JPS63178082A - Thermal transfer recording material for gradation recording - Google Patents

Abstract

PURPOSE:To perform gradation recording capable of obtaining a high density transfer image corresponding to the change in heating temp., by combining a thermal transfer ribbon with a special thermal transfer receiving medium. CONSTITUTION:A thermal transfer ribbon 1 and a thermal transfer receiving medium 4 are combined. The thermal transfer ribbon 1 consists of a base material 2 and resin microporous layers 3Y, 3M, 3C containing yellow, magenta and cyan dyes and the resin microporous layers 3Y, 3M, 3C are arranged on the base material as repeating units continuing along the longitudinal direction thereof. The thermal transfer receiving medium 4 is formed by providing an ink absorbing layer 6 having a porous structure containing oil absorbing particles to a support 5. Each resin microporous layer containing the heat- meltable ink is formed by a method wherein color pigment is mixed with wax and oil-soluble metal solfonate to prepare colored wax which is, in turn, dispersed in a solution of a saturated polyester resin and the obtained liquid mixture is applied to the base material and dried.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermal transfer recording material for gradation recording using a thermal transfer ribbon and a thermal transfer receiving medium.

[Prior art and its problems]

BACKGROUND ART Conventionally, in the field of heat-melting type thermal transfer recording, a thermal transfer ribbon for gradation recording has been used to perform density gradation recording.

Density gradation recording attempts to reproduce a full-color image that is faithful to the original by causing heat-melting ink corresponding to the amount of heat from a color printer's heating head to ooze out from a thermal transfer ribbon and transferring it to a thermal transfer receiving medium. Although it is a thing,
In order to improve the reproducibility of the original image, it is necessary to use a thermal transfer ribbon that provides images with high density and good gradation, and if these conditions are not met, only images with poor reproducibility will be obtained. Thermal transfer ribbons that form gradation records are required to have such performance, but if a thermal transfer ribbon containing heat-melting ink in a resin porous RI layer is used, it will not be possible to reproduce the above-mentioned image. The properties are not necessarily satisfied, and an improvement in -m is desired.

Based on the above-mentioned circumstances, the present inventors conducted repeated research on thermal transfer ribbons having a microporous resin layer, and found that an oil-soluble sulfonic acid metal salt was blended into a resin porous layer made of saturated polyester on a base material. It has been found that a thermal transfer ribbon containing a heat-melting ink exhibits excellent performance as this type of thermal transfer ribbon.

The present invention is based on the above findings, and as a result of further improvement research, it was discovered that by combining the above thermal transfer ribbon with a special thermal transfer receiving medium, it is possible to reproduce excellent transferred images with even higher density. It's arrived.

[Means for solving problems]

That is, the present invention provides: (A) microporous resin layers each containing at least yellow, magenta, and cyan heat-melting inks are provided on the same base material, and the microporous resin layer is formed of saturated polyester; A thermal transfer ribbon containing an oil-soluble sulfonic acid metal salt in a heat-melting ink contained in a resin microporous layer, and (B) an ink absorption layer containing porous oil-absorbing particles on a support. This is a heat-sensitive transfer recording material for gradation recording, which is a combination of a heat-sensitive transfer receiving medium and a heat-sensitive transfer receiving medium.

Next, the present invention will be explained in detail.

Regarding the thermal transfer ribbon (A), this ribbon has a microporous resin layer made of saturated polyester on a base material, and a molten ink containing an oil-soluble sulfonic acid metal salt in the microporous resin layer. It is formed by containing,
The above-mentioned saturated polyester needs to be soluble in solvent and non-transferable when heated, so it has a softening point of 10
Use a temperature of 0°C or higher. Specifically, the product names are Byron 200 (Toyobo ■), Byron 300 (by the same company), and Byron 103 (by Toyobo ■).
), 500 (company), Polyester TP-220
(Nippon Gosei Kagaku Kogyo ■), TP-236 (the company), TP-217 (the company), TP-290 (the company), the same T
P-249 (Company), LP-033 (Company), LP
-011 (Company), LP-035 (Company), LP-
Examples include those having a molecular weight of 400 or more, such as 044 (manufactured by the same company).

Oil-soluble sulfonic acid metal salts blended into hot melt ink include petroleum sulfonates and synthetic sulfonates.
Specifically, the product names are Surhole Ca45N (Matsuzai Oil Research Institute), Surhole Ca45 (the company), Moresco Amber-3C-45N (the company), and Moresco Amber 5.
c-45 (manufactured by the same company).

Waxes as other components blended into the hot melt ink are all incompatible with saturated polyester, such as petroleum waxes such as paraffin wax and microcrystalline wax; natural waxes such as carnauba wax and candelilla wax. Wax: Synthetic waxes such as montan wax, polyethylene wax, castor wax, fatty acid amide; various other waxes, ester waxes, etc. These waxes can be used alone or in combination.

Regarding color pigments as other components to be blended into the hot-melt ink, carbon black, nigrosine base, etc. can be used as color pigments that form black. As the coloring pigment that forms yellow, Hansa Yellow, Benzidine Yellow, Brilliant Fast Yellow, Permanent Yellow, Quinacridone Yellow, etc. can be used. Color pigments that form magenta include permanent red, permanent e-min, permanent lupine, permanent bordeaux,
Watch unbred, brilliant carmine, rhodamine lake, quinacridone pink, quinacridone magenta, quinacridone red, etc. can be used. Furthermore, as the coloring pigment that forms cyan, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue, etc. can be used. In addition, various pigments conventionally used in the field of thermal transfer ribbons can be used.

The resin microporous layer containing hot-melt ink is prepared by mixing wax and oil-soluble sulfonic acid metal salts with colored pigments to make a colored wax, and dispersing this colored wax in a resin solution of saturated polyester. It is formed by applying the liquid mixture to the base material and then drying it.

The resin microporous layer obtained in this way has a smooth layer surface and can have fine pores, but the thickness of the layer is preferably about 2 to 6 microns in order to improve thermal sensitivity. , oil-soluble sulfonic acid metal salt, wax, and coloring pigment are 15 to 60% by weight and 5% by weight, respectively, based on the total amount of the resin microporous layer containing the heat-melting ink.
~30% by weight, 15-60% by weight and 5-25% by weight
It is preferable that they be blended in a proportion of . The base material is preferably a heat-resistant material that does not fuse to the thermal head, but if necessary, a heat-resistant protective film may be provided on the surface that contacts the thermal head. Note that if polyester is used as the base material, the adhesion of the saturated polyester to the resin microporous layer can be improved. The thickness of the base material is 1 to 20
Microns are preferred.

Further, when the thermal transfer ribbon (A) is used for electrical transfer recording, the base material may be made of two layers, and the layer on the side in contact with the electrode may be a resistive layer that generates heat when electricity is applied. This resistance layer can be formed, for example, by dispersing a conductive substance in a resin layer.

In this way, the heat-sensitive transfer ribbon (A) is formed by providing a plurality of resin microporous layers containing heat-melting inks of different colors on the same base material, on which a heat-resistant protective film is provided if necessary. be done.

Next, the thermal transfer receiving medium CB) will be described.

This thermal transfer receiving medium can be applied, for example, to a support made of a suitable material.
The ink absorption layer is composed of oil-absorbing particles with a porous structure such as diatomaceous earth or nacre powder and a binder resin such as polyester, and if desired, a whitening agent such as titanium oxide or a plasticizer such as dioctyl adipate is added. The ink-absorbing layer contains approximately 30% by weight or more of oil-absorbing particles, and the thickness of the ink-absorbing layer is approximately 10 microns or more.

The thermal transfer receiving medium (B) has a Bekk smoothness of the layer surface of 10.
If it is less than 0 seconds, the surface of the layer will become rough and it will be difficult to transfer the seeped hot melt ink evenly, resulting in a Beck smoothness of 10.
If the time exceeds 000 seconds, the ink absorbency decreases and the hot melt ink does not transfer sufficiently and tends to flow, so the surface of the ink absorption layer has a Beck smoothness of 100.
It is preferably within the range of ~10,000 seconds.

A thermal transfer receiving medium (B) having an ink absorbing layer on a support having the composition, structure, and surface smoothness as described above.
For example, specifically, the product name is Peach Coat 5PU.
-125 (Nisshinbo Co., Ltd.: Beck smoothness 300 seconds), Yupo Boat VKF #90 (Oji Yuka Co., Ltd.: Beck smoothness 50 seconds)
0 to 800 seconds).

(Function) The mechanism of action is not necessarily clear as to why excellent transfer images with high density can be reproduced by using the heat-sensitive transfer recording material of the present invention obtained in this way. Because the oil-soluble sulfonic acid metal salt has a strong ionic group of 13O3, it adsorbs to the pigment and stably disperses the pigment in the wax, so the pigment migrates to the resin side forming a microporous layer. In addition, since oil-soluble metal sulfonic acid salts and saturated polyester are incompatible, a structure is created in which the heat-melting ink is contained in the resin micropores of the saturated polyester that forms the continuous phase. There is no affinity between the microporous layer and the heat-melt ink, so the amount of heat-melt ink exuded changes favorably depending on the heating temperature, and the other heat-sensitive transfer receiving medium (B) absorbs the ink. This is thought to be because the layer absorbs the heat-melting ink, so even when the heat-melting ink is pressed by the heating head, the ink does not flow, and therefore the optical reflection density value does not decrease.

Next, the present invention will be explained with reference to the drawings.

In FIGS. 1 and 2, 1 is a thermal transfer ribbon; 4 is a thermal transfer ribbon;
indicates a thermal transfer receiving medium. The thermal transfer ribbon 1 consists of a base material 2 and resin microporous layers 3Y, 3M, and 3C containing yellow, magenta, and cyan inks,
The resin microporous layers 3Y, 3M, and 3C are arranged on the base material 2 in continuous repeating units along its length. The thermal transfer receiving medium 4 is provided with an ink absorbing layer 6 containing oil absorbing particles having a porous structure on a support 5 . This ribbon 1 is used to melt and transfer ink of each color onto a medium 4 by heating with a thermal head to obtain a desired color image. Specifically, for example, yellow ink is melted and transferred onto the medium 4, and then cyan ink is melted and transferred onto the medium 4, and two color inks are deposited in layers on the medium 4 to form a green color image. Use to get.

In addition to the resin microporous layers 3Y, 3M, and 3C, FIG.
In addition, microporous resin containing black ink [3
B is a thermal transfer ribbon formed in a continuous manner on the base material 2 in the same manner. This ribbon is used when it is difficult to reproduce clear black by overlapping three colors of yellow, magenta, and cyan.

FIG. 4 shows a thermal transfer ribbon in which the base material 2 is formed into a thin strip shape, and the lengths of the microporous resin layers 3Y, 3M, and 3C are all the same as the width of the medium 4.

FIG. 5 shows a thermal transfer ribbon in which the base material 2 consists of two layers 2a and 2b, and the layer 2b is a resistive layer that generates heat when energized.

This ribbon is used by energizing it so that a current signal from a power source is scanned over the resistive layer 2b during transfer recording.

〔Example 〕

Next, examples of the present invention will be shown. Parts indicate parts by weight.

(Yellow + 1) Each component was mixed in a heated attritor with the following composition.
A yellow colored wax was produced by timed heating and dispersion.

Carnauba wax 15 parts Polyethylene wax 15 parts Petroleum sulfonate (Note 1)
15 parts Yellow pigment (Note 2) 10 parts 55
Note 1: ■Made by Matsumura Oil Research Institute, product name Sulhole Ca4
5 Note 2: Manufactured by Dainippon Ink Industries, trade name First Yellow 80F Using the above colored wax, each component was dispersed in a water-cooled attritor for 2 hours according to the following formulation, and the fine particles of colored wax were dispersed in a solvent. A dispersion liquid (25% solids) was prepared.

Pigment dispersion wax 55 parts Methyl ethyl ketone 140 parts Toluene -
1 part - 220 parts On the other hand, mix each component according to the following formulation to make 2 parts of the resin.
A 5% solution was made.

Saturated polyester (Note 3) 40 parts Methyl ethyl ketone 60 parts Toluene
60 parts 160 parts Note 3 = Manufactured by Toyobo ■, trade name Vylon #200, softening point 163°C Next, 160 parts of the above resin solution and 220 parts of the above dispersion liquid were mixed to prepare a mixed liquid for yellow. .

(Preparation of bl magenta mixture) The magenta mixture was prepared in the same manner as in the preparation of the yellow mixture except that a magenta pigment (manufactured by Dainippon Ink Co., Ltd., trade name: Red 93058) was used instead of the yellow pigment. I made a liquid.

(Cl cyan) According to 21 people, cyan pigment (Dainichi Seika (made by IS),
Except for using Cyanine Blue 64920G (trade name).
A cyan mixture was prepared in the same manner as the yellow mixture.

(dl) Input preparation for yellow color 1 Same as the preparation of the yellow liquid mixture except that a black pigment (manufactured by Mitsubishi Chemical Corporation, trade name Carbon Black MA-11) was used instead of the yellow pigment. A mixed liquid for black was prepared in the same manner.

(13) Kanjuun Color Ribbon 81 Each mixed solution was coated on a polyester film with a thickness of 6 microns using a gravure printing machine so that the thickness after drying was 3.5 microns. A heat-sensitive transfer color ribbon for gradation recording, shown in the figure, including a plurality of resin microporous layers containing yellow ink, magenta ink, cyan ink, and black ink, respectively, was produced.

(f) Product name: Peach Coat 5PU-1 as a thermal transfer receiving paper
25 (Nisshinbo Co., Ltd.: Beck smoothness 300 seconds) was prepared. In addition, high-quality paper (Kanzaki Paper Co., Ltd., Beck smoothness: 200 seconds) was prepared as a thermal transfer receiving paper for comparison.

Next, the heat-sensitive transfer color ribbon was transferred one color at a time onto these heat-sensitive transfer receiving papers using a thermal printer, and the optical optical reflection density (0, D,) of each color image that was solid-transferred was measured. , the following results were obtained.

○ When the heat-sensitive transfer receiving paper is Beach Coat 5PU-12-5, the head energy (mJ/dot) of the thermal head is 0.28 and 0.35, respectively, as shown by curve a in Figure 6. ．． 0.44, 0.53. 0,63, 0.74.0,86,
0.83, the optical optical reflection density is 0.17 and 0.24, respectively. 0.47, 0.78. 1.02, 1.12. They were 1.33 and 1.45. On the other hand, in the case of high-quality paper for comparison, when the head energy of the thermal head was similarly changed in 8 steps and 6 outputs, the optical optical reflection density was 0.17, 0.24. 0.33, 0.45. 0.60, 0.70. They were 0.82 and 1.02.

The image thermal transfer receiving medium has the trade name Peach Coat 5PU-125.
In this case, as shown by curve a in FIG. 7, when the head energy of the thermal head is changed in eight steps as in the case of the yellow image, the optical optical reflection densities are 0.10 and 0.22, respectively. 0.42, 0.74. 0.98, 1.15. They were 1.20 and 1.20. On the other hand, in the case of high-quality paper as a comparative example,
As shown in the curves in FIG. 7, when the head energy of the thermal head was similarly changed in eight steps, the optical optical reflection density was 0.09 and 0.16, respectively. 0.29, 0.45. 0.65, 0.81° 0.96, 1.05.

02ヱヱヱヱヱヱパ〇Thermal transfer receiving medium (trade name: Peachco) SPU-125
In this case, as shown by curve a in FIG. 8, when the head energy of the thermal head is changed in eight steps as in the case of the yellow image, the optical optical reflection densities are 0.14 and 0.26, respectively. 0.50, 0.81°1.05, 1.27. They were 1.33 and 1.33. On the other hand, in the case of high-quality paper for comparison, when the head energy of the thermal head was similarly changed in 8 steps, the optical optical reflection density was 0.07 and 0.0, respectively, as shown by the curve in Figure 8. .15. 0.28, 0.46. 0.63, 0.85. They were 0.99 and 1.10.

○Thermal transfer receptor medium has the product name Peachco-1-3PU-12
5, the head energy of the thermal head is set to 8 as in the case of the yellow image, as shown by curve a in FIG.
The optical optical reflection densities when changed in stages are 0, 14, and 0.18, 0.37, respectively.
, 0.62.0, 75,
1.01.1, 34,
It was 1.38. On the other hand, in the case of high-quality paper for comparison, the optical optical reflection densities were 0.14 and 0, respectively, when the head energy of the thermal head was similarly changed in 8 steps, as shown by the curves in Figure 9. .18. 0.37, 0.62. 0.75, 0.83. They were 0.90 and 1.00.

In this way, when high-quality paper is combined with the thermal transfer color ribbon, a high-density transferred image can be obtained depending on the energy of the heating head. When a thermal transfer receiving paper is used in combination, a transferred image with even higher density can be obtained depending on the energy level of the heating head.

In addition, the thermal transfer color ribbon can be printed on a video printer (■
When we performed overlapping transfer recording of multiple colors on paper with the trade name Peach Coat 5PU-125 using a Hitachi model VY-50, we were able to obtain a full-color image with extremely high gradation that was faithful to the original. Ta.

〔Effect of the invention 〕

As described above, the present invention provides a heat-sensitive transfer recording material for gradation recording, which allows a transfer image of high density to be obtained in response to changes in heating temperature.

[Brief explanation of the drawing]

FIG. 1 is a schematic plan view of a thermal transfer ribbon used in the present invention;
FIG. 2 is a schematic sectional view of the thermal transfer ribbon and slow transfer receiving medium shown in FIG. 1, FIGS. 3 and 4 are schematic plan views showing other embodiments of the thermal transfer ribbon used in the present invention, and FIG. The figure is a schematic sectional view showing another example of the thermal transfer recording material of the present invention, and FIGS. 6 to 9 are diagrams showing the relationship between the energy of the thermal head and the optical reflection density of the transferred image, respectively. 1 is a thermal transfer ribbon, 2 is a base material, 3Y, 3M, 3C and 3B are resin microporous layers containing heat-melting ink, 4
5 is a support, and 6 is an ink absorbing layer. Patent applicant: Pilot Mannen Pen Co., Ltd. fB 1 unit

Claims (1)

[Claims] (1) (A) A resin microporous layer containing at least yellow, magenta, and cyan heat-melting inks is provided on the same base material, and the resin microporous layer is formed of saturated polyester, and the resin microporous layer is made of saturated polyester. (B) A thermal transfer ribbon comprising a thermal transfer ribbon containing an oil-soluble sulfonic acid metal salt in a heat-melting ink contained in a transparent layer, and (B) an ink absorption layer containing porous oil-absorbing particles on a support. A thermal transfer recording material for gradation recording consisting of a receptor medium, and a combination of the following.