JPH0585064A - Thermal transfer recording medium - Google Patents

Abstract

PURPOSE:To provide a thermal transfer recording medium enhanced in its antistaining properties, following high speed printing, satisfying both of printing quality and image density and having transfer ability and printing runnability even at high temp. without contaminating the surface of a medium to be transferred. CONSTITUTION:In a thermal transfer recording medium consisting of a sheet like base material and the hot-melt ink layer provided on the base material and selectively heated and melted to be transferred to a transfer medium, the hot-melt ink layer contains at least an ethylenic low m.p. crystal material, an ethylenic resin, pigment having a small particle size and pigment having a large particle size.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive transfer recording medium, and more particularly to a heat-sensitive transfer recording medium having an improved heat-meltable ink layer for transfer to a transfer medium using a heat-sensitive head.

[0002]

2. Description of the Related Art In order to transfer a heat-sensitive transfer recording medium to a transfer-receiving medium, the heat-sensitive transfer recording medium and the transfer-receiving medium are brought into close contact with each other on a heat-sensitive head under a constant pressure, and then applied from the heat-sensitive head. The heat-meltable ink layer (heat-meltable color material layer) of the thermal transfer recording medium is melted by heat energy,
A method of transferring onto the transfer medium is adopted.
At the time of this transfer, most of the heat-meltable ink layer on the thermal transfer recording medium is transferred onto the transfer target medium. Therefore, in order to perform recording using the thermal transfer recording medium, it is almost the same as the recording area. A thermal transfer recording medium having the same area is required. Therefore, the recording method using the thermal transfer recording medium has a higher recording cost than the electrophotographic method or the inkjet method.

In order to eliminate such a high recording cost, a multi-time thermal transfer recording medium which can be used a plurality of times has been developed. As such a multi-time heat-sensitive transfer recording medium, for example, a heat-sensitive transfer recording medium in which a resin is made into a fine porous material and the pores thereof are impregnated with a heat-sensitive ink is disclosed in JP-A-54-68253. In the thermal transfer recording medium, since the thermal ink is transferred onto the medium to be transferred by utilizing the permeation phenomenon due to the pores of the thermal ink, it takes time for the thermal ink to be melted by heat and permeate into the pores. However, there was a big problem that it was difficult to obtain a high density transferred image because the permeation amount of the thermal ink was limited. A similar thermal transfer recording medium
Although it is also disclosed in Japanese Patent Laid-Open No. 55-105579, it has the same problem as described above.

Further, in JP-A-56-89984, an organic pigment such as carbon black or a metal such as aluminum or aluminum oxide is contained in a solid ink layer of a recording medium.
A heat-sensitive transfer recording medium which can be used a plurality of times by adding fine powder of metal oxide or other inorganic pigment as a filler is disclosed. In such a thermal transfer recording medium, the compounded filler forms a porous layer, and the voids of the porous layer are impregnated with a solid ink in which a coloring material such as a dye or pigment is dissolved or dispersed in a low melting point resin. The structure is a solid ink layer. When heat is applied to the thermal transfer recording medium, the solid ink is melted and exudes from the porous layer and is transferred onto the transfer medium. However, the heat-sensitive transfer recording medium having the above structure is also unsuitable for high-speed transfer for the same reason as when the fine porous layer made of resin is formed, and it is difficult to obtain a high-density transfer image. Furthermore, when a pigment such as carbon black is used as the filler, some of these fillers are also easily transferred, and in the case of color recording, color turbidity is likely to occur.

On the other hand, a method different from the one used a plurality of times like the above-mentioned multi-time thermal transfer recording medium, for example, thermal transfer without making the feeding speed of the thermal transfer recording medium and the transferred medium the same (1: 1). The above-described object of reducing the recording cost can be achieved even in a mode in which the feeding speed between the recording medium and the transfer-receiving medium is smaller (n times speed) in the thermal transfer recording medium. Specifically, JP-A-60-178088 discloses an n-fold speed thermal transfer recording medium in which an overlayer containing a resin and a wax as a main component is provided on a heat-meltable ink layer. By providing such an over layer, it is possible to prevent rubbing and smearing caused by a difference in pressing pressure and relative speed between the thermal transfer recording medium and the medium to be transferred. However, an excessive melting phenomenon of the thermal transfer recording medium due to thermal storage of the thermal head caused by the slow absolute speed of the thermal transfer recording medium peculiar to n-fold speed printing to the thermal head, and the trailing caused by the accompanying melting of the ink layer after printing There is a problem that stains and whisker-like spread of the melted ink material due to spinnability cannot be prevented.

From the above, the Japanese Patent Laid-Open No. 2040/1990
No. 92 discloses a thermal transfer ink prepared by dispersing a coloring material in a hot-melt binder composed of an ethylene-vinyl acetate copolymer and a wax, and defining the breaking strength at room temperature (25 ° C.). A heat-sensitive transfer recording medium and a heat-sensitive transfer recording method which prevent beard stains are disclosed. However, there is little physical relationship between the mechanical strength of the material at room temperature and the beard stain caused by the spinnability of the material in the molten state, the image density is high, and it is suitable for high-speed transfer. An n-fold speed thermal transfer recording medium capable of solving the above-mentioned problems has not been developed yet.

[0007]

With the recent spread and development of information equipment, printers, which are information output equipment, are becoming faster, smaller, and more precise. However, as described above, a heat-sensitive transfer recording medium that can be used a plurality of times has poor thermal responsiveness, which makes it difficult to follow high-speed printing, resulting in poor printing quality and image density.

Further, as a problem peculiar to the thermal transfer recording medium used a plurality of times, the surface of the thermal transfer recording medium used a plurality of times deteriorates, and the deteriorated surface causes the entire surface of the transferred medium pressed against for transfer. There is a problem of getting dirty. If the thermal response of the thermal transfer recording medium is increased to increase the speed, the stain tends to become more likely to stain. Further, the downsizing of the device causes the temperature inside the device to become higher than that of the conventional device during use, so that the problem of the contamination becomes more and more serious. Moreover, when the device is heated to such a high temperature, there is a peculiar problem, namely, a reverse transfer phenomenon (when the heat-meltable layer of the heat-sensitive transfer recording medium is melt-transferred onto the transfer medium, it is not transferred to the heat-sensitive transfer recording medium. Phenomenon that returns to print defects) and sticking phenomenon (heat-melting layer becomes an adhesive layer and the heat-sensitive transfer recording medium adheres to the transferred medium, resulting in poor conveyance of the heat-sensitive transfer recording medium in the equipment. Phenomenon) occurs. On the other hand, the n-fold speed thermal transfer recording medium has problems of rubbing stains and beard stains in a more severe high temperature state.

The present invention has been made to solve the above-mentioned various problems, and improves the stain resistance of itself,
In addition, it follows high-speed printing, satisfies both printing quality and image density, and has stable transferability and printing runnability at high temperatures without soiling the surface of the medium to be transferred, especially when used multiple times (multi-time), An object of the present invention is to provide a thermal transfer recording medium suitable for n-fold speed printing.

[0010]

The present invention is directed to a sheet-like base material, and a heat-meltable ink layer provided on the base material and selectively heated and melted to be transferred to a transfer medium. In the heat-sensitive transfer recording medium, the heat-meltable ink layer contains at least an ethylene-based low melting point crystal material, an ethylene-based resin material, a pigment having a small particle size and a pigment having a large particle size. Is. As the sheet-shaped substrate, for example, a film having high heat resistance such as a polyester film and a back coating of a silicone resin is used. The heat-meltable ink layer has a thickness of 2 to 8 μm.
It is desirable to set the range to.

The ethylene-based low melting point crystal material, which is the first component of the heat-meltable ink layer, is well compatible with the ethylene-based resin material. In particular, in order to further enhance the compatibility with the ethylene-based resin material, it is desirable to contain other functional groups in addition to the ethylene structure. Examples of such an ethylene-based low melting point crystal material (wax) include low molecular weight polyethylene wax, oxidized polyethylene wax, paraffin wax, oxidized paraffin wax, carnauba wax, cadelic wax, rice wax, and wax.
Beeswax, lanolin, coconut wax, oxidized wax ester, emulsion type oxidized wax, urethane type wax, alcohol type wax, (exposed montan wax, unexposed montan wax, refined wax, acid wax, ester wax, partially saponified ester wax )
PO wax, rosin, rosin methylol amide,
Examples thereof include ester gum and higher fatty acids.

The ethylene-based resin material, which is the second component of the heat-meltable ink layer, has a good compatibility with the ethylene-based low melting point crystalline material, and further has low crystallinity, so that the crystallinity of the transferred medium is low. Has a function of suppressing the isolation of the ethylene-based low-melting-point crystalline material that is easily crystallized. From this, it is preferable that the ethylene resin material has a comonomer content of 25% by weight or more and a large molecular weight. Further, the copolymer of ethylene and a comonomer is preferably a random copolymer, and the Q and e values used as a measure of the monomer reaction ratio of the comonomer have a Q of 1.0 or less, more preferably It is preferably 0.2 or less. Examples of the ethylene-based resin material include a binary copolymer and a ternary copolymer of ethylene and a monomer. Examples of the monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, acrylic acid, methacrylic acid, maleic anhydride, vinyl acetate. , Vinyl chloride, vinylidene chloride and the like are preferable.

Ethylene-based low melting point crystal material (A) and ethylene-based resin material (B), which are components of the heat-meltable ink layer.
The mixing ratio (weight ratio) of A: B is 1: 1 to 3: 1.
Is desirable.

The small particle size pigment which is the third component of the hot melt ink layer has a maximum particle size peak in the range of 10 to 100 nm, and the large particle size pigment is 2
It has a maximum particle size peak in the range of 00 to 500 nm.

The small particle size and large particle size pigments may be formed of the same kind of pigment, or may be formed of two or more kinds of pigments. When forming a small particle size and a large particle size with the same kind of pigment, it is desirable to use a colored pigment as the pigment. When a pigment having a small particle size and a pigment having a large particle diameter are formed from two or more pigments, the pigment having a small particle diameter is used as one or more coloring pigments.
It is desirable to form the large particle size pigment with one or more achromatic pigments.

The mixing volume ratio (L / S) of the small particle size pigment (S) and the large particle size pigment (L) is preferably 0.1 or more. The reason is that if the ratio is less than 0.1, it becomes difficult to increase the print density. The more preferable mixing volume ratio (L / S) is in the range of 0.1 to 1.5.

The ratio of the pigment having the small particle size and the pigment having the large particle size to be blended in the hot-melt ink layer is 25 to 50.
It is desirable to set it in the range of volume%. This is due to the following reasons. 25% by volume of the pigment
If the amount is less than the range, the high temperature storability and printability of the heat-meltable ink layer may be deteriorated. If the proportion of the pigment exceeds 50% by volume, the transferability to the transfer medium may be deteriorated. A more preferable mixing ratio of the pigment is 25 to 40% by volume.

Examples of the color pigments include carbon black, fast yellow G, henzine yellow,
Pigment Yellow, India First Orange, Irgadine Yellow, Carmine FB, Permanent Bordeaux FRR, Pigment Orange R, Resor Red 2
G, rake red C, rhodamine FB, rhodamine B, phthalocyanine green, quinacridone and the like can be used.

As the achromatic pigment, for example, titanium oxide, zinc oxide, silica, fused silica, talc, silica sand, silica balloon, shirasu balloon, crosslinked resin fine particles, crosslinked resin hollow particles and the like can be used. As such an achromatic pigment, it is desirable to select a pigment having an optical refractive index close to that of the ethylene-based low melting point crystal material and the ethylene-based resin material which are the first and second components of the heat-meltable ink layer. In particular, the small particle size pigment is formed by one or more color pigments, and the large particle size pigment is formed by one or more achromatic color pigments, and the small particle size and large particle size pigments are formed in the ratio (L / S). ) Is approximated to 1, it is desirable to select, as the large-diameter achromatic pigment, a pigment having an optical refractive index close to that of the ethylene-based low melting point crystal material and the ethylene-based resin material. This is because the blending of the achromatic color pigment causes turbidity in the color of the color pigment, and in the case of the color ink, a normal color may not be obtained. Therefore, as the achromatic pigment, a resin-based pigment having a refractive index within ± 20% of the refractive index of the first and second components is particularly preferable.

When the heat-sensitive transfer recording medium according to the present invention is used for printing at n-fold speed, an ethylene-based low melting point crystalline material which is the first and second components of the ink layer is formed on the heat-meltable ink layer. Further, it is allowed to further form a layer of the resin composition in which the ethylene resin material is mixed in a desired ratio.

[0021]

According to the present invention, a heat-meltable ink layer containing at least a low melting point crystalline ethylene material, an ethylene resin material, and a pigment having a small particle size and a large particle size is formed on a sheet-like base material. By providing the configuration, when the heat-meltable ink layer is transferred stepwise in the depth direction of the heat-meltable ink layer from the side in contact with the transfer medium, high-speed printing is followed and printing is performed. It is possible to obtain a multi-time heat-sensitive transfer recording medium which satisfies both the quality and the image density, has no print stain at high temperature, and has stable print running property. When the heat-meltable ink layer is transferred stepwise in the longitudinal direction of the thermal transfer recording medium, the same high-speed printing is followed,
It is possible to obtain an n-fold speed thermal transfer recording medium which satisfies both the print quality and the image density, is free from rubbing stains and whiskers at high temperatures, and exhibits stable printing runnability.

That is, an ethylene-based low melting point crystal material (wax) and an ethylene-based resin material having excellent affinity with each other are used as the first and second components constituting the heat-meltable ink layer, and the third component is used as these components. The above-mentioned effects can be achieved by blending a pigment having a small particle size and a large particle size as a component. When wax and resin with poor affinity are mixed, even if they are macroscopically mixed, the wax and resin are microscopically isolated, and the mechanically weak wax component will cause the medium to be transferred to transfer at the time of transfer at high temperature. It becomes a cause of so-called rubbing stains. Since both the wax and the resin that form the heat-meltable ink layer are ethylene-based materials, the compatibility is good, and it is possible to effectively prevent the isolated portion of the wax that causes stains from occurring. as a result,
It is possible to prevent printing stains at high temperatures.

Further, by adding a pigment to the resin material comprising the first and second components, an effect of mechanically reinforcing the mixed structure of the wax and the resin is produced, and the stain resistance is remarkably improved. The reinforcing effect becomes better as the blending amount of the pigment in the heat-meltable ink layer increases and the particle size of the pigment decreases. However, if the amount of the pigment is increased to such an extent that the pigment having a small particle size alone does not cause rubbing stains, the reinforcing effect becomes too strong and cohesive failure in the heat-meltable ink layer is less likely to occur, resulting in a transfer image density descend. On the other hand, when the pigment having a large particle size is used alone, the reinforcing effect is low and the print stain occurs. Moreover, in the case of a pigment having a large particle diameter, whisker stains due to the spinnability also occur in the molten state of the wax and the resin.

Therefore, an ethylene-based low melting point crystal material (wax) and an ethylene-based resin material having excellent affinity with each other are used, and a pigment having a small particle size and a large particle size as the third component is used for these components. By blending the above, it is possible to obtain a heat-sensitive transfer recording medium satisfying the above-mentioned contradictory characteristics (that is, an effect of preventing beard stain due to stain resistance, print stain, and spinnability). Further, the amount of the pigment blended is 25 to
By setting the content to 50% by volume, it is possible to obtain a heat-sensitive transfer recording medium having further excellent characteristics.

Furthermore, when a pigment having a compounding volume ratio (L / S) of the small particle size pigment (S) and the large particle size pigment (L) is 0.1 or more, the transfer performance and the print stain resistance are improved. It can be improved significantly. In particular, stain resistance can be remarkably improved by forming the small particle size pigment as a colored pigment and the large particle size pigment as an achromatic pigment.

[0026]

EXAMPLES Examples of the present invention will be described in detail below.

Table 1 below shows the small particle size pigments used in the examples and comparative examples, Table 2 below the large particle size pigments, Table 3 below the ethylene-based low melting point crystalline materials, and Table 4 shows the ethylene resins. Table 1 (Small particle size pigment) Name name Particle size (nm) CB-1 carbon black (Colombian Yang Carbon 12 company trade name; RAVEN5000) CB-2 carbon black (Mitsubishi Kasei Co. trade name; 29 MA11) CB-3 carbon black (trade name; 56 Printex 25, manufactured by Degussa) CB-4 carbon black (trade name, manufactured by Cabot Co .; 75 STERRING R) YP Disazo pigment (manufactured by Dainippon Ink and Chemicals, Inc. 70 product) Name; KET Yellow 406) RP quinacridone pigment (trade name: KET Red 309, manufactured by Dainippon Ink and Chemicals, Inc. 100) BP Phthalocyanine pigment (trade name: KET Blue 104, manufactured by Dainippon Ink and Chemicals, Inc. 60) Table 2 (Large particle size pigment) Code name Name Particle size (nm) Particle-1 Acrylic Superfine powder (product name by Soken Chemical Industry Co., Ltd .; 400 MP-3010) Particle-2 Silicon resin fine particles (product name by Toshiba Silicone 300 Co., Ltd .; Tospearl 103) Particle-3 Acrylic hollow particles (Nippon Synthetic Rubber 300-400) Company name: SX863 (P)) Table 3 (Ethylene-based low-melting point crystalline material; wax) Code Melting point Acid value Saponification value W-1 75 12 30 W-2 82 11 16 W-3 75 30 80 Table 4 (Ethylene-based resin) Code Ethylene content (% by weight) Comonomer MI R-172 Vinyl acetate 20 R-2 87 Vinyl acetate 20 R-375 Methyl methacrylate 20 Examples 1 to 21

Twenty-one kinds of thermal transfer recording media were manufactured by forming a heat-meltable ink layer having the composition shown in Table 5 below on a polyester film back-coated with a silicone resin. In Table 5, the ethylene-based low melting point crystal material is abbreviated as wax, and the ethylene-based resin is abbreviated as resin. Also,
The symbols in Table 5 mean the symbols in Tables 1 to 4, and the numbers in parentheses indicate the volume% of each component. Table 5 Examples Small particle size pigment 1 Small particle size pigment 2 Large particle size pigment Wax Resin 1 CB-1 CB-4 Particle-1 W-1 R-1 (2) (18) (5) (45) ( 30) 2 CB-2 CB-4 Particle-1 W-1 R-1 (5) (18) (5) (40) (30) 3 CB-3 Particle-1 W-1 R-1 (25) ( 5) (40) (30) 4 CB-4 Particle-1 W-1 R-1 (30) (5) (40) (30) 5 YP Particle-1 W-1 R-1 (10) ( 15) (45) (30) 6 R-P particles-1 W-1 R-1 (10) (15) (45) (30) 7 B-P particles-1 W-1 R-1 (10) ( 15) (45) (30) 8 CB-1 CB-4 particles-2 W-1 R-1 (2) (18) (5) (45) (30) 9 CB-2 CB-4 particles-2 W 1 R-1 (5) (18) (5) (40) (30) 10 CB-3 particles-2 W-1 R-1 (25) (5) (40) (30) 11 CB-4 particles- 2 W-1 R-1 (30) (5) (40) (30) 12 Y-P particles-2 W-1 R-1 (10) (15) (45) (30) 13 R-P particles- 2 W-1 R-1 (10) (15) (45) (30) 14 BP Particle-2 W-1 R-1 (10) (15) (45) (30) 15 CB-1 CB- 4 Particle-3 W-1 R-1 (2) (18) (5) (45) (30) 16 CB-2 CB-4 Particle-3 W-1 R-1 (5) (18) (5) (40) (30) 17 CB-3 Particle-3 W-1 R-1 (25) (5) (40) (30) 18 CB-4 Particle-3 W-1 R-1 (30 (5) (40) (30) 19 Y-P particles-3 W-1 R-1 (10) (15) (45) (30) 20 R-P particles-3 W-1 R-1 (10) (15) (45) (30) 21 B-P particles-3 W-1 R-1 (10) (15) (45) (30)

The thermal transfer recording media of Examples 1 to 21 were personalized word processors (trade name: Toshiba 95; Report 95H).
P) is used to perform printing a plurality of times, and the evaluation methods described below are used to (1) the first and third image densities, (2) print stains, (3) high temperature running property, and (4) high temperature storability. I investigated each. The results are shown in Table 6 below. (1) Image density

A solid image was printed at room temperature (25 ° C.), and the density at the first time and the density at which the solid image was printed three times in succession were measured using a Macbeth reflection densitometer. 1.2 for the first time
As described above, if it was 1.0 or more in the third time, it was evaluated as excellent (◯). (2) Printing stains

When the printing run was carried out a plurality of times up to 10 times in an environment of 40 ° C. and a humidity of 85%, when there was no rubbing stain due to softening of the heat-meltable ink layer or print stain due to heat accumulation of the thermal head, (Image density is 0.1 or less), Δ (image density 0.1 to 0.2) when light stains are present, and X (image density is 0.2 or higher) when severe stains are evaluated. .. (3) High temperature runnability

The printing run was carried out a plurality of times up to 10 times under the environment of 40 ° C. and 85% humidity, and when there was no abnormality in running property, ○, slight reverse transfer of ink and sticking, but the 10th run When traveling between the two, evaluation was made as Δ, and when severe traveling problems such as reverse transfer of ink, sticking, or ribbon breakage occurred, it was evaluated as x. (4) High temperature storability

96 in a state where the thermal transfer recording medium is housed in the ink ribbon cassette under the environment of 55 ° C. and humidity of 85%.
If the ink ribbon is blocked, ink is adhered to the carrying roll in the cassette, and the pressing spring during that time, x is not shown, but there is no blocking or ink adhesion, but the pulling torque of the ink ribbon from the cassette is 2
When it increased by 0% or more, it was evaluated as Δ, and when there was no blocking or ink adhesion, and when the variation of the withdrawal torque was 20% or less, it was evaluated as O. Table 6 Examples Image density Print stains High temperature running property High temperature storage property 1st time 3rd time 1 1.2 1.0 ○ ○ ○ 2 1.3 1.0 ○ ○ ○ 3 1.3 1.1 ○ ○ ○ 4 1 2 1.0 ○ ○ ○ 5 5 1.2 1.0 ○ ○ ○ 6 1.2 1.0 ○ ○ ○ 7 1.2 1.0 ○ ○ ○ 8 1.2 1.0 ○ ○ ○ 9 1 .3 1.0 ○ ○ ○ 10 10 1.3 1.1 ○ ○ ○ 11 1.2 1.0 ○ ○ ○ 12 1.2 1.0 ○ ○ ○ 13 1.2 1.0 ○ ○ ○ 14 1 .2 1.0 ○ ○ ○ 15 1.2 1.0 ○ ○ ○ 16 1.3 1.0 ○ ○ ○ 17 1.3 1.1 ○ ○ ○ 18 1.2 1.0 ○ ○ ○ 19 1 2 1.0 ○ ○ ○ 20 20 1.2 1.0 ○ ○ ○ 21 1.2 1.0 ○ ○ ○ Examples 22 to 42

It has a heat-meltable ink layer having exactly the same composition except that the wax (W-1) shown in Table 3 and blended in Examples 1 to 21 was replaced with the wax of W-2 shown in Table 3. Twenty-one thermal transfer recording media were manufactured.

The thermal transfer recording media of Examples 22 to 42 were personal personal word processors (trade name: Toshiba Corp .; Report 95H).
P) was used to perform printing a plurality of times, and as in Example 1, (1) first and third image densities, (2) printing stains,
(3) High temperature running property and (4) High temperature storage property were examined. The results are shown in Table 7 below. Table 7 Examples Image density Print stains High temperature running property High temperature storage property 1st time 3rd time 22 1.2 1.0 ○ ○ ○ 23 1.3 1.0 1.0 ○ ○ ○ 24 1.3 1.1 ○ ○ ○ 25 1 .2 1.0 ○ ○ ○ 26 1.2 1.0 ○ ○ ○ 27 1.2 1.0 ○ ○ ○ 28 1.2 1.0 ○ ○ ○ 29 1.2 1.0 ○ ○ ○ 30 1 3 1.0 ○ ○ ○ 31 31 1.1 1.1 ○ ○ ○ 32 1.2 1.2 ○ ○ ○ 33 1.2 1.0 ○ ○ ○ 34 1.2 1.0 ○ ○ ○ 35 1 2 1.0 ○ ○ ○ 36 36 1.2 1.0 ○ ○ ○ 37 1.3 1.0 ○ ○ ○ 38 1.3 1.1 ○ ○ ○ 39 1.2 1.0 ○ ○ ○ 40 1 2.2 1.0 ○ ○ ○ 41 1.2 1.0 ○ ○ ○ 42 1.2 1.0 ○ ○ ○ Examples 43 to 63

The wax (W-1) shown in Table 3 compounded in Examples 1 to 21 was replaced with the wax of W-3 shown in Table 3, and the resin (R-1) shown in Table 4 to Table 4 was replaced. R-
Twenty-one kinds of thermal transfer recording media having a heat-meltable ink layer having exactly the same composition except that the resin was replaced with the resin of No. 3 were produced.

The thermal transfer recording media of Examples 43 to 63 were personal personal word processors (trade name: Toshiba Corp .; Report 95H).
P) was used to perform printing a plurality of times, and as in Example 1, (1) first and third image densities, (2) printing stains,
(3) High temperature running property and (4) High temperature storage property were examined. The results are shown in Table 8 below. Table 8 Examples Image density Print stains High temperature running property High temperature storage property 1st time 3rd time 43 1.2 1.0 ○ ○ ○ 44 1.3 1.0 ○ ○ ○ 45 1.3 1.1 ○ ○ ○ 46 1 2 1.0 ○ ○ ○ 47 47 1.2 1.0 ○ ○ ○ 48 1.2 1.0 ○ ○ ○ 49 1.2 1.0 ○ ○ ○ 50 1.2 1.0 ○ ○ ○ 51 1 .3 1.0 ○ ○ ○ 52 52 1.3 1.1 ○ ○ ○ 53 1.2 1.0 ○ ○ ○ 54 1.2 1.0 ○ ○ ○ 55 1.2 1.0 ○ ○ ○ 56 1 2.2 1.0 ○ ○ ○ 57 1.2 1.0 ○ ○ ○ 58 1.3 1.0 ○ ○ ○ 59 1.3 1.1 ○ ○ ○ 60 1.2 1.0 ○ ○ ○ 61 1 2 1.0 ○ ○ ○ 62 1.2 1.0 ○ ○ ○ 63 1.2 1.0 ○ ○ ○ Comparative Examples 1 to 12

Twelve types of thermal transfer recording media were manufactured by forming a hot-melt ink layer having the composition shown in Table 9 below on a polyester film back-coated with a silicone resin. In Table 9 below, the ethylene-based low melting point crystal material is abbreviated as wax, and the ethylene-based resin is abbreviated as resin. Also,
The symbols in Table 9 mean the symbols in Tables 1 to 4, and the numbers in parentheses indicate the volume% of each component. Table 9 Comparative Examples Small particle size pigment 1 Small particle size pigment 2 Large particle size pigment Wax Resin 1 CB-1 CB-4 Particle-1 W-1 R-1 (2) (8) (10) (48) ( 32) 2 CB-1 Particle-1 W-1 R-1 (2) (10) (52) (36) 3 CB-1 W-1 R-1 (10) (53) (37) 4 CB-1 W-1 R-1 (30) (40) (30) 5 CB-2 Particle-2 W-1 R-1 (5) (10) (50) (35) 6 CB-2 W-1 R-1 (10) (53) (37) 7 CB-2 W-1 R-1 (30) (40) (30) 8 CB-3 W-1 R-1 (10) (53) (37) 9 CB- 3 W-1 R-1 (10) (53) (37) 10 CB-3 W-1 R-1 (10) (53) (37) 11 CB-4 W-1 R-1 (30) (53) (37) 12 Y-P W-1 R-1 (30) (53) (37)

The thermal transfer recording media of Comparative Examples 1 to 12 were personal personal word processors (trade name: Toshiba 95; Report 95H).
P) was used to perform printing a plurality of times, and as in Example 1, (1) first and third image densities, (2) printing stains,
(3) High temperature running property and (4) High temperature storage property were examined. The results are shown in Table 10 below. Table 10 Comparative example Image density Print stains High temperature running property High temperature storage property 1st time 3rd time 1 0.8 1.0 × × × 2 0.3 0.5 Δ Δ × × 3 0.5 0.6 × Δ Δ 40 0.1 0.1 ○ ○ ○ 5 0.3 0.5 0.5 △ × × 6 0.7 0.9 × × × 7 0.5 0.5 0.7 △ △ △ 8 1.0 1.2 1.2 × × × 90 0.7 1.0 △ × × 10 1.0 1.1 △ × × 11 0.8 1.0 ○ △ ○ 12 0.7 1.0 ○ △ △ Examples 64-84

A resin composition prepared by mixing the wax of W-1 in Table 3 and the resin of R-1 in Table 4 at a volume composition ratio of 1: 1 on the hot-melt ink layers in Examples 1 to 21 was prepared. 5 μm
Exactly the same 21 kinds of thermal transfer recording media were manufactured except that they were applied in the thickness of.

The thermal transfer recording media of Examples 64 to 84 were printed with n = 1 and n = 3 using a prototype n-fold speed printing evaluation device, and (1) n was evaluated by the evaluation method described below.
The image densities of = 1 and n = 3, (2) print stain, (3) high temperature running property and (4) high temperature storability were examined. The results are shown in Table 11 below. (1) Image density

A solid image is printed at room temperature (25 ° C.) and n =
The density at 1 and the density at n = 3 were measured using a Macbeth reflection densitometer. If n = 1, 1.3 or more, and n = 3, 1.0 or more were evaluated as excellent (◯). (2) Printing stains

When printing is carried out at n = 3 in an environment of 40 ° C. and a humidity of 85%, and there is no rubbing stain or whisker stain due to softening of the heat-meltable ink layer, or print stain due to heat accumulation in the thermal head, during that time. O (image density of 0.1 or less), Δ (image density of 0.1 to 0.2) when slight stains were found, and X (image density of 0.2 or more) when severe stains were evaluated. did. (3) High temperature runnability

When printing is carried out at n = 3 in an environment of 40 ° C. and humidity of 85%, and there is no abnormality in running property, ○, slight reverse transfer of ink, sticking or meandering of the ink ribbon. It was evaluated as Δ when running, and as × when running trouble such as severe reverse transfer of ink, sticking, or meandering of the ink ribbon occurred. (4) High temperature storability

96 in a state where the thermal transfer recording medium is housed in the ink ribbon cassette under the environment of 55 ° C. and humidity of 85%.
If the ink ribbon is blocked, ink is adhered to the carrying roll in the cassette, and the pressing spring during that time, x is not shown, but there is no blocking or ink adhesion, but the pulling torque of the ink ribbon from the cassette is 2
When it increased by 0% or more, it was evaluated as Δ, and when there was no blocking or ink adhesion, and when the fluctuation of the withdrawal torque was 20% or less, it was evaluated as ◯. Table 11 Examples Image density Print stain Printability at high temperature Storage at high temperature n = 1 n = 3 64 1.4 1.0 ○ ○ ○ 65 1.3 1.1 ○ ○ ○ 66 1.4 1.1 ○ ○ ○ 67 1.3 1.0 ○ ○ ○ 68 68 1.3 1.0 ○ ○ ○ 69 1.3 1.0 ○ ○ ○ 70 1.3 1.0 ○ ○ ○ 71 1.4 1.4 ○ ○ ○ 72 1.4 1.0 ○ ○ ○ 73 1.5 1.1 ○ ○ ○ 74 1.4 1.0 ○ ○ ○ 75 1.3 1.0 1.0 ○ ○ ○ 76 1.3 1.0 ○ ○ ○ 77 1.3 1.0 ○ ○ ○ 78 1.3 1.0 ○ ○ ○ 79 1.4 1.0 ○ ○ ○ 80 1.4 1.1 ○ ○ ○ 81 1.3 1.0 ○ ○ ○ 82 1.3 1.0 ○ ○ ○ 83 1.3 1.0 ○ ○ ○ 84 1.3 1.0 ○ ○ ○ Comparative Examples 13 to 24

A resin composition prepared by mixing the wax of W-1 in Table 3 and the resin of R-1 in Table 4 at a volume composition ratio of 1: 1 on the hot-melt ink layers in Comparative Examples 1 to 12 was prepared. 5 μm
Exactly the same 12 kinds of thermal transfer recording media were manufactured except that they were applied in the thickness of.

The thermal transfer recording media of Comparative Examples 13 to 24 were printed with n = 1 and n = 3 using a prototype n-fold speed print evaluation device, and as in Example 64, (1) n = 1 and n
= 3, the image density, (2) print stain, (3) high temperature running property, and (4) high temperature storability were examined. The results are shown in Table 12 below. Table 12 Comparative Example Image density Print stains High temperature running property High temperature storage property n = 1 n = 3 13 0.8 0.3 × × × 14 0.3 0.3 0.1 △ △ × 15 1.2 0.6 × △ △ 16 0.1 0.1 ○ ○ ○ 17 0.4 0.2 △ × × 18 1.1 0.6 × × × 19 1.0 0.5 0.5 △ △ △ 20 1.3 1.0 △ × × 21 1.2 0.8 △ × × 22 1.4 1.1 △ × × × 23 1.2 1.0 ○ △ ○ 24 1.3 1.0 ○ △ △

[0048]

As described above in detail, according to the present invention, the stain resistance of itself is improved, high-speed printing is followed, both the print quality and the image density are satisfied, and the surface of the medium to be transferred is further improved. It is possible to provide a heat-sensitive transfer recording medium which has stable transferability and printing runnability even at high temperature without being contaminated, and is particularly suitable for a plurality of times of use (multi-time) and n-fold speed printing. Further, it is possible to provide a heat-sensitive transfer recording medium capable of high-speed printing of a good transfer image from the transferred medium having a high surface smoothness to the transferred medium having a low smoothness without lowering the resolution.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Noriaki Sato 8 Shinsita-cho, Isogo-ku, Yokohama-shi, Kanagawa Stock company Toshiba Yokohama office

Claims (1)

[Claims] 1. A thermal transfer recording medium comprising a sheet-shaped base material and a heat-meltable ink layer which is provided on the base material and selectively heated and melted to be transferred to a transfer medium. ,
The heat-sensitive transfer recording medium, wherein the heat-meltable ink layer contains at least an ethylene-based low melting point crystal material, an ethylene-based resin material, and a pigment having a small particle size and a large particle size.