JPH0796681A - Water based ink fixing composition, cover film for thermal transfer image using the same, and thermal transfer image recording body - Google Patents

Abstract

PURPOSE:To provide water based ink fixing composition having excellent water base ink absorbing power, water resistance and capable of, for example, fixing a water based stamp on a thermal transfer image, and provide a cover film for the thermal transfer image. CONSTITUTION:A water based ink fixing composition contains an ion exchanger and has water based ink fixing property. For the ion exchanger, a clay intercalation compound or an ion exchanging resin is used. For a binder, a water absorbing resin or a heat melting resin may be used jointly. A water based ink fixing layer 2 is formed on a base material 1 by using the water based ink fixing composition so as to form a cover film for thermal transfer image. In this case, the base material may be treated so as to have release property, and an adhesive layer or a heat melting resin layer may be formed on the water based ink fixing layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based ink fixing composition for forming a protective film for a thermal transfer image, particularly a sublimation thermal transfer image, and further to a thermal transfer image cover film or thermal transfer image using the same. The present invention relates to an image recording body.

[0002]

2. Description of the Related Art In recent years, a so-called "instant video portrait system" is known as a system using a sublimation transfer recording technique. This system shoots a subject with a video camera, etc., and transfers the video image information as a still image to the dye receiving layer of photographic paper by thermal transfer recording technology, and applies the resulting transferred image to various certificates. It has been attracting attention as an alternative to conventional silver halide photography. For example, in Europe, this "instant video portrait system" is applied to identify users such as ski passes and rail commuter passes.

The thermal transfer image formed on such a photographic printing paper may be used for various purposes while being exposed to the outside, but a thermal transfer image cover film is provided on the thermal transfer image for the purpose of protecting the image. Stacking is also widely performed. As such a thermal transfer image cover film,
A polyester film having an adhesive layer formed thereon, or a polyvinyl chloride film or the like which can be laminated by thermocompression bonding itself is used.

[0004]

By the way, there is a case where an aqueous ink image such as a tally or various stamp images is formed by using an aqueous ink on the thermal transfer image of the printing paper on which the thermal transfer image is formed as described above. is there.

However, since the dye receiving layer of the photographic printing paper on which the thermal transfer image is formed is made of a lipophilic or water repellent material such as polyester, it does not absorb or permeate the aqueous ink, and therefore the aqueous ink. It has the drawback of not fixing the image.

Further, since the conventional thermal transfer image cover film is also formed of the lipophilic material as described above, it has a drawback that it does not absorb or permeate the aqueous ink and therefore does not fix the aqueous ink image. Therefore, there is a problem that the water-based ink image formed on the thermal transfer image is easily destroyed by coming into contact with water droplets such as rain and sweat, or by being rubbed by hand.

To solve such a problem, it is considered that the thermal transfer image cover film is composed of only a water-soluble material, but it is very difficult to directly laminate it on the lipophilic dye receiving layer, and However, there is a problem of poor water resistance.

Therefore, the present invention has been proposed in view of such conventional circumstances, and it is possible to impart a fixing property to an aqueous stamp to a thermal transfer image, particularly a sublimation thermal transfer image, and further, a dye receiving layer. With the object of providing a composition for fixing a water-based ink having excellent adhesiveness to water and water resistance, further, a heat transfer image cover film having a good water-based stamp fixing property and tampering preventive property, and a heat transfer image recording body are provided. The purpose is to provide.

[0009]

The present inventors have been able to impart good water-based ink fixability by adding an ion exchanger such as a clay-based intercalation compound and an ion exchange resin to the fixing layer, and the water resistance The inventors have found that there is no problem in terms of sex and have completed the present invention.

That is, the aqueous ink fixing composition of the present invention is characterized by containing an ion exchanger.

The ion exchanger used in the composition for a water-based ink fixing layer of the present invention absorbs water in the water-based ink and swells by itself, and further contains an ion contained in the water-based ink. It has a function of holding the ionic dye itself by an ion exchange action. Therefore,
The presence of the ion exchanger improves the fixability of the aqueous ink image. In this case, it is preferable to use a mixture of an anion exchanger and a cation exchanger so that the ionic dye used can be either a cation or an anion.

As an example of such an ion exchanger, a clay-based intercalation compound having an ion exchange ability can be preferably mentioned. For example, hydrotalcite can be exemplified as the anion-exchangeable clay-based intercalation compound, and montmorillonite group minerals represented by the following formula (1) can be exemplified as the cation-exchangeable clay-based intercalation compound.

(X, Y) pZ ₄ O ₁₀ (OH) ₂ .mH ₂ O. (Wq) (1) (In the formula, X is Al, Fe (III), Mn (III) or Co ( III), Y is Mg, Fe (II), Mn (II), Ni, Zn or Li, and Z is
Is Si or Al, W is K, Na or Ca, H ₂ O is interlayer water, and m is an integer. p is 1 to 3, q is 1 to 3
Is. )

Specific examples of the montmorillonite group mineral represented by the formula (1) include montmorillonite, magnesian montmorillonite, iron montmorillonite, iron magnesian montmorillonite, beidellite, and aluminium, depending on the combination of X and Y and the difference in the number of substitutions. Examples thereof include natural products and synthetic products such as ambidelite, nontronite, aluminian nontronite, sapotite, aluminian saponite, hexitrite, and sauconite. Moreover, what substituted the OH group in Formula (1) with the halogen atoms, such as fluorine, can also be used.

In addition to the montmorillonite group mineral of the formula (1), examples of the cation-exchangeable clay-based intercalation compound include mica group minerals such as sodium silicic mica, sodium teniolite and lithium teniolite.

Alternatively, an ion exchange resin can be used as the ion exchanger. As an ion exchange resin,
Any known products such as synthetic products and semi-synthetic products can be used. As a specific example, as a synthetic product, a polyacrylate type (manufactured by Steel Chemicals Co., Ltd., trade name Aqua Keep, Sumitomo Chemical Co., Ltd., trade name Sumika Gel, Kao Soap Co., trade name Wonder Gel, Dow Chemical Co., trade name
DWAL, Stockhausen, trade name Favor, Arakawa Hayashi Chemical Co., trade name ALASORP, Nippon Shokubai Chemical Co., trade name AQUARIC, saponified vinyl acetate / acrylic acid ester copolymer (Sumitomo Chemical Co., Ltd.) Co., Ltd., trade name Sumikagel, trade name Igetagel), saponified vinyl acetate / maleic acid copolymer (trade name GP from Nippon Synthetic Chemical Industry Co., Ltd.), crosslinked isobutylene / maleic anhydride copolymer (Kuraray Isoprene Chemical) Manufactured by Nippon Exlan Co., trade name Laso Seal, Sumitomo Chemical Co., trade name Sumika Gel) and the like.

As a semi-synthetic product, saponified starch / acrylonitrile graft polymer (manufactured by GPC, trade name Wa
ter-Lock, manufactured by Super Absorbent, trade name Terr
a-sorb, manufactured by Henkel Japan, trade name SGP, manufactured by Nitto Kagaku Co., trade name WAS, starch-acrylic acid graft polymer (manufactured by Sanyo Chemical Industry Co., Ltd., trade name Sun Wet, Lion Co., trade name Lion Polymer), CMC cross-linked product (Hercules, trade name Aqualon, Enca, trade name
Akucell) and the like.

From the viewpoints of water-based ink absorbability and water-based ink image fixability, such an ion exchanger is preferably added in an amount of 10 wt% or more in the water-based ink fixing composition, preferably 20 to 80 wt%. Is more preferable.

The above-mentioned ion exchanger may be used alone as an aqueous ink fixing composition when an ion exchange resin is used, but when a clay intercalation compound or ion exchange resin particles are used, a binder is used. It is necessary to use them together to provide film forming properties.

In this case, the binder may be a water absorbent resin. The water absorbent resin absorbs and holds the water-based ink. As such a water absorbent resin, one having a water absorption rate (20 ° C., 65% RH) of 5% or more, more preferably 10% or more is preferably used. Examples of such a water absorbent resin include allulose-based polymers such as anionic cellulose derivatives, polyvinylpyrrolidone-based polymers such as polyvinylporolidone, and polyvinylpyrrolidone-vinyl acetate copolymers. Among them, polyvinylpyrrolidone-based polymers can be preferably used.

From the viewpoints of water-based ink absorbability and water-based ink image fixability, such a water-absorbent resin is preferably added in an amount of 20% by weight or more, and 30 to 70% by weight in the water-based ink fixing composition. It is more preferable to mix them.

When the above water-absorbent resin is used as a binder, it is preferable to use a water-insoluble resin together for the purpose of improving water resistance. As such a water-insoluble resin, polyvinyl chloride or the like can be used, but a resin compatible with a water-absorbent resin is preferable, and for example, cellulose acetate butyrate (hereinafter abbreviated as CAB) or the like cellulose acetate. And acetalization products of vinyl alcohol such as polyvinyl butyral can be used.

However, since the water-insoluble resin absorbs less water-based ink in the water-based ink fixing layer formed from the water-based ink fixing composition as the blending amount thereof increases, the water-based ink fixing composition. It is preferable to mix it in a proportion of 70% by weight or less. Particularly, in order not to decrease the ink absorption rate, it is preferable to add 30% by weight or less.

Further, when importance is attached to water resistance, adhesion to a heat transfer image, etc., a heat melting resin may be used as a binder. As the heat-melting resin, any resin having heat-melting property can be used, for example, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acetic acid. Examples thereof include vinyl-vinyl alcohol copolymer, vinyl chloride-acrylonitrile copolymer, polyurethane resin, butadiene-acrylonitrile copolymer, polyamide resin, polyvinyl butyral, styrene-butadiene copolymer, polyester resin and acrylic resin.

The water-based ink fixing composition of the present invention can maintain water resistance even when the amount of a water-absorbent resin or an ion exchanger is increased in order to improve the fixability of a water-based ink image. Therefore, a cross-linking agent capable of forming a three-dimensional cross-linked structure may be contained. Like this 3
The dimensional cross-linking structure can hold a water-absorbing resin or an ion exchanger therein, and thus enhances the water resistance of the water-based ink fixing composition even if the compounding amount of the water-absorbing resin or the ion exchanger is increased. be able to. As such a cross-linking agent,
It can be appropriately selected and used from those capable of forming a three-dimensional crosslinked structure.

Since such a crosslinking agent decreases the absorbability of the aqueous ink of the aqueous ink fixing composition as the amount of the crosslinking agent increases, the crosslinking agent is added to the aqueous ink fixing composition at a ratio of 70% by weight or less. Preferably.

The aqueous ink fixing composition of the present invention preferably contains a nonionic surfactant for the purpose of increasing the absorption rate of the aqueous ink to facilitate drying. Such a nonionic surfactant is not particularly limited and can be appropriately selected and used.

However, if the amount of the nonionic surfactant used is too large, blooming is likely to occur, so the proportion of the nonionic surfactant incorporated in the aqueous ink fixing composition is preferably 50% by weight or less.

Further, in the water-based ink fixing composition of the present invention, known ultraviolet absorbers, antioxidants, and
A diluent or the like can be added. However, since the water-based ink fixing layer formed from the water-based ink fixing composition of the present invention covers the thermal transfer image, the water-based ink fixing layer is made light-transmitting.

The aqueous ink fixing composition of the present invention can be produced by a known method. For example, a water-absorbent resin or a heat-fusible resin as a binder and an ion exchanger may be added, if necessary, and other components. It can be produced by uniformly mixing with a solvent such as methyl ethyl ketone using a sand mill.

The above-mentioned aqueous ink fixing composition may be applied directly on the thermal transfer image to form the aqueous ink fixing layer, but it is convenient to handle it in the form of a cover film laminated on the thermal transfer image. is there.

Then, the cover film for thermal transfer image of the present invention using the above-mentioned aqueous ink fixing composition will be described.

The thermal transfer image cover film of the present invention comprises:
A water-based ink fixing layer containing an ion exchanger is formed on a substrate so as to be peelable,
Furthermore, an adhesive layer or a heat-fusible resin layer is formed on the water-based ink fixing layer. Alternatively, it is characterized in that an aqueous ink fixing layer containing an ion exchanger is formed on one surface of the support film, and an adhesive layer or a heat-meltable resin layer is formed on the other surface. .

FIG. 1 shows an example of the thermal transfer image cover film of the present invention. The thermal transfer image cover film shown in FIG. 1 has the simplest structure,
The water-based ink fixing layer 2 is formed on the water-based ink fixing composition. Here, the base material 1 and the water-based ink fixing layer 2 are laminated in a peelable manner.

When this cover film for a thermal transfer image is applied to a thermal transfer image, first, the aqueous ink fixing layer 2 is superposed on the thermal transfer image and thermocompression-bonded, and then the substrate 1 is peeled from the aqueous ink fixing layer 2. As a result, the water-based ink fixing layer 2 is formed on the thermal transfer image, and the water-based ink image can be fixed.

As the base material 1, a polyester film or a polyimide film having heat resistance can be used. If necessary, the surface of the base material 1 on the side of the aqueous ink fixing layer 2 may be subjected to a known release treatment.

The water-based ink fixing layer 2 is a layer that absorbs the water-based ink and fixes the ionic dyes and pigments contained therein to form a water-based ink image. It is formed from the composition. The thickness of the water-based ink fixing layer 2 can be appropriately determined as needed.

FIG. 2 shows another embodiment of the cover film for thermal transfer image of the present invention. This cover film for a thermal transfer image has an adhesive layer 3 on the water-based ink fixing layer 2.
And is effective when the water-based ink fixing layer 2 does not sufficiently adhere to the thermal transfer image due to heat and pressure.

The adhesive for forming the adhesive layer 3 can be appropriately selected from known adhesives that exhibit adhesiveness under the conditions of thermocompression bonding, and the thickness thereof can also be appropriately determined. You can Further, instead of the adhesive layer, a heat-melting resin layer made of a resin having heat-melting property may be formed.

FIG. 3 shows still another embodiment of the thermal transfer image cover film of the present invention. This thermal transfer image cover film comprises a transparent support film 5 having an aqueous ink fixing layer 2 formed on one surface thereof and an adhesive layer 3 formed on the other surface thereof. In this example, the water-based ink fixing layer 2
Are bonded to the support film 5 via the adhesive layer 6.

In the case of the cover film for a thermal transfer image having such a structure, the support film 5 also serves as a cover film, and the thermal transfer image is protected more reliably. In any of the thermal transfer image cover films described above, it is preferable that a protective film be bonded to the surface of the adhesive layer 3 and the protective film be peeled off at the time of use. As the protective film, a polyester film, a polyethylene film, a polypropylene film, or the like can be used, and in some cases, release treatment with a silicone resin or the like may be performed.

The thermal transfer image cover film of the present invention can be produced by a conventional method, for example, by coating a substrate with a water-based ink fixing composition diluted with a solvent and drying it. it can. If necessary, an adhesive layer or a heat-meltable resin layer can be further formed by a conventional method.

The above-described water-based ink fixing layer (heat transfer image cover film) can be combined with an image forming material (so-called ink ribbon). FIG. 4 is a cross-sectional view of a thermal transfer image forming material for color image formation to which the cover film for thermal transfer image of the present invention is applied. This thermal transfer image forming material has a water base ink fixing layer 2, a yellow ink layer 4a, a magenta ink layer 4b and a cyan ink layer 4c formed on a substrate 1. Here, the water-based ink fixing layer 2 and the ink layers 4a to 4c are independently formed on the base material 1 without being laminated on each other.

The method of using the thermal transfer image forming material of FIG.
First, a color image is formed by sequentially superimposing the ink layers 4a to 4c on a dye receiving layer of a photographic paper and performing thermal transfer according to image information, and finally, a color image is formed on the obtained color image. Are laminated and thermocompression-bonded to laminate the water-based ink fixing layer 2 on the color image. Therefore, by forming the thermal transfer image forming material as shown in FIG. 4, it becomes possible to efficiently perform image formation and lamination of the water-based ink fixing layer 2 on the obtained image.

In the thermal transfer image-forming material shown in FIG. 4, the other constituent elements are the same as those of the conventional one except that the water-based ink fixing layer 2 formed from the water-based ink fixing composition of the present invention is used. can do.

The thermal transfer image-forming material shown in FIG. 4 can be produced by a conventional method. For example, a composition prepared by diluting a water-based ink fixing composition with a solvent is applied onto a substrate and dried to form each ink layer. Can be manufactured by sequentially coating and drying the composition for use.

[0047]

In the aqueous ink fixing composition of the present invention,
The ion exchanger holds the ionic dye contained in the aqueous ink by the ion exchange action. In addition, for example, when the water-absorbent resin is used as the binder, the water-based ink is quickly absorbed and fixed. When a heat-meltable resin is used as the binder, water resistance and adhesiveness to a heat transfer image are further secured.

Therefore, when a water-based ink fixing layer is formed by using this composition and used as a thermal transfer image cover film, and the water-based ink fixing layer is transferred and laminated on the heat transfer image, fixability to the water-based ink image is imparted. Thus, for example, the tally mark and various stamp images are surely fixed, and at the same time, the tampering prevention function is imparted.

[0049]

EXAMPLES Examples to which the present invention is applied will be described below in detail with reference to concrete experimental results.

Example 1 In 80 g of methyl ethyl ketone, 10 g of polyvinylpyrrolidone-vinyl acetate copolymer (trade name: Rubiscol VA64, manufactured by BASF) as a water-absorbing resin was added and dissolved, and a synthetic smectite (commercial product) as an ion exchanger (commercial product). 10 g of SWN (manufactured by Coop Chemical Co., Ltd.) was added, and a dispersion treatment was carried out for 2 hours using a sand mill (trade name: KM-200, manufactured by Kaneda Rika Kogyo Co., Ltd.) to obtain a milky white uniform dispersion liquid.

To this dispersion was added a solution prepared by dissolving 3 g of CAB (trade name: 553-0.4, manufactured by Eastman Condac Co.) as a water-insoluble resin in 7 g of a mixed solvent of methyl ethyl ketone-toluene, and stirred uniformly to form an aqueous solution. A dispersion of the ink fixing composition was obtained. The resulting dispersion of the aqueous ink fixing composition was applied to a thickness of 12 μm so that the dry thickness was 15 μm.
A 5 μm polyester film was applied and dried using a doctor blade to form a translucent aqueous ink fixing layer.

Next, a solution prepared by dissolving 20 g of a vinyl chloride-vinyl acetate copolymer (trade name: Denka vinyl # 1000D, manufactured by Denki Kagaku Kogyo) in 80 g of methyl ethyl ketone was dried to a thickness of about 30 μm on the aqueous ink fixing layer. Thus, the adhesive film having excellent transparency was formed by coating and drying, to obtain a cover film for a thermal transfer image.

The adhesive layer of the cover film for a thermal transfer image thus obtained was superposed on the thermal transfer image output on a photographic printing paper (trade name UPC3010P, manufactured by Sony), and a thermocompression laminating apparatus (manufactured by Intercosmos; roller temperature). 14
Thermocompression bonding was performed using 0 ° C and a roller passing speed of 500 mm / min. When the polyester film was peeled off after being left at room temperature, a transparent and glossy aqueous ink fixing layer could be transferred onto the entire surface of the thermal transfer image without blurring.

Next, a stamp image was formed on the water-based ink fixing layer formed on the thermal transfer image using a water-based black ink for stamping (manufactured by Gutenberg Co.), and the ink of the water-based ink fixing layer was formed as shown below. The absorbency and ink fixability were tested and evaluated.

Ink Absorbability A stamp image was formed on the water-based ink fixing layer with the water-based ink, and after 5 minutes, the image was wiped off to remove the water-based ink that had not been absorbed yet. The density of the solid image left on the water-based ink fixing layer was measured using a measuring machine (trade name: TR-924, manufactured by Macbeth Co.) to determine the water-based ink absorbency. A reflection density of 1.5 or more was used as a practical standard.

Ink Fixability The reflection density was measured after drying a solid image on an aqueous stamp. After the measurement, the entire image was immersed in water for 1 minute and dried, and then the reflection density was measured. The density residual ratio before and after the immersion test (= density after test / density before test × 100%) was displayed as ink fixability.

The results are shown in Table 1.

[0058]

[Table 1]

As is clear from Table 1, the water-based ink fixing layer of this example has excellent water-based ink water absorption and fixability.

Example 2 In 80 g of ethanol, a polyvinylpyrrolidone-vinyl acetate copolymer (trade name: Rubiscol V) was used as a water-absorbent resin.
12 g of A64, manufactured by BASF Co., Ltd. was added and dissolved, and further synthetic hectorite (trade name RDS, as an ion exchanger)
8g of Nippon Silica Co., Ltd. was added, and a sand mill (trade name KM) was added.
-200, manufactured by Kaneda Rika Kogyo Co., Ltd.) for 2 hours to obtain a milky white uniform dispersion liquid.

To this dispersion was added a solution prepared by dissolving 4 g of polyvinyl butyral (trade name: Eslec BL-3, manufactured by Sekisui Chemical Co., Ltd.) as a water-insoluble resin in 16 g of ethanol, stirred uniformly, and further, a nonionic surfactant. (Product name NP
-20, manufactured by Nikko Chemical Co., Ltd.) and stirred to obtain a dispersion of the aqueous ink fixing composition.

The resulting dispersion of the aqueous ink fixing composition was applied and dried on a 125 μm-thick polyester film with a doctor blade to a dry thickness of 15 μm, and a semitransparent aqueous ink fixing layer was formed. Formed. next,
A solution of 20 g of a vinyl chloride-vinyl acetate copolymer (trade name: Denka vinyl # 1000D, manufactured by Denki Kagaku Kogyo) dissolved in 80 g of methyl ethyl ketone was applied and dried on the aqueous ink fixing layer to a dry thickness of about 30 μm. Then, an adhesive layer having excellent transparency was formed to produce a cover film for thermal transfer image.

Using the resulting cover film for thermal transfer images, a water-based ink fixing layer was formed on the thermal transfer image in the same manner as in Example 1. As a result, a transparent and glossy aqueous ink was formed on the entire surface of the thermal transfer image. The fixing layer was able to transfer the thermal transfer image without blurring.

Further, in the same manner as in Example 1, an aqueous ink image was formed on the aqueous ink fixing layer, and the ink absorbability and the ink fixing property of the aqueous ink fixing layer were tested and evaluated. The results are also shown in Table 1 above. As is clear from Table 1, the water-based ink fixing layer of this example also showed excellent water-based ink water absorption and fixability.

Example 3 As a water-absorbent resin, polyvinylpyrrolidone-vinyl acetate copolymer (trade name: Rubiscol VA73E, manufactured by BASF) 16 and soluble nylon (trade name: AQ nylon P-)
70, Toray Co., Ltd. 4 g, Montmorillonite (trade name Kunipia F, Kunimine Industry Co., Ltd.) 12 g together with 100 g of isopropyl alcohol, Sand Mill (trade name KM-20).
0, manufactured by Kaneda Rika Kogyo Co., Ltd., and further subjected to a block type polyisocyanate crosslinking agent (trade name Coronate 25
6 (13, manufactured by Nippon Polyurethane Co., Ltd.) was added and stirred to obtain a dispersion liquid of the composition for fixing the aqueous ink.

The resulting dispersion of the aqueous ink fixing composition was applied onto a 125 μm-thick polyester film using a doctor blade so that the dry thickness would be 15 μm, and heated with hot air at 135 ° C. for 15 minutes. A semi-transparent water-based ink fixing layer was formed by drying.

Next, a solution prepared by dissolving 20 g of vinyl chloride-vinyl acetate copolymer (trade name Denka Vinyl # 1000D, manufactured by Denki Kagaku Kogyo) in 80 g of methyl ethyl ketone was dried to a thickness of about 30 μm on the aqueous ink fixing layer. Coated and dried to form an adhesive layer with excellent transparency,
A cover film for a thermal transfer image was manufactured.

Using the obtained cover film for thermal transfer images, a water-based ink fixing layer was formed on the thermal transfer images in the same manner as in Example 1. The transparent and glossy aqueous ink was formed on the entire surface of the thermal transfer images. The fixing layer was able to transfer the thermal transfer image without blurring.

Further, in the same manner as in Example 1, an aqueous ink image was formed on the aqueous ink fixing layer, and the ink absorbability and the ink fixing property of the aqueous ink fixing layer were tested and evaluated. The results are also shown in Table 1 above. As is clear from Table 1, the water-based ink fixing layer of this example also showed excellent water-based ink water absorption and fixability.

Example 4 In 80 g of isopropyl alcohol, 5 g of hydroxypropyl cellulose (trade name HPC-M, manufactured by Nippon Soda Co., Ltd.) as a water-absorbing resin was added and dissolved, and further, a synthetic smectite (trade name SWN, trade name SWN, 15g of Cope Chemical Co., Ltd. was added, and a sand mill (trade name KM-20) was added.
0, manufactured by Kaneda Rika Kogyo Co., Ltd.) for 2 hours to obtain a dispersion liquid of a milky white uniform aqueous ink fixing composition.

The resulting dispersion of the aqueous ink fixing composition was applied to a polyester film having a thickness of 125 μm by a doctor blade so as to have a dry thickness of 15 μm and dried to form a semitransparent aqueous ink fixing layer. Formed.

Next, a solution prepared by dissolving 20 g of a vinyl chloride-vinyl acetate copolymer (trade name Denka Vinyl # 1000D, manufactured by Denki Kagaku Kogyo) in 80 g of methyl ethyl ketone was dried to a thickness of about 30 μm on the aqueous ink fixing layer. Coated and dried to form an adhesive layer with excellent transparency,
A cover film for a thermal transfer image was manufactured.

Using the obtained cover film for thermal transfer images, a water-based ink fixing layer was formed on the thermal transfer images in the same manner as in Example 1. As a result, a transparent and glossy aqueous ink was formed on the entire surface of the thermal transfer images. The fixing layer was able to transfer the thermal transfer image without blurring.

Further, in the same manner as in Example 1, a water-based ink image was formed on the water-based ink fixing layer, and the ink absorbability and ink fixing property of the water-based ink fixing layer were tested and evaluated. The results are also shown in Table 1 above. As is clear from Table 1, the water-based ink fixing layer of this example also showed excellent water-based ink water absorption and fixability.

Example 5 In 80 g of isopropyl alcohol, 10 g of hydroxypropyl cellulose (trade name: HPC-L, manufactured by Nippon Soda Co., Ltd.) and 10 g of synthetic smectite (trade name: Smecton SA, manufactured by Kunimine Industries Co., Ltd.) were mixed as a water absorbent resin. 2 with a sand mill (trade name: KM-200, manufactured by Kaneda Rika Kogyo Co., Ltd.)
Time-dispersion treatment was performed to obtain a milky white uniform dispersion liquid. To this dispersion, 100 g of a reactive urethane resin (trade name: Elastron C-52, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added as a cross-linking agent and uniformly dispersed to obtain a dispersion of the aqueous ink fixing composition.

The resulting dispersion of the aqueous ink fixing composition was applied on a 125 μm-thick polyester film with a doctor blade so that the dry thickness was 15 μm, and then dried by heating with hot air at 135 ° C. for 4 minutes. By doing so, a translucent aqueous ink fixing layer was formed.

Next, a solution prepared by dissolving 20 g of a vinyl chloride-vinyl acetate copolymer (trade name: Denka vinyl # 1000D, manufactured by Denki Kagaku Kogyo) in 80 g of methylethyltoken was dried on the aqueous ink fixing layer to a dry thickness of about 10 μm. A cover film for a thermal transfer image was manufactured by coating and drying so as to have a thickness of 30 μm and forming an adhesive layer having excellent transparency.

Using the obtained cover film for a thermal transfer image, a water-based ink fixing layer was formed on the thermal transfer image in the same manner as in Example 1. The transparent and glossy aqueous ink was formed on the entire surface of the thermal transfer image. The fixing layer was able to transfer the thermal transfer image without blurring.

In the same manner as in Example 1, an aqueous ink image was formed on the aqueous ink fixing layer, and the ink absorbability and the ink fixing property of the aqueous ink fixing layer were tested and evaluated. The results are also shown in Table 1 above. As is clear from Table 1, the water-based ink fixing layer of this example also showed excellent water-based ink water absorption and fixability.

Example 6 Synthetic hectorite (trade name XLS, manufactured by Nippon Silica) 1
00g and hydrotalcite (trade name DHT-4C,
100 g of Kyowa Chemical Co., Ltd., polyvinylpyrrolidone-vinyl acetate copolymer (trade name: Rubiscol VA64, BA
400 g of SF) and 2 kg of a methyl ethyl ketone solution containing 20% by weight of CAB were added, and the mixture was subjected to a dispersion treatment by a roll mill for 1 week to obtain a dispersion liquid of an aqueous ink fixing composition.

Using this dispersion, a color ink ribbon as shown in FIG. 4 having a transparent aqueous ink fixing layer having a dry thickness of about 3 μm was produced. The base material and yellow,
The same color ink ribbon (trade name: VPM-30STA) manufactured by Sony Corporation was used for each of the magenta and cyan ink layers.

This ink ribbon was set in a video printer (trade name CVP-G7, manufactured by Sony Corporation), gradation printing was performed on photographic printing paper (trade name VPM-30STA, manufactured by Sony Corporation), and finally a water-based ink was used. The fixing layer was transferred by solid printing. As a result, a thermal transfer image covered with a highly glossy water-based ink fixing layer was obtained.

Further, in the same manner as in Example 1, an aqueous ink image was formed on the aqueous ink fixing layer, and the ink absorbability and the ink fixing property of the aqueous ink fixing layer were tested and evaluated. The results are also shown in Table 1 above. As is clear from Table 1, the water-based ink fixing layer of this example also showed excellent water-based ink water absorption and fixability.

Example 7 Synthetic Hectorite (trade name XLS, manufactured by Nippon Silica) 1
00 g and 100 g of an ion exchanger (trade name IXE-700, manufactured by Toagosei Kagaku Co., Ltd.) are used as polyvinylpyrrolidone-vinyl acetate copolymer (trade name Rubiscol VA64, BA).
2 kg of an isoprovir alcohol-toluene mixed solution containing 20% by weight of polyvinyl butyral (trade name: Eslec BLS, Sekisui Chemical Co., Ltd.) together with 400 g of SF).
The dispersion liquid of the aqueous ink fixing composition is prepared by adding 50 g of a nonionic surfactant (trade name: PEG400, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) to a dispersion liquid by a roll mill for 1 week. Obtained.

Using this dispersion, a color ink ribbon was manufactured in the same manner as in Example 6. However, an adhesive layer of CAB having a dry thickness of about 3 μm was laminated on the aqueous ink fixing layer. Further, when a thermal transfer image was formed using this ink ribbon and an aqueous ink fixing layer was formed thereon in the same manner as in Example 6, a thermal transfer image covered with the aqueous ink fixing layer having high glossiness was obtained. Was given.

Further, as in Example 1, a water-based ink image was formed on the water-based ink fixing layer, and the ink absorbability and ink fixing property of the water-based ink fixing layer were tested and evaluated. The results are also shown in Table 1 above. As is clear from Table 1, the water-based ink fixing layer of this example also showed excellent water-based ink water absorption and fixability.

Comparative Example 1 A comparative aqueous ink fixing composition was prepared by repeating the same steps as in Example 1 except that the intercalation compound was not used, and using this, a thermal transfer image cover film for comparison was prepared. Manufactured.

Using the resulting cover film for thermal transfer images, a water-based ink fixing layer was formed on the thermal transfer image in the same manner as in Example 1. As a result, a transparent and glossy aqueous ink was formed on the entire surface of the thermal transfer image. The fixing layer was able to transfer the thermal transfer image without blurring. However, in the same manner as in Example 1, a water-based ink image was formed on the water-based ink fixing layer, and the ink absorbability and the ink fixing property of the water-based ink fixing layer were tested and evaluated.
It was found that the water-based ink fixing layer of this comparative example was significantly inferior in the fixability of the water-based ink to the water-based ink fixing layer of each example.

Example 8 While vigorously stirring 1 liter of distilled water, 1 g of a cation exchange resin (manufactured by Sanyo Kasei Co., Ltd., trade name Sunwet: starch-acrylic acid graft polymer) was added little by little, and the whole amount was added. After that, ball mill dispersion was carried out for 2 days to obtain a transparent and viscous swelling liquid. This liquid was applied on a polyester film having a thickness of 150 μm by using a doctor blade so that the thickness when wet was set to 100 μm, and then dried with hot air at 120 ° C. to obtain a transparent layer having a slightly uneven surface. Was given.

Next, 5 g of vinyl chloride-vinyl acetate copolymer (manufactured by Union Carbide Co., trade name VYGF) was dissolved in 45 g of methyl ethyl ketone, and a wet thickness of 50 μm was formed on the above cation exchange resin layer using a doctor blade.
When applied and dried, a highly transparent film was obtained.

Next, the vinyl chloride-vinyl acetate copolymer film was coated with photographic paper (manufactured by Sony Corporation, trade name UPC3010).
P), the heat transfer was carried out between the rollers heated at 120 ° C. at a speed of 1 cm / sec in the form of being superposed on the sublimation heat transfer image, and the uppermost polyester film was peeled off after cooling to room temperature, A slightly opaque glossy layer was formed on the entire surface of the print receiving layer.

This layer was stamped with a commercially available aqueous black ink (stamping ink manufactured by Gutenberg Co., Ltd.) and left for several minutes, but the image did not flow even if touched with a finger, and it did not transfer to other paper or adhesive film. . A similar stamp operation was performed on a sublimation thermal transfer image that has not been subjected to the above-mentioned processing (that is, normal), but if you touch it with your finger or place a paper, it will easily transition and the stamp image will be fixed at all. I didn't.

In this example, the cation exchange resin layer was formed directly on the polyester film, but it is of course possible to form the cation exchange resin layer on the polyester film which has been subjected to the mold release treatment. is there.

The reason why the vinyl chloride-vinyl acetate copolymer is used as the adhesion-imparting resin is as follows. That is, the print receiving layer used in this example contains a resin of the same system as a main component, and the temporal stability of the image after heat fusion (light fading,
This is because there is no adverse effect on dark fading. In addition, since the formed composite layer has the uppermost hydrophilic layer embedded in the lipophilic resin layer, the stamp image immediately flows even if the image is immersed in water after stamping. This is because it behaves like a silver salt photograph.

When water-soluble gelatin or polyvinyl alcohol is used as the adhesion-imparting resin, such a high ink fixing effect cannot be expected.

Example 9 150 g of montmorillonite (Kunimine Industries, Ltd., trade name Kunipia F) was added to 1 kg of an ethanol solution containing 10% by weight of hydroxypropylcellulose, and dispersed by a roll mill for 1 week to obtain a suspension.

This suspension was applied to the ink application surface of the stock film of the ink ribbon manufactured by Sony Corporation in the same screen size after the Y, M, and C application process, dried, and wound. Using a mass production type gravure coater, an almost transparent laminating film having a thickness of 1 μm when dried was obtained. A ribbon cassette in the form of a product was obtained from the obtained ink ribbon original fabric with a laminated layer through a slit and small winding process.

Here, auxiliary additives such as a fluorescent brightening agent and an ultraviolet absorber may be added to the laminate layer as long as they do not impair the adhesiveness to the print receiving layer.

This ribbon cassette was set in a video printer (manufactured by Sony Corporation, trade name G500), gradation printing was performed on STA printing paper, and then solid printing was performed. The laminate layer was printed on the printed image. A fully laminated and glossy image was output. When this image was stamped with a commercially available red water-based ink, the stamp image did not flow even if it was rubbed with a finger immediately after imprinting, and it was fixed on the original image.

Example 10 A suspension prepared in Example 9 on the release treated surface of a polyethylene terephthalate film having a thickness of 6 μm which had been subjected to a release treatment (provided that the ion exchanger manufactured by Kunimine Industries Co., Ltd. was used. Synthetic smectite was used) was applied using a wire bar and dried with hot air to obtain a film having a thickness of 2 μm.

Next, an adhesive composition dissolved in a mixed solvent of ethanol / toluene (1/1 by weight) was set on the film at a thickness of 20 μm when wet and was applied using a doctor blade and dried. A laminated layer having a simple two-layer structure was obtained.

The adhesive composition was produced by uniformly mixing the components having the following compositions with a ball mill. Adhesive composition Nylon (manufactured by Nippon Rilsan Co., Ltd., trade name 1276TE) 5 parts by weight Organoboron compound polymer 1 part by weight (Boron International Co., trade name Hyboron DLG-1100K) Ethanol 50 parts by weight Toluene 50 parts by weight The agent composition was left to stand at 30 ° C. for 10 days, but it could be stably stored without any change.

Separately from the above-mentioned two-layer laminated layer, a film prepared by forming only the above-mentioned adhesive composition on one surface of a polyethylene terephthalate film having a thickness of 25 μm by the same method was prepared. The adhesive layer side of the above laminate layer is opposed to the non-coated side, and thermocompression bonding is performed while feeding between metal rollers heated at 120 ° C at a speed of 3 cm / sec, and after cooling to room temperature, the uppermost layer When the release-treated polyethylene terephthalate film was peeled off, a colorless and transparent laminated film having a form (composite layer structure) as shown in FIG. 3 was obtained.

Then, the adhesive layer of the laminated film having the composite layer structure was placed on the sublimation heat transfer image shown in Example 8 so as to face it, and a commercially available laminating heat roller (manufactured by Meiko Shosha Co., Ltd.,
It passed once through the product name MS Pouch L-100 Mini). Image blurring did not occur even by this operation, and the sublimation heat transfer printing paper and the laminate film of this example were completely integrated via the adhesive layer.

As evidence of this, when the film integrated after lamination using a commercially available gum tape was forcibly peeled from both sides, the interface between the photographic receiving layer and the adhesive layer remained the same, and peeling occurred in the photographic paper. It was This means that it is impossible to directly alter or tamper with the original image after the laminating process of this example. Further, imprinting was performed from the uppermost layer (receiving layer side) of the obtained integrated film by the method shown in Example 8, and fixing of the ink was recognized within 1 minute.

A comparative example is shown below in order to examine the effect of the tamperproof property of the composite layer structure laminated film of this example. When a commercially available laminate film (manufactured by Meiko Shosha Co., Ltd., trade name Pauticco film) was subjected to the same thermal laminating treatment as in this example for the sublimation thermal transfer image shown in Example 8, no blurring of the image occurred. An integrated film was obtained. However, when the film integrated using a commercially available gum tape was forcibly peeled from both sides, complete peeling easily occurred at the interface between the print receiving layer and the adhesive layer, and the original image was exposed as it was.

This means that the original image can be added and corrected after the laminating process.

The specific embodiments to which the present invention is applied have been described above. However, the present invention is not limited to these embodiments, and it goes without saying that various other configurations can be adopted without departing from the gist of the present invention. Is. Further, for example, the cover film of the present invention can be applied to both a sublimation heat transfer type and a melt heat transfer type. Further, as the stamp ink, not only water-based ink but also oil-based ink can be used.

[0109]

As is apparent from the above description, according to the present invention, it is possible to impart a fixing property to an aqueous stamp to a thermal transfer image, and further, an adhesive property to a dye receiving layer,
It is possible to provide an aqueous ink fixing composition having excellent water resistance. Further, according to the present invention, it is possible to provide a thermal transfer image cover film and a thermal transfer image recording material having good water-based stamp fixing property and tampering preventive ability, and further, as an application thereof, a water-based stamp at the same time as image formation. It is possible to provide a thermal transfer image forming material capable of imparting fixability and tamperproofing ability.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of an essential part showing an example of a thermal transfer image cover film to which the present invention is applied.

FIG. 2 is a schematic cross-sectional view of a main part showing another example of a thermal transfer image cover film to which the present invention is applied.

FIG. 3 is a schematic cross-sectional view of a main part showing still another example of the cover film for a thermal transfer image to which the present invention is applied.

FIG. 4 is a schematic sectional view of a main part of a thermal transfer image forming material to which the present invention is applied.

[Explanation of symbols]

 1 ... Substrate 2 ... Aqueous ink fixing layer 3 ... Adhesive layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshio Fujiwara 6-735 Kitashinagawa, Shinagawa-ku, Tokyo Sony Corporation

Claims (19)

[Claims] 1. An aqueous ink fixing composition comprising an ion exchanger. 2. The aqueous ink fixing composition according to claim 1, wherein the ion exchanger is a clay intercalation compound. 3. The aqueous ink fixing composition according to claim 1, wherein the ion exchanger is an ion exchange resin. 4. The aqueous ink fixing composition according to claim 1, wherein the ion exchanger is a mixture of an anion exchanger and a cation exchanger. 5. The aqueous ink fixing composition according to claim 1, further comprising a binder. 6. The water-based ink fixing composition according to claim 5, wherein the binder is a water-absorbent resin. 7. The aqueous ink fixing composition according to claim 5, wherein the binder is a water-absorbent resin and a water-insoluble resin. 8. The water-based ink fixing composition according to claim 6, wherein the water-absorbent resin is a polyvinylpyrrolidone-based polymer. 9. The aqueous ink fixing composition according to claim 1, wherein the binder is a hot-melt resin. 10. The aqueous ink fixing composition according to claim 5, further comprising a crosslinking agent. 11. The aqueous ink fixing composition according to claim 5, further comprising a nonionic surfactant. 12. A cover film for a thermal transfer image, wherein a water-based ink fixing layer containing an ion exchanger is formed on a substrate so as to be peelable. 13. The thermal transfer image cover film according to claim 12, wherein an adhesive layer or a heat-fusible resin layer is formed on the water-based ink fixing layer. 14. The cover film for a thermal transfer image according to claim 12, wherein the base material is subjected to a release treatment. 15. A water-based ink fixing layer containing an ion exchanger is formed on one surface of a support film, and an adhesive layer or a heat-meltable resin layer is formed on the other surface of the support film. Cover film for thermal transfer images. 16. An ink layer containing a dye for image formation and an aqueous ink fixing layer containing an ion exchanger,
A thermal transfer image forming material, which is formed on a base material without being laminated on each other, and the aqueous ink fixing layer is formed so as to be peelable from the base material. 17. A thermal transfer image recording medium, characterized in that the thermal transfer image cover film according to any one of claims 12 to 15 is coated with a thermal transfer image or a thermal transfer image having a protective layer. 18. The thermal transfer image cover film according to claim 12 or 13, wherein any one of the water-based ink fixing layer, the adhesive layer, and the heat-fusible resin layer faces the thermal transfer image or the thermal transfer image having a protective layer. And then thermocompression bonded,
A method for coating a thermal transfer image, which comprises peeling and removing the base material after transfer and lamination onto the thermal transfer image or the thermal transfer image having a protective layer. 19. A thermal transfer image is obtained by stacking the cover film for a thermal transfer image according to claim 15 so that the adhesive layer or the heat-fusible resin layer faces the thermal transfer image or the thermal transfer image having a protective layer, and thermocompression-bonding the film. Alternatively, a thermal transfer image coating method, which comprises transfer-laminating on a thermal transfer image having a protective layer.