JPH0316776A - Ink ribbon for dry transfer material manufacture - Google Patents

Abstract

PURPOSE:To make it possible to improve and adjust pressuresensitive retransfer properties by forming an ink layer containing a coloring agent, a binder and a pressure-sensitive adhesive on one surface of a film-like ribbon base and forming a specific transferable adjustment layer on the ink layer. CONSTITUTION:An ink layer 12 is formed on one surface of a filmlike ribbon base 11, and a transferable adjustment layer 13 is formed in a specified thickness on the ink layer 12. In addition, a sticking protecting layer 14 of heat-resistant resin such as silicon resin is provided on the opposite surface to the coated surface of the ink layer 12 on the ribbon base 11. The ink layer 12 consists of a coloring agent, a binder and a pressure-sensitive adhesive. The transferable adjustment layer 13 is more highly viscous than the ink layer 12 and is constituted as a layer with high thermal adhesion, hardness and coagulation properties. Furthermore, the transferable adjustment layer 13 is composed of a mixture of a resin with high film formation and thermal adhesion properties and silicone oil. Thus it is possible to control thermal transfer and pressure-sensitive retransfer properties and ensure the temporal stability of pressure-sensitive retransfer properties and the simplification of manufacturing process.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a thermal transfer ink ribbon used in the production of dry transfer materials, and particularly to a thermal transfer printer,
Using a typewriter, word processor, etc., it is possible to transfer and print even on surfaces with poor wettability and strong peeling properties, and the transferred image obtained by thermal transfer can be transferred onto the intended transfer object using pressure. The present invention relates to an ink ribbon for producing a dry transfer material that can be effectively pressure-sensitive retransferred.

[Prior Art] In recent years, printing devices such as printers, typewriters, and word processors using a thermal transfer method have been developed, and are now widely used for everything from small-sized personal use to business use. Printing using this thermal transfer method is
A thermal transfer ink ribbon is brought into close contact with a predetermined printing paper by a thermal head, and a desired heating element among the many heating elements of the thermal head is made to generate heat, thereby making contact with the heating element through the support of the thermal transfer ribbon. This is done by melting the heat-melting ink portion of the paper and transferring it to the printing paper.

By the way, this type of thermal transfer ribbon has conventionally been made by simply coating a heat-melting ink consisting of a colorant and a binder agent on a predetermined support, and the binder agent is mainly composed of wax. It was something to do. Furthermore, this type of thermal transfer ribbon was only intended for use with ordinary paper as the transfer material.

By the way, the present inventors have previously developed a thermal transfer ink ribbon that has poor wettability and is intended to enable transfer and printing onto base sheet surfaces with good release and peelability.
Specification of Japanese Patent Application No. 61-275538, Japanese Patent Application No. 61-27
The invention is reported in Japanese Patent Application No. 5539 and Japanese Patent Application No. 85350/1982, and those aimed at improving thermal sensitivity are disclosed in Japanese Patent Application No. 80126/1982.

In conventional thermal transfer devices, ribbon winding is performed by pulling out the ribbon as the head moves due to the frictional force between the ink surface of the ribbon and the paper that is the transfer target, and then removing any slack and excess ribbon. By winding up the
It is being done. However, it has poor wettability and poor mold release properties.
A surface with good peelability has a small coefficient of friction, so the force required to pull out the ribbon is weak. Therefore, if the force required to pull out the ribbon from the cassette is large, the ribbon will not be completely fed. This causes the head to print on the same location on the ribbon (slip), making printing impossible. Also, to prevent this, you can reduce the force required to pull the ribbon out of the cassette.
This time, the running of the ribbon becomes unstable and ribbon meandering occurs. Furthermore, the ribbon pulling force differs greatly between immediately after ink application and after several days have passed, and it also changes when stored at temperatures above 55°C, so consider storage stability and changes over time. However, it is difficult to achieve ribbon running without meandering or slipping when the ribbon is placed in the same position.

The present inventors have previously published Japanese Patent Application No. 62-255761 on a heat-sensitive transfer ink ribbon aimed at simultaneously solving the problems of storage stability and ribbon runnability.
Japanese Patent Application No. 1982-255762, Japanese Patent Application No. 1983-255762
It is reported in the specification of No. 2348 and the specification of CT Application No. 62-297155. However, to date, there have been no reports regarding methods that enable improvement or regulation of pressure-sensitive retransferability.

The present invention has been made to solve the above-mentioned problems, and its first purpose is to provide a thermal transfer ink ribbon for producing dry transfer materials.

A second object of the present invention is to provide an ink ribbon for producing dry transfer materials that has improved heat-sensitive transferability to surfaces with poor wettability. The ink image (transfer image) transferred onto the basic sheet can be easily and completely pressure-sensitively retransferred onto the intended transfer object by applying pressure from behind the basic sheet. In addition, we have developed an ink ribbon for dry transfer material production whose adhesive strength can be adjusted according to the wettability of the basic sheet, and in other words, by adjusting the amount of silicone oil added, it is possible to control heat-sensitive transferability and pressure-sensitive retransferability. It is about providing.

A fourth object of the present invention is to provide an ink ribbon for producing dry transfer materials with good storage stability, and a fifth object of the present invention is to provide an ink ribbon for producing dry transfer materials with good ribbon running properties. The purpose of the present invention is to provide ink ribbons for

[Means for Solving the Problems] In order to achieve this object, the ink ribbon for producing a dry transfer material of the present invention is constructed to have the following features. That is, in an ink ribbon used to form transferred images such as required characters and figures by a thermal transfer method in order to manufacture the desired dry transfer material, one side of a predetermined film-like ribbon base material is colored. an ink layer containing a binder agent, a binder agent, and a pressure-sensitive adhesive, and a heat-sensitive adhesive resin, a tackifier resin, and a silicone oil on the ink layer. A transfer property adjusting layer having a higher viscosity, heat-sensitive adhesive property, hardness and cohesive force than the ink layer was formed.

[Specific structure and operation] The thermal transfer ink ribbon according to the present invention having the above structure has, for example, an ink layer 12 on one surface of a film-like ribbon base material (support) 11, as shown in the drawings. is formed, and a transferability adjusting layer 13 is further formed thereon to a predetermined thickness. An anti-sticking layer 14 made of a heat-resistant resin such as silicone resin is provided on the surface of the ribbon base material 11 opposite to the surface coated with the ink layer 12.

In such a thermal transfer ink ribbon 10 for producing a dry transfer material, the film-like ribbon base material 11 that supports the ink layer 12 may be any of various materials conventionally used as a base material for thermal transfer ink ribbons. Any material can be used, but since a thermal head (printing device) is brought into contact with the ink ribbon for thermal transfer, polyester, polyimide, polycarbonate, and polysulfone, which have a heat resistance temperature of 150°C or higher, are recommended. , resin film made of polyether sulfone, polyphenylene sulfide, etc., or capacitor paper,
Paper such as glassine paper is used as a suitable material, and its thickness will be determined appropriately depending on the type of material, but it is generally desirable to use a thickness in the range of 3 to 20 μm. .

Further, the ink layer 12 mainly includes a colorant, a binder agent, and a pressure-sensitive adhesive.

As the coloring agent, a pigment such as carbon black is mainly used, but an appropriate dye may be added as necessary to adjust the color tone.

The binders constituting this ink layer 12 are mainly vegetable waxes such as candelilla wax, carnauba wax, rice wax, and Japanese wax; animal waxes such as beeswax, lanolin, and spermaceti wax; monk wax; , mineral waxes such as ceresin; waxes made of one or more petroleum waxes such as paraffin wax and microcrystalline wax, and adhesives such as petroleum resins, rosin resins, ketone resins, polyamide resins, and phenolic resins. A compound consisting of supplementary agents is used. In addition, the above waxes include α-
Resin-based waxes such as olefin-maleic anhydride copolymer can also be used, and tackifiers can be used to improve the adhesion and hardness of ink, add cohesive force, tackiness, and tackiness to pressure-sensitive adhesives. It performs the function of Further, the wax and the tackifying agent constituting the binder agent are generally mixed in a ratio of about 15=1 to 3:2 on a weight basis.

Furthermore, the pressure sensitive adhesive constituting the ink layer 12 is as follows:
Vinyl polymers such as polyvinyl chloride, polyacrylic acid ester, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyvinyl acetate, polyvinyl ether, polyvinyl acetal, polyisobutylene; ethyl cellulose, nitrocellulose, cellulose acetate One or more rubber-based polymers such as chlorinated rubber and natural rubber are used in combination.

The coloring agent, binder agent, and pressure sensitive adhesive that constitute the ink layer 12 are generally in a ratio of 5 to 30:40 to 93:2.
It is blended at a ratio of about 30%, preferably 9%.
At a temperature of 5[deg.] C., the ink composition provides a viscosity of less than 3,000 centivoise, particularly about 200 to 1,000 centivoise. Further, such an ink composition may be dissolved or dispersed in an appropriate solvent to form an ink liquid, or heated and mixed to form an ink, and then applied onto the desired film-like ribbon substrate 11 using a known method. Coating or hot-melt coating will be applied according to the requirements.

On the other hand, the transferability adjusting layer 13 as a top coat layer formed on the ink layer 12 is
The transferability adjusting layer 13 has a higher viscosity (under thermal transfer conditions) and a higher heat-sensitive adhesive property, hardness, and cohesive force. This improves thermal transfer properties on surfaces with poor wettability, and the increased cohesive force, viscosity, and hardness effectively improve transfer defects such as crushing and spreading. It also has the function of effectively preventing ink from being scraped together by the head of the device. In addition, during pressure-sensitive retransfer, in which pressure is applied from behind the basic sheet of the dry transfer material to transfer the ink image (transfer image) created by dry transfer to the transferred object, the transferability adjustment layer 13 has a cohesive force. , because the hardness is greater, there is no residual ink from the base sheet,
Together, they make it possible to transfer a predetermined ink image, and the transferred ink also spreads, making it possible to obtain a beautiful image without smearing.At the same time, it protects the transferred image. This makes it strong.

By the way, such a transferability adjusting layer 13 is made of a resin having high film-forming properties and high heat-sensitive adhesive properties, such as ethylene-vinyl acetate copolymer, polyvinyl acetate, ionomer, acrylic polymer, ethylene-ethyl acrylate copolymer. It has a large cohesive force and tackifying properties, and is combined with one or more of ethylene-acrylic acid copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyvinylpyrrolidone, polyvinyl alcohol, polyamide, ethyl cellulose, polyolefin, etc. Resins, such as petroleum resins, rosins, hydrogenated rosins, rosin esters, ketone resins,
It is mainly composed of a mixture of one or more phenolic resins and silicone oil. The amount of heat-sensitive adhesive resin and tack-imparting resin is 0.5 to 1 part by weight of the latter to 1 part by weight of the former.
0 parts by weight, preferably 0.8 to 7 parts by weight, and the silicone oil is mixed in an amount of 1 to 100 parts by weight of the total composition constituting the transferability adjusting layer 13.
It will be blended in a proportion of 50 parts by weight.

The heat-sensitive adhesive resin with high film-forming properties constituting the transferability adjusting layer 13 may be incompatible with the ink layer 12 or
Even if they are compatible, they do not mix easily and form a large heat-sensitive adhesive film on the ink layer 12.
It is added to improve the adhesion with No. 2, increase cohesive force, hardness, and tackiness, and adjust heat-sensitive transferability.

In addition, by dispersing silicone oil in the layer, it can eliminate stickiness and stickiness on the surface of the ink ribbon and reduce frictional resistance.As a result, it has good storage stability without blocking, meandering, and slipping. It provides good ribbon running properties, and depending on the amount added,
It is added to enable control of heat-sensitive transferability and pressure-sensitive retransferability, to simplify the ink ribbon manufacturing process, and to obtain an ink ribbon with excellent stability over time in pressure-sensitive retransferability. It is something.

The composition comprising the heat-sensitive adhesive resin with high film-forming properties, the tackifying resin, and the silicone oil can be used in the form of an aqueous solution or aqueous dispersion, or in the form of a general-purpose resin that does not attack the ink layer 12. In the form of an organic solvent solution or dispersion, the transferability adjusting layer is coated on the ink layer 12 to a predetermined thickness according to a normal coating method. 13 is
Under thermal transfer conditions, the viscosity is higher than that of the ink layer 12, and generally the layer has a viscosity of 3,000 centivoise or more, preferably 10,000 centivoise or more at a temperature of 95°C.

In addition, the transferability adjusting layer 13 formed in this way is further coated with kaolin and talc in order to adjust the film strength and obtain a sharp printed image, and to prevent staining and blocking. , fillers such as bentonite and titanium oxide, and organic or inorganic powders such as metal soaps such as zinc stearate and aluminum stearate.
It is also possible to include it in a proportion not exceeding % by weight and make it exist in the transferability adjustment J113.

Then, using the ink ribbon 10 obtained in this way, the shape of the head heating element, the position of the head heating element,
The desired dry transfer material can be printed and thermally transferred by setting it in a printing device such as a thermal transfer printer that has adjusted the head installation angle, head pressing pressure, winding torque, head printing energy, printing speed, etc. Therefore, it can be manufactured advantageously.

That is, by using such an ink ribbon 10, even if a transfer image such as a desired character or figure is thermally printed on a film (basic sheet) having a surface with poor wettability, it will not spread, collapse, shading, or It is possible to realize a good printed image without causing any problems such as scraping by the head, stringiness, yuzu skin, or insufficient transfer.

Furthermore, even if the image printed in this way is pressure-sensitively retransferred onto the target material such as paper, plastic, or metal by applying pressure from the back side of the film (basic sheet), There is no residual ink on the film, and the transferred image is strong, adhesive, and does not collapse, spread, or become brittle. Furthermore, this pressure-sensitive retransferability does not change over time. It is possible to achieve stability without any problems.

Moreover, even when such an ink ribbon 10 is stored for 24 hours at a temperature of 55° C. or higher, problems such as blocking and disordered winding do not occur at all, and ribbon meandering and slipping do not occur with respect to ribbon runnability. There are no problems such as this, and printing and thermal transfer can be carried out to the end of the ribbon.

[Examples] Below, some embodiments embodying the present invention will be described with reference to the drawings. It goes without saying that the present invention is not limited in any way by such description.

In addition to the following examples and the above-mentioned 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 and the like may be made.

Example 1 To form the ink layer 12 and transferability adjustment layer 13,
An ink and a coating liquid for forming a transferability adjusting layer were prepared as follows. The viscosity of the ink layer 12 formed by this ink is 270 centibois (95°C).
The viscosity of the transferability adjusting layer 13 formed with this coating liquid was 50,000 to 70,000 centipoise (95° C.).

12 ink layers or α-olefin-maleic anhydride copolymer [Dial Karna 30 manufactured by Mitsubishi Chemical Industries, Ltd.] 2 parts by weight Ethylene-vinyl acetate copolymer [(7) EVA210 manufactured by DuPont Mitsui Polychemicals Co., Ltd.] 2 Carbon black [MA-7 manufactured by Mitsubishi Chemical Industries, Ltd.] 2 Methyl isobutyl ketone (solvent) 100 Candelilla wax [Chukyo Yushi Co., Ltd.! 2 Candelilla Roya 2698] 3 Transferability adjustment layer 13 sets Boryamide by weight 4.5 [Versamide 725 manufactured by Henkel Hakusui Co., Ltd.] Microcrystalline wax 9 [Made by Nippon Seiro Co., Ltd.! 11-Hie
1 0 4 5 ] Rosin ester [Super Ester A-1001 manufactured by Arakawa Chemical Co., Ltd. 2 Rosin ester 4.5 [Super Ester Yaichi 1001 manufactured by Arakawa Chemical Co., Ltd. Titanium oxide 1 [manufactured by Ishihara Sangyo Co., Ltd.] Thaipeke A-1001 silicone oil
3 [Kp3 manufactured by Shin-Etsu Chemical Co., Ltd.
58] Isoprobyl alcohol (solvent) 87 Then, a 3.5 μm polyethylene terephthalate (PET) film is used as the ribbon base material 11, and an ink having the above composition is applied onto the film to a dry film thickness of 6 to 7 μm.
By coating and drying, ink layer 1
After forming 2, a transferability adjusting layer-forming coating liquid having the above composition is applied thereon to a dry film thickness of 1 to 2 μm, and dried at 80° C. to achieve the desired purpose. An ink ribbon 10 was obtained.

Next, using the thus obtained ink ribbon, it was set in a controlled thermal transfer printing device (P-Touch, manufactured by Brother Industries, Ltd.), and a polyethylene film (thickness = 100μ
m) By printing on the polyethylene film at 10°C to 35°C, a sufficiently beautiful and good quality printed image could be obtained, and such a printed polyethylene film could be rubbed from the back side and pressure applied. When such a printed image was pressure-sensitively transferred onto a desired surface of paper, plastic, or metal, an image of sufficiently good quality could be completed.

Further, no change in pressure-sensitive retransferability was observed over time (immediately, one day later, three days later).

Further, using such an ink ribbon, the storage stability of the ink ribbon kept at 55° C. for 24 hours was observed, and then a ribbon running test was performed using the ink ribbon 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 runnability, with no meandering or slipping. Furthermore, by adjusting the amount of silicone oil added, it was possible to control the heat-sensitive transferability and the pressure-sensitive retransferability.

Example 2 An ink ribbon 10 was prepared in the same manner as in Example 1 using an ink and a coating liquid that gave the following compositions for the ink layer 12 and transferability adjustment layer 13, and was subjected to heat-sensitive transfer, pressure-sensitive transfer,
Experiments on ribbon running and storage were conducted. As a result, a beautiful printed image of good quality could be obtained, and such a printed image could be transferred onto a desired transfer object as an image of good quality by pressure-sensitive retransfer. In addition, the stability over time of pressure-sensitive retransferability, ribbon runability, and storage stability were also good. The viscosity of the ink layer 12 formed with the ink having the following composition is 700 centipoise (95°C), and the viscosity of the ink layer 12 formed with the following coating liquid.
The viscosity of No. 3 was 50,000 to 70,000 centipoise (95° C.).

Composition of ink layer 12 Parts by weight α-olefin-maleic anhydride 8 copolymer [Dial Caluna 30 manufactured by Mitsubishi Kagaku Kogyo Co., Ltd.] Candelilla wax 5 [Candelilla wax 2 manufactured by Chukyo Yushi Co., Ltd. 6 9 81 Rosin Ester 2 [Super Ester A-1001 manufactured by Arakawa Chemical Co., Ltd. Ethylene-vinyl acetate copolymer [manufactured by DuPont Mitsui Polychemicals Co., Ltd. (7) EVA2 1 0] 3 Carbon black [manufactured by Mitsubishi Chemical Industries, Ltd.] MA-7] 2 Methyl isobutyl ketone (solvent) 1 0 0 Transferability adjustment layer 13 Composition Polyamide [Polymide S-15101 manufactured by Sanyo Chemical Industries, Ltd. 5 parts by weight Ketone resin [Ketone resin manufactured by Arakawa Chemical Industries, Ltd.] K-90] 5 Composition of the transferability adjusting layer 13 ! Parts Ethyl cellulose 2 [Kanto Kagaku Co., Ltd. reagent, 10 cps] Silicone oil 3 [Kp316 made by Shin-Etsu Chemical Co., Ltd.] Isoprobyl alcohol (solvent) 87 Examples 3 Example 1 as an ink for forming the ink layer 12
An ink ribbon was prepared in the same manner as in Example 1, using the same composition as in Example 1, using the coating liquid for forming the transferability adjustment layer as shown below, and subjected to the same thermal transfer test and sensitivity. As a result of conducting a pressure retransfer test, a ribbon running test, and a storage test, good results similar to those of Example 1 were obtained. still,
Transferability adjusting layer 1 formed with a coating liquid having the following composition
The viscosity of No. 3 was 50,000 to 70,000 centiboise (95° C.).

Hydrogenated rosin [Hyperel manufactured by Arakawa Chemical Co., Ltd.] 8 Silicone oil [Kp360 manufactured by Shin-Etsu Chemical Co., Ltd.] 3 Isopropyl alcohol (solvent) 87 Comparative Examples 1 to 3 While using Example 1 ink, transferability adjustment An ink ribbon in which the layer 13 was not formed (Comparative Example 1), an ink ribbon in which the ink of Example 2 was used but no transferability adjustment layer 13 was formed (Comparative Example 2), and a commercially available wax-type thermal transfer ink. When the same transfer test as in Example 1 was conducted using a ribbon [manufactured by Fuji Kagaku Paper Industries Co., Ltd.] (Comparative Example 3), both the heat-sensitive transferability and the pressure-sensitive retransferability were insufficient.

Specifically, regarding heat-sensitive transferability, there are problems such as insufficient transferability due to insufficient adhesive strength, spreading and crushing of transferred prints due to insufficient cohesive force, viscosity, and hardness, scraping of prints by the head, shading of prints, yuzu skin, etc. It was recognized that problems would occur. In addition, regarding pressure-sensitive retransferability, there are problems such as insufficient transfer due to insufficient pressure-sensitive adhesive strength, insufficient adhesion, cohesive force, viscosity, and final transferred print image collapse, spreading, and insufficient strength due to insufficient hardness.
Problems such as residual ink being observed on the film base sheet occurred due to defective integral transfer.

Comparative Examples 4 to 6 In the transferability adjustment of Example 1, ribbon running tests and storage tests were performed using an ink ribbon to which no silicone oil was added (Comparative Example 4), and the same good results as in 1 were obtained. Obtained. However, when a transfer test was conducted, it was found that the ribbon had inferior pressure-sensitive retransferability compared to the ribbon of Example 1. Specifically, insufficient pressure-sensitive retransfer was observed due to increased adhesive strength between the transfer sheet and the ink.

In addition, when ribbon running tests and storage tests were conducted using ink ribbons (Comparative Examples 5 and 6) in which no silicone oil was added in the transferability adjustment layer of Examples 2 to 3, stickiness and tackiness of the ribbon surface was observed. As a result, the ribbon pulling force increased significantly, causing slippage and making printing impossible. There was also the problem of plotting.

[Effects of the Invention] As is clear from the detailed description above, according to the present invention, the ink layer and the top coat layer have heat-sensitive adhesive properties, hardness, and viscosity on the base material (support) of the ink ribbon. ,
By providing a transferability adjustment layer with a large cohesive force to create a double structure and giving this ink layer pressure-sensitive adhesive properties, heat-sensitive transferability to surfaces with poor wettability is significantly improved. The pressure-sensitive retransferability of the printed image formed by thermal transfer to other materials using pressure could also be advantageously improved, and by adding silicone oil to the transferability adjustment layer, ribbon runnability and storage stability could be improved. good quality,
By adjusting the amount added, we were able to control heat-sensitive transferability and pressure-sensitive retransferability, stabilize pressure-sensitive retransferability over time, and simplify the manufacturing process. The great industrial significance of the present invention lies in the fact that a dry transfer material having excellent properties can be advantageously produced.

[Brief explanation of the drawing]

The drawing is a sectional view showing an example of a thermal transfer ink ribbon for producing a dry transfer material according to the present invention. In the figure, 10 is a thermal transfer ink ribbon, 11 is a ribbon base material,
12 is an ink layer, 13 is a transferability adjustment layer, and 14 is an anti-sticking layer.

Claims (1)

[Claims] The ink ribbon is used to form transferred images such as letters and figures by a thermal transfer method, and is composed of a coloring agent, a binder agent, and a pressure-sensitive adhesive on one side of a predetermined film-like ribbon base material. An ink layer having a higher viscosity than the ink layer and comprising a heat-sensitive adhesive resin, a tackifying resin, and a silicone oil is formed on the ink layer. An ink ribbon for producing a dry transfer material, characterized in that a transferability adjusting layer with high hardness and cohesive force is formed.