JPH03219989A - Ink ribbon for dry transfer material - Google Patents

Abstract

PURPOSE:To enhance the thermal transfer properties of a surface inferior in wettability by providing a layer containing a colorant, a binder, a pressure- sensitive adhesive, a resin having heat-sensitive adhesiveness, a resin having adhesiveness imparting properties and a surface modifier to one surface of a film like ribbon base material and continuously varying the composition in the film thickness direction of the layer. CONSTITUTION:The multicolor ink layer 7 formed on a film like ribbon base material 1 constituted of a film material composed of polyethylene terephthalate is formed by repeatedly forming a magenta ink layer 7a, a cyan ink layer 7b and a yellow ink layer 7c on the film like ribbon base material 1 in the longitudinal direction thereof in succession over a predetermined length. The layer consisting of a pressure-sensitive layer 2, a heat-sensitive adhesive layer 3 and the multicolor ink layer 7 is formed on the film like ribbon base material 1 so that the composition thereof in the film thickness direction is continuously inclined. By this constitution, no interface is generated in the ink ribbon layer and, therefore, an interface problem such as the release and destruction of the interface is resolved to a large extent and the heat-sensitive adhesiveness to a surface inferior in wettability can be enhanced to a large extent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an ink ribbon for dry transfer materials, particularly for thermal transfer type color printers and color typewriters.
It is possible to transfer and print on surfaces with poor wettability and strong removability using a word processor, etc., and the transferred image obtained by thermal transfer can be transferred onto the target material using pressure. This invention relates to an ink ribbon for dry transfer material that can be retransferred.

[Prior Art] In recent years, color printers, color typewriters, word processors, and other printing and recording devices using a thermal transfer method have been developed and are now being used in a wide range of applications, from small-sized personal use to business use. By bringing the transfer ink ribbon into close contact with a predetermined printing paper using a thermal head, and by causing only the heating elements necessary for recording to generate heat among the many heating elements of the thermal head, the transfer ink ribbon can be transferred through the support of the transfer ink ribbon. Printing is performed by a sensitive transfer method by melting the heat-melting ink portion that is in contact with the heating element and transferring it onto the printing paper, and multicolor printing has also been put into practical use.

By the way, this type of transfer ink ribbon is constructed by coating only a heat-melting ink consisting of a coloring agent and its binder agent on a predetermined support, and the binder agent does not contain wax. It was the main ingredient. Furthermore, this type of transfer ink ribbon was only intended for use with plain paper as the transfer object.

On the other hand, recently, with the spread of thermal transfer methods, it has become necessary to improve transferability to paper with low smoothness called rough paper, and various patent applications related to this are known. In addition, the same ink ribbon can be used to transfer images over and over again.
Multi-type ribbon enables printing, erases typos,
Various techniques have also been proposed, such as collector pull ribbons that can be modified.

For example, regarding the structure of a sensitive transfer ink ribbon that is intended to enable transfer and print recording on surfaces with poor wettability and good peelability or mold release properties, there has been a
It is described in Japanese Patent Application Laid-open No. 128990, Japanese Patent Application Laid-Open No. 63-128991, and Japanese Patent Application Laid-Open No. 63-251287.

[Problems to be Solved by the Invention] However, in the above-mentioned prior art, two layers are formed on the ribbon base (substrate): a homogeneous monochromatic ink layer containing a pressure-sensitive adhesive and a pigment, and a homogeneous layer containing a heat-sensitive adhesive. or because it consisted of two layers coated on a ribbon base (substrate): a homogeneous layer with a pressure-sensitive adhesive and a homogeneous single-color ink layer with a heat-sensitive adhesive and a pigment. , Part 2
The problem was that peeling or destruction occurred at the layer interface.

On the other hand, in the case of a one-layer structure that has both heat-sensitive adhesiveness and pressure-sensitive adhesiveness, it is difficult to satisfy both heat-sensitive adhesiveness and pressure-sensitive adhesiveness at the same time. Alternatively, it has had the problem of poor transferability to dry thermal transfer materials, and has also had the problem of being usable only for monochrome recording.

Therefore, the present invention was made to solve these problems, and its first purpose is to provide a dry transfer material that has significantly improved heat-sensitive transferability to surfaces with poor wettability. It is located in a place that provides ink ribbons.

Furthermore, a second object is to provide an ink ribbon for dry transfer material that has good storage stability.

The third objective is to provide an ink ribbon for dry transfer materials with excellent ribbon running properties, and by improving the cohesive force of the entire ribbon itself, it can be used to create a thermally receptive paper (retransfer sheet). The ink image transferred onto the top (
By applying pressure from behind the receiving paper (retransfer sheet), the transferred image can be easily transferred to the target object.
To provide an ink ribbon for a dry transfer material that enables pressure-sensitive retransfer in a perfect shape without crushing.

Furthermore, the fourth objective is to eliminate peeling and destruction at the interface caused by the presence of an interface, thereby ensuring a significant improvement in the weather resistance of the pressure-sensitive retransferred ink image. The company provides ink ribbons for materials.

[Means for Solving the Problems] The ink ribbon for dry transfer material of the present invention has a coloring agent, a binder agent, a pressure-sensitive adhesive,
A layer containing a heat-sensitive adhesive resin, a tackifying resin, a surface modifier, etc. was provided, and the composition of the layer in the thickness direction was continuously graded.

[Function] According to the configuration of the present invention described above, a colorant, a binder agent, a pressure-sensitive adhesive, a resin having heat-sensitive adhesive properties, a resin having tackifying properties, and a molecular surface modification of an ink ribbon for a dry transfer material. By continuously sloping the composition in the thickness direction of the layer containing agents, etc., desired characters, figures, etc. can be transferred onto the receiving paper (retransfer sheet), which has a surface with poor wettability. Even if you thermally print a transferred image, it may spread, bleed, shading,
This means that a good printed image can be obtained without causing any problems such as scraping by the head, stringiness, or insufficient transfer.

In addition, by applying pressure from the back side of the receiving paper (retransfer sheet), the printed image printed in this way is transferred to the desired paper,
Even when pressure-sensitive retransfer is performed on a transfer material such as plastics or metal, there is no residual ink on the receiving paper (retransfer sheet), and the transferred printed image is free from smearing, spreading, and brittleness. Therefore, it is possible to obtain a good image with strong pressure-sensitive adhesion on the transferred object.

In addition, the ink ribbon for dry transfer, the dry transfer material produced by heat-sensitive transfer onto a receiving paper (re-transfer sheet), and the image transferred by pressure-sensitive re-transfer onto a transfer object under a condition of 55°C. Even when stored for 24 hours, problems with the interface such as peeling from the interface and destruction, which were problems in the case of the conventional two-layer structure, are significantly improved, and the shelf life of the ribbon is improved. The weather resistance of the pressure-sensitive retransferred image has been greatly improved, and there are no problems such as blocking or irregular winding. Regarding ribbon running, there are no problems such as ribbon meandering or slither roughness, and printing can be performed to the end of the ribbon. , can be thermally transferred.

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

In addition to the following examples and the above-described specific description, the present invention includes various changes, modifications, and changes based on the knowledge of those skilled in the art, as long as they do not depart from the spirit of the present invention. It should be understood that improvements can be made.

FIG. 1 is an enlarged cross-sectional view of a multicolor ink ribbon for dry transfer materials, which implements the ink ribbon for dry transfer materials of the present invention.

That is, the multicolor ink ribbon 4 for dry transfer material has a pressure-sensitive adhesive layer 2, a heat-sensitive adhesive layer 3, an anti-sticking layer 6, and a film-like ribbon base material 1 made of a film material such as polyethylene terephthalate. and multicolor ink layer 7
are constructed by stacking them. The multicolor ink layer 7 includes a magenta ink layer 7a, a cyan ink layer 7b, and a yellow ink layer 7C, which are sequentially and repeatedly formed over a predetermined length in the longitudinal direction of the film-like ribbon substrate 1. has been done. The layer consisting of the pressure-sensitive adhesive layer 2, the heat-sensitive adhesive layer 3, and the multicolor ink layer 7 is formed on the film-like ribbon substrate 1 so that the composition in the film thickness direction is continuously graded. ing.

Then, the multicolor ink ribbon 4 for dry transfer material is applied to the receiving paper (retransfer sheet) 5 by heating it from the film ribbon base material 1 side with a thermal head of a known printing and recording device. A layer consisting of a pressure-adhesive layer 2, a heat-sensitive adhesive layer 3, and a multicolor ink layer 7 is thermally transferred.

Next, a method for manufacturing a multicolor ink ribbon for dry transfer material will be briefly explained while following the steps.

First, in the first step, raw materials for the magenta ink layer 7a of the multicolor ink layer 7, raw materials for the heat-sensitive adhesive layer 3 containing a polymer surface modifier, and materials for the pressure-sensitive adhesive layer 2 are used. The raw materials for each are dissolved or pulverized and dispersed using water as a dispersion medium.

Next, in the second step, the raw material composition for the heat-sensitive adhesive layer 3 and the raw material for the pressure-sensitive adhesive layer 2 are obtained by mixing and stirring each solution or pulverized dispersion liquid prepared in the first step. While keeping the composition and raw material composition for the magenta color ink layer 7a constant, various coating liquids having different weight ratios of the raw materials for the heat-sensitive adhesive layer 3 and the raw materials for the pressure-sensitive adhesive layer 2 were used. ,
Produce as shown in Table 1.

The following is a margin table 1. At that time, the raw material composition for the magenta color ink layer 7a used on the film-like ribbon substrate 1 side is desirably about 150 to 3000 centipoise in a temperature atmosphere of 950C. The raw material composition for the magenta color ink layer 7a used on the front side of the multicolor ink ribbon 4 for transfer material is 1000% in a temperature atmosphere of 95°C.
It is desirable that it be about 0 to 60,000 centipoise.

Next, in the third step, the coating liquid created in the second step is applied to bar coating, blade coating, air knife coating, gravure coating, etc.
It is applied onto a polyethylene terephthalate (PET) film with a thickness of 3.5 μm as the film-like ribbon base material 1 using any coating method such as roll coating, spray coating, or dip coating.

Next, in the fourth step, using one of the coating methods in the third step, the raw material composition for the heat-sensitive adhesive layer 3 and the raw material composition for the pressure-sensitive adhesive layer created in the second step are combined. Various coating solutions with different weight ratios are applied one after another by repeating coating and heating drying 7 to 10 times so that the final dry film thickness is 7 to 10 (μm), and the film thickness is determined so that no micro interfaces occur. A monochromatic ink layer for a dry transfer material for magenta color having a layer whose directional composition is continuously graded is prepared.

Next, in the fifth step, using the first to fourth steps, the monochromatic ink layer for dry transfer for magenta color previously prepared is placed on the film-like ribbon base material 1 in the running direction of the ribbon. A single color ink layer for a dry transfer material for cyan having a cyan ink layer 7b and a single color ink layer for a dry transfer material for yellow having a yellow ink layer 7C are arranged adjacent to each other in order. The ink ribbons are sequentially produced, and finally one multicolor ink ribbon 4 for dry transfer material is produced.

The coating liquid for producing the monochrome ink layer for dry transfer material having the cyan ink layer 7b is prepared as shown in Table 2, and the coating liquid for producing the monochrome ink layer for dry transfer material having the yellow ink layer 7c is prepared as shown in Table 2. The coating liquid for forming the ink layer is prepared as shown in Table 3.

Table 2 Table 3 Next, in the final step, the multicolor ink ribbon 4 for dry transfer material produced in the fifth step is subjected to final heating drying, and as a result, the composition formula is AxB 100-xC. A multicolor ink ribbon 4 for dry transfer material is formed. here,
A represents the composition of the heat-sensitive adhesive layer 3, B represents the composition of the pressure-sensitive adhesive layer 2, and C represents the composition of the multicolor ink layer 7.

FIG. 2 is a diagram showing the composition distribution in the film thickness direction of the monochromatic ink ribbon layer for dry transfer. The vertical axis represents the composition X of the heat-sensitive adhesive layer 3, and the horizontal axis represents the position in the film thickness direction from the film-like ribbon substrate 1 side to the surface side of the multicolor ink ribbon for dry transfer material.

It can be seen that the composition X of the heat-sensitive adhesive layer 3 is continuously graded between O and 100 (%) without the generation of micro interfaces.

Therefore, the characteristics of the multicolor ink ribbon 4 for dry transfer are that the film ribbon base material 1 side has better pressure-sensitive adhesive properties, and the surface side of the multicolor ink ribbon 4 for dry transfer material has better heat-sensitive adhesiveness and hardness. It also exhibits excellent cohesive strength. As a whole, the multicolor ink ribbon for dry transfer material 4 has significantly improved heat-sensitive adhesion during the production of dry transfer materials, resulting in improved heat-sensitive adhesion to surfaces with poor wettability. The significant improvement in viscosity and hardness effectively improves transfer defects such as soaking and spreading, and also effectively prevents ink from being scraped by the thermal head of a printing and recording device. There is.

In addition, the pressure-sensitive adhesive properties during pressure-sensitive re-transfer, in which pressure is applied from behind the receiving paper (re-transfer sheet) 5 to transfer the multicolor ink image created by thermal transfer to the transfer object, are greatly improved. The cohesive force and hardness have also been significantly improved, making it possible to transfer a predetermined multicolor ink image from the receiving paper (retransfer sheet) 5 without any residual ink, and The transferred multicolor ink also spreads, making it possible to obtain a beautiful multicolor image without staining, and at the same time protecting the transferred multicolor image and making it strong.

A heat-resistant resin such as silicone resin,
An anti-sticking layer 6 made of at least one pigment selected from pigments such as barium sulfate, titanium oxide, aluminum hydroxide, zinc oxide, and calcium carbonate is provided.

Furthermore, the tackifier used in the present invention functions to improve the adhesion and hardness of ink, impart cohesive force, impart adhesive force, and impart tackiness to pressure-sensitive adhesives and heat-sensitive adhesives.
Specific examples include those made of petroleum resin, rosin resin, ketone resin, polyamide resin, phenol resin, and the like.

Further, the heat-sensitive adhesive and the tackifier constituting the heat-sensitive adhesive layer 3 are 0.5 to 10 parts by weight of the latter to 1 part by weight of the former.
Parts by weight, preferably 0. It is blended in a proportion of 8 to 7 parts by weight.

Furthermore, it is possible to add 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 surface of the multicolor ink ribbon 4 for dry transfer, and reduces frictional resistance, resulting in good storage stability without blocking, meandering, and slippage. This makes it possible to obtain ribbon runnability.

In addition, the polymeric surface modifier is 0.05 to 10 parts by weight based on 100 parts by weight of the total amount of the heat-sensitive adhesive and the tackifying resin.
It is desirable that they be blended in the proportion of parts by weight.

In addition, the multicolor ink ribbon 4 for dry transfer material formed in this way has a film strength adjusted to obtain a sharp multicolor printed image with good sharpness, and also to prevent staining and blocking. , kaolin, talc, bentonite,
A multicolor ink ribbon for dry transfer material 4, which contains fillers such as titanium oxide and organic or inorganic powders such as metal soaps such as zinc stearate and aluminum stearate in a proportion not exceeding 20% by weight. It is also possible to make it exist within.

Next, the thus obtained multicolor ink ribbon for dry transfer material was set in a heat-sensitive transfer type writer, and a silicone resin was coated as receiving paper (retransfer sheet) 5. Polyethylene film (thickness 100μ)
m) When the printed image was recorded on the polyethylene film, a sufficiently beautiful and good quality multicolor printed image was obtained, and by rubbing the printed polyethylene film from the back side and applying pressure, When a multicolor printed image is pressure-sensitively retransferred onto a desired surface of a transfer object such as paper, plastics, or metal, it has become possible to obtain a multicolor image of sufficiently good quality.

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

That is, the first condition was held at 35°C for 72 hours,
The second condition is storage at 55°C for 24 hours, the third condition is storage at 35°C for 72 hours, and then at 55°C for 24 hours, and the fourth condition is storage at 55°C for 24 hours. The storage properties were observed under four conditions in which the samples were held at 35° C. for 72 hours, and then a ribbon running test was also conducted including those immediately after coating.

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 slippage.

Although a polyethylene terephthalate film was used as the film-like ribbon base material 1 of the multicolor ink ribbon 4 for dry transfer, any of the known materials conventionally used as a base material for thermal transfer ink ribbons may be used. It is usable and there is nothing wrong with it.

In particular, since the thermal head (printing device) is in close contact with the film ribbon base material 1, the heat resistance temperature is 150"C.
As mentioned above, resin films made of polyester such as polybutylene terephthalate, polyimide, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, etc., or papers such as condenser paper and glassine paper can be used as suitable materials. Further, the thickness thereof will be appropriately determined depending on the type of material, but it is particularly desirable to use a thickness in the range of 3 to 20 μm.

Further, a magenta ink layer 7a, a cyan ink layer 7b
, and the yellow ink layer 7C mainly contain a colorant and a binder agent. In the present invention, a leuco dye that develops color with acid is used as a coloring agent in order to express various hues.
Dyes such as diazo dyes that develop color with bases can be used as appropriate, and there is no problem.

Leuco dyes that develop color with acids include phthalide compounds, fluoran compounds, lactone compounds, triphenylmethane compounds, rhodamine lactam compounds,
Also, known materials such as quinone compounds can be mainly used. 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 progresses with the color-forming agent at a color-forming temperature, thereby producing multiple colors.

Furthermore, diazo dyes that develop color with a base are composed of a diazo compound and a coupling compound produced by 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, mention may be made of 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 that a basic substance is added. 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.

Further, in the present invention, a multicolor printing recording method is used in which ink layers having separate magenta, cyan, and yellow hues are overlaid in a field sequential manner, but a single ribbon is used for multicolor printing. There is no problem in using a print recording method or a multicolor print recording method using overlapping coating using a line sequential method.

Microcrystalline wax was used as a binder for forming the magenta ink layer 7a1, the cyan ink layer 7b, and the yellow ink layer 7C. Vegetable waxes: Animal waxes such as beeswax, lanolin, spermaceti; Montan wax,
There is no problem in using mineral waxes such as ceresin; and waxes composed of one or more petroleum waxes such as paraffin wax. Further, as the above-mentioned waxes, resin-based waxes such as α-olefin-maleic anhydride copolymer can also be used.

It is generally desirable that the coloring agent and the binder agent constituting the multicolor ink layer 7 be blended in a ratio of about 1 (1 to 20).

Furthermore, as the pressure-sensitive adhesive layer 2 used in the present invention,
Polyvinyl chloride, polyacrylic acid ester, ethylene-
Vinyl polymers such as vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyvinyl acetate, polyvinyl ether, polyvinyl acetal, polyisobutylene; Fiber polymers such as ethyl cellulose, nitrocellulose, cellulose acetate; chlorinated rubber; One type or a combination of two or more types of rubber-based polymers such as natural rubber are used.

Next, as the heat-sensitive adhesive layer 3 used in the present invention,
Resins with high heat-sensitive adhesive properties, such as ethylene-vinyl acetate copolymer, polyvinyl acetate, ionomer, acrylic polymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, vinyl chloride-vinyl acetate copolymer It is used in combination with one or more of polyvinyl butyral, polyvinylpyrrolidone, polyvinyl alcohol, polyamide, ethyl cellulose, etc.

Further, although water was used as a dispersion medium, there is no problem in using an organic solvent such as methyl isobutyl ketone.

Comparative Examples 1 to 2 In order to compare with the multicolor ink ribbon 4 for dry transfer material of the above-mentioned example, a conventional ink ribbon (
Comparative Example 1) and an ink ribbon (Comparative Example 2) having a conventional one-layer structure but with a homogeneous composition in the film thickness direction were used to produce the same ink ribbon 4 for dry transfer material of the above-mentioned example. A transferability test, a storage test, and a weather resistance test were conducted.

As a result, in particular, in Comparative Example 1, problems such as ink remaining on the receiving paper (retransfer sheet) 5 occurred due to peeling from the interface between the two layers, destruction, or defective integral transfer.

Further, a problem occurred in that either pressure-sensitive retransferability or heat-sensitive transferability was insufficient. Specifically, with regard to pressure-sensitive adhesion, there are problems such as insufficient transfer and adhesion due to insufficient pressure-sensitive adhesive strength, and problems such as crushing, spreading, and insufficient strength of the final transferred printed image due to insufficient cohesive force, viscosity, and hardness. occurred.

In addition, with regard to heat-sensitive adhesive properties, problems such as insufficient transferability due to insufficient adhesive strength, spread of transferred prints due to insufficient cohesive force, viscosity, and hardness, smearing, scraping of prints by the head, and shading of prints occur. It was approved to do so.

[Effects of the Invention] As described above, according to the present invention, the composition of the ink ribbon for dry transfer material is continuously graded in the film thickness direction, which improves dry transfer performance compared to conventional products. Since no interface occurs inside the ink ribbon layer for materials, interface problems such as interfacial peeling and destruction are greatly improved, and the thermal adhesion to surfaces with poor wettability and dry transfer materials Thermal transfer performance has been significantly improved. Furthermore, the pressure-sensitive re-adhesion of printed images created by thermal transfer to other materials using pressure has also been significantly improved.

[Brief explanation of drawings]

FIG. 1 is an enlarged cross-sectional view of a multicolor ink ribbon for dry transfer materials, in which the ink ribbon for dry transfer materials of the present invention is implemented;
FIG. 2 is a diagram showing the composition distribution in the film thickness direction of a multicolor ink ribbon for dry transfer material. Film-like ribbon base Pressure-sensitive adhesive layer Heat-sensitive adhesive layer Multicolor ink ribbon for dry transfer material Receiving paper (retransfer sheet) Anti-sticking layer Multicolor ink layer, magenta ink layer, cyan ink layer, yellow ink Layer diagram 2

Claims (2)

[Claims] (1) Transfer images such as letters and figures obtained by thermal transfer are
In an ink ribbon for dry transfer material that can be pressure-sensitively retransferred onto the target transfer material by pressure, a coloring agent, a binder agent, a pressure-sensitive adhesive, and a heat-sensitive material are coated on one side of a film-like ribbon base material. A dry method characterized by having a layer composed of an adhesive resin, a tackifying resin, a surface modifier, etc., and having the composition of the layer continuously graded in the thickness direction. Ink ribbon for transfer material. (2) The composition of the layer in the thickness direction is made continuous so that the film-like ribbon substrate side of the layer has better pressure-sensitive adhesiveness, and the surface side has better heat-sensitive adhesiveness, hardness, and cohesive force. The ink ribbon for a dry transfer material according to claim 1, characterized in that the ink ribbon is inclined at a angle of .