KR100556093B1 - Image-Receiving Sheet for Thermal Sublimable Dye-Transfer Recording - Google Patents

Abstract

The present invention relates to an ink resin paper for dye-sublimation thermal transfer recording, and more particularly, to provide an adhesive, image clarity, The light resistance is greatly improved. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dye-sublimation thermal transfer recording ink resin, characterized in that an intermediate layer is formed of a polyurethane-based polymer having excellent adhesion to a non-polar substrate surface and a chlorinated polypropylene in the middle of the base and the ink receiving layer. It is a manufacturing method.

Ink Resin for Thermal Transfer Recording

Description

Dye-sublimation thermal ink recording ink resin paper and its manufacturing method {Image-Receiving Sheet for Thermal Sublimable Dye-Transfer Recording}             

The figure shows the cross section of the ink resin paper for dye-sublimation thermal transfer recording of the present invention.

1: Back coating layer 2: Laminated material

3: intermediate layer 4: ink receiving layer

The present invention relates to an ink resin paper for dye-sublimation type thermal transfer recording, and a method of manufacturing the same. More particularly, the present invention relates to excellent adhesion to a substrate, improved curability at printing, and improved image density and light resistance after printing. A dye-sublimation type heat transfer recording ink resin paper and a method of manufacturing the same.

With the rapid market expansion of digital cameras, the digital photo printing industry that outputs digital images is growing significantly. In the conventional silver dye photographing technique, the photographed film is sent to the laboratory for manual photo printing, while the digital photo printing can selectively output only the desired photo from the memory card in which the image is stored. No matter where you are, you can always print photos.

Photo-printing technology for outputting digital photographs has been in the spotlight for such a photo-output switching device. Photo-level full-color digital printing technologies include inkjet, electrophotographic, thermal transfer, and laser thermal transfer. Among these, the dye sublimation thermal transfer printing technology, which belongs to the thermal transfer method, has been widely used in the digital photo printing market recently in such a manner as to provide low noise when printing, excellent printing reliability, and high resolution close to natural colors. This printing method is widely used for printing portraits of ID cards such as ID cards, driver's licenses and membership cards.

The thermal transfer method is a method in which a thermal element mounted in a printer transfers heat to an ink ribbon, whereby a black or trichromatic color pigment of an ink layer coated on a ribbon is transferred to an ink resin to form an image. This technique is classified into a melt type method applied to facsimile, label printing, etc. from the beginning, and the dye sublimation type method described above. In the melt method, the ink layer coated on the ink ribbon is printed on the ink resin paper by simultaneously transferring the dye and the binder material, whereas the dye sublimation method prints only the dye contained in the ink layer. The dye sublimation type is derived from the initial use of the sublimation dye and is still conventionally used. However, the dye sublimation type is also referred to as a dye diffusion type in technical terms according to the transfer mechanism.

The melt type is transferred when the polymer binder constituting the ink layer is melted by the thermal element, and is not transferred during cosmetic melting, and thus, high gradation expression is low and high resolution images cannot be obtained. On the other hand, in the dye sublimation type, the thermal energy applied to the thermal element is changed according to the color concentration of the digitally input image, and the dye concentration transferred is controlled continuously according to the amount of energy. Implement the image.

The dye sublimation thermal transfer recording medium consists of a color ink ribbon and an ink resin paper. The ink ribbon forms an ink layer by mixing synthetic dyes of three primary colors of yellow, magenta, and cyan on a polymer binder on one side of a polyester fabric film, and melt adhesion of the polyester film by a thermal element on the other side. In order to prevent the heat-resistant lubrication layer is coated.

The ink resin for dye-sublimation thermal transfer recording must efficiently absorb the dye transferred from the ink ribbon, form a full color image, and store the image for a long time. Receptors are generally coated with an ink-receiving layer for recording ink pigments on one side, and a backcoating for maintaining printability on the other side using various synthetic resin base films such as synthetic paper, polyethylene terephthalate, and polyvinyl chloride. use.

Since the ink receiving layer of the receiving paper has poor adhesiveness to the base film and easily falls off during printing, a technique for applying an intermediate layer serving as a primer between the base and the ink receiving layer has been reported. Examples of the conventional interlayer introduction technology are described in US Patent No. 4,929,592, European Patent No. 433,496, Japanese Patent Application Laid-Open No. 3-67696, Korean Patent No. 93-16576, and the like. However, the intermediate layer technology has problems such as image resolution and image durability, as well as adhesion to the ink-receiving layer and the base film, for use as a paper for outputting digital photographs which are growing rapidly.

The present invention is used to blend the polyurethane-based polymer and the chlorinated polypropylene polymer as a main binder of the intermediate layer composition to solve the above problems of the prior art, improve the cushioning property, adhesion to the ink resin during printing, printing The purpose is to improve the resolution and durability of the image.

The present invention mixes an organic pigment with one side of the base film by mixing a polypropylene chloride with an inorganic pigment as a main binder of the polyurethane polymer constituting the intermediate layer. Coating techniques used include bar coating, gravure coating, comma coating, knife coating and roll coating. The intermediate layer coating liquid is blended 1-60 parts by weight, preferably 20-40 parts by weight of an inorganic pigment, and 0.1-10 parts by weight of a curing agent for polyurethane, preferably 0.5-3 parts by weight, based on 100 parts by weight of the main binder. Use it.

The coating amount of the intermediate layer on the base film is 0.1 g / m ² to 10 g / m ² , applied with a bar coater and dried, and subsequently the ink receiving layer is also applied with a bar coater, and the backcoating layer is applied to the other side of the substrate. Finally, an ink resin is formed.

As the base material for dye-sublimation recording ink resin, synthetic paper, polyethylene terephthalate, polyester sulfone, polyamide, paper extruded with white pigment dispersed polyethylene, and the like are used. As the polymeric binder used in the ink-receiving layer for directly forming a digital image, polyacrylates, polyesters, polyvinyl chloride / vinylacetate copolymers, polyurethanes, and polycarbonates having excellent affinity with pigment molecules and excellent heat resistance during thermal transfer Organic solvents such as polysiloxanes, and aqueous binders such as polyvinyl alcohol, acrylic emulsion, and cellulose. In order to impart smooth running when printed in contact with a dye-sublimation ink ribbon, silicone oil, silicone resin, natural or synthetic wax, polyterephthalate wax, inorganic solid pigment, and the like are added to the polymer binder as a release agent. . In addition, surfactants, antistatic agents, UV stabilizers, heat stabilizers, antioxidants, and the like may be used to increase the dispersibility, antistatic property, and light resistance of the solid filler.

In the intermediate layer used in the present invention, the main binder is a polyurethane-based polymer having a weight average molecular weight of about 10,000 -100,000, preferably 20,000-80,000. The glass transition temperature of the polymer is in the range of O ^o C-70 ^o C, preferably 10 ^o C-50 ^o C, 0.1-10 parts by weight of polyisocyanate with respect to 100 parts by weight of polyisocyanate as the main binder curing agent, Preferably 0.5-3 parts by weight is used in combination. The inorganic pigment is used in an amount of 1-60 parts by weight, preferably 10-40 parts by weight, based on 100 parts by weight of the main binder.

 After the intermediate layer composition is applied onto the substrate, the interface adhesion between the substrate and the ink receiving layer is greatly improved. In addition, the inorganic pigment dispersed in the intermediate layer composition has the effect of improving the long-term image light resistance by increasing the scattering of ultraviolet rays passing through the ink receiving layer. The polyurethane crosslinked structure having rubber elasticity and the finely dispersed structure of the solid pigment provide physical cushioning property when the heat head contacts with each other during printing, and improve the diffusion effect of the dye molecules into the ink receiving layer. Accordingly, image color development is increased, and a resolution suitable for digital photo printing is realized.

As described above, the present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited thereto.

(Example 1)

An ink resin for dye-sublimation thermal transfer recording was prepared by coating each coating layer on a substrate prepared by laminating a 80-μm-thick synthetic paper (manufactured by Hwa Sang Industry Co., Ltd.) on a basis weight of 95 grams of white paper (signal paper).

A) middle layer

The following composition was applied onto the base film with a bar coater (# 5), and dried at 100 ^° C. for 30 seconds, and then the coating amount was 0.5 g / m ² .

Interlayer Composition

10.0 parts by weight of polyurethane (UB705 manufactured by SKC, Korea)

5.0 parts by weight of polypropylene chloride

     (Hardlen made in Japanese Toyo Kasei Kogyo company)

Curing agent (U9081 manufactured by SKC, Korea) 0.4 parts by weight

2.25 parts by weight of titanium oxide (manufactured by Erimentis, USA)

41.175 parts by weight of methyl ethyl ketone

Toluene 41.175 parts by weight

B) Ink receiving layer

The following composition was applied on the interlayer by a bar coater (# 8), and dried at 100 ^° C. for 60 seconds, and the coating amount was 6.5 g / m ² .

Ink receiving layer composition

7.5 parts by weight of polyester resin (ES100, manufactured by SKC, Korea)

7.5 parts by weight of polyvinyl chloride / acetate acetate copolymer resin (CP427, manufactured by Hanwha Corporation)

0.05 parts by weight of amino-modified silicone oil (manufactured by Nippon Shinwol Chemical, KF393)

0.05 parts by weight of aminoepoxy silicone oil (manufactured by Nippon Shinwol Chemical, X-22-343)

Talc 0.02 parts by weight

42.44 parts by weight of methyl ethyl ketone

Toluene 42.44 parts by weight

C) Back Coating Layer

The following composition was applied on the opposite side of the base film to which the intermediate layer and the ink receiving layer were applied with a bar coater (# 6), and dried at 100 ^° C. for 30 seconds, and then the coating amount was 1.0 g / m ² .

15.0 parts by weight of polyurethane (UB705 manufactured by SKC, Korea)

Curing agent (U9081 manufactured by SKC, Korea) 0.4 parts by weight

Perfume Microcapsules (manufactured by Daehamentech Co., Ltd., Korea) 0.0135 parts by weight

42.29 parts by weight of methyl ethyl ketone

Toluene 42.29 parts by weight

(Example 2)

An ink resin for dye-sublimation thermal transfer recording was prepared in the same manner as in Example 1 except that the intermediate layer was formed as follows.

Interlayer Composition

10.0 parts by weight of polyurethane (UB705 manufactured by SKC, Korea)

5.0 parts by weight of polypropylene chloride

     (Hardlen made in Japanese Toyo Kasei Kogyo company)

Curing agent (U9081 manufactured by SKC, Korea) 0.4 parts by weight

2.25 parts by weight of titanium oxide (manufactured by Erimentis, USA)

41.175 parts by weight of methyl ethyl ketone

Toluene 41.175 parts by weight

(Example 3)

An ink resin for dye-sublimation thermal transfer recording was prepared in the same manner as in Example 1 except that the intermediate layer was formed as follows.

Interlayer Composition

12.0 parts by weight of polyurethane (UB705 manufactured by SKC, Korea)

3.0 parts by weight of polypropylene chloride

     (Hardlen made in Japanese Toyo Kasei Kogyo company)

Curing agent (U9081 manufactured by SKC, Korea) 0.4 parts by weight

Titanium Oxide (manufactured by Erimentis, USA) 1.55 parts by weight

41.525 parts by weight of methyl ethyl ketone

Toluene 41.525 parts by weight

(Example 4)

An ink resin for dye-sublimation thermal transfer recording was prepared in the same manner as in Example 1 except that the intermediate layer was formed as follows.

Interlayer Composition

Polyurethane (UB705 made in Korea SKC Corporation) 8.0 parts by weight

5.0 parts by weight of polyurethane (US203, manufactured by SKC, Korea)

Chlorinated Polypropylene 2.0 parts by weight

    (Hardlen made in Japanese Toyo Kasei Kogyo company)

Curing agent (U9081 manufactured by SKC, Korea) 0.4 parts by weight

2.25 parts by weight of titanium oxide (Erimentis, Inc.)

41.525 parts by weight of methyl ethyl ketone

Toluene 41.525 parts by weight

(Comparative Example 1)

An ink resin for dye-sublimation thermal transfer recording was prepared in the same manner as in Example 1 except that no intermediate layer was applied.

(Comparative Example 2)

An ink resin for dye-sublimation thermal transfer recording was prepared in the same manner as in Example 1 except that the intermediate layer was formed as follows.

Interlayer Composition

15.0 parts by weight of polyester (ES110 manufactured by SKC, Korea)

Curing agent (DN-980S manufactured by Aekyung Chemical Co., Ltd.) 0.4 parts by weight

Titanium Oxide (manufactured by Erimentis, USA) 1.55 parts by weight

41.525 parts by weight of methyl ethyl ketone

Toluene 41.525 parts by weight

(Comparative Example 3)

An ink resin for dye-sublimation thermal transfer recording was prepared in the same manner as in Example 1 except that the intermediate layer was formed as follows.

Interlayer Composition

15.0 parts by weight of polyester (ES110 manufactured by SKC, Korea)

Curing agent (DN-980S manufactured by Aekyung Chemical Co., Ltd.) 0.4 parts by weight

Methyl ethyl ketone 42.3 parts by weight

Toluene 42.3 parts by weight

(Comparative Example 4)

An ink resin for dye-sublimation thermal transfer recording was prepared in the same manner as in Example 1 except that the intermediate layer was formed as follows.

Interlayer Composition

15.0 parts by weight of polyester (ES901 manufactured by SKC Korea)

Curing agent (DN-980S manufactured by Aekyung Chemical Co., Ltd.) 0.4 parts by weight

Methyl ethyl ketone 42.3 parts by weight

Toluene 42.3 parts by weight

Evaluation of physical properties of the Examples and Comparative Examples was carried out in the following manner, the results are shown in Table 1.

<Adhesive test>

3M transparent scotch tape on each of the dye-sublimation type thermal transfer recording ink receiving papers prepared in Examples 1-4 and Comparative Examples 1-4 had a width of 17 mm and a uniform size of 70 mm in length, so that no bubble space was present on the adhesive surface. After 6 times strong pressing and sticking with fingers, the operation of removing the test tape is repeated three times. In Table 1, O represents a state in which the ink receiving layer is not peeled at all, Δ represents a fine peeling state, and X represents complete peeling.

<Light resistance test>

Using a dye-sublimation photo printer (P-400, manufactured by Olympus Japan) and a dedicated color ink ribbon, each of the dye-sublimation thermal transfer recording ink resins prepared in Examples 1-4 and Comparative Examples 1-4 was commercially available. A standard specimen is prepared by printing each of the gradation charts of K, Y, M, and C in eight steps. The light resistance test was performed using a UV weather meter (model QB Lab. Products of the U.S .; UVB-313), and after 24 hours of ultraviolet exposure (pig wavelength; 310 nm) at 45 ^o C, the reflected optical density of the discolored gradation chart was measured. It evaluated by comparison with before exposure. In Table 1, O is microdiscoloration (reflection optical density difference (delta) is 0-0.05 before / after exposure), △ is intermediate discoloration (delta is 0.05-0.10), and X is high discoloration (delta is 0.10- 0.5 range).

                                     TABLE 1

Experiment Adhesion Test Results Light resistance test result Example 1 O O Example 2 O O Example 3 O O Example 4 O O Comparative Example 1 X △ Comparative Example 2 △ O Comparative Example 3 △ △ Comparative Example 4 △ △

As can be seen from the above results, the intermediate layer composed of the polyurethane-based binder and the propylene chloride binder devised in the present invention with an inorganic pigment and a curing agent not only greatly improves the adhesion between the substrate and the ink-receiving layer, but also has high cushioning properties during printing. Since the color development is increased and the image light resistance is improved due to the light scattering effect on the ultraviolet rays of the dispersed inorganic pigment, it can be applied as a dye-sublimation thermal ink recording ink suitable for high-quality digital photo printing.

Claims (8)

An intermediate layer applied by using a synthetic base material and a polypropylene chloride on the surface thereof as a main binder polymer, mixed with an inorganic pigment and a curing agent to form a crosslinked structure, and an ink receiving layer formed on the intermediate layer, and the opposite side of the base film A dye-sublimation type thermal transfer ink ink paper formed by applying a backcoaiting layer to a film. The ink resin paper for dye-sublimation thermal transfer recording according to claim 1, wherein the polyurethane uses a polymer having a weight average molecular weight of 20,000 to 80,000. The ink resin paper for dye sublimation thermal transfer recording according to claim 1, wherein the polypropylene chloride is used in an amount of 30 to 60 parts by weight based on 100 parts by weight of the polyurethane binder. The ink resin paper for dye-sublimation type thermal transfer recording according to claim 1, wherein an inorganic pigment is used in an amount of 10 to 40 parts by weight based on 100 parts by weight of the main binder. The ink resin paper for dye-sublimation thermal transfer recording according to claim 3, wherein the inorganic pigment material is selected from titanium oxide, talc, and silica. The ink resin paper for dye-sublimation thermal transfer recording according to claim 1, wherein 0.5 to 3 parts by weight of polyisocyanate is used as the curing agent with respect to 100 parts by weight of the main binder. The method of claim 1, wherein the coating amount of the intermediate layer is 0.1g / m ² to 10g / m ² characterized in that Is ink dye paper for dye-sublimation thermal transfer recording. The ink resin paper for dye-sublimation thermal transfer recording according to claim 1, wherein the back coating layer uses 0.05-20 parts by weight of the fragrance material made of microcapsules with respect to 100 parts by weight of the main binder.

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