KR19990053054A - Sublimation Thermal Transfer Ink Ribbon - Google Patents

Abstract

The present invention relates to a sublimation type thermal transfer ink ribbon, and more particularly, polyvinyl foam is essentially contained as a binder component in the transfer ink layer composition of the thermal transfer ink ribbon to increase the transfer sensitivity and improve adhesion to the base film. The present invention relates to a sublimation type thermal transfer ink ribbon capable of improving the peeling of the dye layer from the base film during printing.

Description

Sublimation Thermal Transfer Ink Ribbon

The present invention relates to a sublimation type thermal transfer ink ribbon, and more particularly, polyvinyl foam is essentially contained as a binder component in the transfer ink layer composition of the thermal transfer ink ribbon to increase the transfer sensitivity and improve adhesion to the base film. The present invention relates to a sublimation type thermal transfer ink ribbon capable of improving the peeling of the dye layer from the base film during printing.

As a method of recording a color image, an electrophotographic method, an inkjet method, a thermal transfer method, and the like are used, but the dual thermal transfer recording method has an advantage of no noise during printing and easy maintenance of a device.

In the thermal transfer recording method, color images reproduced by an electrical signal are color-separated by a color filter and separated into three images of red (R), green (G), and blue (B). The signal is transmitted to the thermal element of the printer. According to the transmitted signal, the thermal element applies thermal energy to the opposite side of the surface on which the transfer ink layer of the thermal transfer ink ribbon is applied, so that four color materials including yellow, magenta, cyan, or black are transferred to the award sheet. And an image is obtained.

The thermal transfer method is classified into a melt type and a sublimation type according to the characteristics of the transfer ink layer. The melt method is a method in which the transfer ink layer has heat melting property, and the transfer ink layer is melted by heat applied from the thermal element, and is transferred to the water phase sheet and then solidified again. In this system, not only the colorant but also the binder component is transferred to the water sheet. On the other hand, in the sublimation type, the transfer ink layer is composed of a thermal sublimable dye and a binder resin, and is also called a dye diffusion type in which only the dye is transferred to the water sheet in order to form an image in proportion to the thermal energy applied by the thermal element. The sublimation type has the advantage that it is easy to express continuous gradation gradation in the transfer image because the amount of dye transferred is controlled in proportion to the applied thermal energy.

Therefore, the sublimation thermal transfer recording method can obtain very high quality images, so it is not only widely used in office automation equipment such as facsimile machines and copiers, but also electrically expressed from fields such as CAD, CAM, graphic design, or color video cameras. Is also used to print through a color printer. In addition, since images can be obtained on the fly at a high speed, their use for issuance of instant ID cards has recently been expanded. In manufacturing a sublimation thermal transfer ink ribbon, it is important to select a polymer material having suitable physical properties as a composition of the transfer ink layer, and in particular, as a binder component of the transfer ink layer.

The sublimation thermal transfer recording medium is composed of a thermal transfer ink ribbon which transfers dyes in accordance with an electrical signal of an image, and an award sheet containing transferred dyes.

The thermal transfer ink ribbon has a transfer ink layer coated on one side of the substrate, and an adhesive layer is formed between the transfer ink layer and the substrate to improve the adhesion between the ink layer and the substrate, and on the other side, the heat during printing The heat-resistant lubrication layer for preventing the base film from sticking to the thermal element by the heat generated in the element is applied. In addition, the award sheet is mainly used in the form of a coating coated with a receiving layer that can accommodate the transfer of dye on one side, such as synthetic paper, PVC cards and the like have been used in recent years to use for identification purposes.

The transfer ink layer of the thermal transfer ink ribbon is composed of a dye which is transferred to an aqueous sheet by heat and a binder resin for keeping the dye on a base film. In the manufacture of a sublimation thermal transfer ink ribbon, it is very important to select a binder resin having appropriate physical properties. The physical properties required for the binder resin are as follows:

1) It must be easy to transfer dye from the transfer ink layer to the award sheet in order to obtain high transfer sensitivity, and 2) the material and adhesive force used as the base of the sublimation type thermal transfer ink ribbon must be excellent, and 3) the award for printing No fusion with the sheet should occur, 4) proper affinity with the dye, no recrystallization of the dye, and 5) low transfer sensitivity at low applied energy to obtain good gradation.

Conventionally, binder resins used in the transfer ink layer of a sublimation thermal transfer ink ribbon include cellulose resins such as cellulose acetate butyrate, ethyl cellulose, and cellulose acetate phthalate [US Patent No. 4,700,207] and polyvinyl butyral resin [US Patent 4,650,494 or polyvinyl acetoacetal resins (European Patent No. 0,271,861) and the like are widely used. However, the cellulose-based resin as a binder resin has a problem that the transfer ink layer falls from the base film during image printing due to lack of adhesive strength with a polyethylene terephthalate (PET) film widely used as a base material. Polyvinyl butyral resins generally have a high transfer sensitivity, but have a high transfer sensitivity at low applied energy and thus have a disadvantage in expressing gray scales, and also have a weak adhesive strength with the base film. In addition, polyvinyl acetoacetal resin has a disadvantage of low transfer sensitivity.

Accordingly, the inventors of the present invention conducted extensive experiments with various types of polymer resins as a transfer ink layer binder component of a thermal sublimation thermal transfer ink ribbon, and as a result, polyvinyl foam had a higher transfer concentration than other types of polymer resins. The present invention has been completed by finding that it has excellent gradation and excellent adhesion to the base film.

Therefore, the present invention includes a polyvinyl foam as an essential component in the transfer ink layer composition of the thermal transfer ink ribbon to increase the transfer sensitivity, improve the adhesion to the substrate, and cause the dye layer to peel off from the substrate during printing. It is an object of the present invention to provide a sublimation thermal transfer ink ribbon capable of reducing the amount of ink.

The present invention provides a sublimation type thermal transfer ink ribbon in which a heat-resistant lubricating layer is applied to one side of a base film and a heat transfer ink layer having a thermal transfer dye is applied to the opposite side thereof. It is characterized by containing polyvinyl foam alone or as a binder component or a mixture of polyvinyl foam and a binder resin commonly used.

The present invention will be described in more detail as follows.

Polyvinyl foam (Poly vinyl formal) used as the binder component in the present invention is preferably used that contains 60% by weight or more of vinyl foam group. In addition, the polyvinyl foam may be contained alone as a binder component, or even when used together with a known resin commonly applied as a binder component of a transfer ink layer, the effect required by the present invention is obtained. When the polyvinyl foam and a known binder resin are used together as the binder component, the required physical properties may vary depending on the content ratio, but the physical properties of the thermal transfer ink ribbon according to the present invention are not largely changed. Preferably, the known binder resin is contained in less than 1: 1 weight ratio with respect to the polyvinyl foam contained as a binder component.

Typical binder resins applicable to the present invention include cellulose resins such as ethyl cellulose, hydroxyethyl cellulose, methyl cellulose, cellulose acetate formate, cellulose acetate propionate, and cellulose acetate butyrate; Vinyl-based resins such as polyvinyl alcohol, polyvinylacetate, polyvinyl butyral, polyvinylpinolidon, and polyvinylacetacetal.

The binder resin as described above is to be contained 20 to 80% by weight based on the solid component forming the transfer ink layer.

The coating liquid for producing a transfer ink layer of the present invention is prepared by dissolving a binder resin and a sublimation dye having a thermal transfer property in a suitable solvent and then adding various additives.

On the other hand, as a sublimation dye having thermal transfer properties, red dyes such as Magenta VP, MS Red G, Macrolex Red Violet R, MS Magenta HM-1450; Yellow dyes such as Waxoline Yellow GFW, Kayaset Yellow GN and Foron Brilliant Yellow 6GL; Blue dyes such as Kayaset Blue 714, Waxoline Blue AP-FW, MS Cyan HM-1238 may be used, and these dyes may be used alone or in a weight ratio of 1: 1.5 to 20.0 with respect to the binder resin. Do.

In addition, the thickness of the transfer ink layer to be applied is preferably 0.5 to 5.0 탆 in a dry state. In the transfer ink layer composition, in addition to the above-mentioned components, antioxidants, ultraviolet absorbers, dye crystallization inhibitors, etc. which are commonly used according to the purpose may be added.

In addition, the substrate used in the manufacture of the sublimation thermal transfer ink ribbon includes polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyamide, polyacrylate, polycarbonate, cellulose ester, fluorine resin, polyacetal or polyimide. Films and the like can be used, of which polyethylene terephthalate film is most suitable in terms of economical and mechanical strength. At this time, 2-20 micrometers is suitable for the thickness of the base material used.

Further, in order to improve the adhesion with the transfer ink layer, an adhesive layer is often applied on the base film, or a corona discharge or plasma treatment is often performed, and a dye layer is coated on the gravure coating or bar coating.

On the opposite side of the surface to which the transfer ink layer of the base film is applied, the purpose is to prevent the base film from deforming when it comes in contact with the heat element that generates heat up to 400 ° C. The heat resistant lubrication layer can be designed. Materials used for this purpose include carboxylates, sulfonates, phosphates, aliphatic amine salts, polyoxyethylene alkyl esters, silicone oils or synthetic oils.

The aqueous sheet used in combination with the above-mentioned thermal transfer ink ribbon is made of any sheet-like material having a property of accommodating the transferred dye, and may be polyester, polycarbonate, vinyl chloride-vinylacetate copolymer, polyvinyl. Chloride, ABS resin and the like are used. Recently, a card made of polyvinyl chloride as an award sheet has also been used to manufacture various identification cards such as bank cards and credit cards.

It is also possible to use paper, metal, glass or synthetic resins that do not have dye solubility. At this time, at least one surface is coated with a water-based sheet made of a dye and water-soluble resin.

Although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.

Example 1

The transfer ink layer after applying the adhesive layer composition using the Mayer bar of # 4 on the surface of the polyethylene terephthalate film (F531, Toray Industries, Japan) having a thickness of 5.7 μm, which was heat-treated on the back surface, was not subjected to the heat treatment. The composition was applied with a bar coater using the Meyer bar of # 7 to prepare a sublimation thermal transfer ink ribbon.

Adhesive layer composition:

p -chlorophenol 3.00 wt%

Toluene 97.00 wt%

Transfer ink layer composition:

Magenta Dye (Made in Japan, Magenta VP) 7.00 wt%

Polyvinyl foam (Japanese Tooth Soap, PVF-E) 5.00 wt%

Toluene 44.00 wt%

N , N -dimethylformamide 44.00 wt%

Example 2

A sublimation thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except that the transfer ink layer composition was changed to the following compounding ratio.

Transfer ink layer composition:

Magenta Dye (Made in Japan, Magenta VP) 7.00 wt%

Polyvinyl foam (Japanese Tooth Soap, PVF-H) 5.00 wt%

Toluene 44.00 wt%

N , N -dimethylformamide 44.00 wt%

Example 3

A sublimation thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except that the transfer ink layer composition was changed to the following compounding ratio.

Transfer ink layer composition:

Magenta dye (HM-1450 made in Japan Mitsui Doatsu) 7.00 wt%

Polyvinyl foam (Japanese Tooth Soap, PVF-K) 5.00 wt%

Toluene 44.00 wt%

N , N -dimethylformamide 44.00 wt%

Example 4

A sublimation thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except that the transfer ink layer composition was changed to the following compounding ratio.

Transfer ink layer composition:

Cyan dye (Japanese powder, Kayaset Blue 714) 7.00 wt%

Polyvinyl foam (Japanese Tooth Soap, PVF-L) 5.00 wt%

Toluene 44.00 wt%

N , N -dimethylformamide 44.00 wt%

Example 5

A sublimation thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except that the transfer ink layer composition was changed to the following compounding ratio.

Transfer ink layer composition:

Cyan dye (Japanese powder, Kayaset Blue 714) 7.00 wt%

Polyvinyl foam (manufactured by Aldrich, USA) 5.00 wt%

Toluene 44.00 wt%

N , N -dimethylformamide 44.00 wt%

Example 6

A sublimation thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except that the transfer ink layer composition was changed to the following compounding ratio.

Transfer ink layer composition:

Magenta Dye (Made in Japan, Magenta VP) 7.00 wt%

3.00% by weight of polyvinyl foam (Japanese tooth plasticizer, PVF-E)

2.00% by weight of polyvinyl butyral (manufactured by JP Chemical, BX-1)

Toluene 44.00 wt%

N , N -dimethylformamide 44.00 wt%

Example 7

A sublimation thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except that the transfer ink layer composition was changed to the following compounding ratio.

Transfer ink layer composition:

Magenta Dye (Made in Japan, Magenta VP) 7.00 wt%

3.00% by weight of polyvinyl foam (Japanese tooth plasticizer, PVF-E)

2.00 wt% of polyvinyl acetoacetal

Toluene 44.00 wt%

N , N -dimethylformamide 44.00 wt%

Example 8

A sublimation thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except that the transfer ink layer composition was changed to the following compounding ratio.

Transfer ink layer composition:

Magenta Dye (Made in Japan, Magenta VP) 7.00 wt%

3.00% by weight of polyvinyl foam (Japanese tooth plasticizer, PVF-E)

2.00% by weight of cellulose acetate butyrate (manufactured by Akros, Japan)

Toluene 44.00 wt%

N , N -dimethylformamide 44.00 wt%

Comparative Example 1

A sublimation thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except that the transfer ink layer composition was changed to a composition having the following compounding ratio.

Transfer ink layer composition:

Magenta Dye (Made in Japan, Magenta VP) 7.00 wt%

Polyvinyl Butyral (manufactured by Japan Epoxy Chemical, BX-1) 5.00 wt%

Toluene 44.00 wt%

N , N -dimethylformamide 44.00 wt%

Comparative Example 2

A sublimation thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except that the transfer ink layer composition was changed to a composition having the following compounding ratio.

Transfer ink layer composition:

Magenta Dye (Made in Japan, Magenta VP) 7.00 wt%

5.00 wt% of polyvinyl acetoacetal

Toluene 44.00 wt%

N , N -dimethylformamide 44.00 wt%

Comparative Example 3

A thermal transfer ink ribbon was manufactured by sublimation in the same manner as in Example 1 except that the transfer ink layer composition was changed to a composition having the following compounding ratio.

Transfer ink layer composition:

Magenta Dye (Made in Japan, Magenta VP) 7.00 wt%

Cellulose acetate butyrate (made by Akros Japan) 5.00 wt%

Toluene 44.00 wt%

N , N -dimethylformamide 44.00 wt%

Comparative Example 4

A sublimation thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except that the transfer ink layer composition was changed to a composition having the following compounding ratio.

Transfer ink layer composition:

Cyan dye (HM-1450, manufactured by Mitsui Dotsu Japan) 7.00 wt%

5.00 wt% of polyvinyl acetoacetal

Toluene 44.00 wt%

N , N -dimethylformamide 44.00 wt%

Comparative Example 5

A sublimation thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except that the transfer ink layer composition was changed to a composition having the following compounding ratio.

Transfer ink layer composition:

Cyan Dye (Kayaset Blue 714) 7.00 wt%

5.00% by weight of polyvinyl acetoacetal (manufactured by Japan's Integral Chemicals, KS-1)

Toluene 44.00 wt%

N , N -dimethylformamide 44.00 wt%

Experimental Example

Sublimation type thermal transfer ink ribbons prepared in Examples 1 to 8 and Comparative Examples 1 to 5 were observed for transfer sensitivity, adhesion to PET film used as a base film, and the occurrence of tearing of the dye layer during actual printing.

Transfer sensitivity was measured by transferring the grayscale image to a resin paper specially manufactured for Rainbow, a thermal sublimation transfer type thermal transfer printer of the US 3M, and a PVC card used for issuance of instant ID cards, and then measuring the optical density of McBeth, USA. Optical density was measured using the apparatus TR-1224.

In order to transfer grayscale images to 3M thermal sublimation thermal printers, a dynamic generator (model name: TH-FMR) manufactured by Takasago, Japan was used. Printing conditions of the dynamic generator were fixed at a pressure of 3.7 kg / cm 2 and a voltage of 24V, and then the printing time was increased by 0.2 msec between 1.0 and 3.6 msec.

When the gray scale image was transferred to the PVC card, the gray scale image was printed using a card printer manufactured by Pago Co., Ltd., Persona Cheetah II. The gradation image used at this time was made by dividing the 256 gradations of magenta and cyan colors into 10 by using Adobe Photo Shop software.

The adhesive force with the polyethylene terephthalate film used as the base film was evaluated by dividing the area where the transfer ink layer was torn off by 5 equal parts using the Scotch Magic Tape of 3M of USA.

Evaluation of the torn area :

0% → A,

1-25% → B,

26-50% → C,

51-75% → D,

76-100% → E

Whether the dye layer is torn during actual printing is visually checked whether the dye layer is fused to the PVC card and the dye layer is peeled off from the base film when printing gray scale evaluation images using Persona Cheetah II, a card printer manufactured by Pago, USA. It observed, and the evaluation results are shown in Table 1 below.

division Transcription sensitivity Adhesion to the substrate No tearing 3M receiving area PVC card 1.0 msec 3.6 msec Stage 1 10 steps Example 1 0.20 1.94 0.25 1.70 A clear Example 2 0.20 1.92 0.23 1.72 A Example 3 0.23 1.88 0.25 1.67 A Example 4 0.25 1.90 0.25 1.68 A Example 5 0.24 1.92 0.23 1.67 A Example 6 0.22 1.88 0.25 1.65 B Example 7 0.20 1.87 0.24 1.65 A Example 8 0.25 1.93 0.24 1.70 B Comparative Example 1 0.26 1.76 0.32 - C Tearing Comparative Example 2 0.21 1.82 0.27 1.59 A clear Comparative Example 3 0.23 1.85 0.22 - C Tearing Comparative Example 4 0.25 1.78 0.30 1.56 A clear Comparative Example 5 0.25 1.80 0.24 1.58 A

As described above, the sublimation type thermal transfer ink ribbon containing polyvinyl foam as the thermal transfer ink layer binder component increases the transfer sensitivity and improves adhesion to the substrate so that the dye layer is peeled from the substrate film during printing. It can be seen that the phenomenon is reduced.

Claims (4)

In the sublimation type thermal transfer ink ribbon in which a heat-resistant lubrication layer is applied to one side of the base film, and a thermal transfer ink layer having a thermal transfer dye is applied to the opposite side thereof. The thermal transfer ink layer includes a polyvinyl foam alone or a mixture of polyvinyl foam and a binder resin commonly used as a binder component. The sublimation thermal transfer ink ribbon according to claim 1, wherein the polyvinyl foam contains 60 wt% or more of vinyl foam groups. The sublimation thermal transfer ink ribbon according to claim 1, wherein the binder component is contained in a range of 20 to 80% by weight based on the solids forming the thermal transfer ink layer. The sublimation thermal transfer ink ribbon according to claim 1, wherein the conventional binder resin contained in the binder component is used in less than 1: 1 weight ratio with respect to the polyvinyl foam.