JPS61255895A - Thermal transfer recording medium - Google Patents

Abstract

PURPOSE:To obtain a thermal transfer recording medium having repeated life and capable of performing high density printing even on a transfer sheet of low or high surface smoothness, by providing a heat-fusing color material layer containing a compound of polyoxyethylene series directly on an adhesive layer formed on a substrate. CONSTITUTION:The substance which has a fusing point 300-120 deg.C and is solid in an ordinary temperature is preferably used for a compound of polyoxyethylene series having the structure in its molecular shown by the formula. The compound having the sum of average molecular weights 2,000-20,000 in its polyoxyethylene part is preferred in order to relatively increase the amount to be transferred at a time and obtain a high-density printing many times. Whether the compound of polyoxyethylene series contained in a color material layer is in a dispersed condition or in a miscible or pseudo-miscible condition in its molecular level depends on its loadings, polar character or miscibility with the selected wax of A-group. Since the miscibility, particularly, depends largely on the molecular weight of the polyoxyethylene chain part in the molecular in the compound, for example, the compound group having the sum of molecular weight range 2,000-20,000 in its polyoxyethylene chain part can be easily contained in the color material layer in the dispersed condition thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermal transfer recording medium, and more particularly to a repeatable thermal transfer recording medium.

(Background of the Invention) In recent years, print recording has changed from impact recording using conventional pressure-sensitive ribbons to reducing printer costs, eliminating noise, and
Technology is progressing toward non-impact recording that can reduce maintenance. Among various non-impact recording methods, the thermal transfer recording method not only meets the above requirements, but also attracts particular attention because of its advantages such as image stability and reliability.

However, in current thermal transfer recording, □
Ribbons do not have repeatability, and the biggest challenge is reducing running costs, and there is a strong hope for the development of conventional one-time ribbons into repeatable thermal transfer recording media. Several techniques for this purpose have been disclosed to date.

For example, in JP-A No. 54-68253, a microporous membrane of a resin component is formed using a volatile solvent, and an ink is thermally melted using the resin component as a solid base material to form a heat-fusible colorant. A method of oozing from a coloring material layer (hereinafter simply referred to as a coloring material layer) is disclosed in Japanese Patent Application Laid-Open No. 55-105579. In this method, for example, a heat-resistant ink of 120° C. or higher or a polymer is used as the solid base material.

Furthermore, JP-A No. 57-160691 discloses a method for exuding ink using solvent dye as a colorant as a t-solid base material of inorganic or organic fine powder (e.g. carbon black). Disclosed.

Furthermore, JP-A-57-185192 discloses a method in which porous paper is used as a solid base material, impregnated with ink, and oozed out by thermal melting.

All of these techniques are based on the idea that ink that becomes leached by heating is made to exist in a porous solid base material, and thereby the ink is transferred little by little from the coloring material 1. This idea, for example,
The technology of carbon paper for pressure-sensitive transfer as disclosed in No. 5-13426 is utilized for carbon paper for thermal transfer.

However, in the case of thermal transfer, the presence of a solid matrix onto which the ink is transferred little by little is another major drawback.

That is, upon application of energy, the solid base material itself does not melt or mix, and is substantially non-transferable. By including such a non-transferable material in the coloring material layer, the entire coloring material layer becomes thicker, and the transfer efficiency per unit volume of the coloring material layer decreases. As a result, a decrease in sensitivity, a decrease in printing speed, a decrease in the density of a transferred image, an excessive load on the thermal head, or a decrease in print quality such as resolution is induced.

Therefore, it is desired to develop a recording medium that does not use a solid base material and has repeated durability, and its basic performance is to prevent the entire thickness of all the coloring material layers from being transferred at least once. The layer and support must contain sufficient adhesion.

The technology for this purpose has long been known for pressure-sensitive sheets, but it is also used in the field of heat-sensitive transfer.
No. 53, No. 55-105579, No. 57-36698
No. 59-96992 discloses a technique in which an adhesive layer is interposed.

However, as described above, when a solid base material is not used, it is difficult to appropriately control the amount of ink transfer just by interposing an adhesive layer.

That is, according to the exploratory study by the present inventors, conventionally,
Basic materials commonly used in one-time ribbons, such as various waxes, carbon black, cage colorants such as pigments, low softening point resins, softeners (castor oil, mineral oil, hydrogenated vegetable oil, white petrolatum, It is not possible to properly control the amount of ink transfer by simply incorporating one kind of oily or semi-solid substance (at room temperature) such as lanolin or hydrophilic vaseline into the coloring material layer. For example, even if attempts are made to soften the coloring layer by using a semi-solid lubricant or oily softener at room temperature and a solid heat-melting substance, the amount of ink transferred may vary depending on various types of transfer paper. It is not possible to make it suitable. In addition, it is useful to use a low softening point resin to provide film-forming properties and ensure full adhesive strength with the underlying layer, as in the case of ordinary one-time ribbons, but this is not enough. However, it is not possible to achieve high density, high print quality, and repeated durability on any transfer paper.

For example, even if it is possible to print multiple times on paper with high Bekk smoothness, with paper with low Bekk smoothness, the amount of transfer at one time will be too large, and the print density will decrease after the second time. .

Alternatively, if an attempt is made to print a suitable number of times on paper with low smoothness, problems such as the amount of transfer per time on paper with high smoothness will be too small and the density will be low will occur.

Furthermore, there are problems such as essentially low density and poor print quality, regardless of the smoothness of the transfer paper.

<Objective of the present invention> To provide a heat-sensitive transfer recording medium that has high density and repeat durability on both A6 transfer paper with low surface smoothness and transfer paper with high surface smoothness.

b. To provide a heat-sensitive transfer recording medium with high sensitivity, high resolution, and long print quality and repeated durability.

C. Providing a heat-sensitive transfer recording medium that has a low coating production cost for an ink layer and is durable for repeated use.

d. To provide a thermal transfer recording medium in which blocking and soiling are minimized and an intermediate density of 1 can be obtained by selecting applied energy.

(Structure of the Invention) The object of the present invention is to provide a heat-sensitive transfer recording medium having a heat-fusible coloring material layer containing a coloring material and a heat-fusible substance on a support. This is achieved by a heat-sensitive transfer recording medium characterized in that the layer contains a polyoxyethylene compound, is provided directly on an adhesive layer provided on a support, and is configured to have repeated durability.

As a preferred embodiment of the present invention, (1) Embodiment 1 [Group A] in which the coloring material 1 contains at least 181 heat-melting substances selected from the following [Group A]: animal-based, plant-based; (2) Embodiment in which the coloring material layer contains a low softening point resin (3)
The melt viscosity of the composition of the coloring material layer is 30 to 30 at 100°C.
(4) The polyoxyethylene compound has (-0-CH, -CH,
An embodiment in which the average molecular weight of the + part is 2000 to 20000, especially an embodiment in which the average molecular weight of the + part is 4000 to 1 sooo-shiny. as 40
-300, and the like.

Next, the present invention will be explained in detail.

Similarly, the ink referred to in the present invention is a composition that is contained in a coloring material layer and exudes from the coloring material layer by thermal melting.

According to research conducted by the present inventors, the amount of ink transferred to transfer paper is determined by the viscosity of the molten ink, the releasability of the coloring material layer from the adhesive layer (so-called cohesive failure in the coloring material layer), and the stick ink It seems to depend on the thermal expansion, surface tension, and other physical properties of the ink and transfer paper.

If these parameters are combined and designed to suit the design based on experiments, development in which the coloring material layer is sequentially transferred from the top occurs characteristically during repeated use, and the dependence of the transfer density on the surface smoothness of the transfer paper can be kept small. can.

This is determined by the mutual cohesive force of the two materials that make up the ink! Viscosity, which affects the difficulty of transfer, transfer tv
The magnitude of the cohesive failure in the coloring material layer to be suppressed, the wetted area or wetted volume of the transfer paper that receives the ink, the cooling of the ink that is affected by the thermal expansion and surface tension of the ink as a transfer driving force, specific heat, etc. This seems to depend on the overall mechanical balance of solidification speed, pressure contact of the recording medium (ink ribbon) having a coloring material layer, and peeling performance.

Therefore, it is almost impossible to create an optimized design that achieves a repeat durability of 8V and high-density transfer by simply combining the conventional and general materials mentioned above, so we selected specially selected materials. It is necessary to combine them.

As a result of intensive research by the present inventors, we have found that relatively non-polar waxes selected from Group A, and relatively polar waxes such as the polyoxyethylene compound according to the present invention,
In addition, by incorporating a substance that has special miscibility with Group A into the color material layer, the mutual cohesive force can be sufficiently adjusted, and the necessary minimum film formability is maintained. At the same time, it was found that the adhesive force with the adhesive layer can be maintained at t''.

Mutual cohesive force is caused by intermolecular interactions of compounds contained in the coloring material layer. Therefore, it is thought that the magnitude of the mutual cohesive force changes depending on the structure and presence or absence of seabird tissue based on the immiscibility of the compounds in terms of molecular chromatography.

The present invention attempts to control the cohesive force by combining the above-mentioned large group and a polyoxyethylene compound.

In addition, in the present invention, using a small amount of low melting point resin guarantees the film formability of the coloring material layer, the adhesive strength between the coloring material layer and the adhesive layer, and controls the amount of transfer. This is particularly preferred as a method for optimizing viscosity. A viscosity of 30 to 900 centimeters is particularly useful when printing is to be performed multiple times on transfer paper with low surface smoothness. The viscosity of the ink layer is preferably 30 to 900 centivoise. If the viscosity is too high,
This may cause blurring of prints, a decrease in density, etc., and it is difficult to optimize the transfer amount only by adjusting the mutual cohesive force between the λ group wax and the polyoxyethylene compound. Furthermore, if it is too low, the resolution will decrease or it will be difficult to print multiple times at high density.

JP-A-58-129094 discloses that polyhydric alcohol is contained in the color material layer of a one-time ink ribbon to transfer the entire amount of ink in the color material layer to improve print quality. In the present invention, the adhesive layer is provided on the adhesive layer and controls the transfer of ink by adjusting the adhesive force at the interface with the material layer and the support, provides a necessary and sufficient amount of ink transfer, and is durable for repeated use. Even if it has the function and effect of smoothing, the function and effect and technical idea are completely different from the disclosed technology.

The polyoxyethylene compound according to the present invention is a compound having an integer moiety of (-OCR, CH, -)nn: 2 or more in the molecule.

The compound is preferably a substance with a melting point of 300 to 120°C that is solid at room temperature, particularly preferably a substance with a melting point of 40 to 100°C.
It is ℃.

moOCR,CH,-)n(Mw=4
The total molecular weight of the 4 n ) moieties is an important factor determining the amount of transcription in the present invention. The amount of transfer must be appropriate for various types of transfer paper, and varies depending on the molecular weight of the compound or portions other than the polyoxyethylene portion, but can be stated as follows.

The total average molecular weight of the polyoxyethylene part is 2000~
20,000 has a comparatively large amount of transfer and can be preferably used to obtain high-density printing many times. Among these, 4000 to 18000 is particularly preferable.

Furthermore, when the total average molecular weight of the polyoxyethylene portion is 40 to 300, it can be used many times with particularly long print quality for transfer paper with low Bekk smoothness.

Of course, the molecular weight of the polyethylene oxide part is 30
Even if it is higher than 0 and lower than 2000, the same effect can be obtained, but the total molecular weight of the polyoxyethylene portion is preferably 4 to 300 and 2000 to 20,000.

In particular, the effect of 2000 to 20000 (more preferably 4000 to 18000) is a surprising effect,
It can be preferably used in the present invention. This is believed to be due to its miscibility with the selected Group A waxes.

The amount of the polyoxyethylene compound of the present invention,
Depending on the polarity or the miscibility with the selected Group A wax, the polyoxylic acid in the compound molecule may be contained in the coloring material layer in a dispersed state, a mixed state at the molecular level, or a pseudo-mixed state. The miscibility largely depends on the molecular weight of the ethylene chain moieties, and for example, the total molecular weight range of the polyoxyethylene chain moieties preferred as the compound of the present invention is 2,000 to 20,000 (particularly 4,000 to 18
000) can be easily contained in the coloring material layer in a dispersed state.

In the present invention, a polyoxyethylene compound is contained in a continuous layer of a compound other than a polyoxyethylene compound, including a wax selected from the λ group, in a dispersed state, that is, as a discontinuous seabird structure. It is particularly preferred that the

However, the -polyoxyethylene compound may form the entire continuous layer, and the Group A wax may form a sea-island structure.

Further, the effects of the present invention can be seen not necessarily in a clearly dispersed state but also in a pseudo-mixed state or even in a mixed state. The dispersion means is not particularly limited, but if it is immiscible with the above wax compounds, for example,
It can be dispersed by vigorous stirring.

Alternatively, an organic solvent may be used to intentionally form a dispersed state during coating.

For example, it is also possible to use a dispersing machine such as a dispersion machine, mixer, sand grinder, or ball mill. Although the dispersed particle size can be changed depending on the dispersion method and other factors, the dispersed particle size is preferably 10 μm or less in the present invention.

In the present invention, it is possible to easily determine K111 by observing the coloring material layer composition excluding the coloring material in the dispersed state of the compound in the coloring material layer in a hot melt state or in a coated state. In this observation, if a seabird tissue is formed, or a cloudy state, a droplet (oil droplet) state, or a phase separation state is formed, it can be determined that the compound is highly immiscible.

In the present invention, as described above, high immiscibility is preferred because it is easy to form a dispersed state.

Regarding the immiscibility, the miscibility of the Group A wax and the polyoxyethylene compound can be described as follows. That is, for example, if the miscibility with liquid paraffin is used as a representative value for the miscibility of Group A waxes (for example, at a concentration of 10%), ■ immiscible with liquid paraffin at any temperature ■ miscible with liquid paraffin above 40°C, but , those that are immiscible at temperatures below 40° C.■ Those that are miscible with liquid paraffin at any temperature.When considering repeated durability and productivity, ■ and ■ are preferred.

However, even if it is (2), the effects of the present invention are of course still present.

The polyoxyethylene compound according to the present invention refers to a compound having a polyoxyethylene moiety in the molecule as described above, but to explain it in more detail, it can be classified into polyethylene glycol and polyethylene glycol derivatives.

Among these, polyethylene glycol derivatives will be particularly explained.

In order to derive the derivative, one or two alcoholic -0H groups of polyethylene glycol are reacted with various organic compounds. In this case, ether bonds, ester bonds, bonds with sulfur atoms or nitrogen atoms, urethane bonds, and other various bonds are possible, and the bond form for induction is essential for the present invention. This is not a problem and is not particularly limited.

Rather, the induction is aimed at optimizing blocking performance, prevention of bleed-out, cohesive failure force, and viscosity (°molecular weight, λ
This is preferably carried out based on molecular design (including miscibility with groups, number of polar groups, etc.). However, representative examples of particularly preferred induction include ether induction and ester induction.

Next, specific examples of particularly preferred polyoxyethylene compounds in the present invention will be given. The preferred range of the molecular weight of the polyoxyethylene chain portion is as described above (2000
~20,000), but if the molecule has multiple polyoxyethylene chains, the above range (2,000~2,000
It is preferable that the sum of their molecular weights be included in 0).

(1) Polyethylene glycol (-CHICH, 0+. The average molecular weight of the part is 20,000
.

Specific examples include polyethylene glycol and diethylene glycol with numbers 12000.9000.6000.1000.400 and 100.

(2) Mono- or diester/I/I conductors of polyethylene glycol, especially when deriving from fatty acids, such as fatty acids;
The fatty acid preferably has 1 carbon number, 1.0 to 1 carbon number, and more preferably 19 to 50 carbon atoms.

That is, specific examples include capric acid, undecanoic acid,
Preferred are lauric acid, tridecanoic acid, myristic acid, hentadecanoic acid, balmitic acid, margaric acid, and stearic acid, and more preferred are mono- or diesters of nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosaic acid, lignoceric acid, etc. It may be a mono- or diester derivative of polyethylene glycol derived from various organic acids.

Specific examples include linear monoenoic acids, di-, tri-, or tetraenoic acids, synthetic fatty acids, tertiary fatty acids, branched fatty acids, dimer acids, dibasic acids, polybasic acids, oxycarboxylic acids, fatty acid chlorides, fatty acid anhydrides. , polycarboxylic acid, and other compounds containing one or more carboxyl groups in the molecule.

Compared to polyethylene glycol and polyethylene glycol monoester, polyethylene glycol diester has better dispersion properties and does not deteriorate the dispersibility of coloring materials. Furthermore, it can be printed at stable high density and multiple times. Furthermore, even when paper with low surface smoothness is used as the transfer paper, it exhibits the effect of providing high density and high print quality. Polyethylene glycol diesters are preferred as the compounds of the invention.

The diester portions may be the same or different.

Specific example polyethylene glycol monobehenene) (PE0
4000) Polyethylene glycol distearate (
P'BG 6000) Polyethylene glycol monopalmitate (paG 600) Polyethylene glycol dibehenate (PE014000) Polyethylene glycol laurinate (PEG 100) Same, +CH, CM, O+ in parentheses. The average molecular weight of the part (PE0 part) is shown. Same from now on.

+31 Ho! Monoalkyl, arylalkyl aryl ether derivatives of J oxyethylene ether (compounds in which one 10H group of polyethylene glycol is derived from an ether) The above ethers preferably have 6 or more carbon atoms, particularly preferably 18 or more and 50 or less carbon atoms. of alkyl and alkylaryl with polyoxyethylene ether.

Alkyl may be a straight chain and branched hydrocarbon. Also,
These halides may be used. Furthermore, in special cases, unsaturated hydrocarbons, synthetic alcohols, oxycarboxylic acids, and polyoxyethylene ethers of nitrogen-containing sulfur compounds may be used.

Specific examples Polyethylene glycol mono-P-nonylphenyl ether (PP!G 900) Polyethylene glycol monobehenyl ether (PE
06000) Polyethylene glycol monocetyl ether (PEG 200) Polyethylene glycol monooleyl ether (PBG 4000) (41+31
Ether or ester derivatives of monoether derivatives (3) The remaining 10H groups of the monoalkyl or arylalkyl aryl ether derivatives of polyoxyethylene ether are ether-derived or ester-derived.

In this case, ester induction is based on the case (21), and ether induction is based on the case (3).

Specific example Polyethylene glycol mono-P nonylphenyl ether (monopehene) (PI3
G 800) Monostearate of polyethylene glycol monostearyl ether
(PEG 9000) Polyethylene glycol dibehenyl ether (PE06000) Polyethylene glycol monooleyl ether monobehenyl ether (PE04
000) (5) The compound described as polyquine ethylene ether derivative of polyhydric alcohol is a compound having two or more alcoholic OH in the molecule, such as glycerin, polyglycerin, propylene glycol, pentaerythritol, polypropylene glycol, sorbitan (1, 5-Sorbitan,
(1.4- or 3.6-sorbitan, isosorbite), mannitol, and other popal with a molecular weight of 800 or less, and furthermore, they contain a single or two or more alcohols (ioH) in the molecule (2) and /'! It is a polyoxyethylene ether derivative of an ether and/or ester derived compound according to Take (3).

The polyoxyethylene ether derivative may have a single polyoxyethylene chain or a plurality of polyoxyethylene chains in the molecule.

Further, it is preferable that one end of the polyoxyethylene chain of the polyoxyethylene ether derivative is ester- and/or ether-derived according to 121 and +31.

In the present invention, the polyhydric alcohols may have a structure tV in which two or more sets of polyhydric alcohols are bonded to each other, or may have a structure in which they are crosslinked by polyoxyethylene chains.

Specific examples Glycerin polyoxyethylene monostearate Glycerin di(polyoxyethylene monostearate) Fulvitan monobehenate polyoxyethylene monobehenyl ether Hatyl alcohol polyoxyethylene ether Propylene glycol monooleate polyoxyethylene Oleate Block copolymer of polypropylene glycol and polyoxyethylene glycol Polyglycerin Polystearate Polyoxyethylene ether Pentaerythritol Distearyl ether Polyoxyethylene ether Behenate Sorbitan ester Polyoxyethylene ether Pentaerythritol Polyoxy Ethylene ether Polyglycerin ester Polyoxyethylene ether Patyl alcohol ester Polyoxyethylene ether ester Mannitol ester Polyoxyethylene ether (
6) Specific examples of polyoxyethylene derivatives of molecules containing a sulfur atom center or a nitrogen atom include alkylthiopolyoxyethylene ether, polyoxyethylene fatty acid amide, and polyoxyethylene alkylamine.

(7) Polyoxyethylene derivatives of polymers or copolymers, such as alkylaryl formaldehyde condensed polyoxyethylene ethers, polyoxyethylene ether esters of copolymers, and polyoxyethylene ether derivatives of α-olefin maleic anhydride copolymers. It will be done.

(8) Synthetic polymers such as polyester and polyurethane and polyoxyethylene block polymers (9)
Examples of anionic compounds include carboxylates of polyoxyethylene alkyl (allyl) ethers, sulfates of polyoxyethylene fatty acid esters, sulfates of polyoxyethylene alkyl (allyl) ethers, and polyoxyethylene alkyl ethers. Examples include polyoxyethylene-containing anion activators such as (allyl)ether phosphates, polyoxyethylene alkyl(allyl)amide phosphates, and carboxylates of polyoxyethylene fatty acid esters.

αG Compounds of i′ with cationic properties, such as polyoxyethylene-containing cationic active agents and amphoteric surfactants such as alkyl (allyl) polyoxyethylene ether ammonium salts and polyoxyethylene hydroxy ammonium salts (in this case, non-cationic].

Next, the heat-melting substances of [Group A] (animal wax, vegetable wax, mineral wax, petroleum wax, synthetic hydrocarbon wax, and modified wax) according to the present invention will be explained. The wax compounds to be used include waxes that are solid at room temperature, preferably those with a melting point (Yanagimoto MPJ -
Examples include waxes having a temperature of 40 to 80°C (measured value by Type 2), and specifically the waxes listed below are used.

Examples of animal waxes include beeswax, insect wax, shellac wax, spermaceti wax, wool wax, etc., and examples of vegetable waxes include carnauba wax, tree wax, auricilla wax, esparto wax, candelilla wax, etc. Mineral waxes include montan wax, osikelite, ceresin, etc., petroleum waxes include paraffin wax, microcrystalline wax, ester wax, petrolatum, etc., and synthetic hydrocarbon waxes include Fischer-Tropsche wax. , polyethylene wax, low molecular weight polypropylene, low molecular weight polyethylene and derivatives thereof, etc., and modified waxes include oxidized wax, montan wax derivatives, paraffin or microwax derivatives.

These may be used alone or in combination of two or more. In addition, in the present invention, hydrogenated waxes such as castor wax, opal wax, etc. and α
It is also possible to use a wax that does not belong to the above wax compound group of olefin and maleic anhydride copolymer.

The waxes of group A are preferably used as a continuous binder layer in the coloring material layer.

The coloring agent used in the heat-melting coloring material layer of the present invention may be appropriately selected from various pigments, and is preferably a direct dye, an acid dye, a basic dye, a disperse dye, an oil-soluble dye, or a metal-containing dye. (including oil-soluble dyes), etc. The dye used in the color material layer of the present invention may be any dye as long as it can be transferred (migrated) together with the heat-melting substance.
It may be coated with pigment. In addition, specifically, the following can be mentioned.

As yellow pigments, Kayalon Polyester Rad Yellow 5G-8 (Nippon Kayaku), Oil Ye''-8-7 (
white clay), Eisen Subiron Yellow GRH Special (
(Hodogaya), Sumiplast Yellow FG (order), Eisens Viron Yellow GRH (Hodogaya), etc. are preferably used. Red pigments include Diaceritone Fast Red R (Mitsubishi Kasei), Dianics Brilliant Red B8-E (Mitsubishi Kasei), Sumipura Tread FB (order), Sumipura Tread HFG (order), Kayalon Polyester Pink RCL -E (Nippon Kayaku), Eisenspiron Red GEH Special (Hodogaya), etc. are preferably used. As blue pigments, Diaceritone 7 Test Brilliant Blue R (Mitsubishi Kayaku Dainik Sprue BB-E (Mitsubishi Kasei), Kayalon Polyester Blue B = SP Co, Nku (Nippon Kayaku), Sumiplast Blue 3
R (order), Sumiplast Blue G (order), etc. are preferably used. In addition, indoaniline dyes and azomethine dyes used as photographic dyes can also be suitably used. In addition, as a yellow pigment, Hansa Yellow 3G
.

Tabetrazine Lake etc. are used as red pigments,
Brilliant Carmine FB-Viair (Yamaba Pigment), Brilliant Carmine 6B (Yamaba Pigment), Alizarin Lake, etc. are used, and as blue pigments, Cerulean Blue, Sumikablin Tocyanine Blue GN-0 (order), Phthalocyanine Blue, etc. are used. , as a black pigment,
Carbon black, oil black, etc. are used. The most preferred colorant used in the present invention is carbon black.

It is particularly preferable to include a low softening point resin in the colorant layer of the present invention in order to adjust the viscosity and cohesive force.

Examples of the low softening point resin include polymers having a softening point (ring and ball method) of less than 110° C. in order to prevent a decrease in sensitivity.

In the present invention, the resin component does not need to act as a solid base material (non-transferable), is miscible with the wax binder of Group A, and is preferably added in a small amount. The preferable addition amount is 1% or more and less than 20% based on the entire coloring material layer.
Being miscible with Group A wax binders is
Colorants can be applied without solvent.

Specifically, polyethylene or ethylene copolymers such as ethylene-ethyl acrylate copolymer and ethylene-vinyl acetate copolymer, α-olefin polymers such as polypropylene or copolymers thereof, polystyrene, styrene-butadiene, and styrene. -Rubbers such as isoprene copolymers and polybutadiene can be mentioned.

- ten thousand, polyamide, gelatin, polyvinyl alcohol,
Vinyl chloride-acetate copolymer, polyvinylidene chloride, polyvinyl acetate, and the like are not preferred because they are immiscible and require the use of volatile solvents.

The preferable addition amount is 28 wt% or less of the entire 11 color material layers;
More preferably 5 to 25%.

The adhesive layer according to the present invention refers to a layer that is located on the support and has the function of ensuring sufficient adhesive strength between the support and the coloring material layer.

In order for the adhesive layer to have a sufficient function, it is preferable that the adhesive layer is made of a resin component or is formed as a main component of the resin pipe.

In the present invention, whether the adhesive force is sufficient is determined by taking into account the cohesive force of the coloring material layer located above it, and -
I can't express it in general.

In other words, in order to achieve repeated durability, it is necessary that the adhesive force between the support and the coloring material layer exceeds the mutual cohesive force of the coloring material layer at the minimum, and this mechanical balance is necessary for transferring the ink ribbon. It also changes depending on the method of peeling from the paper and the temperature at that time.

Such performance can be examined, for example, by a peel test in which adhesive tape is placed on the coloring material layer.

, the softening point (melting point) of the adhesive layer is at least 50
The temperature is preferably 70°C or higher, and more preferably 70°C or higher.

The adhesive layer preferably has high thermal conductivity. The thickness of the adhesive layer is preferably 0.1 to 5.0 μm, more preferably 0.3 to 3 μm, and the adhesive layer has a high thermal conductivity. If it is sufficient, a thin layer is preferable.

As a coating method for the subbing layer, conventionally known methods such as gravure coating, extrusion coating, roll coating, wire barcoding, dip coating, etc. can be used.

The form of the coating liquid can be selected from hot melt, aqueous solution, latex aqueous solution, and M-solvent solution, which are conventionally known for coating compounds such as resins.

The resin that can be used for the adhesive layer may be either a thermoplastic resin or a 1' thermosetting resin.

Examples of preferable specific compounds include acrylic resin, ethylene-vinyl acetate resin, vinyl acetate resin, and borietele/vinyl acetate resin.
Resin, polyurethane resin, phenoxy resin, polyvinyl butyral resin, polycarbonate, polyester resin,
Examples include epoxy resin and ethylene-ethyl acrylate resin.

[Example] Examples will be given below, but the present invention is not limited thereto. In addition, "part" used below means "part by weight"
shows.

Example 1 Ethylene-ethyl acrylate resin (NUC-6
070 (manufactured by Nippon Unicar Co., Ltd.) solution to form an adhesive layer,
After drying, the following color material layer coating solution (hot melt dispersion using Disilver) was hot melt coated using a wire bar to a film thickness of 12 μm, and then heated in a dryer at 100°C for 12 minutes. Thermal transfer recording medium sample of the present invention (
A ribbon-like product (2) with a width of 8 m was obtained.

Colorant layer coating liquid Carnauba wax 20 parts Paraffin wax (MP 75℃) 101 Microcrystalline wax (MP 78℃) 15 #Oxide wax 10I Carbon black 151 Bees wax
101 compounds x (listed in Table 1) 20 I This thermal transfer recording medium sample (■) was subjected to an applied energy of 1.0 using a serial thermal printer (prototype machine equipped with a thin film type serial head with a heating element density of 8 dots/mm).
mj/dot vc- was given and recorded (printed) on plain paper. this? : Repeated three times, the optical reflection density after solid printing was determined. Note that commercially available high-quality paper and rough paper were used as the plain paper. The results are shown in Table 1. When polyethylene glycol was added, when the smoothness was 200 #i or 67, printing could be performed with small fluctuations in transfer density over many times.

If this is not added, printing can only be done once and the next time.

Example 2 The following formulation was used in the same manner as in Example 1.

The results are shown in table 7. : As shown in the table below, high density printing is possible regardless of whether the surface smoothness is high or low. On the other hand, if there is no adhesive layer,
Practically speaking, it can only be printed once.

Furthermore, when wax is used instead of polyethylene glycol dibehenate, the reduction in transfer density is small, especially when using transfer paper with low Peck smoothness.
Even when the Peck smoothness was high, the transfer density was low and the print quality was also poor.

Also, I'm sorry to hear about the blocking nature of ■ and ■.

In the blocking test, the sample was stacked with polyethylene terephthalate film, a load of 1 full d was applied, and the sample was heated at 45°C.
, and left for 2 days at 20% RH. Thereafter, it was peeled off and its blocking resistance was examined. As a result, in case (■) there was no blocking at all, but in case (2) there was blocking, and the stacked polyethylene terephthalate films were cloudy white after being peeled off.

Example 3 The following formulation was used in the same manner as in Example 1.

Carnauba wax 20 parts Polyethylene wax 51 Ceresin wax
51 Paraffin Wax 2
0 l Candelilla wax 5I carbon black 15 I ethylene-vinyl acetate copolymer lOI compound
As shown in Table 201, by adding various polyoxyethylene compounds, good multi-time printing without staining was obtained.

On the other hand, in comparison, not only was there a decrease in the transfer density especially when the Beck smoothness was low, but also the transfer density was low even when the Beck smoothness was high. , 300~
With No. 2000, some peeling may occur in the etched areas, but it has been found that this can be improved by changing the ribbon peeling method, so it can be used satisfactorily.

In addition, especially when the molecular weight is 2000 or more, the transfer density is high and the printing quality is good.

Example 4 Polyethylene glycol monobehenyl ether (M w
9000) 35 parts of the residue was variously modified with paraffin wax and ethylene vinyl acetate copolymer resin.

As shown in the printing table on the transfer paper with the viscosity and Bekk smoothness of 98 at that time, good printing quality is obtained in the viscosity range of 30 to 900 centipoise.

If the viscosity is too high, print quality may deteriorate, such as a decrease in density and blurring. This tendency is particularly noticeable when printing is performed on transfer paper with low Bekk smoothness.

The printing quality is rated ◎ for very clear characters (kanji, hiragana, alphabets) with no blurring or blurring, 0 for good, Δ for slightly poor, and X for poor.
Visual evaluation was performed by 0 people. The evaluation was performed on characters that were printed solidly for the first time and then printed at a position above the ribbon (ie, for the second time).

(Effects of the Invention) In addition to achieving the purpose of the present invention, as one of the other advantages,
One advantage is that the color material layer can be hot-melt coated in the same way as in the one-time coating.

When containing a solid matrix, it is forced to use a volatile solvent during application.

However, the use of volatile solvents not only causes social problems such as pollution and the environment, but also increases production costs, and as a result, the original objective of reducing running costs is hindered.

In the case of the present invention, it is possible to hot-melt coat the coloring material layer, and it is possible to keep production costs low and prevent social problems from occurring.

The method of applying the ink layer of the present invention is not limited to hot melt coating.

Applicant Roku Konishi Photo Industry Co., Ltd. Procedural Amendment August 9, 1985 1. Indication of the case 1985 Patent Application No. 98493 2. Name of the invention Thermal transfer recording medium 3. Person making the amendment Relationship to the case Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Contact address: Konishiroku Photo Industry Co., Ltd., 1 Sakura-cho, Hino-shi, Tokyo 191 (Telephone: 0425-83-152)
1) Patent Part 4, Date of amendment order Vol. 5, "Detailed description of the invention" column of the specification to be amended, 6. Contents of the amendment l) Page 7, lines 16 and 20 of the specification, Page 11, line 5.

Line 11, page 16, line 11, page 18, line 16.

Correct "average molecular weight" to "weight average molecular weight."

2) On page 10, line 16, "300-120°C" was corrected to "30-120°C." 3) On page 29, lines 7-8, "Preferably...25%. ” will be deleted.

4) Page 30, line 14 Correct the phrase "subbing layer" to "adhesive layer."

Procedural amendment December 11, 1985

Claims (1)

[Claims] In a heat-sensitive transfer recording medium having a heat-melting coloring material layer containing a coloring material and a heat-melting substance on a support, the heat-melting coloring material layer contains a polyoxyethylene compound, and A heat-sensitive transfer recording medium characterized in that it is provided directly on an adhesive layer provided on a support and is configured to have repeated durability.