JPH05155139A - Thermal transfer recording medium and ink ribbon cassette - Google Patents

Abstract

PURPOSE:To obtain a thermal transfer recording medium having excellent printing quality in printing at high speed by forming a heat-fusing ink layer containing a colorant and a heat-fusing material having specific melting point, complex elastic modulus and pour point onto a sheet-shaped base material. CONSTITUTION:A solvent dispersion containing each fixed quantity of a colorant, an ethylene group low-melting point crystal material and an ethylene resin material is prepared. A heat-fusing ink layer is formed onto a sheet-shaped base material such as a polyethylene terephthalate film from a fixed quantity of the solvent dispersion, and a thermal transfer recording medium is supported. The ethylene group low melting-point crystal material and the ethylene resin material must have the melting point of 70-90 deg.C, the magnitude of complex elastic modulus at 100 deg.C of 10<6>Pa-10<7>Pa and the pour point of 150 deg.C or higher. Carbon black, first yellow G, into first orange, irgazin red, etc., are sited as examples of the colorant constituting the heat-fusing ink layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an information recording medium such as an optical disk, an optical card, an optical tape used for recording and reproducing information.

[0002]

2. Description of the Related Art Conventionally, in order to transfer a heat-sensitive transfer recording medium to a medium to be transferred, the heat-sensitive transfer recording medium and the medium to be transferred are pressed on a heat-sensitive head under a constant pressure, and the heat-sensitive transfer recording medium is brought from this heat-sensitive head. A method has been adopted in which a heat-fusible color material layer (ink layer) of a heat-sensitive transfer recording medium is melted with heat energy and transferred onto a transfer medium. During this transfer, most of the heat-fusible color material layer on the heat-sensitive transfer recording medium is transferred onto the medium to be transferred. From this, in order to perform recording using the thermal transfer recording medium, a thermal recording medium having the same area or more as the recording 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 solve this high recording cost, a thermal transfer recording medium which can be used a plurality of times has been developed. As such a heat-sensitive transfer recording medium that can be used a plurality of times, for example, as described in JP-A-54-68253, a resin is used to form a fine porous layer, and its pores are formed. There is one in which a thermal transfer recording medium is formed by impregnating a thermal ink into the voids. In such a heat-sensitive transfer recording medium, the heat-sensitive ink is transferred from its pores onto the medium to be transferred by a permeation phenomenon. However,
It takes time until the thermal ink melts due to heat and oozes through the pores, so the printing speed becomes slower and the permeation amount of the thermal ink is limited, making it difficult to obtain a high-density transferred image. There is such a drawback. A similar proposal is disclosed in JP-A-55-105579, but it has the same drawbacks as described above.

In Japanese Patent Laid-Open No. 56-89984, an organic pigment such as carbon black, a metal such as aluminum or aluminum oxide, a fine powder of a metal oxide, or the like is contained in a solid ink layer of a recording medium. Discloses a heat-sensitive transfer recording medium containing the inorganic pigment as a filler, which can be used plural times. This thermal transfer recording medium is
A solid ink layer including a porous layer formed of a filler mixed in a recording medium and a solid ink impregnated in the voids of the porous layer. The solid ink is obtained by dissolving or dispersing a coloring material such as a dye or a pigment in a low melting point resin. When heat is applied to this recording medium,
The solid ink is melted, exudes from the porous layer, and is transferred onto the transfer medium. However, such a recording medium is also unsuitable for high-speed transfer for the same reason as the fine porous layer made of resin, and it is difficult to obtain a high-density transferred image. Further, when a coloring material such as carbon black is used as the filling material, a part of these filling materials is easily transferred, so that there is a drawback that color turbidity is likely to occur in the case of color recording.

With the spread and development of information equipment in recent years,
Printers, which are information output devices, have become faster, smaller, and more detailed. However, as described above, in the thermal transfer recording medium that can be used a plurality of times, it is difficult to follow high-speed printing because of poor thermal response, and only printing quality and image density are poor.

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 for transfer. There is a problem of getting dirty. This stain tends to be more likely to become dirty when the thermal response of the thermal transfer recording medium is increased for speeding up. Further, as the size of the equipment becomes smaller, the temperature inside the equipment during use becomes higher than that of the conventional equipment, which causes more and more dirt. In addition, such a high temperature of the device causes a unique problem. 1
The other is a reverse transfer phenomenon, that is, a printing failure phenomenon that occurs even if the heat-meltable layer of the heat-sensitive transfer recording medium is melt-transferred onto the medium to be transferred and returns to the heat-sensitive transfer recording medium without being transferred. The other is a phenomenon of sticking, that is, a poor running property between the non-transfer member and the heat-sensitive transfer recording medium, which occurs when the heat-meltable layer serves as an adhesive layer and the heat-sensitive transfer recording medium adheres to the medium to be transferred.

Further, as a method of eliminating the high recording cost, there is a method of not using the same thermal transfer recording medium a plurality of times. According to this method, the feeding speed of the thermal transfer recording medium and that of the transferred medium are not the same (1: 1), but the speed of the thermal transfer recording medium is smaller than that of the transferred medium (n times speed), thereby reducing the recording cost. Attempts have been made to achieve a reduction in Printing in this manner is called n-fold speed printing.

For example, Japanese Patent Laid-Open No. 60-178088 discloses a heat-sensitive transfer recording medium characterized in that an over layer containing a resin and a wax as main components is provided on a heat-meltable ink layer. There is. By providing such an over layer, it is possible to prevent rubbing stains caused by the difference in pressing pressure and relative speed between the heat-sensitive transfer recording medium and the transferred medium. However, in the n-fold speed printing, the absolute speed of the thermal transfer recording medium with respect to the thermal head is low. This causes an excessive melting phenomenon of the heat-sensitive transfer recording medium due to heat storage of the thermal head. Along with this, rubbing stains caused by melting of the ink after printing, and beard stains caused by the spinnability of the melted ink material are likely to occur.

Further, JP-A-2-204092 discloses a thermal transfer ink containing a heat-meltable binder composed of an ethylene-vinyl acetate copolymer and a wax, and a coloring material dispersed in the binder, which is used at room temperature. (25
A heat-sensitive transfer recording medium and a heat-sensitive transfer recording method are disclosed in which whisker stains are prevented by defining the breaking strength at (° C.). However, there is little physical relationship between the breaking strength, which indicates the mechanical strength of the material at room temperature, and the beard stain caused by the spinnability of the material in the molten state. Therefore, an n-fold speed thermal transfer recording medium which has a high image density and is suitable for high-speed transfer and which sufficiently solves the above problems has not yet been provided.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to follow high-speed printing by transferring a heat-meltable ink layer stepwise in the depth direction of the ink layer from the side in contact with the transfer medium. It is an object of the present invention to provide a heat-sensitive transfer recording medium which does not stain the surface of the recording medium to be transferred, has stable transferability and printing runnability even at high temperature, and can obtain an image having sufficient printing quality and image density. ..

Another object of the present invention is to follow high-speed printing and to obtain sufficient printing quality and image density by transferring the heat-meltable ink layer stepwise in the longitudinal direction of the thermal transfer recording medium. An object of the present invention is to provide a heat-sensitive transfer recording medium which can obtain a desired image and is free from rubbing stains and whisker stains even at high temperatures and which is suitable for multiple use (multi-time) and n-fold speed printing.

[0012]

According to the first aspect of the present invention, a sheet-shaped base material and a colorant and a heat-fusible material provided on the base material are selectively contained. A heat-meltable ink layer that is heated and melted and transferred to a non-transfer medium,

The heat melting material has a melting point Tm of 70 to 90.
The magnitude of complex elastic modulus at 10 ° C and 100 ° C is 10 ⁶ Pa
~ 10 ⁷ Provided is a thermal transfer recording medium having Pa and a pour point Tp of 150 ° C. or higher. According to the second aspect of the present invention, a sheet-shaped substrate,

A heat-meltable ink layer which is provided on this substrate, contains a colorant, an ethylene-based low melting point crystal material, and an ethylene-based resin material, and is selectively heated and melted and transferred to a non-transfer medium. Then

The heat-meltable ink layer is in an amorphous or microcrystalline state, and the diffraction peak intensity at 21.3 to 21.5 ° derived from ethylene-based crystals measured by the X-ray diffraction method is I, and is amorphous. Provided is a thermal transfer recording medium satisfying the following formula I / I ₀ ≦ 0.9, where I ₀ is the halo intensity at 16 to 17 ° derived from the part. According to a third aspect of the present invention, a sheet-shaped base material,

Provided on this substrate, 30 to 50% by weight
A colorant, a low melting point crystalline material having an acid value of 5 to 40 mgKOH / g and a saponification value of 10 to 100 mgKOH / g, and an ethylene resin material containing a copolymer resin of ethylene and a monomer having a carbonyl group. Thirty
A heat-meltable ink layer containing 50% by weight of the ethylene resin material, and the ethylene resin has an ethylene content of 65 to 80% by weight.
And a thermal transfer recording medium having a melt index of 60 or less is provided.

In these embodiments, the heat-meltable ink layer preferably has an endothermic peak curve measured by a differential scanning calorimeter DSC within a temperature range of ± 30 ° C. of the peak temperature. Hereinafter, the above three aspects will be described in more detail.

First, the heat-sensitive transfer recording medium according to the first aspect is substantially composed of a sheet-shaped base material and a heat-meltable ink layer provided on the sheet-shaped base material as described above. The heat-meltable ink layer contains a colorant and a heat-meltable material, and the heat-meltable material has a melting point Tm of 70 to 90.
The magnitude of complex elastic modulus at 10 ° C and 100 ° C is 10 ⁶ Pa
~ 10 ⁷ Pa and pour point Tp are 150 ° C. or higher. The melting point Tm and the pour point Tp referred to here mean the melting point and the pour point obtained by measuring the complex elastic modulus described below.

The complex elastic modulus in the present invention means an inner diameter of 16
Fill the sample into a container made of aluminum with a diameter of 3 mm and a diameter of 3 mm.
Then, from above, make a disk made of aluminum with a diameter of 12 mm
Excited up and down with an exciter at a frequency of 3 Hz,
So-called forced vibration method, which measures elastic modulus from displacement and stress
Required by. At this time, the elastic modulus is the complex elastic modulus E.
^・And between the storage elastic modulus E ′ and the loss elastic modulus E ″.
Is E^・= E '+ iE' '(where i is an imaginary number). Also,
The magnitude of complex elastic modulus is | E^・| = {(E ')² + (E '')² }^1,2  It is represented by. The sample cell is heated in a thermostatic chamber.
The temperature is raised by indirectly heating with air as a medium.
The speed is 0.5 ° C./min. The melting point Tm of the material is
Under the measurement conditions of complex elastic modulus of
Its complex elastic modulus is 5 × 10⁷ When it dropped to Pa
Let it be the temperature of the mushroom.

The pour point Tp is the temperature at which the loss elastic modulus (E '') is larger than the storage elastic modulus (E '), that is, the temperature at which the rubbery plateau region, which is viscoelasticity, enters the flow region. Means

The thermal transfer recording medium of the present invention realizes printing a plurality of times by performing stepwise transfer of the heat-fusible layer. This is achieved only when the physical properties of the material are configured so that a cohesive failure phenomenon occurs inside the heat-meltable layer.

A heat-fusible layer having a melting point Tm of 70 ° C. or lower cannot be used because of poor storage stability at high temperature. Also, the melting point Tm is 9
If the temperature is 0 ° C or higher, the melting temperature shifts to a high temperature, and thus the transferability decreases. Therefore, the melting point Tm of the heat-fusible material is 70-
90 ° C. The melting point Tm is preferably 75 to 85 ° C. When the melting point Tm exceeds 85 ° C, the melting point Tm is low (0-10
(° C) environment, the transferability tends to decrease, and when it is less than 75 ° C, the transferability tends to deteriorate with time in a storage test at 55 ° C and a long-term storage test at room temperature.

Further, it is necessary that this material be easily melted by heating and flow / deform on the medium to be transferred by the transfer pressure. For this purpose, the complex elastic modulus at 100 ° C. is 10 ⁷ Must be below Pa. Further, in order to stabilize the printing runnability of the material at high temperature, it is desirable that the mechanical strength of the material at the time of melting is large to some extent, and for this purpose, the complex elastic modulus is 10 ⁶ It is more than Pa. The complex elastic modulus at 100 ° C. is preferably 8 × 10 ^6. Or 2
× 10 ⁶ Pa. 2 x 10 ⁶ If it is less than Pa, the pour point decreases almost in proportion to the magnitude of the complex elastic modulus at 100 ° C. because the melting point is almost constant, and the high temperature (30 to 40
(° C) Printing stains tend to occur in an environment of 8 x 1
0 ⁶ When it exceeds Pa, the amount of deformation of the ink layer due to the transfer pressure is reduced, and the adhesive surface to the transfer medium is reduced, so that the transferability of rough paper tends to be reduced.

The cohesive failure in the ink layer is stable in the central portion of the heat-meltable layer when the heat-meltable layer is in a molten state and its mechanical strength does not change so much in the thickness direction. Occurs. The heat-fusible layer is actually hotter near the thermal head and cooler near the transfer medium. Therefore, in order to establish such a condition that the mechanical strength is uniform,
It can be realized by minimizing the temperature change of the complex elastic modulus of the material in the molten state.

Therefore, in the present invention, the pour point Tp is set to 150 ° C. or higher and such mechanical condition is set to 1
Established between 00 and 150 ° C. However, if the molecular weight of the resin becomes too large, the elastic modulus of the entire ink layer becomes large, which increases the cohesive force and prevents cohesive failure in the ink layer. This makes it less likely that damage will occur at the interface between the ink layer and the non-transfer paper. If this cohesive failure does not occur, a transfer failure such as a reverse transfer phenomenon of the ink layer tends to occur. Therefore, the pour point Tp of the entire ink layer is preferably 200 ° C. or lower. If the temperature exceeds 200 ° C., cohesive failure of ink at the interface between the ink layer and the transfer paper becomes difficult to occur, and transfer failure tends to occur.

The heat-sensitive transfer recording medium according to the second aspect of the present invention is substantially composed of a sheet-shaped base material and a heat-meltable ink layer provided on the base material. The ink layer contains a colorant, an ethylene-based low melting point crystal material, and an ethylene-based resin material, and the heat-meltable ink layer is in an amorphous or microcrystalline state, and the ethylene-based crystal measured by an X-ray diffraction method. Derived from 21.3 to 21.5 °
The intensity of the diffraction peak at is 1
When the halo intensity at 6 to 17 ° is I ₀ , the following formula I / I ₀ ≦ 0.9 is satisfied.

In order to follow high-speed printing, the heat-meltable ink material must be melted quickly. The thermal transfer recording medium of the present invention has an intensity ratio I / I of the diffraction peak from the ethylene-based crystal to the halo intensity of the amorphous portion.
_{Since o} is 0.9 or less, the crystallinity of the ethylene-based low melting point crystalline material is extremely low. Therefore, it is considered that the heat-meltable ink material is in a microcrystalline state or an amorphous state. This is because the heat energy required for melting the crystals is small and the sensitivity is high, as compared with the case where the crystal grains of wax, which is a low melting point crystalline material, grow large in the heat melting ink layer. The intensity ratio I / I _o of this diffraction peak is preferably 0.8 or less.

Further, the heat-sensitive transfer recording medium of the present invention is well mixed with the ethylene-based resin material in order to reduce the crystallinity of the ethylene-based low-melting-point crystalline material which is extremely easily crystallized, and causes a stain. The isolated portion of the wax is very low. Therefore, printing stains at high temperatures are extremely small.

As described above, in order for the ethylene-based low melting point crystalline material and the ethylene-based resin material to be well mixed, it is desirable that the affinity between them is extremely high. For this,
As the ethylene-based low melting point crystalline material, a material having some other functional group in addition to the ethylene structure is more preferable.

Further, the ethylene resin material is required to have a high affinity with the low melting point crystalline material of ethylene and a low crystallinity of the resin material itself in order to lower the crystallinity of the mixture. For this purpose, it is desirable that the content of the comonomer in the ethylene resin material is 25 wt% or more.

Further, the copolymer of ethylene and the comonomer is most preferably a random copolymer, and the monomer reactivity ratio of the comonomer is preferably close to that of the ethylene monomer. As such a monomer, Q and e values (T. Alfrey,
In JJ, Bohrer, H. Mark Copolymeization (1951)) is preferably 1.0 or less, more preferably 0.2 or less. Further, the content of the ethylene-based resin material is 20 in order to suppress the occurrence of reverse transfer, sticking and stain, which are problems peculiar to the above-mentioned thermal transfer recording medium which is used a plurality of times.
It is preferably ˜30 wt%.

The ethylene-based low-melting-point crystalline material forming the heat-meltable ink layer mixes well with the ethylene-based resin material, takes a microcrystalline or amorphous state in the heat-meltable ink layer, and causes stains. In order to reduce the isolated portion of the wax that becomes the wax, the content thereof is preferably 1: 1 to 1: 3 with respect to the ethylene resin material, and 30 to 5 is preferable.
It is preferably 0% by weight. The thermal transfer recording medium satisfying the physical properties shown in the first and second aspects has, for example, a composition as shown in the third aspect below. The thermal transfer recording medium according to the third aspect of the present invention is

It is substantially composed of a sheet-shaped base material and a heat-meltable ink layer provided on the base material. The heat-meltable ink layer contains 30 to 50% by weight of a colorant and an acid. Value 5-40mg KOH / g, Saponification value 10-100mg
It contains 15 to 30% by weight of an ethylene-based resin material containing a copolymer resin having a low melting point of KOH / g and a monomer having ethylene and a carbonyl group, and the ethylene-based resin material has an ethylene content of 65 to 65%.
It is 80% by weight and has a melt index of 60 or less.

Such a thermal transfer recording medium is achieved by increasing the affinity between the resin material and the low melting point crystalline material forming the heat fusible ink layer. When a resin with poor affinity and wax, which is a low-melting-point crystalline material, are mixed, the resin and wax are isolated microscopically even if they are macroscopically mixed, and mechanically weak wax components are transferred at high temperatures. It sometimes causes the transfer medium to be soiled.

Since the wax and the resin used in the third aspect of the present invention are both materials having a carbonyl group, they have good compatibility. To achieve good affinity between resin and wax, the low melting point crystalline material forming the hot melt ink layer has an acid value of 5 to 40 mgKOH / g and a saponification value of 1.
It is 0 to 100 mgKOH / g, and is a copolymer resin of ethylene and a monomer having a carbonyl group as a resin material for forming the heat-meltable ink layer, and the ethylene content of the ethylene copolymer resin is 65 to 65. 80% by weight is preferred.

The melt index of this resin is 6
When a high molecular weight resin having a molecular weight of 0 or less is used, the melt viscoelasticity is increased, and the print stain and the high temperature running property are further excellent. However, if the molecular weight is too large, the melt viscoelasticity becomes too large and the transferability tends to deteriorate, so the melt index of the resin is preferably 1 or more.

Similarly, if the amount of the resin added is 15% by weight or less, the effect of increasing the melt viscoelasticity is low, and printing stains cannot be prevented. Becomes

Examples of the low-melting-point crystalline material containing a carbonyl group which forms such a heat-meltable ink layer include the following organic substances which melt at a predetermined temperature. Oxidized paraffin wax, carnauba wax, candelilla wax, rice wax, wooden wax, beeswax, lanolin, coconut wax, oxidized wax ester, emulsion type oxidized wax, urethane type wax, alcohol type wax, oxidized microcrystalline wax,
Amides wax, waxes based on montan wax (bleached montan wax, unbleached montan wax,
Purified wax, acid wax, ester wax, partially saponified ester wax), PO wax, polyethylene oxide wax, rosin, rosin methylol amide,
Examples include ester gum and higher fatty acids.

Further, it is also effective to add the following low melting point crystalline materials containing no carbonyl group to these low melting point crystalline materials for adjusting the melting point. Such materials include paraffin wax, microcrystalline wax, low molecular weight polyethylene wax, oxidized polyethylene wax, and polyethylene wax.
These materials are not preferable because the wax and the resin are isolated unless the addition amount is 10% by weight or less in the low melting point crystalline material.

Examples of the carbonyl group-containing monomer copolymerizable with ethylene include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate and iso-
Monomers such as propyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, acrylic acid, methacrylic acid, maleic acid, vinyl acetate are preferred. As the ethylene copolymer, a binary copolymer of these monomers and ethylene or a ternary copolymer can be used in the present invention. Further, a monomer such as vinyl chloride or vinylidene chloride can be used for the ethylene resin material in the second aspect.

As the colorant which constitutes the heat-meltable ink layer, for example, carbon black, fast yellow G, benzidine yellow, pigment yellow,
India First Orange, Irgadine Red, Carmine FB, Permanent Bordeaux FRR, Pigment, Orange R, Resor Red 2G, Rake Red C, Rhodamine FB, Rhodamine B, Phthalocyanine Blue,
Pigment Blue, Brilliant Green B, Phthalocyanine Green, Quinacridone and the like can be used as required. If the addition amount of these coloring agents is too large, it causes transfer failure, and if the addition amount is too small, storage stability at high temperature is lost, so 30 to 50% by weight is preferable. If the specific gravities of the coloring materials are greatly different, the amounts of these coloring agents added will be excessive or insufficient within the above-mentioned weight% range.
Therefore, more accurately, it is preferable to add 20 to 40% by volume.

Since the addition of a large amount of expensive dyes / pigments as the ink material is contrary to the purpose of providing a good product at a lower cost, silica, silica sand, titanium oxide, zinc oxide, talc, etc. Addition material is the colorant component 5
It is also effective to add up to 0% by volume.

As the substrate, for example, a polyethylene terephthalate film, a polyethylene naphthalate film, a polyphenylene sulfide film, an aramid film or the like can be used.

The cohesive failure in the heat-meltable ink layer means the center of the heat-meltable ink layer when the heat-meltable ink layer is in a molten state and its mechanical strength does not change so much in the thickness direction. It occurs stably in the department. The heat-meltable ink layer is actually hotter near the thermal head and cooler near the transfer medium. Therefore, in order to establish such a condition that the mechanical strength is uniform, it is possible to realize by making the temperature change of the complex elastic modulus of the molten state of the material as small as possible.

In the third embodiment of the present invention, a resin having a melt index of 60 or less is added to the material system in an amount of 15 to 30% by weight, and the affinity of the entire material system is controlled so that the pour point Tp is 150 ° C. As described above, such a mechanical condition is established between 100 and 150 ° C., high-speed printing is followed, printing quality and image density are both satisfied, and the surface of the recording medium to be transferred is not contaminated, and even at high temperature. The present invention provides a heat-sensitive transfer recording medium having stable transferability and printing runnability.

It is necessary to increase the molecular weight of the resin in order to set the pour point Tp to 150 ° C. or higher and the rubber plateau region to 150 ° C. or higher. For this purpose, it is preferable that the melt index of the resin be 60 or less. The melt index is preferably 10 or more. If the molecular weight of the resin becomes too large, the elastic modulus of the entire ink layer becomes large, the amount of deformation due to the stress applied at the time of transfer becomes small, and the adhesive surface decreases. Transferability to a certain thing is lowered, and since the molecular weight is increased, the cohesive force is increased and the cohesive failure in the ink layer does not occur. As a result, destruction occurs at the interface between the ink layer and the non-transfer paper, and a reverse transfer phenomenon of the ink layer or a transfer failure such as sticking of the ink layer as an adhesive layer tends to occur.

By the way, in order to follow high-speed printing, the heat-meltable ink material must be rapidly melted. This requires that the heat-meltable ink material has a low melting energy. The thermal properties of materials such as melting energy
It can be measured using a DSC (differential scanning calorimeter). When the heat-meltable ink material is also measured by DSC, an endothermic peak curve having the softening point as its center is obtained.

This endothermic peak curve is as sharp as possible, that is, the peak curve is as narrow as possible within a narrow temperature range, in order to obtain a heat-sensitive transfer recording medium which follows high-speed printing and shows stable printing runnability without printing stains at high temperature. It is desirable to obtain it. When the endothermic peak curve is broad, that is, when the melting characteristic is broad, it takes time for the heat-meltable ink material transferred onto the transfer medium to completely solidify, so that it cannot sufficiently adhere to the transfer medium. .. Therefore, when the thermal transfer recording medium is used a plurality of times, reverse transfer and sticking easily occur. Further, at the time of transfer, it is necessary to supply heat energy to at least a temperature range where the melting of the heat-meltable ink material is completed. If the melting characteristic is broad, this temperature range shifts to a higher temperature side. In a heat-sensitive transfer recording medium that can be used multiple times, if the heat-meltable ink layer is thickened to increase the number of times of repeated use, the heat energy from the heat-sensitive head will not be sufficiently supplied and the heat will not reach the above temperature range. Transfer of the fusible ink material onto the transfer medium is performed without the temperature rising. For this reason, if the melting property is broad, defective printing is likely to occur. Further, when the melting property is broad, the softening of the heat-meltable ink material starts from a low temperature range, so that stains easily occur.

In the heat-sensitive transfer recording medium of the present invention, the endothermic peak curve measured by DSC is sharp, that is, the heat-meltable ink material is melted within a narrower temperature range, so that the above problems do not occur. Following high-speed printing, it has stable printing runnability without printing stains at high temperatures. In order to prevent all the reverse transfer, sticking, and stains, the melting is ± 3 with the peak temperature as the center.
It is desirable to complete in the temperature range of 0 ° C., and therefore, the endothermic peak measured by DSC is preferably within the temperature range of ± 30 ° C. around the peak temperature.

As described above, according to the present invention, a printer capable of high-speed printing has excellent transferability for printing a plurality of times, satisfies both print quality and image density, and does not stain the surface of the recording medium to be transferred. Thus, it is possible to obtain a heat-sensitive transfer recording medium having stable transferability and printing runnability even at high temperatures. Further, it is possible to provide a thermal transfer recording medium capable of forming a good transferred image by high-speed printing without lowering the resolution from a medium having a high surface smoothness to a medium having a low surface smoothness.

[0051]

EXAMPLES The present invention will be described in detail below with reference to examples. Example 1 Table 1 shows the physical properties of the wax used in Example 1 in Table 2.
Indicates the physical properties of the resin. Table 1 Wax physical properties No. Melting point Tm Acid value Saponification value ° C mgKOH / g mgKOH / g 1 75 12 30 2 63 30 80 3 75 0 0 4 82 11 16 Wax 2 in Table 1 above has a melting point Tm of 70 ° C. The wax 3 has an acid value and a saponification value outside the scope of the present invention. Table 2 Physical Properties of Resin No. Ethylene Comonomer Melt-in Content Dex 172 Vinyl Acetate 20 2 87 Vinyl Acetate 20 3 3 72 Vinyl Acetate 300 475 Methyl Methacrylate 20 In Table 2 above, Resin 2 has 8 ethylene contents.
It exceeds 0 wt%, and the melt index of Resin 3 exceeds 60. Using the waxes and resins shown in Tables 1 and 2, thermal transfer recording media were prepared with the compounding ratios shown in Table 3 below. Table 3 Example composition Wax Resin Colorant Melting point Complex elastic modulus Pour point Tp No. No. (° C) (10 ⁶ ) (℃) 1-1 1 35% 1 20% 45% 78 8 170 2 1 35% 4 25% 40% 82 8 165 3 4 35% 1 20% 45% 85 7 160 4 4 35% 4 25% 40 % 87 9 170 5 4 25% + 1 12% + 45% 78 4.3 155 2 100% 3 8% (coloring material is Degussa Germany, carbon black PRINTEX35)

Each of Examples 1-1 to 1-5 follows high-speed printing, satisfies both print quality and image density, does not stain the surface of the recording medium to be transferred, and has stable transferability at high temperature. It was confirmed to have print runnability.

That is, when a printing test was carried out at 35 ° C. and a humidity of 85%, the printing density (solid black) measured by a Macbeth reflection densitometer was 1.2 or more at the first printing, and at the third printing. It was very good at 1.0 or more. Also,
The storage stability test at 55 ° C. × 85% × 96H could be sufficiently cleared. Next, Table 4 shows the composition of the comparative example. Table 4 Comparative example composition Wax Resin Colorant Melting point Complex elastic modulus Pour point Tp No. No. (℃) (10 ⁶ ) (℃) 1-1 2 35% 2 20% 45% 74 5 × 10 ⁶ 155 2 2 35% 3 25% 40% 69 8 × 10 ⁵ 135 3 3 35% 2 20% 45% 80 7 × 10 ⁶ 160 43 35% 3 25% 40% 78 9 × 10 ⁵ 145 5 3 25% + 1 5% + 45% 80 4 × 10 ⁶ 120 4 10% 3 15% In all of Comparative Examples 1-1 to 1-5, it was confirmed that the print stain was severe at the temperature and the normal temperature, and the printing characteristics at multiple times were also defective.

In particular, in Comparative Examples 1-1 and 1-2, it was possible to print a plurality of times, but the storability was very poor, and in Comparative Examples 1-3 and 1-4, it was not possible to print a plurality of times. Or
The stain on the print was also severe.

In Example 1-5, the melting point and the complex male ratio at 100 ° C. are almost the same as those of Comparative Example 1-5, and only the pour point is large. Comparing the two, Comparative Example 5 is room temperature (25 ° C) and high temperature (35 ° C).
In contrast, in Example 5, the print stain is generated violently, but in Example 5, the print stain is not generated at room temperature at all, and the print stain is slightly recognized at the high temperature. From this result, it was confirmed that the thermal transfer recording medium of the present invention was excellent. From the results of Examples and Comparative Examples, it was confirmed that the thermal transfer recording medium of the present invention was excellent.

If the thermal transfer recording medium described above is stored in a commercially available case and is used as an ink ribbon cassette that can be conveyed to a position facing the paper surface according to printing, an existing printer, for example, a word processor is used. It can be used with a page printer. It is clear from the above results that it is particularly suitable as a multi-time ink ribbon. Example 2

Materials used in this example and comparative examples are shown below. Table 5 shows the physical property values of the ethylene-based low melting point crystalline material (wax), and Table 6 shows the physical property values of the ethylene-based resin material. Further, each material is represented by using a symbol for simplification. Pigment: Carbon black pigment: P-1 (trade name: Printex 25 manufactured by Degussa). Table 5 Melting point (° C) Acid value Ken number mgKOH / g mgKOH / g Ethylene-based low melting point crystalline wax: W-1 75 12 30 Ethylene low-melting point crystalline wax: W-2 63 28 75 Ethylene low-melting point crystalline Wax: W-3 83 14 38 Ethylene-based low-melting crystalline wax: W-4 86 680 80 Table 6 Melt ethylene content Softening point (° C) Index (wt%) Ethylene-based resin: R-1 400 72 40 Ethylene-based Resin: R-2 150 72 40 Ethylene resin: R-3 15 72 40

A heat-meltable ink layer having the composition shown in Table 7 below was formed on a polyester film having a back surface coated with a heat-resistant slip layer to form the heat-sensitive transfer recording media of Examples 2-1 to 2-77. Created. In addition, in Table 7, each material is shown in Table 5.
And the symbols described in 6 are used. In addition, the numbers in Table 7 represent the volume% of each material. Table 7

Example W-1 W-2 W-3 W-4 R-1 R-2 R-3 P-1 2-1 45 25 30 2 45 25 30 30 3 45 25 30 4 45 45 30 30 5 45 25 30 6 45 25 30 30 7 45 25 25 30 8 45 25 30 30 45 45 25 30 10 45 20 20 35 11 45 20 35 35 12 45 20 35 35 13 45 20 20 35 14 45 20 35 35 15 45 20 20 35 16 45 45 20 35 35 18 45 20 45 20 35 19 40 40 20 40 20 20 40 20 40 21 40 40 20 40 22 40 20 40 23 40 40 20 40 24 40 20 20 40 25 40 40 20 40 26 26 40 20 40 27 27 40 20 40 28 28 35 20 45 45 29 35 20 20 45 30. 45 31 35 20 45 32 32 35 20 45 33 35 0 45 34 35 35 20 45 35 35 35 20 45 36 36 35 20 45 37 37 25 20 15 10 10 30 38 25 25 20 10 15 15 30 39 25 20 15 15 10 30 40 40 25 20 10 15 15 30 41 15 15 20 10 10 10 30 42 10 15 20 10 43 15 20 10 10 30 30 44 15 15 20 10 10 30 30 45 15 15 20 10 10 30 46 46 15 20 10 10 10 30 47 47 15 20 10 10 30 30 48 15 15 20 10 10 30 30 49 15 15 20 10 10 10 30 50 15 15 20 6 14 45 20 14 6 45 52 52 15 20 6 14 45 53 15 20 20 14 6 45 54 15 20 20 6 14 45 55 55 15 20 14 6 45 56 56 15 20 6 6 14 45 57 57 15 20 14 14 6 45 58 58 15 20 6 14 45 59 15 20 14 6 45 60 60 15 20 6 14 45 45 61 15 20 14 14 6 45 62 25 25 10 8 12 12 45 63 63 25 10 12 8 45 45 64 25 10 10 8 12 45 65 25 25 10 12 12 8 45 45 66 25 10 8 25 12 67 12 8 45 68 68 25 10 8 12 12 45 69 25 25 10 12 8 45 45 70 25 10 8 12 12 45 71 71 25 10 12 8 45 72 72 25 10 8 12 12 45 73 25 10 10 12 8 45 45 74 45 5 20 30 30 75 45 35 5 5 35 5 15 45 77 77 25 5 5 20 45 Next, a heat-meltable ink layer having the composition shown in Table 8 below was formed on a polyester film having a back surface coated with a heat resistant slipping layer, and Comparative Example 2-1. 2-29 thermal transfer recording medium was prepared. In Table 8, each material is represented by the symbol shown in Tables 5 and 6. Further, the numbers in Table 8 represent the weight% of each material. Table 8

Comparative Example W-1 W-2 W-3 W-4 R-1 R-2 R-3 P-1 2-1 15 25 60 2 15 25 60 60 3 15 25 60 60 4 15 25 60 60 5 15 25 60 6 15 25 25 60 7 15 25 25 60 8 15 25 60 60 9 15 25 60 60 10 40 15 45 45 11 40 15 45 45 12 40 15 45 45 13 40 15 15 45 14 40 15 45 45 15 40 15 15 45 16 40 40 15 45 45 18 40 40 15 45 19 19 55 25 20 20 20 55 25 20 21 21 55 25 20 20 22 55 25 25 20 23 55 55 25 20 24 24 55 25 20 25 25 55 25 20 26 26 55 25 20 27 55 55 25 20 28 40 40 15 15 30 29 10 10 30 As described above, Examples 2-1 to 2-77 and Comparative Examples 2-1 to 2-
Twenty-nine heat-sensitive transfer recording media were cut into a length of 30 mm × 5 mm, and both ends were fixed on a slide glass with adhesive tape to prepare a sample for X-ray diffraction measurement. Using this, the diffraction intensity of the thermal transfer recording medium was measured by a thin film X-ray diffractometer (manufactured by JEOL Ltd.). The X-ray diffractometer used is
The angle of incidence of monochromatic X-rays on the sample surface is made smaller than in the case of ordinary θ-2θ measurement, the scattered X-rays from the base material are made smaller, and diffraction peaks that are normally buried in the background and cannot be discriminated. Can be measured. (Thin film measurement method) The measurement conditions are as follows. Target: Cu Voltage 50 kV Current 200 mA Firing incident angle: 0.1 °

By this method, Examples 2-1 to 2-77
And the thermal transfer recording media of Comparative Examples 2-1 to 2-29.
Then, the diffraction intensity was measured by thin film measurement. Diffraction obtained
Diffraction peak intensity I (c
ps; count / sec.) and incident angle 2θ at that time,
Halo strength of amorphous part I_o(Incident angle 16 to 17
°), intensity ratio I / I_oAbout Examples 2-1 to 2-77
The results are shown in Table 9, and the results of Comparative Examples 2-1 to 2-29 are shown in Table 1.
It shows in 0. Table 9 Example Incident angle (2θ) I (cps) I_o(cps) I / I_o  2-1 21.4 1465 1703 0.86 2 21.2 1478 1760 0.84 3 21.4 1101 1932 0.57 4 21.4 1489 1673 0.89 5 21.3 1367 1627 0.84 6 21. 0 1268 1838 0.69 7 21.1 1566 1956 0.80 8 21.2 1453 1863 0.78 9 21.4 1354 1934 0.70 10 21.4 1436 1651 0.87 11 21.4 1672 1990 90. 84 12 21.4 1252 1897 0.66 13 21.4 1741 1956 0.89 14 21.3 1655 1994 0.83 15 21.3 1423 1801 0.79 16 21.0 1462 1949 0.75 17 21.3 1353 1879 0.72 18 21. 1368 1927 0.71 19 21.3 1324 1697 0.78 20 21.1 1323 1890 0.70 21 21.2 1211 1922 0.63 22 21.5 1534 1918 0.80 23 21.0 1442 1803 0.80 24 21.1 1329 1927 0.69 25 21.4 1449 1882 0.77 26 21.4 1458 1846 0.79 27 21.5 1252 1869 0.67 28 21.3 1347 1952 0.69 29 21.2 1110 1947 0.57 30 21.1 1252 1869 0.63 31 21.0 1423 1923 0.74 32 21.4 1294 1961 0.66 33 21.3 1159 1964 0.59 34 21.2 1191 1985 0.60 35 21 2 1145 1877 0.61 36 21.3 1297 1936 0.67 37 21.3 1122 1700 0.66 38 21.2 1168 1980 0.59 39 21.2 1357 1967 0.69 40 21.2 1249 1810 0. 69 41 21.1 1032 1811 0.57 42 21.3 1145 1941 0.59 43 21.4 1086 1975 0.55 44 21.2 1223 1911 0.64 45 21.2 1122 1781 0.63 46 21.3 1045 1771 0.59 47 21.4 1145 1974 0.58 48 21.4 1355 1964 0.69 49 21.4 1012 1879 0.56 50 21.4 1257 1905 0.66 51 21.4 1455 1993 0.73 52 2 2 1221 1878 0.65 53 21.2 1592 1990 0.80 54 21.2 1697 1928 0.88 55 21.2 1320 1886 0.70 56 21.3 1604 1933 0.83 57 21.3 1509 1818 0. .83 58 21.1 1431 1988 0.72 59 21.3 1530 1937 0.79 60 21.2 1761 2096 0.84 61 21.0 1541 1857 0.83 62 21.1 1523 1928 0.79 63 21. 4 1139 1651 0.69 64 21.4 1333 1877 0.71 65 21.3 1624 1957 0.83 66 21.3 1430 1857 0.77 67 21.3 1029 1744 0.59 68 21.4 1199 1966 0. 61 69 1.1 1255 1992 0.63 70 21.2 1453 1964 0.74 71 21.2 1561 2001 0.78 72 21.4 1176 1704 0.69 73 21.1 1468 1906 0.77 74 21.4 1200 1700 0.71 75 21.4 885 1244 0.71 76 21.3 1195 1709 0.70 77 21.3 729 1266 0.58 Table 10 Comparative Example Incident Angle (2θ) I (cps) I_o(cps) I / I_o  2-1 21.3 1763 1712 1.03 2 21.2 1934 1727 1.12 3 21.2 1972 1826 1.08 4 21.2 1835 1748 1.05 5 21.3 1769 1608 1.10 6 21. 4 1888 1869 1.07 21.2 1902 1598 1.19 8 21.2 2134 2013 1.06 9 21.3 2374 2219 1.07 10 21.2 1965 1638 1.20 11 21.3 2540 2209 1. 15 12 21.4 2239 1736 1.29 13 21.3 2341 2251 1.04 14 21.3 1968 1587 1.24 15 21.2 2546 2005 1.27 16 21.3 2041 1759 1.16 17 21.2 2328 2116 1.10 18 21. 1911 1874 1.02 19 21.3 2544 1884 1.35 20 21.3 2419 1634 1.48 21 21.3 2312 1806 1.28 22 21.2 2100 1533 1.37 23 21.3 2344 1639 1.43 24 21.4 2320 1706 1.36 25 21.3 2178 1756 1.24 26 21.3 2199 1653 1.33 27 21.3 2308 1592 1.45 28 21.4 2208 1768 1.25 29 21.4 1963 1810 1.09

The thermal transfer recording media of Examples 2-1 to 2-77 and Comparative Examples 2-1 to 2-29 are mounted on a thermal transfer printer (Personal word processor JW-95HP manufactured by Toshiba, printing speed: 70 / ANK 105). Then, each time printing was performed, the ribbon was rewound and printing was repeated 5 times so that the Chinese character and the solid black pattern could be printed at the same location on the thermal transfer dedicated paper (Beck smoothness 400 seconds). Using the black solid pattern of the obtained transferred image, the reflection image densities of the first and third printings were measured by Macbeth reflection densitometer RD918.

Next, in Example 2 at 35 ° C. and 80% environment.
Repeat the thermal transfer recording media of -1 to 2-77 and Comparative Examples 2-1 to 2-29 using the thermal transfer printer 1
Printing was run 0 times. First, the high-temperature running property of the thermal transfer recording medium was examined during printing running, and the occurrence of running troubles such as sticking and bending of the thermal transfer recording medium was evaluated.
The obtained transfer print was visually evaluated for the presence of trailing stains at the end of the print and fog stains on the entire print. Further, with respect to the obtained transfer printing, the presence or absence of occurrence of reverse transfer was visually evaluated. The results of Examples 2-1 to 2-77 are shown in Table 11 for the results of the reflection image density, print stain, reverse transfer, and high temperature running property of the first and third printings.
Table 12 shows the results of Comparative Examples 2-1 to 2-29. Table 11 Examples Image density Print stain Reverse transfer Reverse transfer trouble 1st time 3rd time 2-1 1.2 1.0 No No No 2 1.3 1.0 No No No 3 1.3 1.0 No No No 4 1 .3 1.0 No No No 5 1.2 1.0 No No No 6 1.3 1.0 No No No 7 1.2 1.0 No No No 8 1.3 1.0 No No No 9 1 .3 1.0 No No No 10 1.3 1.0 No No No No 11 1.3 1.0 No No No 12 1.3 1.0 No No No 13 1.3 1.0 No No No 14 1 3 1.0 No No No 15 1.2 1.0 No No No 16 1.2 1.0 No No No 17 1.3 1.0 No No No 18 1.2 1.0 No No No 19 1 2.2 1.0 No No No 20 1.3 1.0 No No No No 21 1.3 1.0 No No No 22 1.3 1.0 No No No 23 1.3 1.0 No No No 24 1 .3 1.0 No No 25 1.2 1.0 No No No 26 1.3 1.0 No No No No 27 1.2 1.0 No No No 28 1.3 1.0 No No No No 29 1.3 1.0 No No No 30 1.3 1.0 No No No No 31 1.2 1.0 No No No No 32 1.3 1.0 No No No 33 1.3 1.0 No No No No 34 1.3 1.0 No No No 35 1.3 1.0 No No No 36 36 1.0 1.0 No No No 37 1.3 1.0 1.0 No No No 38 1.3 1.0 No No No 39 1.3 1.3 1.0 No No No 40 1.3 1.0 No No No 41 1.3 1.0 1.0 No No No 42 1.3 1.0 No No No 43 1.3 1.0 No No No No 44 1.3 1.0 No None None 45 1.3 1.0 None None None 46 1.3 1.0 None None None 47 1.3 1.0 None None None 48 1.3 1.0 None None None 49 1.3 1.0 None None None 50 1. 1.0 No No No 51 1.3 1.0 No No No 52 1.3 1.0 No No No 53 1.3 1.0 No No No 54 1.3 1.0 No No No 55 1.3 1.0 No No No 56 1.3 1.0 No No No 57 1.3 1.0 1.0 No No No 58 1.2 1.0 No No No 59 1.2 1.0 No No No 60 1.3 1.0 No No No 61 1.3 1.0 No No No 62 1.2 1.0 No No No 63 1.3 1.0 No No No 64 1.3 1.0 No No No 65 1.3 1.0 No No No 66 1.2 1.0 No No No 67 1.3 1.0 1.0 No No No 68 1.3 1.0 No No No 69 1.3 1.0 1.0 No No No 70 1.3 1.0 No No No 71 1.3 1.0 No No No 72 1.3 1.0 No No No 73 1.3 1.0 No No No 74 1.3 1.0 No No No 75 1.3 1.0 No No No 76 1.3 1.0 No No No 77 1.2 1.0 No No No Table 12 Comparative Example Image Density Print Dirt Reverse Soil Reverse Trouble 1st 3rd 2-1 0.3 0.3 Yes No No 20 2 0.1 Yes No No 3 0.2 0.1 Yes Yes Yes 4 0.4 0.2 Yes Yes Yes No 5 0.3 0.3 Yes Yes No 6 0.3 0.1 Yes Yes Yes Yes 7 0 2 0.2 Yes Yes Yes Yes 8 0.3 0.3 Yes Yes Yes 9 0.1 0.1 Yes Yes Yes 10 1.2 0.9 Yes No No 11 1.1 1.0 1.0 Yes No No 120 1.9 1.0 Yes No No 13 1.2 1.0 Yes No No 14 0.9 0.7 Yes No No 15 1.3 1.0 Yes No No 16 1.2 0.9 Yes No No 17 1 0.0 0.8 Yes No No 18 1.3 1.0 Yes No No 19 1.4 0.6 Yes No No 20 1.5 0.7 Yes No No 21 1.3 1.0 Yes No No 22 1 .6 0.8 No No 23 1.4 0.7 Yes No No 24 1.4 0.9 Yes No No 25 1.5 1.0 Yes No No 26 1.4 0.9 Yes No No 27 1.3 0.9 Yes No No 28 1.3 1.0 Yes No No 29 1.4 0.8 Yes No No No

Further, the thermal transfer recording media of Examples 2-1 to 2-77 and Comparative examples 2-1 to 2-29 were cut into 1 cm square pieces to obtain DSC measurement samples. 5 ℃ /
DSC measurement was performed at a temperature rising rate of min. A typical example of the obtained endothermic peak curve is shown in FIG.

A straight line (indicated by a dotted line in FIG. 1) connecting two inflection points was drawn on the DSC curve obtained as shown in FIG. 1 to obtain temperatures at two intersections of the straight line and the DSC curve. .. Of these, the temperature on the low temperature side is ta and the temperature on the high temperature side is tb. The temperature of the endothermic peak of the DSC curve is tp. When there are two or more peaks which are considered to be endothermic peaks as shown in the DSC curve 2 in FIG. 1, one having the largest peak size is selected and the temperature of the peak is set to tp. And Therefore, Example 1
.About.77 and Comparative Examples 1 to 29, the respective temperatures ta, tp, and tb were measured from the DSC curves. The results are shown in Tables 13 and 14. Table 13 Examples ta (° C.) tp (° C.) tb (° C.) 2-1 53 74 91 91 2 46 75 75 87 3 49 73 73 82 4 50 50 68 79 5 53 53 61 84 6 6 42 62 85 7 7 52 80 93 9 8 59 81 90 9 54 81 93 103 10 58 76 92 92 11 46 78 78 87 12 53 53 74 94 13 43 43 67 91 91 14 44 62 62 82 15 46 46 63 81 16 54 54 82 92 17 17 56 84 96 96 18 52 83 83 98 19 49 73 73 93 20 21 48 48 70 97 71 97 22 22 40 64 64 94 23 42 68 68 97 24 41 70 99 25 25 53 80 101 26 26 57 81 97 97 27 59 59 82 99 28 40 40 77 107 107 29 49 79 79 103 30 54 76 76 102 31 31 38 60 60 86 32 36 36 62 84 90 34 59 5 100 35 61 85 85 99 36 56 56 82 109 109 37 50 79 79 101 38 38 59 80 102 39 39 61 82 109 109 40 57 81 81 110 41 60 83 83 104 42 51 51 79 99 43 43 52 79 94 44 44 47 73 73 102 45 51 74 72 93 47 54 84 113 113 48 53 81 81 110 49 55 81 81 106 50 52 77 77 103 51 46 74 100 100 52 52 76 76 105 53 50 50 76 106 54 54 41 70 70 99 55 55 39 68 90 90 56 42 69 69 97 57 57 38 66 91 58 53 57 101 101 84 110 60 56 56 80 104 61 59 59 82 111 62 52 52 78 99 63 63 49 79 107 64 64 51 76 105 105 65 52 52 79 101 101 66 43 43 70 92 67 67 45 71 9 68 40 69 69 98 69 43 43 71 93 70 70 52 80 109 71 71 60 84 114 114 72 56 85 85 112 73 59 59 85 110 74 74 48 74 80 75 75 54 80 107 76 76 58 83 110 110 77 57 82 111 Table 14 Example ta (° C.) tp ( C) tb (C) 2-1 31 77 103 2 2 29 79 98 3 3 35 74 74 110 4 36 62 62 100 5 28 60 60 94 6 31 31 64 99 7 48 82 82 109 8 54 81 81 112 9 50 85 111 111 10 47 74 109 109 11 38 77 108 12 39 39 73 102 13 13 31 64 92 14 30 30 64 90 15 34 34 62 89 16 39 39 80 106 106 17 43 82 82 111 18 30 81 108 19 19 36 70 99 99 20 39 71 71 103 21 32 32 69 112 112 22 34 6 95 23 35 63 91 24 31 59 89 25 40 79 108 26 43 77 99 27 51 80 116 28 30 74 102 29 38 75 107

From the results shown in Table 9, the heat-sensitive transfer recording medium of the present invention has a diffraction peak intensity ratio I / I _o of 0.9 or less, and the ethylene-based low melting point crystalline material has extremely low crystallinity and high sensitivity. Yes, it is possible to support high-speed printing. Regarding this, the results of Tables 8 and 10, that is, the thermal transfer recording medium of the present invention obtained an image density of 1.0 or more even at the third printing, and print stains, reverse transfer, running troubles, etc. occurred. The thermal transfer recording medium of the present invention is sufficiently compatible with high-speed printing because it has not been melted and melting is completed within a temperature range of ± 30 ° C. around the melting point and the melting characteristics are sharp. Recognize. 2 to 9 show some examples of the present invention and comparative examples.
Graph or X showing the relationship between the complex elastic modulus and temperature
The line diffraction measurement result is shown. 2 and 3 show the first embodiment, respectively.
5 is a graph showing the relationship between complex elastic modulus and temperature for Comparative Example 1-5. 4 to 9 show the second embodiment.
-74 to 2-77, and Comparative Examples 2-28 and 2-2
9 is a graph showing the relationship between the complex elastic modulus and temperature for Sample No. 9.

The thermal transfer recording medium as described above is
It is generally used as an ink ribbon and is housed in a cassette case to form an ink ribbon cassette.

[0068]

EFFECTS OF THE INVENTION According to the present invention, a printer capable of high-speed printing has good transferability for printing a plurality of times, both print quality and image density are satisfied, and the surface of the recording medium to be transferred is not contaminated. It is possible to obtain a heat-sensitive transfer recording medium having stable transferability and printing runnability. Further, it is possible to provide a thermal transfer recording medium capable of forming a good transferred image by high-speed printing without lowering the resolution from a medium having a high surface smoothness to a medium having a low surface smoothness.

[Brief description of drawings]

FIG. 1 is a graph showing an endothermic peak curve obtained by DSC measurement of an example of a thermal transfer recording medium of the present invention.

FIG. 2 is a graph showing the relationship between temperature and complex elastic modulus at a frequency of 3 Hz of the heat-meltable ink layer according to Example 1-5.

FIG. 3 is a graph showing the relationship between temperature and complex elastic modulus at a frequency of 3 Hz of the heat-meltable ink layer according to Comparative Example 1-5.

FIG. 4 is a graph showing an X-ray diffraction result by a thin film method at an incident angle of 0.1 ° of the heat-meltable ink layer according to Example 2-74.

FIG. 5 is a graph showing an X-ray diffraction result by the thin film method at an incident angle of 0.1 ° of the heat-meltable ink layer according to Example 2-75.

FIG. 6 is a graph showing an X-ray diffraction result by a thin film method at an incident angle of 0.1 ° of the heat-meltable ink layer according to Example 2-76.

FIG. 7 is a graph showing an X-ray diffraction result by a thin film method at an incident angle of 0.1 ° of the heat-meltable ink layer according to Example 2-77.

FIG. 8 is a graph showing an X-ray diffraction result by a thin-film method at an incident angle of 0.1 ° of the heat-meltable ink layer according to Comparative Example 2-28.

FIG. 9 is a graph showing an X-ray diffraction result by a thin film method at an incident angle of 0.1 ° of the heat-meltable ink layer according to Comparative Example 2-29.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Noriaki Sato 8 Shinsugita-cho, Isogo-ku, Yokohama-shi, Kanagawa Stock company, Toshiba Yokohama Works (72) Inventor Tadayuki Nakamura 8 Shinsugita-cho, Isogo-ku, Yokohama, Kanagawa Company Toshiba Yokohama Office

Claims (5)

[Claims] 1. A sheet-shaped base material, and a heat-meltable ink layer which is provided on the base material, contains a colorant and a heat-meltable material, and is selectively heat-melted and transferred to a non-transfer medium. And a melting point Tm of 70 to 90 ° C.,
Complex elastic modulus at 100 ° C is 10 ⁶ Pa to 10 ⁷ P
a, a thermal transfer recording medium having a pour point Tp of 150 ° C. or higher. 2. A sheet-shaped base material, which is provided on the base material and contains a colorant, an ethylene-based low melting point crystal material, and an ethylene-based resin material, and is selectively heated and melted and transferred to a non-transfer medium. A heat-meltable ink layer, wherein the heat-meltable ink layer is in an amorphous or microcrystalline state, and is 21.3 to 2 derived from ethylene-based crystals measured by an X-ray diffraction method.
When the diffraction peak intensity at 1.5 ° is I and the halo intensity at 16 to 17 ° derived from the amorphous portion is I ₀ , the relation expressed by the following formula I / I ₀ ≦ 0.9 must be satisfied. A thermal transfer recording medium characterized by: 3. A sheet-shaped base material, a coloring agent of 30 to 50% by weight and an acid value of 5 to 40 mgK provided on the base material.
OH / g, a low melting point crystalline material having a saponification value of 10 to 100 mgKOH / g, and a heat-meltable ink layer containing 15 to 30% by weight of an ethylene resin material containing a copolymer resin of ethylene and a monomer having a carbonyl group. Wherein the ethylene-based resin material has an ethylene content of 65 to 80% by weight and a melt index of 60 or less. 4. The thermal transfer recording medium according to claim 1, wherein the thermal transfer recording medium is a multi-time thermal transfer recording medium that can be used a plurality of times. 5. An ink ribbon cassette comprising a cassette case and an ink ribbon which is provided in the cassette case and which substantially consists of the heat-sensitive transfer recording medium according to any one of claims 1 to 3.