JPH0725228B2 - Thermal transfer material and thermal transfer recording method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention is a heat-sensitive transfer material used for heat-sensitive transfer recording, on a recording medium having low surface smoothness, recording of good print quality and capable of lift-off erasing. The present invention relates to a heat-sensitive transfer material capable of obtaining an image and a heat-sensitive transfer recording method.

[Conventional technology]

In thermal transfer recording, the equipment used is light and compact, there is no noise, and it has excellent operability and maintainability. In addition to the general characteristics of thermal recording, coloring type processed paper is not required, and the durability of the recorded image is high. It is also widely used recently. However, even in such a thermal transfer recording method, there are still some points to be improved.

The first point is that the quality of the transferred and recorded image on the recording medium such as paper having poor surface smoothness is poor. The second point is that the transfer-recorded image obtained by the thermal transfer recording method cannot be easily erased even if it is due to erroneous printing.

As a general erasing means for erroneous recording, there is the use of a hiding paint which has recently been used in recent years, and even in the thermal transfer recording method, it contains a hiding colorant having almost the same color as the color of the recording medium. A method of using a heat-sensitive transfer material having a heat-transferable ink layer and coating an erroneous recording portion with this transfer ink layer has already been proposed. However, in the method of coating with the transfer ink layer, the color of the recording medium and the hiding colorant are not completely the same, and the erased portion rises due to the coating of the ink layer, which makes it easy to distinguish the erased portion and is preferable in appearance. Not a thing. As another erasing means, there has been proposed a method of peeling off an erroneously recorded image formed on a recording medium with a heat-sensitive adhesive tape, that is, a lift-off erasing method.

However, these erasing methods require both a heat-sensitive transfer material that gives a transfer-recorded image on a recording medium and an erasing sheet for erasing the transfer-recorded image, and a tape for printing and erasing in a heat-sensitive transfer printer. However, there is a drawback in that the structure of the printer is complicated and the printer becomes large in size.

As a method for improving the above-mentioned drawbacks, a thermal transfer material has been proposed which is capable of performing lift-off erasing (self-correctable) by using a thermal transfer material which gives a transferred and recorded image on a recording paper as it is. JP-A-58-74368 discloses a heat-sensitive laminate capable of both recording and erasing with an active layer on a resistive support. That is, this active layer is configured to develop an adhesive force when it is heated to a temperature lower than the heating temperature during recording, and to be erased by peeling the transferred recorded image. Further, JP-A-61-23992 proposes a thermal transfer agent comprising a colorant, a binder agent and a heat-adhesive material having a softening point higher than that of the binder agent on a support, and a thermal transfer agent as a heat source. It is disclosed that recording is performed with low thermal energy using a head, and thermal energy higher than that during recording is applied to remove and erase an erroneously recorded image.

[Problems to be solved by the invention]

However, a heat-sensitive transfer material which gives a transfer-recorded image with good recording quality even on a recording medium having a low surface smoothness and which also satisfies the self-correction effect has not been obtained, and its development is desired. According to the conventional self-collectable heat-sensitive transfer material, particularly in a recording medium having low smoothness, only the erroneous recording image on the convex portion of the recording medium can be peeled off, and the recording image in the concave portion cannot be peeled off. In many cases, erasure was incomplete.

Further, JP-A-62-156993 discloses a self-collectable thermal transfer material having a support with a separation layer having a relatively low melt viscosity. It is necessary that the material used for this separation layer does not deteriorate upon storage and has a low melt viscosity.However, such a material generally tends to be hard and brittle, and when the lift-off is erased, the material is removed from the support. Defects such as peeling off of the entire ink layer are likely to occur. Therefore, there are drawbacks that the use conditions such as applied energy are limited and the erasing is likely to be incomplete. In order to eliminate this, it is unavoidable to use a component having a relatively high viscosity in the separation layer, which requires a large force for separation from the support at the time of recording, and the recording surface with low surface smoothness is required. A recorded image with many defects is likely to be formed on the body.

The present invention solves the above-mentioned drawbacks of the prior art, and not only for a recording medium having a good surface smoothness, but also for a recording medium having a low surface smoothness, the density is high, and the print cutout is good. ,
Moreover, it is an object of the present invention to provide a heat-sensitive transfer material capable of obtaining a transfer-recorded image free from transfer defects and further erasing the transfer-recorded image by lift-off, and a heat-sensitive transfer recording method using the heat-sensitive transfer material.

[Means for solving problems]

The heat-sensitive transfer material of the present invention has at least a first ink layer, a second ink layer and a third ink layer on a support in this order from the support side, and the first ink layer has a glass transition temperature. Is a substantially non-transferable layer containing a thermoplastic resin of −40 to 30 ° C., and when the second ink layer is heated for recording, the second ink layer is divided within the second ink layer. The third ink layer is a layer containing a thermoplastic resin as a main component, and at least the third ink layer contains a colorant.

Further, the heat-sensitive transfer recording method of the present invention has at least a first ink layer, a second ink layer and a third ink layer on a support in order from the support side, and the first ink layer is a glass. A substantially non-transferable layer containing a thermoplastic resin having a transition temperature of −40 to 30 ° C., the third ink layer is a layer containing a thermoplastic resin as a main component, and at least the third ink layer is colored. When performing transfer recording on a recording medium using a heat-sensitive transfer material containing an agent, the heat-sensitive transfer is performed immediately after the heat-sensitive transfer material is heated in a pattern and before the strength of the second ink layer becomes sufficiently strong. By peeling the material from the recording medium, the material is divided inside the second ink layer to form a recording image on the recording medium, and the thermal transfer material is brought into contact with the recording image to heat the recording image. When the strength of the second ink layer becomes sufficiently strong, the heat-sensitive material is removed from the recording medium. By peeling the transfer material, the recorded image on the recording material is peeled off from the recording material to the heat-sensitive transfer material side.

Hereinafter, an example of the present invention will be described in detail with reference to the drawings as necessary. In the following description, “%” and “part” representing the quantitative ratio are based on weight unless otherwise specified.

As shown in FIG. 1, the thermal transfer material 1 of the present invention comprises a support 2
A first ink layer 3, a second ink layer 4, and a third ink layer 5 are laminated in this order from the support side. The first ink layer 3 is firmly adhered to the support 2 without being divided even at the time of recording by heating or at the interface with the support 2 or inside thereof. That is, the first ink layer 3 is not completely melted even if it is softened by heating, the adhesiveness with the support 1 is not reduced, and the first ink layer 3 is not substantially transferred to the recording material side, that is, substantially non-transferability. Layers. The second ink layer 4 is divided inside the ink layer 4 during recording by heating,
The ink layer 5 is easily transferred to the recording medium. However, since the non-heated portion of the second ink layer 4 is not melted or softened, it is firmly adhered to the first ink layer 3 and the third ink 5, and the ink layer 5 is transferred to the recording medium. Suppress. The contrast between the heated portion and the non-heated portion has a great influence particularly on the “cut” of the transferred recording image.

The thermal transfer material 1 of the present invention is peeled off from the recording medium immediately after being heated in a pattern and before the strength of the second ink layer 4 becomes sufficiently strong, whereby the second ink A recording image is formed on the recording medium by being divided by the layer 4, and after the thermal transfer material 1 is brought into contact with the recording image on the recording medium and heated, the strength of the second ink layer 4 becomes sufficiently strong. At this time, the heat-sensitive transfer material 1 is peeled off from the recording medium so that the recorded image on the recording medium is peeled off.

In the present invention, the first ink layer 3 provided between the support 2 and the second ink layer 4 is a layer formed by coating, and this layer provides adhesion between the support 2 and the entire ink layer. It improves and enables lift-off erasure. This is because the support film 2 used for the heat-sensitive transfer material is generally made of a plastic film, and the plastic film is used so as to satisfy various properties such as heat resistance, tensile strength, elongation, and tear strength. Since the film is subjected to a uniaxial or biaxial stretching treatment, the molecular chains of the film are oriented in a fixed direction. As a result, the above various properties of the plastic film are improved, and other properties may be deteriorated even if they reach a satisfactory level. For example, the surface adhesiveness may be reduced. For example, when the polyester film has poor adhesiveness, has a sharp melt property such as the second ink layer 4, and has a component mainly composed of a material having a low melt viscosity as an ink layer on the polyester film,
Defects such as ink peeling are very likely to occur. Therefore, if a conventional thermal transfer material having no lift-off erasing function is used for lift-off erasing, the erroneously recorded image cannot be peeled off to the thermal transfer material side, and peeling occurs at the interface between the support and the ink layer. "Reverse transfer" occurs in which the ink layer of the thermal transfer material is peeled off on the recording material side. In this respect, the heat-sensitive transfer material of the present invention can be formed by forming an ink layer by coating like a first ink layer on a support such as a plastic film.
Since the molecular chains in the coating film are randomly present, the adhesiveness between the second ink layer and the support 2 is improved, and ink peeling can be avoided.

In particular, by using a material having a low glass transition temperature as the main component of the first ink layer, the flexibility of the first ink layer is improved and the first ink layer is prevented from peeling from the support, Reverse transfer does not occur even if lift-off erasing is performed. Further, by providing the first ink layer 3 with flexibility, the third ink layer 5 can follow the unevenness of the erroneously recorded image well and sufficiently contact when the erroneously recorded image is peeled and erased. Very preferable.

The first ink layer 3 is configured to contain a thermoplastic resin so that the first ink layer 3 has a high cohesive force when heated and a high adhesive force to the support. The thermoplastic resin contained in the first ink layer 3 has a glass transition temperature of −40 ° C. to 30 ° C., and further −30 ° C.
It is preferably from 15 to 15 ° C, particularly from -18 to 15 ° C. When the thermoplastic resin is a mixture of a plurality of thermoplastic resins, the glass transition temperature Tg _M of such a mixture of thermoplastic resins, When defined as, Tg _M is also preferably within the above temperature range.
That is, even when the thermoplastic resin is a mixture of a plurality of kinds of resins, if the glass transition temperature of the mixture is defined as in the above formula (A), the mixture of the thermoplastic resins is composed of a single resin. Can be considered as a thermoplastic resin.
In the above formula (A), Tgn is the glass transition temperature of one thermoplastic resin that constitutes the thermoplastic resin mixture, W is the total weight of the thermoplastic resin mixture, and wn is the thermoplastic resin mixture 1 The weight of two thermoplastics. If the glass transition temperature of the thermoplastic resin is too high, the flexibility is lost and the adhesion with the support is lowered. On the other hand, if the glass transition temperature is too low, the tackiness will be excessive and the handling during production will be hindered.

In order to further increase the cohesive force of the first ink layer 3, the first
The weight average molecular weight of the thermoplastic resin contained in the ink layer 3 is preferably 10,000 or more, more preferably 50,000 or more.
The weight average molecular weight referred to here is a value measured by GPC (gel permeation chromatography). When the thermoplastic resin is a mixture of a plurality of resins, the weight average molecular weight means the weight average molecular weight of the whole mixture.

Examples of the thermoplastic resin used in the first ink layer 3 include polyvinyl acetate resin such as vinyl acetate-ethylene copolymer, epoxy resin, polyurethane resin, acrylic resin, polyester resin, styrene-butadiene rubber. Elastomers such as isoprene rubber can be used. Among them, vinyl acetate-ethylene copolymer, polyurethane resin, acrylic resin, polyester resin can be preferably used. Further, petroleum-based resin, phenol-based resin, melamine-based resin, urea-based resin, polystyrene-based resin may be appropriately mixed and used. Further, if necessary, a filler such as titanium oxide, clay, zinc white, or alumina hydrate, a plasticizer, a stabilizer and the like may be appropriately mixed and used in the above materials.

The first ink layer 3 can be obtained by appropriately adjusting the molecular weight and crystallinity of the above materials, or by mixing a plurality of the materials.

The content of the thermoplastic resin in the first ink layer 3 is 70%
It is preferably 100% or more and 90% or more and 100% or less.

The first ink layer 3 may be completely melted as long as it does not prevent the second ink layer from dividing during recording. The viscosity at the time of melting, particularly at 150 ° C., may be 5000 cps or more, preferably 10,000 cps or more.

The second ink layer 4 is preferably one that undergoes a rapid melt by heating. The first ink layer 3 and the third ink layer 4 have a high cohesive force when heated and further contain a relatively large amount of a thermoplastic resin. Therefore, it is preferable that the second ink layer 4 has a melting point of 50 ° C. or higher and a melt viscosity at 150 ° C. of 500 cps or lower in view of the requirement for the sharp melt property. Second
The following materials are preferable as the material forming the ink layer 4, and waxes are particularly preferable.

Examples of the above-mentioned waxes include natural waxes such as carnauba waxes, candelilla waxes, rice waxes, wood waxes and other plant waxes, ceresin waxes, montan waxes and other mineral waxes, and derivatives thereof.
For example, examples of derivatives of Montan wax include acid wax, ester wax, and partially saponified ester wax. In addition, petroleum wax includes paraffin wax and microcrystalline wax. As the synthetic wax, polyethylene wax, especially low molecular weight polyethylene oxide, Fisher Tropsch wax can be used. The waxes are contained in the second ink layer 4 in an amount of 80% or more, more preferably 90% or more, and are prepared individually or in a mixture so as to satisfy the melting point and the melt viscosity.

The melt viscosity of the second ink layer 4 is 200, especially at 150 ° C.
It is preferably cps or less, more preferably 100 cps or less. Carnauba wax and paraffin wax are very suitable in the above conditions and sharp melt characteristics. The carnauba wax and paraffin wax are used as the second ink layer 4
The above characteristics can be sufficiently satisfied even by containing 40% or more, and further 50% or more with respect to the total wax contained in the above.

The melt viscosity referred to in the present invention is measured by using a Rotovisco RV12 rotational viscometer manufactured by Haake, West Germany. The cone type of this rotational viscometer was PKI 0.3 ° (diameter 28 mm, stainless steel).

In addition, if necessary, fillers such as titanium oxide, clay, zinc oxide, and alumina hydrate, plasticizers,
The second ink layer 4 by appropriately mixing a surfactant, a stabilizer and the like.
Can also be

The third ink layer 5 has a function of giving a transfer image capable of lift-off erasing even to a recording medium having low smoothness.
The third ink layer 5 is formed of a heat-meltable material as a main component,
In addition to the heat-melting material, if necessary, it is composed of a colorant, a dispersant, a plasticizer, an oil agent, a filler and the like.

By using a thermoplastic resin as the thermofusible material forming the third ink layer 5, the ink layer bridges the convex portions and the convex portions on the surface of the recording medium even for the recording medium having low smoothness. Since the transfer is carried out in a crosswise manner, a transfer recorded image having no transfer defects and no character breakage and excellent scratch resistance can be obtained. The thermoplastic resin is contained in the third ink layer 5 in an amount of 50% or more, preferably 70% or more. It is desirable that the cohesive force and molecular weight of the thermoplastic resin are high in order to obtain good transferability to a recording medium having a low surface smoothness.

The melt viscosity of the third ink layer at 150 ℃ is 600 cps in order to obtain good transferability to the recording material with low surface smoothness.
More preferably, it is 1000 cps or more, especially 5000 cps. In addition, the differential scanning calorimeter (DS
C) (Hereinafter, in the present invention, the melting point is the temperature of the endothermic peak measured by DSC (model: Perkin-Elmer Seven series thermal analysis system) at a heating rate of 5 ° C / min). Although not limited, 50 ° C to 200 ° C, and 70 ° C to 150
It is desirable that the temperature is ℃ or less. Regarding the melting point, if it exceeds 200 ° C, it is not preferable because the kind of the support is remarkably limited or the durability of the thermal head is deteriorated due to the problem of heat resistance to the support. The use of the heat-meltable material is not preferable because stains and the like are likely to occur.

Examples of the heat-meltable material contained in the third ink layer 5 include polyolefin resin, polyamide resin, polyester resin, epoxy resin, polyurethane resin, polyacrylic resin, polyvinyl chloride resin, cellulose resin. , Polyvinyl alcohol resin, petroleum resin, phenol resin, polystyrene resin, vinyl acetate resin,
Natural rubber, styrene butadiene rubber, isoprene rubber,
Elastomers such as chloroprene rubber, polyisobutylene, polybutene, etc. are preferably used. Among them, polymer materials containing olefin as a main component, such as ethylene-
Vinyl acetate copolymer, vinyl acetate-ethylene copolymer,
50% or more based on the heat-meltable material containing ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid ester copolymer, etc., polyamide, polyester etc. in the third ink layer It is preferably used. In addition, in some cases, natural waxes such as whale wax, beeswax, lanolin, carnauba wax, kiyandelilla wax, montan wax, ceresin wax, paraffin wax, microcrystalline wax, and oxidized wax other than resin. , Synthetic waxes such as Esterwax and Fisher Tropschwax, higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, higher alcohols such as stearyl alcohol and behenyl alcohol, fatty acid esters of sucrose, Esters such as fatty acid esters of sorbitan, amides such as oleylamide, or plasticizers and oil agents such as mineral oil and vegetable oil are appropriately mixed, and the melting point of the third ink layer 5 is adjusted to 50 ° C. or higher and 200 ° C. or lower and used. It is preferable.

As the colorant, various dyes and pigments widely used in the field of print recording are used. At least a third colorant
It is contained in the ink layer 5. Colorant content is 1st, 2nd,
A range of 3 to 60% is suitable for the entire third ink layer. In particular, it is preferable that the third ink layer 5 contains a colorant in an amount of 3 to 80%, more preferably 5 to 60%, based on the third ink layer 5. Further, if necessary, an additive such as a dispersant or a filler made of metal fine powder, inorganic fine powder, metal oxide or the like may be appropriately added to the third ink layer 5.

Specifically showing the colorant used in the recording medium of the present invention,
For example, carbon black, Nigrosine dye, lamp black, Sudan Black SM, Farst Yellow G, Benzidine Yellow, Pigment Yellow, Indian Farst Orange, Irgadine Red, Paranitroaniline Red, Toluidine Red, Carmin FB , Permanent Bordeaux FRR, Pigment Orange R, Resor
Red 2G, Rake Red C, Rhodamine FB, Rhodamine B
Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green
B, Phthalocyanine Green, Oil Yellow GG, Zabon Farst Yellow CGG, Kayaset Y963, Kayaset YG,
Sumiplast Yellow GG, Zabon Farst Orange R
R, Oil Scarlett, Sumiplast Orange G, Orazol Brown G, Zabonghurst Scarlett CG,
One or more known dyes / pigments such as Eisenspiron Red BEH, Oil Pink OP, Victoria Blue F4R, Farstogen Blue 5007, Sudan Blue, and Oil Pekotsk Blue can be used.

The layer structure of the third ink layer 5 is not particularly limited to a single layer structure containing the above-mentioned heat-melting material, colorant, dispersant, plasticizer, filler, etc., and when heated by a thermal head. In addition, the function may be further separated into two layers of a layer having a function of expressing an adhesive force to a recording medium and a layer having a coloring function, or may have a layer structure of three or more layers.

As shown in FIG. 2, when the third ink layer 5 has a two-layer structure (the first ink layer, the second ink layer, the third ink layer, and the fourth ink layer are arranged in this order from the support side). ), The third ink layer 51 has a coloring function, and the fourth ink layer 52 has a function of adhering to the paper of the heat application section. Further, both the third ink layer 51 and the fourth ink layer 52 have appropriate film strength as in the third ink layer 5 shown in FIG. Transfer so as to bridge between the convex parts of. As the material forming the third ink layer 51 and the fourth ink layer 52, the material of the third ink layer 5 previously fried can be used as it is. It is preferable that the third ink layer 51 and the fourth ink layer 52 each contain a thermoplastic resin in an amount of 50% or more, further 70% or more with respect to each layer.

The melt viscosity of the third ink layer 51 and the fourth ink layer 52 at 150 ° C. is also 600 cps or more, more preferably 1000 cps or more, and particularly preferably 5000 cps, as in the case of the third ink layer 5 shown in FIG. .

When the third ink layer 5 has a two-layer structure, it is preferable that the colorant is contained only in the third ink layer 51, but it may be contained in the second ink layer 4 or the fourth ink layer 52. . The content of the colorant is preferably in the range of 3 to 60% with respect to the entire first, second, third and fourth ink layers. If it is less than 3%, the density is low, and if it is more than 60%, the transfer property is deteriorated. The third ink layer 51 preferably contains a colorant in an amount of 3 to 80%, more preferably 5 to 60%, relative to the third ink layer 5.

The third ink layer 51 and the fourth ink layer 52 can basically use the same material except for the content of the colorant,
The fourth ink layer 52 is made of a material having a large adhesive force with the recording medium,
For example, olefin homopolymers or copolymers such as polyethylene, polypropylene, polyisobutylene, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-ethyl acrylate copolymers or derivatives thereof, polyamides, polyesters. A single or two or more substances such as polyurethane or acrylic heat-sensitive adhesives and styrene block copolymers such as styrene-isobutylene, styrene-butadiene, styrene-ethylene-butylene and the like may be appropriately mixed. Further, tackifiers such as alicyclic hydrocarbons, terpenes and rosins, fillers such as talc and calcium carbonate, and stabilizers such as antioxidants may be added.

The thickness of the first ink layer 3 is preferably 0.5 μm or more in consideration of the conformability to a recording medium having low surface smoothness, and 10 μm or less, more preferably 5 μm or less in consideration of heat conduction.

The thicknesses of the second ink layer 4 and the third ink layer 5 are respectively
The range is preferably 0.5 to 10 μm, more preferably 0.5 to 5 μm, and the above range is preferable for each layer even when the third ink layer 5 is functionally separated into two or more layers. Further, the total thickness of the first, second and third ink layers is 2 to 20 μm, preferably 3 to 15 μm.
When the third ink layer is functionally separated into two or more layers, the total thickness of the ink layer is preferably 13 to 30 μm, more preferably 15 to 25 μm.

As the support 2, a conventionally known film can be used as it is, and for example, a plastic film having relatively good heat resistance such as polyester, polycarbonate, triacetyl cellulose, polyamide, or polyimide can be preferably used.

Further, when a thermal head is used as a means for applying heat to the thermal transfer material, on the surface of the support which comes into contact with the thermal head,
The heat resistance of the support can be improved by providing a heat resistance protective layer made of silicone resin, fluorine resin, polyimide resin, epoxy resin, phenol resin, melamine resin, nitrocellulose, etc., or it cannot be used conventionally. Support materials can also be used.

The thickness of the support 2 is preferably about 1 to 15 .mu. When considering a thermal head as a heat source at the time of thermal transfer, but for example, a heat source capable of selectively heating the thermal transfer ink layer such as laser light is used. There is no particular limitation in this case.

In order to obtain the heat-sensitive transfer material 1 of the present invention, first, the above-mentioned heat-melting material and, if necessary, a coloring agent and an additive are melt-kneaded by using a dispersing device such as an attritor or an appropriate method. It is kneaded with a solvent to obtain a heat-meltable or solution-form or dispersion-form coating ink. Next, the coating ink is applied onto the support 2 using an applicator, a mayer bar or the like, and dried if necessary to complete the thermal transfer material 1.

Next, a heat-sensitive transfer recording method using the heat-sensitive transfer material of the present invention will be described by taking the case of using the heat-sensitive transfer material 1 shown in FIG.

In FIG. 3, the thermal transfer material 1 has the third ink layer 5
The recording material 7 is brought into contact with the recording material 7, and thermal energy is applied in a pattern from the heating element 9 of the thermal recording head 8 from the support 2 side. Immediately after the application of this heat energy and before the strength of the second ink layer becomes sufficiently strong (preferably, 20 msec. Or less, more preferably 10 msec. Or less after the application of the energy).
Then, the thermal transfer material 1 is peeled off from the recording medium 7. The first ink layer 3 of the heat-sensitive transfer material 1 firmly adheres to the support 2 even when the thermal energy is applied, and does not transfer to the recording medium 7 side. However, the third ink layer 5 is the recording medium 7
Adhesive force is developed to the recording medium 7 and the film is transferred to the recording medium 7 with an appropriate film strength. Further, at this time, the heat application portion of the second ink layer 4 undergoes shear melting to become a semi-liquid state or a liquid state, the melt viscosity is lowered, and cohesive failure is very likely to occur.

However, since the non-heat application portion of the second ink layer 4 does not melt, the high cohesive force is maintained and the first ink layer 3 and the third ink layer 5 maintain strong adhesion. As a result, the contrast of the adhesive force between the heat-applied portion and the non-heat-applied portion becomes extremely clear, and the "cut" of the obtained transfer image 6 is improved. Moreover, the applied heat energy can be reduced due to the sharp melt property of the second ink layer 4.

Next, an erasing method using the thermal transfer material of the present invention will be described. In FIG. 4, a transfer recording image 6 is formed on the recording medium 7 by the heat-sensitive transfer material of the present invention. The transfer recording image 6 and the third ink layer 5 of the heat-sensitive transfer material 1 are brought into contact with each other, and heat is applied from the heating element 9 of the heat-sensitive recording head 8 from the support 2 side to an area which is the same as or larger than the transfer recording image 6. Energy is applied. As a result, the third ink layer 5 of the heat-sensitive transfer material 1 develops an adhesive force as in recording, and adheres to the transfer-recorded image 6 on the recording medium 7. At this time, the cohesive force of the second ink layer 4 of the thermal transfer material 1 is reduced, but
As shown in the figure, the peeling member 10 is projected to peel off the recording medium 7 and the thermal transfer material 1 from the strength of the second ink layer, that is, the adhesion between the first ink layer 3 and the third ink layer 5. After the force and the cohesive force of the second ink layer are recovered (preferably within 50 msec. Or more, more preferably 100 msec. Or more after application of the energy), the recording medium and the thermal transfer material 1 are peeled off. . At this time, the third ink layer 5 and the transfer recording image 6
The adhesive force between the transfer recording image 6 and the transfer recording image 6 is also increased by using the thermal transfer material 1.

Hereinafter, the present invention will be described more specifically by way of examples. still,
The weight ratios shown below are ratios of solids.

[Example 1] An emulsion (nonvolatile content 40%) using a vinyl acetate-ethylene copolymer resin (ethylene content 20%) having a glass transition temperature of 0 ° C and a weight average molecular weight of 779000 was applied on a polyethylene terephthalate film of 6 µm using an applicator. Coating, dry for 1 minute in hot air drying at 80 ℃,
A first ink layer having a thickness of 2.0 μm was obtained.

Next, an aqueous dispersion of the following Formulation 1 was diluted 2-fold on the first ink layer, coated with an applicator, and dried for 1 minute in hot air drying at 60 ° C. to a thickness of 1.5. μm
Second ink layer was provided. The melting point of this second ink layer was 80 ° C., and the melt viscosity at 150 ° C. was 20 cps.

The formulation of the above Formula 2 was uniformly mixed with a propeller stirrer to obtain a coating liquid 2. The coating liquid 2 is applied onto the second ink layer using an applicator and dried with hot air at 60 ° C. for 30 minutes to form a third ink layer having a thickness of 3.5 μm. ) Got.

[Example 2] The above formulations 3 and 4 were uniformly mixed with a propeller stirrer to obtain coating liquids 3 and 4. The coating liquid 3 was applied onto the second ink layer of Example 1 using an applicator, and the temperature was 60 ° C. 1
Hot air drying for 1 minute was performed to obtain a third ink layer having a layer thickness of 1.5 μm. Apply coating liquid 4 on it using an applicator and dry with hot air at 60 ° C for 1 minute to obtain a fourth layer with a layer thickness of 1.7 μm.
The ink transfer layer (II) was provided to obtain a heat-sensitive transfer material (II).

[Example 3] The formulation 1 of Example 1 was replaced with a 25% solution of the oxidized polyethylene emulsion of the above formulation 5 which was emulsified under pressure and heating, and otherwise the same as in Example 1 except that the thermal transfer material (III) was used.
Got The melting point of this second ink layer was 100 ° C., and the melt viscosity at 150 ° C. was 120 cps.

[Example 4] The thermal transfer material (IV) was obtained in the same manner as in Example 1 except that the formulation 1 of Example 1 was replaced with a 25% solution of the oxidized polyethylene emulsion of Formulation 6 emulsified under pressure and heating. It was The second ink layer had a melting point of 130 ° C. and a melting point viscosity at 150 ° C. of 5500 cps.

Example 5 The first ink layer having a thickness of 2.0 μm in Example 1 was prepared by using an emulsion containing a vinyl acetate-ethylene copolymer resin (ethylene content: 35%) having a glass transition temperature of −18 ° C. and a weight average molecular weight of 1,000,000. On the contrary, the second and third ink layers were obtained in the same manner as in Example 1 to obtain a heat-sensitive transfer material (V).

Example 6 The first ink layer having a thickness of 2.0 μm of Example 1 was formed from acrylic resin emulsion (Acronal YJ-1600D manufactured by Mitsubishi Petrochemical Verdishu Co., Ltd.) having a glass transition temperature of 7 ° C. For the third ink layer, a thermal transfer material (VI) was obtained in the same manner as in Example 1.

Example 7 The first ink layer having a thickness of 2.0 μm of Example 1 was formed by acrylic resin emulsion (Acronal YJ-1560D manufactured by Mitsubishi Petrochemical Verdice Co., Ltd.) having a glass transition temperature of 15 ° C. For the third ink layer, a thermal transfer material (VII) was obtained in the same manner as in Example 1.

Comparative Example 1 A thermal transfer material (VIII) was obtained in the same manner as in Example 1 except that the first ink layer of Example 1 was not provided.

[Comparative Example 2] A thermal transfer material (IX) was obtained in the same manner as in Example 3 except that the first ink layer of Example 3 was not provided.

[Comparative Example 3] The heat-sensitive transfer material was prepared in the same manner as in Example 2, except that the first ink layer in Example 2 was not provided, the second ink layer in Example 2 was changed to the formulation 5 in Example 3, and the other conditions were the same. (X) was obtained.

Next, the thermal transfer materials (I) obtained in the above Examples and Comparative Examples
(X) is cut to a width of 8 mm, electronic typewriter SP400X manufactured by Canon Inc. is used, and bond paper with low smoothness (bedding smoothness of 2-3 seconds) and high thermal transfer as recording medium. Recording and lift-off erasing were evaluated using special paper (bec smoothness of 200 seconds). The typewriter SP
In 400X, a heating heater was incorporated in the thermal recording head for the purpose of heating the thermal transfer material to room temperature or above prior to the recording operation, but in this evaluation, the heater was not operated. Lift-off erasure can be evaluated by loading the thermal transfer materials (I) to (X) in the thermal correction tape housing portion of the SP400X.

The evaluation results are shown in Table 1.

As described above, according to the present invention, according to the present invention, the first ink layer that is firmly adhered to the support during printing, the second ink layer that divides the printing inside during printing, and the thermoplastic A thermal transfer material provided with at least a third ink layer containing a resin as a main component provides a transfer-recorded image with good print quality not only on a recording medium having high smoothness but also on a recording medium having low smoothness. In addition, lift-off erasing can be performed using the heat-sensitive transfer material.

[Brief description of drawings]

1 and 2 are schematic cross-sectional views of the thermal transfer material of the present invention,
FIG. 3 is a schematic sectional view for explaining a thermal transfer recording method when an example of the thermal transfer material of the present invention is used, and FIGS. 4 and 5 are schematic sectional views for explaining a lift-off erasing method. 1 ... Thermal transfer material 2 ... Support 3 ... First ink layer 4 ... Second ink layer 5,51 ... Third ink layer 52 ... Fourth ink layer 6 ... Transfer recording Image 7 ... Recorded object 8 ... Thermal recording head 9 ... Heating element

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Koichi Taima 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Masanobu Asaoka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Incorporated (56) Reference JP 62-156993 (JP, A) JP 62-183389 (JP, A) JP 62-189190 (JP, A) JP 62-189191 (JP, A) JP 62-189192 (JP, A) JP 62-121092 (JP, A) JP 62-116187 (JP, A) JP 58-220795 (JP, A) JP 62 -104794 (JP, A) JP 61-144393 (JP, A) JP 60-101083 (JP, A) JP 60-56592 (JP, A)

Claims (9)

[Claims] 1. A thermal transfer material having at least a first ink layer, a second ink layer and a third ink layer on a support in order from the side of the support, wherein the first ink layer has a glass transition temperature. It is a substantially non-transferable layer containing a thermoplastic resin at -40 to 30 ° C., and when the second ink layer is heated for recording, the second ink layer is divided within the second ink layer. The third ink layer is a layer containing a thermoplastic resin as a main component, and at least the third ink layer contains a colorant. 2. The heat-sensitive transfer material according to claim 1, wherein the content of the thermoplastic resin in the first ink layer is 70 to 100%. 3. The heat-sensitive transfer material according to claim 2, wherein the content of the thermoplastic resin is 90 to 100%. 4. The heat-sensitive transfer material according to claim 1, wherein the glass transition temperature is −30 to 15 ° C. 5. The heat-sensitive transfer material according to claim 4, wherein the glass transition temperature is −18 to 15 ° C. 6. The melting point of the second ink layer is 50 ° C. or higher,
The melt viscosity at 150 ° C is 500 cps or less.
The heat-sensitive transfer material according to the item. 7. The heat-sensitive transfer material according to claim 1, wherein the second ink layer contains 80% or more of wax. 8. The heat-sensitive transfer material according to claim 1, wherein the content of the wax is 90% or more. 9. A support has at least a first ink layer, a second ink layer and a third ink layer in order from the support side, and the first ink layer has a glass transition temperature of -40 to 40. 30
A substantially non-transferable layer containing a thermoplastic resin at ℃,
The third ink layer is a layer containing a thermoplastic resin as a main component, and at the time of performing transfer recording on a recording medium using a heat-sensitive transfer material containing a coloring agent in at least the third ink layer, the heat-sensitive transfer material is used. Immediately after the pattern is heated, and before the strength of the second ink layer becomes sufficiently strong, the heat-sensitive transfer material is peeled off from the recording medium to divide it inside the second ink layer, thereby recording the recording medium. After a recording image is formed on the recording image and the thermal transfer material is brought into contact with the recording image and heated, the thermal transfer material is peeled from the recording medium when the strength of the second ink layer becomes sufficiently strong. By doing so, the recording image on the recording medium is peeled off from the recording medium toward the thermal transfer material side.