JP3760554B2 - Thermal transfer sheet - Google Patents

Thermal transfer sheet Download PDF

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Publication number
JP3760554B2
JP3760554B2 JP07861497A JP7861497A JP3760554B2 JP 3760554 B2 JP3760554 B2 JP 3760554B2 JP 07861497 A JP07861497 A JP 07861497A JP 7861497 A JP7861497 A JP 7861497A JP 3760554 B2 JP3760554 B2 JP 3760554B2
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Japan
Prior art keywords
thermal transfer
layer
dye
acid ester
heat
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Expired - Fee Related
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JP07861497A
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Japanese (ja)
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JPH10272853A (en
Inventor
フイ サム
慶 小幡
宏晃 小笠原
正芳 砂金
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ソニー株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thermal transfer sheet, and more particularly to a thermal transfer sheet excellent in running property during transfer and dye storage stability.
[0002]
[Prior art]
In the thermal transfer method using a sublimation dye, a large number of color dots are transferred to a material to be transferred by heating for a very short time, and a full color image is reproduced with multicolored color dots.
[0003]
In this thermal transfer system, as the thermal transfer sheet, a so-called sublimation type thermal transfer sheet in which a dye layer composed of a sublimable dye and a binder is provided on one surface of a base sheet such as a polyester film is used.
[0004]
In the thermal transfer system, the thermal transfer sheet is heated from behind according to image information by a thermal head, and the dye contained in the dye layer is transferred to a transfer material (printing paper) to form an image.
[0005]
At this time, the surface of the thermal transfer sheet that is in contact with the thermal head is required to have stable and low friction from low density printing to high density printing, and generally the thermal transfer sheet is fused to the thermal head. In order to prevent and impart smooth running properties, a heat resistant slipping layer is provided on the surface opposite to the surface on which the dye layer is formed.
[0006]
[Problems to be solved by the invention]
By the way, when printing on photographic paper with a thermal transfer sheet, heat is applied to the heat-resistant slipping layer from the thermal head and the dye in the dye layer on the opposite side is transferred to the photographic paper, but the color density is proportional to the amount of heat. Accordingly, the surface temperature of the thermal head changes in units of several hundred degrees. Therefore, when the thermal transfer sheet moves on the thermal head, the friction coefficient between the thermal head and the heat-resistant slipping layer is likely to change due to a temperature change. When the coefficient of friction between the thermal head and the heat resistant slipping layer changes, the thermal transfer sheet becomes difficult to move at a constant speed, and a clear image cannot be obtained.
[0007]
For example, when the coefficient of friction is large, the movement of the thermal transfer sheet is temporarily slowed, and so-called sticking (linear printing unevenness) in which the density increases only in that portion occurs.
[0008]
In order to prevent this sticking, it is necessary to reduce the coefficient of friction particularly at high temperatures. Conventionally, phosphate esters have been used as lubricants for reducing the coefficient of friction at high temperatures.
[0009]
However, the phosphoric acid ester has strong acidity, and when this is used alone for the heat resistant slipping layer, various disadvantages are caused.
[0010]
For example, when the thermal transfer sheet is stored in a wound state, contact between the dye layer and the heat-resistant slip layer occurs, and particularly in a high-temperature storage state, a highly soluble phosphate ester partially dissolves the dye from the dye layer. As a result, a decrease in density or uneven printing occurs during printing.
[0011]
In addition, if a highly acidic lubricant such as a phosphate ester is used, a dye that is easily decomposed or chemically changed under acid conditions, such as an indoaniline pigment, is deteriorated, resulting in a change in color developability or a decrease in transfer density. Occur.
[0012]
Therefore, the present invention has been proposed in view of such a conventional situation, and a thermal transfer sheet that can stably realize a low friction coefficient in a heating temperature range by a thermal head and is excellent in storage stability. The purpose is to provide.
[0013]
[Means for Solving the Problems]
In order to achieve the above-described object, the thermal transfer sheet of the present invention has a thermal transfer dye layer on one side of a base sheet and a heat-resistant slip layer on the other side. of 1 contains a polyglycerol fatty acid ester and phosphoric acid ester represented by, a ratio is the weight ratio of polyglycerol fatty acid ester and phosphoric acid ester 10: 1 to 1: 2, polyglycerol fatty acid ester and phosphoric acid it is characterized in that the amount containing a combination of the ester is 10 to 50 by weight% of the total heat-resistant lubricating layer.
[0014]
When only a phosphate ester is used as a lubricant for the heat-resistant slipping layer, the acidity is too strong and adversely affects the dye layer.
[0015]
By using a polyglycerin fatty acid ester in combination, the above-mentioned adverse effects, for example, deterioration of the dye and the like are suppressed, and storage stability is improved. In addition, the polyglycerin fatty acid ester also has a function as a lubricant and a friction coefficient is reduced.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below.
[0017]
For example, as shown in FIG. 1, the thermal transfer sheet has a thermal transfer dye layer 2 formed on a base sheet 1 and a heat resistant slipping layer 3 formed on the opposite side.
[0018]
Various conventionally known base materials can be used for the base material sheet. For example, a polyester film, a polystyrene film, a polypropylene film, a polysulfone film, a polycarbonate film, a polyimide film, an aramid film, or the like can be used. Although the thickness of this base material sheet is arbitrary, it is 1-30 micrometers, for example, Preferably it is 2-10 micrometers.
[0019]
A thermal transfer dye layer 2 is formed on the surface of the base sheet 1 facing the photographic paper. The thermal transfer dye layer 2 is formed as a continuous layer on the entire surface of the base sheet 1 in the case of a single color. Is done. In order to deal with a full-color image, the yellow, magenta, and cyan dye layers 2 are generally formed separately and sequentially.
[0020]
FIG. 2 shows an example of a thermal transfer sheet in which a detection mark 4 for position detection, a yellow dye layer 2Y, a magenta dye layer 2M, and a cyan dye layer 2C are repeatedly formed.
[0021]
Here, the order of forming yellow, magenta, and cyan is not necessarily limited to this. Further, four colors of yellow, magenta, cyan and black may be repeated. Furthermore, as shown in FIG. 3, detection marks 4 may be provided between the color dye layers 2.
[0022]
Further, as shown in FIG. 4, after the thermal transfer dye layer 2 is repeated, a transparent transfer protective layer 5 may be provided to transfer the image onto the printed screen after printing to protect the printed screen. Alternatively, as shown in FIG. 5, before the thermal transfer dye layer 2 is repeated, a transfer type receiving layer 6 for transferring to the plain paper is provided, and prior to the transfer of the thermal transfer dye layer 2, the receiving layer is formed on the plain paper surface. May be formed.
[0023]
The thermal transfer dye layer 2 is composed of at least each color dye and a binder, and heretofore known binders can be used as the binder. Examples thereof include water-soluble resins such as cellulose-based, acrylic acid-based, and starch-based resins, acrylic resins, polyphenylene oxide, polysulfone, polyethersulfone, acetylcellulose, and other organic solvents or water-soluble resins. From the viewpoint of recording sensitivity and storage stability of the transfer body, those having a heat deformation temperature of 70 to 150 ° C. are excellent. Therefore, polystyrene, polyvinyl butyral, polycarbonate, methacrylic resin, acrylonitrile / styrene copolymer, polyester Resins, urethane resins, chlorinated polyethylene, chlorinated polypropylene and the like are preferable.
[0024]
Any dye can be used, for example, yellow dyes such as azo, disiazo, methine, and pyridone azo, and mixtures thereof, and magenta dyes such as azo, anthraquinone, styryl, and heterocyclic. As the azo dye, a mixed system thereof, and a cyan dye, an indoaniline type, anthraquinone type, naphthoquinone type, heterocyclic azo dye and a mixed system thereof can be used.
[0025]
Among these, an indoaniline dye used as a cyan dye has a structure shown in the following chemical formula 3, and is easily decomposed and deteriorated under acidity, resulting in a decrease in color density.
[0026]
[Chemical 3]
[0027]
Therefore, the present invention is suitable for application to a thermal transfer sheet using this indoaniline dye.
[0028]
On the other hand, since the surface opposite to the thermal transfer dye layer 2 runs in contact with the thermal head, a heat resistant slipping layer 3 is provided.
[0029]
In the present invention, the heat-resistant slip layer 3 is characterized by containing a polyglycerol fatty acid ester and a phosphate ester.
[0030]
Polyglycerin fatty acid ester is a compound represented by the following chemical formula 4, and there are various compounds depending on the type of fatty acid. Any of these can be used, and specific examples include diglyceryl dioleate, tetraglyceryl pentastearate, decaglyceryl monolaurate, and the like.
[0031]
[Formula 4]
[0032]
On the other hand, as the phosphoric acid ester, any commercially available phosphoric acid ester can be used, and examples thereof include polyoxyethylene alkyl ether phosphoric acid ester.
[0033]
The polyglycerol fatty acid ester and phosphoric acid ester, the ratio is 10: 1 to 1: Ru used in combination so that 2. When the ratio of the phosphoric acid ester is too large outside this ratio range, deterioration of the storage stability of the dye layer due to an increase in acidity becomes a problem. On the other hand, if the proportion of polyglycerin fatty acid ester is too large, a decrease in running performance becomes a problem.
[0034]
Further, the addition amount of the combined these polyglycerol fatty acid ester and phosphoric acid ester shall be the 10 to 50 wt% of the total heat-resistant lubricating layer. If the amount of these additives is too large, drying failure may occur during film formation of the heat resistant slipping layer, or blocking may easily occur in the wound state. On the other hand, if the added amount is too small, the effect of reducing the friction coefficient is insufficient.
[0035]
The heat-resistant slip layer 3 is a layer mainly composed of a binder having excellent heat resistance, and the polyglycerin fatty acid ester and the phosphate ester are added to the layer, and any conventionally known binder can be used. For example, cellulose acetate, polyvinyl acetal, acrylic resin and the like can be used.
[0036]
The binder is preferably cross-linked with a polyisocyanate compound in view of heat resistance stability and the like. Particularly, the above-mentioned polyoxyalkylene sorbite fatty acid ester and polyglycerin fatty acid ester are cross-linked at the same time, so that the binder is extremely stable. It is possible to form the heat-resistant slip layer 3 that exhibits a lubricating effect.
[0037]
As the polyisocyanate compound to be used, any isocyanate compound having at least two isocyanate groups in the molecule can be used. For example, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-xylene diisocyanate, hexamethylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2 , 6-diisocyanate, 1,3-di (isocyanatemethyl) cyclohexane, isophorone diisocyanate, trimethyl hexamethylene diisocyanate, etc., and adducts (polyisocyanate prepolymer) in which diisocyanate and polyol are partially added and reacted, such as tolylene diene An adduct obtained by reacting isocyanate and trimethylolpropane can be used.
[0038]
The heat-resistant slip layer 3 may contain various lubricants and fillers as necessary in addition to the binder.
[0039]
Fillers that can be used for the heat-resistant slip layer 3 include inorganic fillers such as silica, talc, clay, zeolite, titanium oxide, zinc oxide, and carbon, and organic materials such as silicon resin, polytetrafluoroethylene, and benzoguanamine resin. Fillers can be used.
[0040]
However, when there is too much addition of these, it becomes easy to cause a dry defect at the time of film-forming of the heat-resistant slipping layer 3, or it becomes a cause of blocking in a winding state.
[0041]
【Example】
Hereinafter, specific examples to which the present invention is applied will be described in detail based on experimental results.
[0042]
A thermal transfer sheet sample was prepared by the following method.
[0043]
Formation of Dye Layer First, a polyester film having a thickness of 6 μm (trade name: Lumirror, manufactured by Toray Industries, Inc.) was used as a base sheet, and the following ink composition was applied to one side of the substrate so as to have a thickness of 1 μm after drying. .
[0044]
Indoaniline dye 5.0 parts by weight Polyvinyl resin (product name BX-1 manufactured by Sekisui Chemical Co., Ltd.) 5.0 parts by weight Methyl ethyl ketone 45.0 parts by weight Toluene 45.0 parts by weight In the indoaniline dyes shown in Chemical Formula 3, three types of dyes having different substituents as shown in Table 1 were used.
[0045]
[Table 1]
[0046]
Formation of heat-resistant slip layer Next, a heat-resistant slip layer having the following composition was applied to the opposite surface of the substrate sheet coated with the dye layer so as to have a thickness of 1 μm after drying, and thermal transfer was performed. A sheet was obtained.
[0047]
Polyacetal resin 5.0 parts by weight (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name Denka Butyral # 3000K)
0.5 parts by weight of polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name Coronate L)
0.5 parts by weight of spherical silica (made by Nippon Silica Kogyo Co., Ltd., trade name Nipsil E-200A)
A lubricant was added to and mixed with the composition shown in Table 2 in the types and addition amounts. At this time, the amount of the composition was adjusted so as to be 100 parts by weight as a whole. This was made into a paint with a solvent (methyl ethyl ketone: toluene = 1: 1) and applied to a base material sheet.
[0048]
Polyglycerin fatty acid esters include diglyceryl dioleate (Nikko Chemicals, trade name: NIKKOL DGMS), monolaurate hexaglyceryl (Nikko Chemicals, trade name: NIKKOL Hexagin 1-L), decastearate decaglyceryl ( There are four types: Nikko Chemicals, trade name NIKKOL Decaglyn 10-S), and pentaoleate decaglyceryl (trade name, NIKKOL Decaglyn 5-O, manufactured by Nikko Chemicals). For comparison, fatty acid (myristic acid: manufactured by Kao Corporation, trade name Lunac MY-98) or fatty acid ester (butyl stearate: manufactured by Nikko Chemicals, trade name NIKKOL BS) is used instead of polyglycerol fatty acid ester. I also made a sample. As phosphate ester, phosphate ester A (made by Toho Chemical Industry Co., Ltd., trade name PHOSPHANOL RL-210), phosphate ester B (made by Toho Chemical Industry Co., Ltd., trade name PHOSPHANOL RS-410), phosphate ester C (Toho) Three types of chemical industry, trade name PHOSPHANOL RD-720).
[0049]
The thermal transfer sheet samples (Sample 1 to Sample 12) were prepared as described above. Table 2 shows the types of dyes and lubricants used in each sample tape, and the amount added.
[0050]
[Table 2]
[0051]
Each of the above samples was examined for running property, sticking, and dye storage stability.
[0052]
In other words, the obtained thermal transfer sheet is mounted on a full color printer (trade name UP-D7000) manufactured by Sony, and gradation printing (16 gradations) is made on photographic paper (trade name UPC7010, manufactured by Sony Corporation), and visually sticking is performed. I investigated. In the case where sticking did not occur, the case where the sticking did not occur was indicated by ◯, and the case where the sticking occurred was indicated by ×.
[0053]
In addition, for dye storage stability, the two heat transfer sheets (20 cm x 20 cm) obtained are overlapped with the dye layer and the heat-resistant slip layer, sandwiched between two glass plates, and a weight of 5 kg is applied from above. And stored in an oven at 50 ° C. for 48 hours. The thermal transfer sheet before and after storage is mounted on a Sony full color printer (trade name UP-D7000) and printed with gradation (16 gradations) on photographic paper (product name UPC7010). The highest density was measured by reflection density measurement using a Macbeth densitometer (trade name TR-924). The maximum density after storage / maximum density before storage x 100 (%) was calculated to evaluate dye storage stability. The results are shown in Table 3.
[0054]
[Table 3]
[0055]
Table 1 As is clear from looking at each sample in combination with polyglycerin fatty acid ester and phosphoric acid ester (samples 1 to 8) is a dye preservability is excellent, 90 more than in the stomach displacement is achieved, practical Above, there was no problem. Decreasing dye storage stability leads to changes in color development and transfer density, and in order to form a high quality image, the dye storage stability needs to be at least about 90%.
[0056]
However, when the ratio of phosphate ester was too small (sample 7) or when the total amount was too small (sample 8), the effect was insufficient and sticking was observed. On the contrary, when the ratio of the phosphate ester is too large (sample 11), deterioration of dye storage stability was observed. When the total amount was too large (Sample 12), the state of the heat resistant slipping layer was poor and evaluation was impossible.
[0057]
On the other hand, in the samples using fatty acids and fatty acid esters (sample 9 and sample 10), sticking was confirmed and satisfactory results could not be obtained.
[0058]
【The invention's effect】
As apparent from the above description, according to the present invention, a combination of a polyglycerol fatty acid ester and phosphoric acid ester as a lubricant heat-resistant lubricating layer, the ratio of the polyglycerol fatty acid ester and phosphoric acid ester weight The ratio is 10: 1 to 1: 2, and the combined content of polyglycerin fatty acid ester and phosphate ester is 10 to 50% by weight of the entire heat-resistant slipping layer. It is possible to obtain a thermal transfer sheet which is excellent in properties and can provide a clear image.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view illustrating a configuration example of a thermal transfer sheet.
FIG. 2 is a schematic plan view illustrating a configuration example of a thermal transfer sheet.
FIG. 3 is a schematic plan view showing an example of a thermal transfer sheet in which detection marks are provided between the dye layers.
FIG. 4 is a schematic plan view showing an example of a thermal transfer sheet provided with a transfer protective layer.
FIG. 5 is a schematic plan view showing an example of a thermal transfer sheet provided with a transfer receiving layer.
[Explanation of symbols]
1 base sheet, 2 thermal transfer dye layer, 3 heat-resistant slipping layer

Claims (2)

  1. While having a thermal transfer dye layer on one side of the base sheet, and having a heat-resistant slipping layer on the other side,
    The heat-resistant lubricating layer contains a polyglycerol fatty acid ester and phosphoric acid ester represented by the following formula 1,
    The ratio of the polyglycerin fatty acid ester and the phosphate ester is 10: 1 to 1: 2 by weight,
    The thermal transfer sheet , wherein the total content of the polyglycerin fatty acid ester and the phosphate ester is 10 to 50% by weight of the entire heat resistant slipping layer .
  2. 2. The thermal transfer sheet according to claim 1, wherein the thermal transfer dye layer contains an indoaniline pigment represented by the following chemical formula (2).
JP07861497A 1997-03-28 1997-03-28 Thermal transfer sheet Expired - Fee Related JP3760554B2 (en)

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4333002B2 (en) * 2000-06-30 2009-09-16 ソニー株式会社 Thermal transfer sheet
JP4380575B2 (en) * 2005-03-31 2009-12-09 ソニー株式会社 Thermal transfer sheet
JP4962504B2 (en) * 2009-02-04 2012-06-27 ソニー株式会社 Thermal transfer sheet
JP6075085B2 (en) * 2013-01-28 2017-02-08 大日本印刷株式会社 Thermal transfer sheet
JP6379940B2 (en) * 2014-09-30 2018-08-29 大日本印刷株式会社 Thermal transfer sheet

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