JPH0494971A - Ink ribbon - Google Patents

Abstract

PURPOSE:To enable multicolour simultaneous recording to be performed by a method wherein an ink ribbon is prepared by making a microcapsule contain respectively independently each set of a dye and a colour erase agent. CONSTITUTION:Microcapsules 3, 4, 5, 6, 7, and 8 involving independently leuco type dyes LY1, LC1, LY2, LM2, LY3, and LM4 presenting respective series of, from a low temperature side, yellow, magenta, cyan, middle colour between cyan and yellow, middle colour among cyan, yellow, and magenta, middle colour between cyan and magenta, and middle colour between magenta and yellow, and diazo type dyes of DM1, DC2, and DM3, are prepared. Microcapsules 9 involving respectively independently colour erase agents DE1, DE3 erasing respective colour series of yellow, magenta, cyan, middle colour between yellow and magenta and middle colour between cyan and magenta and a microcapsule 10 containing respectively independently LE2 and LE4, are respectively prepared. Microcapsule solution is applied to a ribbon material 2.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to an ink ribbon used for forming recorded images, and in particular, the present invention relates to an ink ribbon used for forming recorded images, and in particular, to improve wettability by using a thermal transfer type color printer, color typewriter, word processor, etc. This is an ink ribbon that enables transfer printing even on surfaces with strong peeling properties, and also allows the transfer image obtained by thermal transfer to be effectively pressure-sensitive re-transferred onto the target transfer object using pressure. Regarding structure.

[Prior Art] In recent years, monochrome ink ribbons for producing dry transfer materials have been put into practical use. Each ink cartridge consisting of a single-color ink ribbon for dry transfer material manufacturing is housed in a dry transfer material manufacturing device, and only the heating elements necessary for recording generate heat among the many heating elements of the built-in thermal head. By applying this method, it is possible to produce dry transfer materials in various colors. For example, regarding the structure of a monochrome ink ribbon for dry transfer material production, Japanese Patent Application Laid-Open No. 63-128990, Japanese Patent Application Laid-Open No. 63-128991, and Japanese Patent Application Laid-Open No. 63-2512
It is described in Publication No. 87, etc.

[Problem to be solved by the invention] However, in the above-mentioned prior art, the ribbon base Murakami
Two layers: a homogeneous monochromatic ink layer with pressure-sensitive adhesiveness and a pigment, and a homogeneous layer with heat-sensitive adhesiveness, or a homogeneous layer with pressure-sensitive adhesiveness, a homogeneous layer with heat-sensitive adhesiveness and a pigment on a ribbon substrate. Since it is composed of two coated homogeneous single-color ink layers, it can only be used for single-color recording and has the problem of not being able to perform multi-color recording simultaneously.

The present invention has been made to solve these problems, and its object is to provide an ink ribbon that enables simultaneous multicolor recording.

[Means for Solving the Problems] The ink ribbon of the present invention is an ink ribbon that is incorporated in an image recording device that forms recorded images such as characters and figures, and is used when forming recorded images. At least two or more types of microcapsules selected from a group of microcapsules that separately contain a combination of at least one or more dyes selected from acid coloring dyes, basic coloring dyes, and sublimable dyes on one side of the At least one selected from the group of microcapsules each containing a decolorizing agent for decolorizing each combination dye.
It is characterized by uniformly containing more than one type of microcapsules.

[Function] According to the configuration of the present invention described above, since the ink ribbon is prepared by separately containing each combination dye and decoloring agent in microcapsules, simultaneous recording of multiple colors becomes possible. be.

[Example] The present invention will be described in detail below, but it goes without saying that the present invention is not limited in any way by such description.

Furthermore, it is understood that, in addition to the following examples, various changes, modifications, improvements, etc. can be made to the present invention based on the knowledge of those skilled in the art, as long as they do not depart from the spirit of the present invention. This is where it should be done.

FIG. 1 is an enlarged cross-sectional schematic diagram of a multicolor ink ribbon for producing a dry transfer material of the present invention and a dry transfer material produced by simultaneous multicolor recording.

1 is a thermal head, and 2 is a ribbon base material.

3 is a microcapsule containing yellow leuco dye;
4 is a microcapsule containing magenta diazo dye;
5 is a microcapsule containing magenta leuco dye;
6 is a microcapsule containing cyan-based leuco dye, 7
is a microcapsule containing a cyan diazo dye and a magenta diazo dye, and the temperature is 140 (℃) to 150 (℃).
A microcapsule wall material that has heat permeability between cyan diazo dye DC2 and magenta diazo dye D.
M3 is included in the same ratio.

8 is a microcapsule containing a magenta leuco dye and a yellow leuco dye, and the temperature is 160 (℃) to 170℃.
A microcapsule wall material having heat permeability between ('C) and containing magenta leuco dye LM4 and yellow leuco dye LY3 in the same ratio.

Microcapsule 3 containing yellow leuco dye is
Microcapsule wall material with heat permeability between 60 (0C) and 70 ('C) and yellow leuco dye LY
I alone and inclusion, and 110('C) to 1
It is composed of a microcapsule wall material having heat permeability between 20 ('C) and a yellow leuco dye LY2 contained therein.

Microcapsules 4 containing magenta diazo dye are
A microcapsule wall material that has thermal permeability between 80 ('C) and 90 (℃) and contains magenta diazo dye DM.
It is composed of a substance that contains I alone.

Microcapsules 5 containing magenta leuco dye are
A microcapsule wall material that has heat permeability between 120 (℃) and 130 (℃) and contains magenta leuco dye L.
It is composed of a substance that contains and encapsulates M2 alone.

The microcapsules 6 containing cyan-based leuco dye are 1
Microcapsule wall material with heat permeability between 00 ('C) and 110 ('C), containing cyan-based leuco dye L
It is composed of a material that contains and encapsulates CI alone.

In addition, 7 contains cyan and magenta diazo dyes in the same ratio, so it is possible to produce an intermediate color between cyan and magenta, but cyan and magenta diazo dyes By changing the content ratio of the dye, it is also possible to freely create various intermediate colors between cyan and magenta.

Similarly, since 8 contains magenta and yellow leuco dyes in the same ratio, it is possible to produce a color intermediate between magenta and yellow, but magenta and yellow leuco dyes By changing the content ratio of the dye, it is also possible to freely create various intermediate colors between magenta and yellow.

As mentioned above, the microcapsule wall has thermal permeability, and to be more specific, only while the microcapsule wall is heated to a predetermined temperature or higher using applied thermal energy, It has the characteristic that the contained substance passes through the microcapsule wall and is released, or the substance outside the microcapsule passes through the microcapsule wall and enters the inside of the microcapsule.

Therefore, each microcapsule has a specific glass transition temperature, and more specifically, a specific thermochromic temperature. In this case, known wall materials such as polyurethane, polyurea, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene methacrylate copolymer, styrene-acrylate copolymer are used as the microcapsule wall material. , gelatin, polyvinylpyrrolidone, polyvinyl alcohol, and the like can be used.

On the other hand, the microcapsules 9 containing a diazo dye coupler are composed of one containing and encapsulating the coupler DEI alone, and one containing the coupler DE3 alone, and a microcapsule 9 containing a leuco dye developer. The capsule 10 is composed of one containing and encapsulating the color developer LE2 alone, and the other containing and encapsulating the color developer LE4 alone, and is capable of erasing the color of each combined dye.
And the color developer has a function as a color erasing agent.

The coupler, DEI, is contained in a microcapsule wall material that has heat permeability between 70 ('C) and 80 (℃), and has a yellowish color between 60 (℃) and 70 (℃). It is possible to erase the color.

The color developer, LE2, was contained in a microcapsule wall material that had heat permeability between 90 (°C) and 100 (°C), and developed a color between 80 ('C) and 90 (°C). It is possible to erase the magenta color.

Coupler, DE3 is 130(℃) to 14o('c)
) is contained in a microcapsule wall material that has heat permeability between It is.

The color developer, LE4, is contained in a microcapsule wall material that has heat permeability between 150 ('C) and 160 (°C), and develops a color between 140 ('C) and 150 ('C). It is possible to erase intermediate colors between cyan and magenta.

For the coupler as a decolorizing agent and the color developer, known materials can be used. For example, in the case of a coupler, thermoplastic polyethers, alcohols, polyethylene glycol derivatives, acetamide, stearamide, and Inorganic organic ammonium salts, organic amines, urea and thiourea, and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidacillins, triazoles, morpholines, piperidines, It is possible to use it by containing at least one kind selected from nitrogen-containing compounds such as amidines, formazines, and pyridines.

The multicolor ink section 12 is configured to contain 3 to 1 o.

Further, 11 is a heat-sensitive adhesive layer, and the multicolor ink ribbon for producing a dry transfer material is configured to contain 2 to 11.

Next, the first example shows how each hue required for recording can be obtained simultaneously and freely by controlling the thermal energy applied to the heating element of the thermal head 1.
This is a dry transfer material consisting of 13, 14, and 15 in the figure, and shows that it exhibits a magenta color, and an intermediate color between cyan and magenta.

13 is a dry transfer material portion exhibiting a magenta color, and 14 is a dry transfer material portion exhibiting an intermediate color between cyan and magenta, allowing simultaneous multicolor recording. Furthermore, 1
5 is a retransfer sheet.

FIG. 2 is a diagram showing the results of measuring thermal coloring characteristics using the multicolor ink ribbon for dry transfer material production of the present invention. The horizontal axis shows the thermal coloring temperature (°C) and the dye involved in coloring, and the vertical axis shows the optical density (0, D, = Optical Den
city).

When the thermal coloring temperature is from 60 (℃) to 70 ('C),
It exhibits a yellow color, and when the temperature is raised from 70 (°C) to 80 (°C), the yellow color disappears.

Similarly, when the thermal coloring temperature is controlled and increased sequentially, magenta coloring, magenta decolorization, cyan coloring, intermediate coloring between cyan and yellow, and intermediate coloring between cyan, yellow, and magenta occur. Intermediate color erasure between cyan, yellow and magenta, intermediate color development between cyan and magenta, intermediate color erasure between cyan and magenta, and intermediate color development between magenta and yellow. The images are obtained sequentially, making it possible to simultaneously record seven colors.

In addition, the optical density of each prefecture has been sufficiently obtained.

Further, in the case of each prefecture, no difference was observed between the thermal coloring start temperature and the thermal coloring temperature, and the slope of the rise of coloring was sufficiently obtained, indicating that the thermal coloring characteristics were particularly excellent. Furthermore, the fall of color erasure is steep, and sufficient color erasing properties are obtained.

Next, an outline of the manufacturing method will be explained while following the steps, and the present invention will be explained in detail.

First, in the first step, a dispersion or emulsion having pressure-sensitive adhesive properties is prepared using the composition shown in FIG.

In the second step, the dispersion or emulsion prepared in the first step is encapsulated with a microcapsule wall material having a specific glass transition temperature, and yellow, magenta and cyan are added from the low temperature side. A color intermediate between cyan and yellow, a color intermediate between cyan, yellow and magenta, a color intermediate between cyan and magenta, and a color intermediate between magenta and yellow. Leuco-type dyes LYIXLC1, LY2, LM2, and L
Y3 and LM4, diazo dye DMI, and DC2 and D
Microcapsules 3.4.5.6.7 and 8 containing and encapsulating M3 separately are prepared.

As the leuco dye in this case, known materials such as phthalide compounds, fluoran compounds, lactone compounds, triphenylmethane compounds, rhodamine lactam compounds, and quinone compounds can be mainly used. can.

A phenol-based substance or an acidic substance is mainly used as a color developer in the color-forming component, and the mechanism is such that a color-forming reaction proceeds at a color-forming temperature to develop multiple colors.

Diazo dyes that develop color with a base are composed of a coupling compound formed by a diazo compound and a coupler, and develop multiple colors when substances come into contact with each other through heating. The diazo compound is a diazonium salt represented by the general formula A r N2+X- (wherein N2+ represents a diazonium group, X- represents an acid anion, and Ar represents an aromatic alkyl group), Known materials can be used with couplers, including, but not limited to, in the case of diazo compounds, aromatic diazonium salts, diazosulfonate compounds, and diazoamino compounds. In addition, since the coupling reaction between these diazo compounds and couplers is particularly likely to occur in a basic atmosphere, it is known to add a basic substance.
A slightly water-soluble or water-insoluble basic substance is used. Specific examples include inorganic and organic ammonium salts, organic amines, amides, urea and derivatives thereof. Furthermore, there is no problem in using two or more basic substances in combination.

The third step is to use a color erasing agent DE that can erase yellow, magenta, cyan, yellow, and magenta intermediate colors, and cyan and magenta intermediate colors.
Dispersions or emulsions each containing equal amounts of I, LE2, DE3, and LE4 are prepared.

Then, in the fourth step, each dispersion prepared in the third step,
Alternatively, the emulsion is encapsulated with a microcapsule wall material having a specific glass transition temperature to produce yellow, magenta, cyan, yellow and magenta intermediate colors, and cyan and magenta intermediate colors. Microcapsules 9 containing and encapsulating decolorizing agents DEI and DE3 capable of decolorizing threads, and microcapsules 10 containing and encapsulating LE2 and L-port 4 separately.
Prepare each.

The microcapsule wall at that time is thermally permeable, and the second
The processes have different specific glass transition temperatures.

In the fifth step, each microcapsule prepared in the second step and the fourth step is dispersed or emulsified using a wax binder to prepare a microcapsule liquid.

In the sixth step, the microcave cell solution prepared in the fifth step is applied using a known coating method, such as a bar coating method, a blade coating method, an air knife coating method, a gravure coating method, a roll coating coating method, a spray coating method, or It is applied onto the polyethylene terephthalate (PET) of the ribbon base material 2 by a dip coating method or the like.

In the seventh step, a dispersion or emulsion having heat-sensitive adhesive properties is prepared using the composition shown in FIG.

In the eighth step, the dispersion or emulsion having heat-sensitive adhesive properties prepared in the seventh step is applied using a known coating method, such as bar coating, plate coating, air knife coating, gravure coating, or roll coating. Using a coating method, a spray coating method, a dip coating method, or the like, layer coating is applied on the coating film obtained in the sixth step.

In the final step, the final multicolor ink ribbon for dry transfer material production obtained through the eighth step is subjected to final heating drying to form the final multicolor ink ribbon for dry transfer material production.

At that time, the viscosity of the microcapsule liquid obtained in the fifth step is 150 to 3000 in a temperature atmosphere of 95°C.
It is desirable that the viscosity of the dispersion or emulsion obtained in the seventh step is about 95°C.
It is desirable that it be about 10,000 to 60,000 centipoise in a temperature atmosphere of .

Next, using the thus obtained multicolor ink ribbon for dry transfer material production, it was set in a heat-sensitive transfer type writer, and multiple prints were made on a polyethylene film (thickness 100 μm) coated with silicone resin. By simultaneous color recording, we were able to simultaneously obtain a sufficiently beautiful and good quality multicolor printed image, and by rubbing the polyethylene film printed on it from the back side and applying pressure, we were able to obtain a multicolor printed image. Pressure sensitive retransfer of the image onto the desired substrate surface of paper, plastic or metal made it possible to simultaneously obtain multicolor images of sufficiently good quality.

Furthermore, using the thus obtained multicolor ink ribbon for dry transfer material production, ribbon storage stability and runnability tests were conducted under the following conditions.

That is, the first condition is storage at 40°C for 72 hours, the second condition is storage at 55°C for 48 hours, and the third condition is storage at 40°C for 72 hours. and further held in an atmosphere of 55°C for 48 hours,
The fourth condition was holding at 55°C for 48 hours, and then holding at 40°C for 72 hours. In addition, a ribbon running test was also conducted.

As a result, good results were obtained regarding storage stability, with no blocking or disordered winding, and good results were obtained regarding ribbon running properties, with no meandering or slipping.

In addition, in the ribbon base material 2, in order to prevent sticking, a heat-resistant resin layer such as silicone resin is coated on the surface opposite to the coated surface of the multicolor ink ribbon for dry transfer material production.
It is possible to contain pigments such as barium sulfate, titanium oxide, aluminum hydroxide, zinc oxide, and calcium carbonate.

Furthermore, there is no problem in adding a polymeric surface modifier composed of at least one selected from fluorine-based polymers, silicone-based polymers, and the like. The polymer surface modifier eliminates stickiness and stickiness on the ink ribbon surface and reduces frictional resistance, thereby achieving good storage stability without blocking, and good ribbon running properties without meandering or slipping. This makes it even more possible.

In addition, the polymer surface modifier should be added in an amount of 0.05 to 1 part by weight per 100 parts by weight of the total amount of the heat-sensitive adhesive component and the tackifying resin.
It is particularly desirable to incorporate it in a proportion of 0 parts by weight.

In addition, in order to adjust the film strength of the multicolor ink ribbon for dry transfer material production produced in this way and obtain a sharp multicolor printed image with good sharpness, it is also necessary to prevent staining and blocking. Fillers such as kaolin, talc, bentonite, titanium oxide, or zinc stearate,
organics such as metal soaps such as aluminum stearate;
Alternatively, an inorganic powder can be blended in a proportion not exceeding 20 (wt%) and present in a multicolor ink ribbon for producing a dry transfer material.

Although polyethylene terephthalate was used as the film-like ribbon base material 2 used in such multicolor ink ribbons for producing dry transfer materials, there are no known materials conventionally used as base materials for thermal transfer ink ribbons. All of them can be used and there is nothing wrong with that. In particular, because the thermal head comes into close contact with the ink ribbon base material, a resin film made of polyester such as polybutylene terephthalate, polyimide, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, etc., with a heat-resistant temperature of 150°C or higher is used as the ink ribbon base material. Alternatively, paper such as capacitor paper or glassine paper may be used as the desired material, and its thickness may be selected as appropriate depending on the type of material.
) is particularly desirable.

Microcrystalline wax was used as a binder agent for the microcapsules containing each primary color, each intermediate color, and their decolorizing agents, but other materials such as candelilla wax, carnauba wax, rice wax, and wax Waxes composed of one or more of animal waxes such as beeswax, lanolin, and spermaceti; mineral waxes such as montan wax and ceresin; and petroleum waxes such as paraffin wax are used. However, it is irreplaceable.

Further, as the above-mentioned waxes, resin-based waxes such as α-olefin-maleic anhydride copolymer can also be used.

In general, the microcapsules and binder agent constituting the multicolor ink portion 12 are as follows: 1. (1~
20) is preferably blended.

Furthermore, it is particularly preferable to use paraffin wax as the wax binder constituting the microcapsule liquid prepared in the fifth step, but the binder is not limited to the same.

Furthermore, in the present invention, rosin esters and ketones are used as tackifiers in order to improve the adhesion and hardness of the ink, impart cohesive force, impart adhesive force, and impart adhesive functions to pressure-sensitive adhesive properties and heat-sensitive adhesive properties. Although a resin was used, there is no problem in using a resin made of petroleum resin, rosin resin, polyamide resin, phenol resin, etc.

The heat-sensitive adhesive component and the tackifier constituting the heat-sensitive adhesive layer are 0.5 to 1 part by weight of the latter to 1 part by weight of the former.
It is especially desirable that the amount is 0 parts by weight, preferably 0.8 to 7 parts by weight.

Next, in the present invention, hydroxypropyl cellulose was used as a component having direct heat-sensitive adhesive properties, but resins with large heat-sensitive adhesive properties, such as ethylene-vinyl acetate copolymer, polyvinyl acetate, ionomer, acrylic polymer, etc. , ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyamide, ethyl cellulose, etc., or two or more thereof. There is nothing wrong with using it.

Further, in Tables 1 and 2, water was used as the dispersion medium, but there is no problem in using an organic solvent such as toluene.

Further, as a method for destroying the microcapsule walls, a method of destruction using thermal transmission was used, but there is no problem in using a method of thermal destruction such as thermal melting, or a method of destruction using pressure. In this case, the microcapsule wall material is a known material, such as wax etc. in the case of the destruction method by heat melting, melamine formaldehyde resin, urea-formaldehyde resin, gelatin, gum arabic, etc. in the case of the destruction method by pressure. , polyvinyl alcohol,
Egg white, alginate, zein, casein, methylcellulose, carboxymethylcellulose, carrageenan, ethylene-maleic anhydride copolymer, vinyl methyl ether-maleic anhydride copolymer, urea-formalin resin,
It is possible to use melamine-formalin resin, polyurethane resin, polyurea, etc.

As a way to express multiple hues, subtractive color mixing was used to create magenta (purplish red), yellow, and cyan (greenish blue), or purplish blue, green, and yellowish red. There is no harm in using known expression methods such as the additive color mixing method of It is not limited.

In addition, the color developer necessary for coloring the leuco dye can be contained in the core substance in the second step, or it can be contained outside the microcapsule as a dispersion in the fifth step. is also irreplaceable.

Further, the present invention is also effective for ink ribbons other than ink ribbons for producing dry transfer materials, such as thermal ribbons, and is not subject to the same restrictions.

[Effects of the Invention] As described above, according to the present invention, by producing a multicolor ink ribbon for dry transfer material production with a single ribbon structure, simultaneous multicolor recording is possible compared to the conventional method. made possible. Additionally, since it is a single ribbon, manufacturing costs are also significantly reduced.

Therefore, it has great effects.

[Brief explanation of the drawing]

FIG. 1 is an enlarged cross-sectional schematic diagram of a multicolor ink ribbon for producing a dry transfer material of the present invention and a dry transfer material produced by simultaneous multicolor recording, and FIG. FIG. 3 is an explanatory diagram showing the results of measuring thermal coloring characteristics using a multicolor ink ribbon, FIG. 3 is an explanatory diagram of a dispersion or emulsion having pressure-sensitive adhesive properties, and FIG. FIG. 2 is an explanatory diagram showing the composition of a dispersion or emulsion having adhesive properties. 1 Thermal head. 2 Ribbon base material. 3 Microcapsules containing yellow leuco dye. 4 Microcapsules containing magenta diazo dye. 5 Microcapsules containing magenta leuco dye. 6. Microcuff cell containing cyan-based leuco dye. 7 Microcapsules containing cyan diazo dye and magenta diazo dye. 8 Microcapsules containing magenta leuco dye and yellow leuco dye. 9. Microcapsules containing a diazo dye coupler. 10 Microcapsules containing a leuco dye developer. 11 Heat-sensitive adhesive layer. 12 Multicolor ink section. 13 Part of the dry transfer material exhibiting a magenta color. 14 The dry transfer material part exhibits a color intermediate between cyan and magenta. 15 Retransfer sheet.

Claims (1)

[Claims] 1. In an ink ribbon that is built into an image recording device that forms recorded images such as characters and figures and is used when forming recorded images, one side of a film-like ribbon base material is coated with an acid coloring dye, a base coloring dye, and At least one or more types of dyes selected from sublimable dyes are combined, and at least two or more types of microcapsules selected from a group of microcapsules that are separately contained and a decoloring agent for decoloring each combined dye are used. An ink ribbon characterized in that it uniformly contains at least one type of each of the microcapsules selected from the group of microcapsules that are individually contained.