KR19990061685A - Heat-resistant layer composition of thermal transfer ink ribbon - Google Patents

Abstract

The present invention relates to a heat-resistant layer composition of a thermal transfer ink ribbon, and more particularly, in a thermal transfer ink ribbon in which an adhesive layer and an ink layer are sequentially formed on one side of a base film, and a heat-resistant layer is formed on the opposite side. The heat transfer head by peeling off the heat resistant layer even when the heat transfer head travels on the ink ribbon when printing with excellent adhesion to the base film by containing a grafted silicone-acrylic polymer as a lubricant in the heat resistant layer composition as a lubricant. The present invention relates to a heat-resistant layer composition of a thermal transfer ink ribbon, which has no concern about contamination, has excellent heat-lubricating activity, and has little heat-transfer layer transition of an ink layer dye.

Description

Heat-resistant layer composition of thermal transfer ink ribbon

The present invention relates to a heat-resistant layer composition of a thermal transfer ink ribbon, and more particularly, in a thermal transfer ink ribbon in which an adhesive layer and an ink layer are sequentially formed on one side of a base film, and a heat-resistant layer is formed on the opposite side. The heat transfer head by peeling off the heat resistant layer even when the heat transfer head travels on the ink ribbon when printing with excellent adhesion to the base film by containing a grafted silicone-acrylic polymer as a lubricant in the heat resistant layer composition as a lubricant. The present invention relates to a heat-resistant layer composition of a thermal transfer ink ribbon, which has no concern about contamination, has excellent heat-lubricating activity, and has little heat-transfer layer transition of an ink layer dye.

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 head, which is a thermal element of the printer. According to this transmitted signal, the thermal transfer head 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 included in the ink receptor. Is delivered to obtain an image.

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 is thermally soluble, and the transfer ink layer is melted by the heat applied from the thermal transfer head, transferred to the ink receptor, and then solidified again. In this method, not only the colorant but also the binder component is transferred to the ink receptor. On the other hand, in the sublimation type, the transfer ink layer is composed of a thermal sublimable dye and a binder resin, and dye is diffused in a manner in which only the dye is transferred to the ink receptor in proportion to the thermal energy applied by the thermal transfer head to form an image. Thermal transfer (D2T2) is also called. The sublimation type has a merit that it is easy to express a continuous gray level in the transfer image because the amount of dye to be 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.

The general structure of the thermal transfer ink ribbon has a transfer ink layer for transferring ink to an ink receptor (card, OHP, receiving paper, etc.) on one side of the substrate film, and to improve the adhesion between the ink layer and the substrate. An adhesive layer is formed between the transfer ink layer and the base film, and a heat-resistant layer is applied on the opposite side to prevent the base film from sticking to the heat transfer head by the heat generated from the heat transfer head.

When the image is transferred using the thermal transfer ink ribbon, the instantaneous heat transferred to the ink ribbon as the thermal transfer head moves up to 400 ° C. If the heat resistance of the heat-resistant layer is inferior, the portion of the ink ribbon heated during image transfer becomes weak due to thermal deformation, and in severe cases, tearing of the ribbon occurs. In addition, if the heat transfer head travels on the ink ribbon and there is no lubricity in the heat-resistant layer, severe friction occurs between the heat transfer head and the ink ribbon, so that a symmetrical bow pattern remains on the ink ribbon in the opposite direction to the heat transfer head travel direction. This pattern is also called 'smile pattern' because it looks like a person's smile. In particular, when printing a dark color image, since a lot of heat is applied to the ink ribbon from the thermal transfer head, the tearing phenomenon and the smile pattern of the ink ribbon appear severely. Therefore, in order to properly print various images, a heat resistant layer having excellent heat resistance and lubricity should be formed on the ink ribbon.

Since the ink ribbon is usually wound on a reel, the ink layer of the ink ribbon is in contact with the heat resistant layer, and the dye of the ink layer gradually transfers to the heat resistant layer over a long time. The dye on the heat-resistant layer contaminates the head while driving the heat transfer head and damages the heat transfer head. Therefore, in order to reduce dye transfer of the ink layer, the binder of the ink layer should adhere the dye well, and the affinity between the heat-resistant layer and the ink layer dye should be low.

The heat-resistant layer is generally composed of a binder and a lubricant. As a binder, a polymer having adhesion to a base film and a high glass transition temperature and a softening point is used. The lubricant is silicone oil, fatty acid metal salt, phosphate ester, metal stearyl phosphate, etc. use. Moreover, in order to raise the adhesive force between a heat resistant layer and a base film, an adhesive layer may be provided. The method of forming the adhesive layer includes a surface treatment method through corona discharge, a method of coating vinyl-based resins such as vinyl chloride or vinyl acetate and copolymers thereof, polyester resins, derivatives including p -chlorophenol, and the like.

As a known heat-resistant layer composition, US Pat. No. 4,559,273 contains polyvinyl butyral and isocyanate as binders to increase the strength of the film by thermosetting, and phosphate esters are used as lubricants. In US Pat. No. 4,572,860, urethane resins are used as binders and fatty acids are used as lubricants. However, when the thermosetting polymer is used as a heat resistant layer, an appropriate curing temperature and curing time cannot be found, so that the side reaction of the heat resistant layer proceeds with time, thereby deteriorating the physical properties of the heat resistant layer, and the proper curing temperature and curing time in a large-capacity coater. There is a problem that can not be implemented.

As another example, there is an example in which inorganic or organic particles are used as a lubricant contained in the heat resistant layer. For example, inorganic particles having a plate-like or lamellar shape (US Pat. No. 4,806,421), ester waxes (US Pat. No. 4,916,112), small particles of about 1/10 the size of round and relatively large particles and large particles. Lubricant particles consisting of US Pat. No. 5,143,782, and examples of using a combination of large particles with relatively small particles and alkyl metal phosphate salts [US Pat. Nos. 5,260,127 and 5,593,940] are known. However, when the lubricant particles are introduced into the heat-resistant layer by the conventional method, the dispersibility between the particles and the binder should be good, and the inorganic particles should not be separated from the binder during the coating process. In addition, by using a lubricant as particles, the adhesive force between the heat resistant layer and the base film may be lowered, and the heat resistant layer may peel off when the heat transfer head travels.

In addition, there is a method of using a silicone polymer having excellent lubricity as a lubricant to react with a binder or to disperse it and introduce it into a heat resistant layer. For example, aminoalkylpolysiloxanes were dispersed in cellulose polymers as lubricants (US Pat. No. 4,753,920), or polyurethanes and organic particles substituted with silicones were thermally cured (US Pat. No. 4,961,997). In addition, a method of photocuring a silicone oil having a functional group capable of bonding to a binder and both sides (US Pat. No. 5,308,681) and a method of curing a polysiloxane containing a methacrylicoxy functional group by applying an electron beam or ultraviolet light [US Patent No. 5,445,867 is known.

When oil-based aminoalkylpolysiloxane is dispersed in a binder and used in a heat resistant layer [US Pat. No. 4,753,920], the oil-like aminoalkylpolysiloxane is transferred to the ink layer while being wound on the ink ribbon reel for a long time to prevent ink transfer. After the aminoalkylpolysiloxane is transferred, the heat resistance of the heat-resistant layer itself is also inferior. Other methods of forming a heat-resistant layer by thermal or photocuring [US Pat. Nos. 4,961,997, 5,308,681, 5,445,867] are difficult to find suitable curing conditions.

Accordingly, the present invention is useful as a lubricant in the heat-resistant layer composition of the thermal transfer ink ribbon because the grafted silicone-acrylic polymer has a low affinity with the dye of the transfer ink layer but also has excellent adhesion with the base film when used with a conventional binder. By knowing the present invention was completed.

Therefore, the present invention is a common binder and a silicone-acrylic graft polymer used as a lubricant in the heat-resistant layer, there is no fear of the problem caused by the dispersibility decrease due to the use of a particulate lubricant, damage to the thermal transfer head, etc. There is no problem, and it is an object of the present invention to provide a thermal transfer ink ribbon which does not have a risk of being transferred to the ink layer because it is not a liquid at room temperature as in general silicone oil.

The present invention is characterized in that the heat-resistant layer composition of the thermal transfer ink ribbon composed of a binder component and a lubricant component contains a silicone-acrylic polymer grafted with the lubricant component.

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

The grafted silicone-acrylic polymer used as a lubricant component in the heat-resistant layer composition of the thermal transfer ink ribbon of the present invention has a structure in which a silicone group is located as a pendant group in an acrylic backbone. The silicone group has an excellent slip property and serves to greatly reduce the friction between the thermal transfer head and the ink ribbon, and the acrylic polymer has a function of providing adhesion to the base film. Therefore, in the present invention, by using the grafted silicone-acrylic polymer, the friction between the thermal transfer head and the ink ribbon can be greatly reduced, and the effect of improving the adhesion with the base film can be obtained.

The acrylic monomer constituting the main chain of the grafted silicone-acrylic polymer according to the present invention may be represented by the following formula (1).

In Formula 1 above:

X represents -CH = CHC (O) X 'or -C (O) X';

Y represents H or CH ₃ ;

X 'represents -R, -OR or -NR ¹ R ² ;

R is a C ₁ to C ₂₀ alkyl group; C ~ C alkenyl group of _{1 20;} Alkadi group in the C ₁ ~ C _20; A cycloalkyl group of C ₆ to C ₂₀ ; Alkali group; Aryl group; Or an alkyl, alkenyl, alkadienyl, C ₆ -C ₂₀ cycloalkyl, aralkyl group or aryl group containing an ether bond; And

R ¹ and R ² are the same as or different from each other and represent a C ₁ to C ₄ alkyl group.

More specifically exemplified by the acrylic monomer represented by Formula 1, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl eta Acrylate, glycosyl methacrylate, sorbyl acrylate, 2- (dimethylamino) ethyl methacrylate, 3,3-dimethoxypropyl acrylate, 3-methacryloxypropyl acrylate, 2-acetoxyethyl methacrylate Rate, p -tolyl methacrylate, 4-fluorophenylacrylate, 2-methacryloxyethyl acrylate, propylvinyl ketoneethyl 2-chloroacrylate, 3-methoxypropyl methacrylate, 2-[(1 -Propenyl) oxy] methacrylate, phenylacrylate, 2- (trimethyllooxy) ethyl methacrylate, allyl acrylate, allyl methacrylate and the like A derivative thereof may be used.

In addition, the silicone group-containing monomer constituting the side chain of the grafted silicone-acrylic polymer may be represented by the following formula (2).

In Chemical Formula 2:

A represents a C ₁ to C ₂₀ alkyl group or phenyl group;

D and E are the same as or different from each other, and represent a C ₁ to C ₅ alkyl group, a phenyl group or (A ₃ SiO) _m −;

Q represents H or CH ₃ ;

m is an integer from 1 to 5;

n is an integer of 1-3.

Specific examples of the silicone group-containing monomer represented by the formula (2) include pentamethyldisiloxanylmethyl methacrylate, heptamethyltrisiloxanylethyl acrylate and tris (trimethylsiloxy) -γ- (methacryloxypropyl Silane), phenyltetramethyldisiloxanylethyl acrylate, phenyltetraethyldisiloxanylethyl methacrylate, triphenyldimethyldisiloxanylmethyl acrylate, isobutyl hexamethyltrisiloxaneanylmethyl methacrylate, methyldi ( Trimethylsiloxy) methacryloxymethylsilane, propyloctamethyltetrasiloxanylpropylmethacrylate, pentamethyldi (trimethylsiloxy) acryloxymethylsilane, t-butyltetramethyldisiloxanylethylacrylate, pentylhexa Silicone groups, including methyltrisiloxanylmethylmethacrylate, tripropyltetramethyltrisiloxanylethyl acrylate, and the like Yudoen there are other acrylic derivatives it may be used.

In order for the grafted silicone-acrylic polymer as described above to exhibit lubricity, it is appropriate to add in the range of 2 to 50% by weight in the total composition. If the content is less than 2% by weight, there is no great effect on lubricity. If the content is more than 50% by weight, the adhesive force between the binder and the base film is reduced, resulting in peeling of the heat-resistant layer during the running of the thermal transfer head. When the heat-resistant layer peels off and the materials added to the heat-resistant layer adhere to the heat transfer head, it causes a problem in the head during long-term running of the heat transfer head, which causes a heat transfer head failure.

In addition, when the grafted silicone-acrylic polymer described above is contained alone in the heat-resistant layer without a binder component, the adhesive force with polyethylene terephthalate, which is a base film, is degraded, so that the grafted silicone-acrylic polymer is included in the heat-resistant layer composition together with the binder. The binder component that can be used together with the lubricant component of the grafted silicone-acrylic polymer is well soluble in a solvent, does not occur phase separation when mixed with the lubricant, and has a good heat resistance with a glass transition temperature (T _g ) of 80 ° C or higher. It must be a polymer. Examples of the binder having such physical properties include polyvinyl acetal resin and polyvinyl acetal resin including polyvinyl butyral resin; Acrylate resins including polymethyl methacrylate. The binder is contained in 2 to 30% by weight of the total heat-resistant layer composition.

When coating the heat-resistant layer composition on the base film, when the adhesive force between the polyethylene terephthalate base film and the heat-resistant layer is inferior, if necessary, after the adhesive layer coating on the base film and then coated on the heat-resistant layer or the adhesive layer treatment base film The heat resistant layer may be coated on it. The appropriate coating thickness of the heat resistant layer is preferably maintained to a thickness of 0.5 to 2.0 ㎛ after drying. Since the heat-resistant layer is important to maintain a constant coating thickness, if the coating thickness is less than 0.5 μm, the ribbon does not have an effect as a heat-resistant layer. When the coating thickness exceeds 2.0 μm, the color density of the transferred image becomes light. there is a problem.

In addition, according to the purpose, an appropriate amount of an antistatic agent, an antioxidant, and the like can be added to the heat resistant layer.

Meanwhile, as the base film of the present invention, polyester films such as polyethylene terephthalate, polyamides, polyacrylates, polycarbonates, cellulose esters, fluorine-based resins, polyacetals, polyimide films, and the like can be used. Terephthalate film is used. At this time, 2-20 micrometers is suitable for the thickness of a base material.

In order to provide adhesion to the base film, an adhesive layer is formed on the opposite side of the base film on which the heat-resistant layer is formed, which dissolves a corona treatment method, a solution of a p -chlorophenol solution, a vinyl chloride-vinylacetate copolymer, or a polyester polymer. It forms using the method of coating a solution, etc. Preferably, a solution obtained by dissolving the p -chlorophenol solution and the vinyl chloride-vinylacetate copolymer together is coated with an adhesive layer or an adhesive layer-treated film manufactured by Toray Industries, Japan. After drying the adhesive layer, the coating thickness is appropriately set at 0.02 to 1.0 µm in view of adhesion and transfer sensitivity.

After the adhesive layer is coated on the base film as described above, an ink layer is coated thereon. In the present invention, a sublimation ink layer or a molten ink layer is coated.

When the ink layer of the thermal transfer ink ribbon is a sublimation type, the thermal sublimable dye and the binder are composed of main components. Dyes which may be used herein include red dyes such as Magenta VP, MS RED G, Macrolex Red Violet R, MS Magenta HM-1450; Yellow dyes such as Waxoline Yellow GFW, Kayajet Yellow GN and Foron Brilliant Yellow 6GL; Blue dyes such as Kayajet Blue 714, Waxoline Blue AP-FW, and MS Cyan HM-1238 may be used. In addition, binders that can be used with these dyes in the ink layer of the ink ribbon include cellulose derivatives such as ethyl cellulose, methyl cellulose, cellulose acetate formate, cellulose acetate propionate, and cellulose acetate butyrate, polyvinyl alcohol, and polyvinyl acetate. , Vinyl-based resins such as polyvinyl butyral, polyvinylpyrrolidone, and polyvinyl acetoacetal may be used. Preferably, polyvinyl butyral and polyvinyl acetoacetal are used. The thickness of the ink layer is suitably about 0.2 to 5.0 µm, and the heat-sublimation dye is suitably 5 to 20% by weight based on the entire ink layer.

In addition, when the ink layer of the thermal transfer ink ribbon is a melt type, it is mainly composed of a pigment or dye and a material which can be melted by heat. The pigment may be an inorganic pigment such as carbon black, an azo or polycyclic organic pigment, and the like, and the dye may be a dye including sulfonic acid, a basic dye, or the like. As a material melted by heat, a wax having a melting point of 40 to 120 ° C. is used, and such wax may be carnauba wax, montan wax, microcrystalline wax, synthetic wax in the form of fat, or the like. In addition, the binders used in the above-described sublimation ink layer may be applied to mix the binder in the ink layer to increase the adhesion.

The thermal transfer ink layer may include a release agent, an antioxidant, an ultraviolet absorber, an inorganic or organic filler, or the like depending on the purpose.

On the other hand, as the ink receptor of the thermal transfer ink ribbon, synthetic paper, OHP, card, etc. may be used, and on the surface of the ink receptor, polyester, polycarbonate, polyvinyl chloride, ABS which can accept dye transferred from the ink layer by heat An image receiving layer made of resin or the like is coated or laminated.

As described above, in the present invention, in addition to the usual binder component in the heat-resistant layer composition of the thermal transfer ink ribbon, the grafted silicone-acrylic polymer is included as a lubricant, so that the thermal transfer head at the time of printing with excellent adhesion with the base film is Even when traveling on the ink ribbon, there is no contamination of the thermal transfer head due to peeling of the heat resistant layer, excellent heat lubrication activity, and low heat transfer of ink layer dye.

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

Example 1

On one side of the F552 film (Toray Industries, Inc.), the following heat-resistant layer composition was barcoated using No. 7 Meyer Bar and dried, and then the coating thickness was maintained at 1.0-1.3 μm. On the other side of the heat-resistant layer-coated film, the next adhesive layer was coated with a bar coater using No. 4 Meyer Bar, and the ink layer composition was bar-coated in order of yellow, magenta, and cyan using No. 7 Meyer Bar. Ribbon was prepared.

Heat Resistant Layer Composition:

Silicone-acrylic (made in Japan Shin-Etsu, X-24-3544A, 40% solution) 10.0 weight%

12.0% by weight of polyvinyl acetoacetal (manufactured by Japan Epoxy Chemical, KS-1)

Methyl ethyl ketone 39.0 wt%

Toluene 39.0 wt%

Adhesive layer composition:

Vinyl Chloride-Vinyl Acetate Copolymer

1.2 wt% (US Union Carbide, VAGH)

p -chlorophenol 4.8 wt%

Methyl ethyl ketone 9.4 wt%

Toluene 84.6 wt%

Ink layer composition:

1) Yellow color solution

5.00% by weight of yellow dye (WIC, made by UK ICI, Waxoline Yellow GFW)

5.00 wt% of polyvinyl butyral (BX1)

Dimethylformamide 45.00 wt%

Toluene 45.00 wt%

2) magenta color liquid

Magenta dye (Made in Japan Mitsui Toatsu, Magenta VP) 8.96 wt%

4.34 wt% of polyvinyl butyral (manufactured by Japan Epoxy Chemical, BX1)

Dimethylformamide 43.35 wt%

Toluene 43.35 wt%

3) Cyan Color Liquid

Cyan dye (Japanese gunpowder, Kayajet Blue 714) 7.00 wt%

5.00 wt% of polyvinyl acetacetal

Dimethylformamide 44.00 wt%

Toluene 44.00 wt%

Example 2

A thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except for the following heat-resistant layer composition.

Heat Resistant Layer Composition:

4.5 weight% of silicone-acrylic (product made in Japan Shin-Etsu, X-24-3544A, 40% solution)

5.4% by weight of polyvinyl butyral (manufactured by Japan Epoxy Chemical, BX-55)

Methyl ethyl ketone 45.1 wt%

Toluene 45.0 wt%

Example 3

A thermal transfer ink ribbon was manufactured in the same manner as in Example 1, except that the following heat-resistant layer composition and coating thickness were 1.5 to 2.0 μm.

Heat Resistant Layer Composition:

Silicone-acrylic (made in Japan Shin-Etsu, X-24-3544A, 40% solution) 10.0 weight%

Polymethyl methacrylate (made in Japan Mitsubishi Rayon, BR85) 10.0 wt%

Methyl ethyl ketone 40.0 wt%

Toluene 40.0 wt%

Example 4

A thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except for the following heat-resistant layer composition.

Heat Resistant Layer Composition:

Silicone-acrylic (made in Japan Shin-Etsu, X-24-3544A, 40% solution) 7.2 wt%

Polymethyl methacrylate (A21, USA Rohm and Hass) 18.0 wt%

Methyl ethyl ketone 37.4 wt%

Toluene 37.4 wt%

Example 5

A thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except for the following heat-resistant layer composition.

Heat Resistant Layer Composition:

Silicone-acrylic (made in Japan Shin-Etsu, X-24-3544A, 40% solution) 7.2 wt%

Methyl methacrylate-butyl methacrylate copolymer

(B60, Rohm Hass, USA) 18.0 wt%

Methyl ethyl ketone 37.4 wt%

Toluene 37.4 wt%

Example 6

A thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except for the following heat-resistant layer composition.

Heat Resistant Layer Composition:

Silicone-acrylic (made by Japan Dong-A Synthetic Chemical Co., Ltd., US350, 30% solution 12.0 wt%

Polymethyl methacrylate (made in Japan Mitsubishi Rayon, BR85) 10.0 wt%

Toluene 39.0 wt%

Methyl ethyl ketone 39.0 wt%

Example 7

In the same manner as in Example 6, using the Mayer bar No. 7, the following black ink layer composition was coated with a bar coater to prepare a thermal transfer ink ribbon.

Black Ink Liquid Composition:

10.0 wt% paraffin wax

Carnauba Wax 10.0 wt%

Ethylene-vinylacetate (manufactured by Tsumito Chemical Co., Ltd., Tumidate HC-10) 1.0 wt%

Carbon black (made by Tokai Denkyoku, Sister 3) 2.0 wt%

Toluene 38.5 wt%

Methyl ethyl ketone 38.5 wt%

Comparative Example 1

A thermal transfer ink ribbon was manufactured in the same manner as in Example 1, except that the heat resistant layer was not formed on the F531 film (Toray Industries, Ltd.).

Comparative Example 2

A thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except for the following heat-resistant layer composition.

Heat Resistant Layer Composition:

Amino modified silicone (KF857 made by Shin-Etsu, Japan) 0.60 wt%

Carboxy Modified Silicon (X-22-162C, manufactured by Shin-Etsu, Japan) 0.60 wt%

8.55% by weight of acrylic resin (Mitsubishi Rayon, BR108)

0.25 wt% of silica (R812, Germany)

Toluene 60.00 wt%

Methyl ethyl ketone 30.00 wt%

Comparative Example 3

A thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except for the following heat-resistant layer composition.

Heat Resistant Layer Composition:

Silicone-acrylic (made in Japan Shin-Etsu, X-24-3544A, 40% solution) 40.0 weight%

Toluene 30.0 wt%

Methyl ethyl ketone 30.0 wt%

Comparative Example 4

A thermal transfer ink ribbon was manufactured in the same manner as in Example 1 except for the following heat-resistant layer composition.

Heat Resistant Layer Composition:

Silicone-acrylic (made in Japan Shin-Etsu, X-24-3544A, 40% solution) 0.6 wt%

Polymethyl methacrylate (A21, USA Rohm and Hass) 18.0 wt%

Methyl ethyl ketone 40.7 wt%

Toluene 40.7 wt%

Comparative Example 5

A thermal transfer ink ribbon was manufactured in the same manner as in Example 1, except that the following heat-resistant layer composition and coating thickness were 2.5 to 3.0 μm.

Heat Resistant Layer Composition:

Silicone-acrylic (made in Japan Shin-Etsu, X-24-3544A, 40% solution) 27.0 weight%

Polymethyl methacrylate (A21, USA Rohm and Hass) 18.0 wt%

Methyl ethyl ketone 27.5 wt%

Toluene 27.5 wt%

Experimental Example

Adhesion between heat-resistant layer and base film, thermal transfer head contamination, black image gradation evaluation, and heat-resistant layer transfer of sublimation type or melt type thermal transfer ink ribbon prepared in Examples 1-7 and Comparative Examples 1-5. The degree was measured.

The adhesive force between the heat-resistant layer and the base film was cut to about 1.90 cm × 5 cm of 3M Scotch Magic Tape, and the adhesive side of the tape was attached to the heat-resistant layer coating surface, and then rubbed 10 times with a hand, and then the heat-resistant layer at the time of desorption. The peeling or burying was evaluated three times.

The thermal transfer head was contaminated by Fargo's Persona Cheetah card printer, and ten front images were continuously printed, and the thermal transfer head was visually observed to evaluate the degree of contamination. In this case, a PVC card having a thickness of 0.84 mm was used as the ink receptor.

In order to test the heat-resistant lubrication of the heat-resistant layer, a 7-step black image output was performed on a 0.84 mm thick PVC card with a Fargo Persona Cheetah card printer. The output image is a black gradation image consisting of seven levels from light black to dark black, and yellow, magenta, and cyan inks are transferred to form black.

The pale black has less energy transmitted from the thermal head, but the darker the energy is transmitted from the thermal head. The order of image transfer was to transfer 7 steps in sequence from light black to dark black, and the level of black gradation in which the smile pattern first appeared on the card to which the image was transferred was measured. That is, the higher the level of black gradation in which the smile pattern first appears, the better the heat-resistant lubrication of the heat-resistant layer.

The degree of transition of the heat-resistant layer of the dye was placed on the surface of the magenta dye layer on the surface of the heat-resistant layer, and placed on a steel plate weighing 2 kg and left at 50 ° C. for one day. ΔE values on Lab coordinates, which is a color coordinate system, were measured. The reference value was measured by measuring the heat-resistant layer surface before the magenta dye was transferred, and the ΔE value was obtained from the difference between the measured value and the reference value, ΔL, Δa, and Δb, as shown in Equation 1 below.

In Equation 1: The smaller the ΔE value, the less the amount of dye transfer to the heat-resistant layer.

When the molten type ink layer of Example 7 was coated, it was visually checked whether the text was output clearly without outputting black gradation.

The results measured as described above are shown in Table 1 below.

division Adhesion Thermal head contamination Black Image Evaluation Heat-resistant layer transition of dyes (ΔE) Example 1 ◎ none 7 steps 0.98 Example 2 ◎ none 7 steps 1.05 Example 3 ◎ none 7 steps 0.92 Example 4 ◎ none No smile 1.03 Example 5 ◎ none No smile 1.11 Example 6 ◎ none 7 steps 1.07 Example 7 ◎ none (Clean warrior) - Comparative Example 1 ◎ none 3 to 4 steps 1.87 Comparative Example 2 ◎ Yes (particle) 7 steps 1.00 Comparative Example 3 × has exist No smile - Comparative Example 4 ◎ none 5 steps 1.05 Comparative Example 5 × has exist No smile - (Note) ◎: No tearing or staining by tape ×: No tearing or staining by tape

As shown in Table 1, the thermal transfer ribbons (Examples 1 to 7) containing the silicone-acrylic polymer and the binder grafted to the heat-resistant layer composition according to the present invention have good compatibility with each other, Since the adhesion between the adhesive layers is excellent, there was no contamination of the thermal transfer head. On the contrary, when the adhesion between the heat-resistant layer and the adhesive layer of the base film fell, contamination of the thermal transfer head occurred (Comparative Examples 3 and 5), and silica, a heat-resistant layer composition, was released from the heat-resistant layer (Comparative Example 2). ).

In addition, when the content of the grafted silicone-acrylic polymer with respect to the binder was appropriate (Examples 1 to 6), the thermal lubrication activity was excellent in the black image evaluation, but the addition amount of the grafted silicone-acrylic polymer was small (comparative) In Example 4), the thermal lubrication activity was decreased, and in the case where the amount of the grafted silicone-acrylic polymer was added (Comparative Example 5), the thermal lubrication activity was excellent, but as mentioned above, the thermal transfer head was contaminated. Even when the heat-resistant layer is coated on the opposite side to which the molten ink layer is coated (Example 7), text characters are clearly output, so that the composition of the present invention is not only a sublimation type thermal transfer ink ribbon but also a melt type thermal transfer ink ribbon. Has been shown to be applicable.

The heat resistant layer (Comparative Example 1) of the Japan Toray F531 film is lower than the heat resistant layer of the example in terms of heat lubrication activity, and ΔE is larger than those of Examples 1 to 6 even before the heat resistant layer of the dye layer, so that the ink ribbon is applied to the reel. It can be seen that when the long-term storage in the wound state, the heat transfer layer transition of the dye is much higher.

As described above, the thermal transfer ink ribbon of the present invention uses a silicon-acrylic graft polymer as a lubricant component together with a conventional binder component in a heat-resistant layer, so that the thermal transfer head has an ink ribbon when printing with excellent adhesion to the base film. Even when traveling above, there is no contamination of the thermal transfer head due to the peeling of the heat resistant layer, excellent heat lubrication activity, and low heat transfer of the ink layer dye.

Claims (5)

A heat-resistant layer composition of a thermal transfer ink ribbon composed of a binder component and a lubricant component, wherein the heat-resistant layer composition of the thermal transfer ink ribbon is characterized by containing a silicone-acrylic polymer grafted with the lubricant component. The heat-resistant layer composition of the thermal transfer ink ribbon according to claim 1, wherein the grafted silicone-acrylic polymer is contained in an amount of 2 to 50 wt% based on the heat-resistant layer composition. The grafted silicone-acrylic polymer according to claim 1 or 2, wherein the acrylic monomer represented by the following Chemical Formula 1 constitutes a backbone, and the silicone group-containing monomer represented by the following Chemical Formula 2 is pendant (pendant). The heat-resistant layer composition of the thermal transfer ink ribbon, characterized in that the group). Formula 1 Formula 2 In the above formulas: X represents -CH = CHC (O) X 'or -C (O) X'; Y represents H or CH ₃ ; X 'represents -R, -OR or -NR ¹ R ² ; R is a C ₁ to C ₂₀ alkyl group; C ~ C alkenyl group of _{1 20;} Alkadi group in the C ₁ ~ C _20; A cycloalkyl group of C ₆ to C ₂₀ ; Alkali group; Aryl group; Or an alkyl, alkenyl, alkadienyl, C ₆ -C ₂₀ cycloalkyl, aralkyl group or aryl group containing an ether bond; R ¹ and R ² are the same as or different from each other and represent a C ₁ to C ₄ alkyl group; A represents a C ₁ to C ₂₀ alkyl group or phenyl group; D and E are the same as or different from each other, and represent a C ₁ to C ₅ alkyl group, a phenyl group or (A ₃ SiO) _m −; Q represents H or CH ₃ ; m is an integer from 1 to 5; n is an integer of 1-3. The heat-resistant layer composition of the thermal transfer ink ribbon according to claim 1, wherein the binder component is a polyvinyl acetal polymer or a polyacrylate polymer. The heat-resistant layer composition of the thermal transfer ink ribbon according to claim 1, wherein the heat-resistant layer has a coating thickness of 0.5 to 2.0 µm.