copolymer. It is formed by preparing, applying and drying.

  In the undercoat layer 2, the water-soluble polymer and the vinylpyrrolidone-vinylcaprolactam copolymer are essential components. In particular, the water-soluble polymer and the vinylpyrrolidone-vinylcaprolactam copolymer are the main components of the undercoat layer 2. Preferably there is.

  Here, the main component means that, in addition to the water-soluble polymer and the vinylpyrrolidone-vinylcaprolactam copolymer, other components may be added unless the effects of the present invention are impaired. The total of the functional polymer and the vinylpyrrolidone-vinylcaprolactam copolymer is more than 50% by mass as viewed from the whole when the undercoat layer is formed, but is preferably 80% by mass or more.

  Examples of water-soluble polymers include polyvinyl alcohol, polyvinyl pyrrolidone, starch, gelatin, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, sodium alginate and the like. Among these, polyvinyl alcohol and polyvinyl pyrrolidone are preferable, and polyvinyl alcohol is more preferable. The polyvinyl alcohol here is generally obtained by saponifying polyvinyl acetate, and so-called partially saponified polyvinyl alcohol in which several tens percent of acetic acid groups remain, so that only a few percent of acetic acid groups remain. It includes up to fully saponified polyvinyl alcohol and is not particularly limited.

  The vinylpyrrolidone-vinylcaprolactam copolymer is a copolymer of an N-vinylpyrrolidone monomer and vinylcaprolactam which is a vinyl polymerizable monomer. The form of copolymerization is not limited to any of random copolymerization, block copolymerization, and graft copolymerization. Here, the N-vinyl pyrrolidone-based monomer refers to N-vinyl pyrrolidone (N-vinyl-2-pyrrolidone, N-vinyl-4-pyrrolidone, etc.) and derivatives thereof. Examples of those having a substituent on the pyrrolidone ring such as vinyl-3-methylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinyl-3-benzylpyrrolidone, N-vinyl-3,3,5-trimethylpyrrolidone However, it is not particularly limited.

  The vinyl pyrrolidone-vinyl caprolactam copolymer is considered to have been compensated by the vinyl caprolactam component for the poor heat resistance and moisture resistance of the water-soluble polymer component and the vinyl pyrrolidone component. The adhesiveness between the material and the dye layer is high, so that abnormal transfer in printing can be prevented, and the function of reducing the shine in the high density portion during high-speed printing can be exhibited. Here, in the vinylpyrrolidone-vinylcaprolactam copolymer, the polymerization ratio of vinylpyrrolidone and vinylcaprolactam is preferably (vinylpyrrolidone) / (vinylcaprolactam) = 8/2 to 2/8 in a molar ratio. In some cases, the above functions can be sufficiently exhibited.

  The mixing ratio of the water-soluble polymer and the vinylpyrrolidone-vinylcaprolactam copolymer is (water-soluble polymer) / (vinylpyrrolidone-vinylcaprolactam copolymer) = 8/2 to 2/8 on a mass basis. It is preferable. Further, when considering the transfer sensitivity at the time of high-speed printing and the adhesion to the substrate or the dye layer, it is preferably 7/3 to 3/7. By satisfying this range, the transfer sensitivity during high-speed printing is higher, high-density prints with less shine are obtained, and there is no abnormal transfer in printing even after storage under high temperature and high humidity. A sufficiently satisfactory print can be obtained.

  The undercoat layer 2 may contain known additives such as an isocyanate compound, a silane coupling agent, a dispersant, a viscosity modifier, and a stabilizer as long as the performance is not impaired.

The coating amount after drying of the undercoat layer 2 is not generally limited, but is preferably in the range of 0.10 g / m ^{2 to} 0.30 g / m ² . If it is less than 0.10 g / m ² , the transfer sensitivity at the time of high-speed printing is insufficient due to deterioration at the time of laminating the dye layer, and there is a concern that the adhesion to the substrate or the dye layer has a problem. On the other hand, if it exceeds 0.30 g / m ² , the sensitivity of the thermal transfer recording medium itself is affected, and there is a fear that the transfer sensitivity at the time of high-speed printing is insufficient.

The dye layer 3 may be a conventionally known one, and is formed, for example, by preparing a coating solution for forming a dye layer by blending a heat transfer dye, a binder, a solvent, and the like, and applying and drying. An appropriate coating amount of the dye layer 3 after drying is about 1.0 g / m ² . In addition, the dye layer 3 can be composed of a single layer of one color, or a plurality of dye layers containing dyes having different hues can be repeatedly formed on the same surface of the same base material in the surface order.

  The heat transferable dye of the dye layer 3 is not particularly limited as long as it is a dye that melts, diffuses or sublimates and transfers due to heat. For example, the yellow component may be solvent yellow 56, 16, 30, 93, 33, Disperse Yellow 201, 231, 33 and the like. Examples of the magenta component include C.I. I. Disperse thread 60, C.I. I. Disperse violet 26, C.I. I. Solvent Red 27, or C.I. I. Solvent Red 19 etc. can be mentioned. As the cyan component, C.I. I. Disperse Blue 354, C.I. I. Solvent Blue 63, C.I. I. Solvent Blue 36, or C.I. I. Disperse Blue 24 and the like. As a black ink dye, it is common to perform color matching by combining the above dyes.

  As the binder contained in the dye layer 3, any conventionally known resin binder can be used, and is not particularly limited, but cellulose such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate and the like. Examples thereof include vinyl resins such as resin, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl pyrrolidone, and polyacrylamide, polyester resins, styrene-acrylonitrile copolymer resins, and phenoxy resins.

  Here, the blending ratio of the dye and the binder in the dye layer 3 is preferably (dye) / (binder) = 10/100 to 300/100 on a mass basis. This is because when the ratio of (dye) / (binder) is less than 10/100, the amount of dye is too small and the color development sensitivity becomes insufficient, and a good thermal transfer image cannot be obtained, and this ratio is 300/100. If it exceeds the upper limit, the solubility of the dye in the binder is extremely lowered, so that when it becomes a thermal transfer recording medium, the storage stability is deteriorated and the dye is likely to precipitate. In addition, the dye layer 3 may contain known additives such as an isocyanate compound, a silane coupling agent, a dispersant, a viscosity modifier, and a stabilizer as long as the performance is not impaired.

  The heat resistant slipping layer 4, the undercoat layer 2, and the dye layer 3 can be formed by applying and drying by a conventionally known coating method. Examples of the application method include a gravure coating method, a screen printing method, a spray coating method, and a reverse roll coating method.

  Hereinafter, specific Examples 1 to 8 and Comparative Examples 1 to 6 according to the present invention will be manufactured and compared. In the text, “part” is based on mass unless otherwise specified. Further, a lubricant whose melting point is described after the material name of the coating solution is a lubricant.

Example 1
As the base material 1, a polyethylene terephthalate film with a single-sided easy-adhesion treatment of 4.5 μm is used, and a heat-resistant slipping layer coating solution-1 having the following composition is applied to the non-adhesive-adhesive treated surface by a gravure coating method. After coating and drying so that the coating amount becomes 1.0 g / m ² , it is aged in a 40 ° C. environment for 1 week, and undercoat layer coating solution-1 having the following composition is applied to the surface with easy adhesion by a gravure coating method. The undercoat layer 2 was formed by applying and drying so that the coating amount after drying was 0.20 g / m ² . Subsequently, a dye layer coating solution having the following composition is applied onto the undercoat layer 2 by a gravure coating method so that the coating amount after drying is 0.70 g / m ² and dried. Layer 3 was formed to obtain the thermal transfer recording medium of Example 1.

<Heat resistant slipping layer coating solution-1>
Acrylic polyol resin (solid content 50%) 12.5 parts Polyoxyalkylene alkyl ether / phosphate ester (melting point 15 ° C.) 2 parts Stearyl acid phosphate (melting point 70 ° C.) 1 part Talc (Mohs hardness 1) 6.0 parts 2,6-tolylene diisocyanate prepolymer 4.0 parts Toluene 49.5 parts Methyl ethyl ketone 20.0 parts Ethyl acetate 5.0 parts <Undercoat layer coating solution-1>
Polyvinylpyrrolidone 1.0 part Vinylpyrrolidone-vinylcaprolactam copolymer 4.0 parts
[Copolymerization ratio (molar ratio): 3/7]
Pure water 76.0 parts Isopropyl alcohol 19.0 parts <Dye layer coating solution>
C. I. Solvent Blue 63 6.0 parts Polyvinyl acetal resin 4.0 parts Toluene 45.0 parts Methyl ethyl ketone 45.0 parts (Example 2)
In the thermal transfer recording medium produced in Example 1, the thermal recording transfer of Example 2 was performed in the same manner as in Example 1 except that the heat resistant slipping layer coating liquid was changed to the heat resistant slipping layer coating liquid-2 having the following composition. A medium was obtained.

<Heat resistant slipping layer coating solution-2>
Acrylic polyol resin (solid content 50%) 12.5 parts Polyoxyalkylene alkyl ether / phosphate ester (melting point 15 ° C.) 3 parts Stearyl acid phosphate (melting point 70 ° C.) 2 parts Talc (Mohs hardness 1) 6.0 parts 2,6-tolylene diisocyanate prepolymer 4.0 parts toluene 47.5 parts methyl ethyl ketone 20.0 parts ethyl acetate 5.0 parts (Example 3)
In the thermal transfer recording medium produced in Example 1, the thermal recording transfer of Example 3 was performed in the same manner as in Example 1 except that the heat resistant slipping layer coating liquid was changed to the heat resistant slipping layer coating liquid-3 having the following composition. A medium was obtained.

<Heat resistant slipping layer coating solution-3>
Acrylic polyol resin (solid content 50%) 12.5 parts Polyoxyalkylene alkyl ether / phosphate ester (melting point 15 ° C.) 0.5 part Stearyl acid phosphate (melting point 70 ° C.) 0.5 part Talc 6.0 parts 6 -Tolylene diisocyanate prepolymer 4.0 parts Toluene 51.5 parts Methyl ethyl ketone 20.0 parts Ethyl acetate 5.0 parts (Example 4)
In the thermal transfer recording medium produced in Example 1, the thermal recording transfer of Example 4 was performed in the same manner as in Example 1 except that the heat resistant slipping layer coating solution was changed to the heat resistant slipping layer coating solution-4 having the following composition. A medium was obtained.

<Heat resistant slipping layer coating solution-4>
Acrylic polyol resin (solid content 50%) 12.5 parts Polyoxyalkylene alkyl ether / phosphate ester (melting point 15 ° C.) 2 parts Zinc stearate (melting point 120 ° C.) 1 part Talc (Mohs hardness 1) 6.0 parts 2 , 6-Tolylene diisocyanate prepolymer 4.0 parts Toluene 49.5 parts Methyl ethyl ketone 20.0 parts Ethyl acetate 5.0 parts (Example 5)
In the thermal transfer recording medium produced in Example 1, the thermal recording transfer of Example 5 was performed in the same manner as in Example 1 except that the heat resistant slipping layer coating solution was changed to the heat resistant slipping layer coating solution-5 having the following composition. A medium was obtained.

<Heat resistant slipping layer coating solution-5>
Acrylic polyol resin (solid content 50%) 12.5 parts Polyoxyalkylene alkyl ether / phosphate ester (melting point 15 ° C.) 2 parts Zinc hydroxystearate (melting point 150 ° C.) 1 part Talc (Mohs hardness 1) 6.0 parts 2,6-tolylene diisocyanate prepolymer 4.0 parts toluene 49.5 parts methyl ethyl ketone 20.0 parts ethyl acetate 5.0 parts (Example 6)
In the thermal transfer recording medium produced in Example 1, the thermal recording transfer of Example 6 was performed in the same manner as in Example 1 except that the heat resistant slipping layer coating solution was changed to the heat resistant slipping layer coating solution-6 having the following composition. A medium was obtained.

<Heat resistant slipping layer coating solution-6>
Acrylic polyol resin (solid content 50%) 12.5 parts Polyoxyalkylene alkyl ether / phosphate ester (melting point 15 ° C.) 2 parts Cyclic neopentanetetraylbisphosphite (melting point 45 ° C.) 1 part Talc (Mohs hardness 1 ) 6.0 parts 2,6-tolylene diisocyanate prepolymer 4.0 parts toluene 49.5 parts methyl ethyl ketone 20.0 parts ethyl acetate 5.0 parts (Example 7)
In the thermal transfer recording medium produced in Example 1, the thermal recording transfer of Example 7 was performed in the same manner as in Example 1 except that the heat resistant slipping layer coating liquid was changed to the heat resistant slipping layer coating liquid-7 having the following composition. A medium was obtained.

<Heat resistant slipping layer coating solution-7>
Acrylic polyol resin (solid content 50%) 12.5 parts Polyoxyalkylene alkyl ether / phosphate ester (melting point 15 ° C.) 2 parts Cyclic neopentanetetraylbisphosphite (melting point 50 ° C.) 1 part Talc (Mohs hardness 1 ) 6.0 parts 2,6-tolylene diisocyanate prepolymer 4.0 parts toluene 49.5 parts methyl ethyl ketone 20.0 parts ethyl acetate 5.0 parts (Example 8)
In the thermal transfer recording medium produced in Example 1, the thermal recording transfer medium of Example 8 was the same as Example 1 except that the heat resistant slipping layer coating liquid was changed to the undercoat layer coating liquid-2 of the following composition. Got.

<Undercoat layer coating solution-2>
Polyvinyl alcohol 1.0 part Vinylpyrrolidone-vinylcaprolactam copolymer 4.0 parts
[Copolymerization ratio (molar ratio): 3/7]
Pure water 76.0 parts Isopropyl alcohol 19.0 parts (Comparative Example 1)
In the thermal transfer recording medium produced in Example 1, the thermal recording transfer of Comparative Example 1 was performed in the same manner as in Example 1 except that the heat resistant slipping layer coating liquid was changed to the heat resistant slipping layer coating liquid-8 having the following composition. A medium was obtained.

<Heat resistant slipping layer coating solution-8>
Acrylic polyol resin (solid content 50%) 12.5 parts Polyoxyalkylene alkyl ether / phosphate ester (melting point 15 ° C.) 0.4 part Stearyl acid phosphate (melting point 70 ° C.) 0.3 part Talc (Mohs hardness 1) 6.0 parts 2,6-tolylene diisocyanate prepolymer 4.0 parts toluene 51.8 parts methyl ethyl ketone 20.0 parts ethyl acetate 5.0 parts (Comparative Example 2)
In the thermal transfer recording medium produced in Example 1, the thermal recording transfer of Comparative Example 2 was performed in the same manner as in Example 1 except that the heat resistant slipping layer coating solution was changed to the heat resistant slipping layer coating solution-9 having the following composition. A medium was obtained.

<Heat-resistant slip layer coating solution-9>
Acrylic polyol resin (solid content 50%) 12.5 parts Polyoxyalkylene alkyl ether / phosphate ester (melting point 15 ° C.) 3 parts Stearyl acid phosphate (melting point 70 ° C.) 3 parts Talc (Mohs hardness 1) 6.0 parts 2,6-tolylene diisocyanate prepolymer 4.0 parts toluene 46.5 parts methyl ethyl ketone 20.0 parts ethyl acetate 5.0 parts (Comparative Example 3)
In the thermal transfer recording medium produced in Example 1, the thermal recording transfer of Comparative Example 3 was performed in the same manner as in Example 1 except that the heat resistant slipping layer coating solution was changed to the heat resistant slipping layer coating solution-10 having the following composition. A medium was obtained.

<Heat resistant slipping layer coating solution-10>
Acrylic polyol resin (solid content 50%) 12.5 parts Stearyl acid phosphate (melting point 70 ° C.) 3 parts Talc (Mohs hardness 1) 6.0 parts 2,6-tolylene diisocyanate prepolymer 4.0 parts Toluene 49. 5 parts methyl ethyl ketone 20.0 parts ethyl acetate 5.0 parts (Comparative Example 4)
In the thermal transfer recording medium produced in Example 1, the thermal recording transfer of Comparative Example 4 was carried out in the same manner as in Example 1 except that the heat resistant slipping layer coating solution was changed to the heat resistant slipping layer coating solution-11 having the following composition. A medium was obtained.

<Heat resistant slipping layer coating solution-11>
Acrylic polyol resin (solid content 50%) 12.5 parts Polyoxyalkylene alkyl ether / phosphate ester (melting point 15 ° C.) 2 parts Stearyl acid phosphate (melting point 70 ° C.) 1 part Polystyrene particles (Mohs hardness 2.7) 6.0 parts 2,6-tolylene diisocyanate prepolymer 4.0 parts toluene 49.5 parts methyl ethyl ketone 20.0 parts ethyl acetate 5.0 parts (Comparative Example 5)
In the thermal transfer recording medium produced in Example 1, the thermal recording transfer of Comparative Example 5 was performed in the same manner as in Example 1 except that the heat resistant slipping layer coating liquid was changed to the heat resistant slipping layer coating liquid-12 having the following composition. A medium was obtained.

<Heat resistant slipping layer coating solution-12>
Acrylic polyol resin (solid content 50%) 12.5 parts Polyoxyalkylene alkyl ether / phosphate ester (melting point 15 ° C.) 2 parts Stearyl acid phosphate (melting point 70 ° C.) 1 part Boehmite (Mohs hardness 3.7) 0 parts 2,6-tolylene diisocyanate prepolymer 4.0 parts toluene 49.5 parts methyl ethyl ketone 20.0 parts ethyl acetate 5.0 parts (Comparative Example 5)
In the thermal transfer recording medium produced in Example 1, a thermal recording transfer medium of Comparative Example 5 was obtained in the same manner as in Example 1 except that the undercoat layer was not formed.

<Preparation of Transferred Member Having Image Receiving Layer Formed with Water-Based Coating Solution>
A 188 μm white foamed polyethylene terephthalate film is used as the base material 1, and the image receiving layer coating solution-1 having the following composition is applied to one surface thereof by a gravure coating method so that the coating amount after drying is 5.0 g / m ² . By applying and drying as described above, a transfer object having an image receiving layer formed with an aqueous coating solution for thermal transfer was produced.

<Image-receiving layer coating solution-1>
Polyester resin emulsion 65 parts Silica 25 parts Pure water 10 parts <Preparation of transferred body having image receiving layer formed by solvent-based coating solution>
A 188 μm white foamed polyethylene terephthalate film is used as the base material 1, and the image receiving layer coating liquid-2 having the following composition is applied to one surface thereof by a gravure coating method so that the coating amount after drying is 5.0 g / m ² . By applying and drying as described above, a transfer target having an image receiving layer formed with a solvent-based coating solution for thermal transfer was produced.

<Image-receiving layer coating solution-2>
Vinyl chloride-vinyl acetate-vinyl alcohol copolymer 19.5 parts Amino-modified silicone oil 0.5 part Toluene 40.0 parts Methyl ethyl ketone 40.0 parts Thermal transfer obtained for Examples 1-8 and Comparative Examples 1-6 The dye layer surface of the recording medium and the two types of transferred materials were respectively overlapped, the dye was transferred using a thermal head, and image formation was performed to produce a printed matter.

  The printed matter on which the image was formed was measured for reflection density, visually evaluated for print wrinkles and image defects. Further, the stability of the coating solution for the heat resistant slipping layer 2 was confirmed. The conditions for evaluating the printed matter are shown below.

[Print wrinkle status]
○: No printing wrinkles △: Slight printing wrinkles ×: Many printing wrinkles
[Image defects in prints]
○: Small image defect △: Image defect (slightly noticeable)
×: Image defect (conspicuous)
[Stability of heat resistant slipping layer coating solution]
○: No problem after storage at 25 ° C. for 1 week ×: Solidification after storage at 25 ° C. for 1 week * No problems in practical use for all items Δ or more The thermal transfer recording media of Examples 1 to 8 obtained the results shown in Table 1. . In other words, in the case of the thermal transfer recording media of Examples 1 to 4, it can be seen that there are few printing lines and image defects, and there is almost no problem in practical use. It was also confirmed that the heat resistant slipping layer coating solution had no problem after 1 week of storage.

  Further, the thermal transfer recording media of Examples 5 to 7 also have the stability of the heat resistant slipping layer coating solution, and the printing wrinkles and image defects are worse than those of the thermal transfer recording medium of Example 1. This is a level where there is no practical problem.

  The heat-sensitive transfer recording medium of Example 8 also has the stability of the heat resistant slipping layer coating solution, and there are few printing wrinkles and image defects, and it is understood that there is almost no problem in practical use. It can also be seen that the reflection density is improved by using polyvinyl alcohol for the undercoat layer 2.

  In contrast, it can be seen that the thermal transfer recording medium of Comparative Example 1 is worse in the state of printing wrinkles and image defects as shown in Table 1 than the thermal transfer recording medium of Example 1.

  Further, it can be seen that the thermal transfer recording medium of Comparative Example 2 has better printing wrinkles and image defects than the thermal transfer recording medium of Example 1, but lacks the stability of the coating liquid.

  That is, when the total amount of the lubricant is out of the range of 5 to 25% by mass, the printing wrinkle, the image defect, or the coating liquid stability is deficient.

  Further, it can be seen that the thermal transfer recording medium of Comparative Example 3 has greatly deteriorated printing wrinkles. That is, it can be considered that the use of a single lubricant makes it impossible to provide uniform slipperiness in all temperature ranges from low to high, resulting in deterioration in printing wrinkles.

  It can be seen that the thermal transfer recording medium of Comparative Example 4 has greatly deteriorated printing wrinkles. It is considered that by using a filler having a Mohs hardness of 3 or less as an organic filler, the heat resistance of the heat resistant slipping layer 4 is deteriorated, and printing wrinkles are deteriorated.

  It can also be seen that the image transfer defect of the thermal transfer recording medium of Comparative Example 5 is greatly deteriorated. It is considered that by making the Mohs hardness of the filler made of an inorganic material higher than 3, the flexibility of the thermal transfer recording medium is deteriorated and the image defect is deteriorated.

  It can be seen that the thermal transfer recording medium of Comparative Example 6 has a greatly reduced reflection density due to the absence of the undercoat layer 2.

In addition, when a transferred object having an image receiving layer formed with an aqueous coating liquid is compared with a printed material having information received on a transferred object having an image receiving layer formed with a solvent-based coating liquid, the image receiving layer formed with an aqueous coating liquid The transferred material having the image quality tends to deteriorate with respect to printing wrinkles. That is, particularly with respect to a transfer target having an image receiving layer formed with an aqueous coating solution, problems such as printing wrinkles are likely to occur in a commonly used thermal transfer recording medium, but by using the thermal transfer recording medium of the present invention, It can be seen that it can be raised to a level where there is no practical problem.

  The present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the scope of the invention at the stage of implementation. Furthermore, the above embodiments include inventions at various stages, and various inventions can be extracted by appropriately combining a plurality of disclosed constituent elements.

  For example, even if some constituent elements are deleted from all the constituent elements shown in the embodiment, the problems described in the column of problems to be solved by the invention can be solved, and the effects described in the effects of the invention can be obtained. In some cases, a configuration from which this configuration requirement is deleted can be extracted as an invention.

  According to the present invention, when printing is performed on a transfer medium having an image receiving layer formed with an aqueous coating liquid that has a small elongation of a thermal transfer recording medium and needs to be given more heat, even in high-speed printing of self-service. Therefore, it is possible to obtain a printed material with no image defect and no breakage.

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Undercoat layer 3 ... Dye layer 3Y ... Yellow dye layer 3M ... Magenta dye layer 3C ... Cyan dye layer 4 ... Heat-resistant slip layer 5 ... Thermal transfer recording medium

Claims (6)

In the heat-sensitive transfer recording medium provided with a heat-resistant slipping layer on one surface of the substrate, and provided with an undercoat layer and a dye layer in this order on the other surface of the substrate,
The undercoat layer includes at least a water-soluble polymer and a vinylpyrrolidone-vinylcaprolactam copolymer, and the heat-resistant slipping layer includes a lubricant having a melting point different from that of a filler made of an inorganic material and having a Mohs hardness of 3 or less. A thermal transfer recording medium comprising two or more kinds, wherein the total amount of the lubricant is 5 to 25% by mass with respect to the heat-resistant slip layer.   2. The thermal transfer recording medium according to claim 1, wherein a melting point of at least one of the lubricants in the heat-resistant lubricant layer is 50 ° C. to 140 ° C.   3. The thermal transfer recording medium according to claim 1, wherein the melting point of at least one of the lubricants in the heat resistant slipping layer is less than 20 ° C. 3.   4. The thermal transfer recording medium according to claim 1, wherein a difference in melting point between any two of the lubricants contained in the heat resistant slipping layer is 40 ° C. or more. 5.   The thermal transfer recording medium according to claim 1, wherein the water-soluble polymer contained in the undercoat layer is polyvinyl alcohol.   6. A printed material, wherein the thermal transfer recording medium according to any one of claims 1 to 5 is used, and information is printed on a transfer target having an aqueous image receiving layer.

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