JP6897262B2 - Thermal transfer image receiving sheet - Google Patents

Description

The present invention relates to a thermal transfer recording medium used in a thermal transfer printer, and in particular, a back layer is provided on one side of a base sheet, and at least a porous layer and a dye receiver are provided on the side opposite to the back layer side. The present invention relates to a thermal transfer image receiving sheet in which layers are sequentially formed.

Generally, as a heat-sensitive transfer method, a heat-melting type thermal transfer sheet in which an ink in which pigments and the like are dispersed in a wax or a resin is provided on a base film is used, and a sublimation dye is inked with a binder resin to form a base. Some use a sublimation type thermal transfer sheet provided on the material.

In the case of a thermal transfer method using a sublimation type thermal transfer sheet, a thermal transfer image receiving sheet having a dye receiving layer made of a resin material that can be dyed with a sublimating dye, for example, a heat receiving layer is provided on the surface of paper or a plastic film. Methods for forming various full-color images on the transferred body have been proposed.

In this case, the thermal head of the printer is used as the heating means, and a large number of three-color or four-color dots are transferred to the transferred object by heating for an extremely short time, and the large number of color dots transfer the full-color image of the original. Is to reproduce.

Since the color material used in the image formed in this way is a dye, it is very clear and has excellent transparency, so that the obtained image is excellent in reproducibility and gradation of neutral colors. ..

Therefore, it is possible to form a high-quality image that is similar to the image obtained by conventional offset printing or gravure printing and is comparable to a full-color photographic image.

For this reason, the sublimation type thermal transfer method is widely used for self-printing of digital cameras, cards such as identification cards, and output products for amusement.

By the way, the thermal transfer image receiving sheet used in such a sublimation type thermal transfer method is required to exhibit excellent releasability in relation to the thermal transfer sheet.

If the releasability of the dye receiving layer provided on the thermal transfer image receiving sheet is low, the binder resin on the thermal transfer sheet side and the dye receiving layer are likely to be fused, and the binder resin on the thermal transfer sheet side is on the thermal transfer image receiving sheet side at the time of printing. In the worst case, the printed matter may not be ejected normally from the printer.

To solve such a problem, as in Patent Document 1, the molecular weight and kinematic viscosity of the silicone oil added as a mold release agent in order to give the thermal transfer image receiving sheet a mold release property are being studied. An example is presented.

However, it cannot be said that these inventions have been sufficiently studied regarding the bleed-out of low molecular weight silicone oil, and regarding the transfer of the silicone oil to the back surface when the thermal transfer image receiving sheet is wound into a roll. Has not been considered.

JP-A-2007-90650

The present invention has been made in view of the above background technique, and an object of the present invention is to suppress abnormal transfer such as sticking at the time of printing and to set off when the thermal transfer image receiving sheet is wound into a roll. It is an object of the present invention to provide a thermal transfer image receiving sheet in which a sufficient printing density can be obtained.

The present invention has been made to solve these problems.
That is, the invention according to claim 1 is a thermal transfer image receiving sheet in which at least a back surface layer, a base material sheet, a porous layer, and a dye receiving layer are laminated.
The dye receiving layer contains a vinyl chloride resin, a cross-linking agent, and a modified silicone oil, and the modified silicone oil does not have a reactive functional group in the side chain or the terminal. Non-reactive silicone oil (A) And a mixture of one or more reactive silicone oils (B) each having a reactive functional group.
The mass ratio of the non-reactive silicone oil (A) and the reactive silicone oil (B) is, meets the equation 1, and,
The modified silicone oil contained in the dye receiving layer is
The non-reactive silicone oil (A) is in the range of 1 to 7 parts by mass and the reactive silicone oil (B) is in the range of 0.1 to 2 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. a thermal transfer image receiving sheet according to claim.
0.5 ≤ A / B ≤ 70 ... Equation 1

The invention according to claim 2 is the thermal transfer image receiving sheet according to claim 1, wherein the vinyl chloride resin is an aqueous dispersion type vinyl chloride resin.

In the invention according to claim 3 , the cross-linking agent contained in the dye receiving layer is an aziridine-based compound.
The thermal transfer image receiving sheet according to claim 1 or 2, wherein the vinyl chloride resin is blended in a range of 3 to 12 parts by mass with respect to 100 parts by mass.

According to the present invention, by adding the reactive silicone oil and the non-reactive silicone oil in the above-mentioned blending ratio, the reactive silicone oil is fixed to the resin by the cross-linking reaction of the resin in the dye receiving layer. While suppressing the bleed-out of the silicone oil, the non-reactive silicone oil appears on the surface of the dye receiving layer, so that sufficient releasability can be imparted.

It is sectional drawing which shows the structural example of the thermal transfer image receiving sheet which concerns on embodiment of this invention. It is sectional drawing which shows the structural example of the thermal transfer sheet.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. It should be noted that each drawing shows an example of the embodiment of the present invention, and is not limited thereto.

In FIG. 1, as a configuration example of the thermal transfer image receiving sheet 10, a back surface layer 12 is provided on one surface of the base sheet 11, and a porous layer 13, a base layer 14, and a dye receiver are provided on the opposite surface. The layers 15 are laminated in this order.

Here, as the base sheet 11, conventionally known ones can be used, for example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefins such as polypropylene and polyethylene, polyvinyl chloride, polycarbonate, and the like. A film made of a synthetic resin such as polyvinyl alcohol, polystyrene, or polyimide, and papers such as high-quality paper, medium-quality paper, coated paper, art paper, and resin laminated paper can be used alone or as a composite. it can.

The thickness of the base sheet 11 can be in the range of 25 μm or more and 250 μm or less in consideration of the stiffness, strength, heat resistance, etc. of the printed matter, but more preferably 50 μm or more and 200 μm or less. preferable.

Further, the base sheet 11 may be subjected to various treatments such as an antistatic treatment and an easy-adhesion treatment, if necessary.

A back layer 12 is provided on one surface of the base sheet 11 as described above, and the back layer 12 improves printer transportability, prevents blocking with the dye receiving layer 15, and further heat transfers before and after printing. It is provided for the purpose of preventing curling of the image receiving sheet.

As the material used for the back layer 12, conventionally known materials can be used, for example, polyolefin resins such as polyethylene resin and polypropylene resin, acrylic resins, polycarbonate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polyester resins, and the like. Binder resins such as polystyrene resin and polyamide resin can be used.

Further, various known additives such as fillers and antistatic agents may be added to the back layer 12 as needed.

Next, as the porous layer 13 provided on the surface opposite to the back surface layer 12 of the base sheet 11, a conventionally known one can be adopted, for example, organic or inorganic. Hollow particles and porous materials made of binder resin, foamed polypropylene films such as foamed polypropylene film and foamed polyethylene terephthalate, and composites with skin layers on one or both sides of the foamed film. Examples thereof include those provided with a film, but the present invention is not limited to these.

However, in consideration of smoothness and glossiness that affect the image quality, it is preferable to use a composite film having a skin layer on one side or both sides of the foamed film.

The thickness of the porous layer 13 can be in the range of 10 μm or more and 80 μm or less, but more preferably 20 μm or more and 60 μm or less.

Subsequently, by providing the base layer 14, it is expected that the adhesion of the dye receiving layer 15 will be improved, and the printing density at the time of image formation can be adjusted.

The base layer 14 can be formed by coating an aqueous solvent with an aqueous coating agent in which a water-soluble resin or a water-soluble polymer is dissolved or dispersed, or an aqueous coating agent composed of an aqueous emulsion or the like.

Examples of the water-soluble resin or water-soluble polymer include polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, polyacrylic acid ester, polyacrylic acid ester copolymer, water-soluble acrylic resin such as polymethacrylic acid, gelatin, starch, and casein. And their variants, etc., but are not limited to these.

Examples of aqueous emulsions include vinyl chloride resin emulsions such as polyolefin emulsions, vinyl chloride resin emulsions, vinyl chloride-vinyl acetate resin emulsions, vinyl chloride-acrylic resin emulsions, acrylic resin emulsions, and urethane resin emulsions. be able to.

These various resins or polymers may be used alone or as a mixture.

The thickness of the base layer 14 can be provided in the range of 0.1 μm or more and 3 μm or less, but more preferably 0.2 μm or more and 1.0 μm or less.

This is because if the film thickness of the base layer 14 is less than 0.1 μm, it becomes difficult to adjust the film thickness, and if the film thickness is less than 0.1 μm and variation occurs, the porous layer 13 and the dye receiving layer 15 This is because there is a risk of reducing the adhesion between the two, and if the film thickness is too thick, the printing density may be lowered.

Further, the base layer 14 may contain a cross-linking agent, an antioxidant, a fluorescent dye, or a known additive, if necessary.

Next, the dye receiving layer 15 is a layer containing at least a binder resin, a cross-linking agent, and a modified silicone oil, and has a function of receiving and dyeing a sublimation dye released from the thermal transfer sheet.

As the binder resin used for the dye receiving layer 15, a vinyl chloride resin can be preferably used.

Examples of the vinyl chloride resin include vinyl chloride resin, vinyl chloride-acrylic copolymer, vinyl chloride-vinyl acetate copolymer and the like.

Further, the dye receiving layer 15 can be formed by coating with a solvent-based coating agent using an organic solvent as a solvent or a dispersion medium, but it is desirable to reduce the amount of the organic solvent in consideration of environmental problems, and thermal transfer is also possible. From the viewpoint of reducing the solvent odor when the image receiving sheet is unpacked and used, it can be said that it is desirable to coat the image-receiving sheet with an aqueous coating agent using an aqueous solvent as a solvent or a dispersion medium.

Therefore, as the binder resin, a water-dispersed vinyl chloride-based resin can be preferably used as the aqueous resin emulsion, and among them, a vinyl chloride-acrylic copolymer emulsion and a vinyl chloride-acrylic core shell can be said to be more preferable.

Any known material can be used as the cross-linking agent added to the dye receiving layer 15 made of the resin as described above. However, considering the reaction with the carboxyl group, for example, an isocyanate compound and a block-type isocyanate compound can be used. , Oxazoline-based compounds, aziridine-based compounds, carbodiimide-based compounds and the like can be appropriately used, and it can be said that aziridine-based compounds having excellent pot life and reactivity are particularly preferable.

When the aziridine compound is used as a cross-linking agent, the amount added is preferably 3 parts by mass or more and 12 parts by mass or less, more preferably 5 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. It is less than a part by mass.

This is because if the amount is less than 3 parts by mass, the vinyl chloride resin, which is the resin of the dye receiving layer 15, cannot sufficiently form a network structure by cross-linking, and when the resins are thermocompression bonded to the binder resin on the thermal transfer sheet side, the resins are bonded to each other. This is because tackiness is likely to occur due to the above, causing abnormal transfer, and if the amount is more than 12 parts by mass, the acceptability of the dye is lowered and a sufficient printing density cannot be obtained.

Further, as the silicone oil added to impart releasability, a modified silicone oil having an organic substituent such as an alkyl group or an aryl group introduced is preferably used.

Among them, side chain type modified silicone oil and one-ended type modified silicone oil are more preferably used.

This is because the organic substituent portion having excellent compatibility with the binder resin is fixed in the binder resin, and the degree of freedom of the silicone skeleton portion that imparts releasability is secured even when the silicone oil is held. This is thought to be because it is easy and it is easy to exhibit releasability.

As the non-reactive silicone oil (A) having no reactive functional group, any one having an organic substituent introduced therein can be applied, for example, alkyl-modified silicone, polyether-modified silicone, and the like. Examples thereof include phenyl-modified silicone, methylstyryl-modified silicone, higher fatty acid ester-modified silicone, hydrophilic special-modified silicone, and fluorine-modified silicone, but polyether-modified silicone oil whose compatibility can be easily adjusted is more preferably used. ..

The amount of such non-reactive silicone oil (A) added is preferably 1 part by mass or more and 7 parts by mass or less, more preferably 3 parts by mass or more, with respect to 100 parts by mass of the vinyl chloride resin. It is 5 parts by mass or less.

This is because if the amount of the non-reactive silicone oil (A) added is less than 1 part by mass, the releasability is not sufficiently exhibited, abnormal transfer occurs, and if it is more than 7 parts by mass, image formation is performed. This is because when the thermal transferable protective layer is to be transferred onto the dye receiving layer later, transfer failure of the thermal transferable protective layer occurs.

Here, the thermal transfer protective layer is formed for the purpose of protecting the image after forming an image on the dye receiving layer using the thermal transfer sheet. For example, the thermal transfer sheet 20 is illustrated in FIG. A method of juxtaposing it on a thermal transfer sheet together with a sublimation dye layer 23 of each color such as cyan, magenta, and yellow provided in sequence on the surface and transferring it onto the dye receiving layer 15 after image formation is conceivable. FIG. 2 will be described later.

As the reactive silicone oil (B) having a reactive functional group, any one in which a functional group having a reactivity with a vinyl chloride resin or a cross-linking agent is introduced can be used, but amino polyether. Modified silicone oil and carboxyl-modified silicone oil are more preferably used.

The amount of the reactive silicone oil (B) added is preferably 0.1 part by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin, and more preferably 0.1. It is equal to or more than 1 part by mass and less than 1 part by mass.

This is because if the amount of the reactive silicone oil (B) added is less than 0.1 parts by mass, sufficient releasability cannot be exhibited and abnormal transfer occurs, and if it is more than 2 parts by mass, abnormal transfer occurs. To do.

The reason why such a phenomenon occurs is considered to be that when a large amount of reactive silicone oil is added, the crosslink density of the binder resin is affected.

Further, it is desirable that the mass ratio A / B of such non-reactive silicone oil (A) and reactive silicone oil (B) satisfies the following formula 1.
0.5 ≤ A / B ≤ 70 ... Equation 1

This makes it possible to balance the releasability of the surface of the dye receiving layer 15 with the suppression of bleed-out of the modified silicone oil, and it is possible to provide a dye receiving layer suitable as a thermal transfer image receiving sheet.

Further, the dye receiving layer 15 may contain various fillers, waxes, antioxidants, catalysts, fluorescent dyes, various known additives and the like, if necessary.

The thickness of the dye receiving layer 15 can be 0.1 μm or more and 10 μm or less, but 0.2 μm or more and 8 μm or less is preferably used.

By using the thermal transfer image receiving sheet obtained as described above, the effect of appropriately blending the reactive silicone oil and the non-reactive silicone oil exerts sufficient releasability to the thermal transfer sheet and abnormal transfer occurs. In addition to suppressing it, it is possible to reduce bleed-out of silicone oil and set-off during winding processing, and further, due to the effect of the vinyl chloride resin and the cross-linking agent, it is possible to obtain a sufficient printing density without abnormal transfer. It will be possible.

(Thermal transfer sheet)
As an example of the thermal transfer sheet provided together with the thermal transfer image receiving sheet obtained as described above, for example, the thermal transfer sheet as shown in FIG. 2 can be exemplified.

In FIG. 2, in the thermal transfer sheet 20, a sublimation dye layer 23 having different hues and a release layer 27 are sequentially formed on one surface of the base material 21, and a heat-resistant slipping layer 22 is formed on the other surface. On the release layer 27, a thermal transferable protective layer 24 is formed in which the release layer 26 and the adhesive layer 25 are sequentially laminated.

Since the base material 21 is required to have heat resistance and strength that do not soften and deform due to heat pressure during thermal transfer recording, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, cellophane, acetate, polycarbonate, polysulfone, polyimide, polyvinyl alcohol, and fragrance. Films made of synthetic resins such as group polyamide, aramid, and polystyrene, and papers such as condenser paper and paraffin paper can be used alone or as a composite.

Among them, polyethylene terephthalate film is preferable in consideration of physical characteristics, processability, cost, etc., and a film having a thickness in the range of about 2 μm to 50 μm can be used.

The heat-resistant slippery layer 22 provided on one surface of the base material 21 is for preventing heat shrinkage of the base material due to the heat of the thermal head and breakage of the base material due to friction with the thermal head, and is conventionally known. Any material may be used as long as it is a material for a heat-resistant slippery layer used for a thermal transfer sheet.

Specifically, for example, a binder resin such as a cellulose resin, a polyester resin, an acrylic resin, a vinyl resin, a polyurethane resin, a polyether resin, a polycarbonate resin, or an acetal resin is used as a main component, and a lubricant and a curing agent are used. Examples thereof include those to which additives such as agents and particles are added.

The sublimation dye layer 23 is composed of a sublimation dye and a binder resin, and a mold release agent or the like can be added as needed.

As the sublimation dye, a sublimation disperse dye is mainly preferably used, and any known sublimation disperse dye can be used. Specifically, diarylmethane type, triarylmethane type, thiazole type, etc. Examples of various disperse dyes such as methine-based, azomethane-based, xanthene-based, axazine-based, thiazine-based, azine-based, acridine-based, azo-based, spirodipyran-based, isodorinospiropyran-based, fluoran-based, rhodamine dactane-based, and anthraquinone-based be able to.

As the binder resin, any conventionally known resin can be used, and vinyl resins such as polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, polyvinyl acetal and polyvinyl butyral, and cellulose resins such as ethyl cellulose, methyl cellulose, and hydroxyethyl cellulose can be used. , Polyester resin, phenoxy resin, styrene-acrylonitrile copolymer resin, polycarbonate resin, polyacrylamide resin and the like can be exemplified.

The binder resin used for the release layer 27 is not particularly limited, and is, for example, a water-soluble polymer such as polyvinyl alcohol, polyvinylpyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, rubber chloride, and cyclized rubber. Natural rubber derivatives such as, various waxes, cellulose derivatives, thermosetting resins and the like can be exemplified. Further, an additive such as a charge control agent may be added to the release layer 27.

As the thermal transferable protective layer 23 provided on the release layer 27 as described above, for example, as shown in FIG. 2, a layer composed of a release layer 26 and an adhesive layer 25 can be exemplified.

The adhesive layer 25 is a layer for adjusting the adhesiveness with the dye receiving layer which is a transfer material, and the release layer 26 enables the adhesive layer 25 to be easily separated from the release layer 27 at the time of thermal transfer. , It is for imparting durability such as abrasion resistance after thermal transfer recording.

The resin used for the adhesive layer 25 is not particularly limited except for heat meltability, and is, for example, a styrene resin, an acrylic resin, a vinyl resin, a polyester resin, a polyamide resin, a polyurethane resin, or ethylene. -Various copolymers such as acrylic acid esters, various materials such as olefin resins and waxes can be arbitrarily selected.

Further, if necessary, a functional additive such as an ultraviolet absorber, a light stabilizer, an antioxidant, a catalyst accelerator, a colorant, a gloss adjuster, and a fluorescent whitening agent is added to the adhesive layer 25. There is no problem even if there is.

The binder resin used for the release layer 26 is not particularly limited, but for example, a styrene resin, an acrylic resin, a vinyl resin, a polyester resin, a polyamide resin, an epoxy resin, a polyurethane resin, etc. Examples thereof include cellulose derivatives and various rubbers.

Hereinafter, examples will be described in detail, but the present invention is not limited to the examples. Table 1 shows an example of the structure of the dye receiving layer of the thermal transfer image receiving sheet used in each Example and Comparative Example.

[Preparation of thermal transfer image receiving sheet]
(Example 1)
A long high-quality paper having a thickness of 140 μm was used as a base sheet, and a polyethylene resin layer having a thickness of 30 μm was formed as a back surface layer by a melt extrusion method.

Next, the polyethylene resin is melt-extruded between the surface opposite to the polyethylene resin layer side of the base material and the surface opposite to the porous layer to form a polyethylene resin layer having a thickness of 15 μm. The base sheet and the porous layer were bonded together. As the porous layer, a foamed polypropylene film having a thickness of 40 μm having a skin layer provided on one side was used, and the polyethylene resin was melt-extruded and bonded to the surface not provided with the skin layer.

Next, the following base layer coating agent composed of an aqueous emulsion was applied onto the porous layer so that the thickness after drying was 0.5 μm, and the base layer was formed by drying.

Further, the following dye receiving layer coating agent composed of an aqueous emulsion is appropriately diluted with a diluting solvent such as pure water on the base layer, applied to a dry thickness of 3 μm, and dried to receive the dye. A layer was formed.

Unless otherwise specified, the term "part" in the text is based on mass.

<Underlayer coating agent>
20 parts of polyolefin emulsion (Arrow Base SB-1010, manufactured by Unitika Ltd.)
20 parts of vinyl chloride copolymer emulsion (Viniblanc 603, manufactured by Nisshin Kagaku Kogyo Co., Ltd.)
Tripropylene glycol monomethyl ether 4 parts pure water 56 parts

<Dye receiving layer coating agent-1>
100 parts of vinyl chloride copolymer emulsion (in terms of solid content)
(Viniblanc 701, manufactured by Nissin Chemical Industry Co., Ltd.)
Non-reactive silicone oil 1 part (KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.)
2 parts of reactive silicone oil (X-22-3939A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Aziridine-based cross-linking agent 7 parts (PZ-33, manufactured by Nippon Shokubai Co., Ltd.)

(Example 2)
In the thermal transfer image receiving sheet prepared in Example 1, the thermal transfer image receiving sheet of Example 2 was obtained in the same manner as in Example 1 except that the dye receiving layer was a dye receiving layer coating agent-2 having the following composition.

<Dye receiving layer coating agent-2>
100 parts of vinyl chloride copolymer emulsion (in terms of solid content)
(Viniblanc 701, manufactured by Nissin Chemical Industry Co., Ltd.)
Non-reactive silicone oil 3 parts (KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Reactive Silicone Oil Part 1 (X-22-3939A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Aziridine-based cross-linking agent 7 parts (PZ-33, manufactured by Nippon Shokubai Co., Ltd.)

(Example 3)
In the thermal transfer image receiving sheet prepared in Example 1, the thermal transfer image receiving sheet of Example 3 was obtained in the same manner as in Example 1 except that the dye receiving layer was a dye receiving layer coating agent-3 having the following composition.

<Dye receiving layer coating agent-3>
100 parts of vinyl chloride copolymer emulsion (in terms of solid content)
(Viniblanc 701, manufactured by Nissin Chemical Industry Co., Ltd.)
5 parts of non-reactive silicone oil (KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Reactive silicone oil 0.5 part (X-22-3939A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Aziridine-based cross-linking agent 7 parts (PZ-33, manufactured by Nippon Shokubai Co., Ltd.)

(Example 4)
In the thermal transfer image receiving sheet prepared in Example 1, the thermal transfer image receiving sheet of Example 4 was obtained in the same manner as in Example 1 except that the dye receiving layer was a dye receiving layer coating agent-4 having the following composition.

<Dye receiving layer coating agent-4>
100 parts of vinyl chloride copolymer emulsion (in terms of solid content)
(Viniblanc 701, manufactured by Nissin Chemical Industry Co., Ltd.)
5 parts of non-reactive silicone oil (KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Reactive silicone oil 0.5 part (X-22-3939A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Aziridine-based cross-linking agent 12 parts (PZ-33, manufactured by Nippon Shokubai Co., Ltd.)

(Example 5)
In the thermal transfer image receiving sheet prepared in Example 1, the thermal transfer image receiving sheet of Example 5 was obtained in the same manner as in Example 1 except that the dye receiving layer was a dye receiving layer coating agent-5 having the following composition.

<Dye Receptive Layer Coating Agent-5>
100 parts of vinyl chloride copolymer emulsion (in terms of solid content)
(Viniblanc 701, manufactured by Nissin Chemical Industry Co., Ltd.)
7 parts of non-reactive silicone oil (KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Reactive Silicone Oil 0.1 Part (X-22-3939A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Aziridine-based cross-linking agent 7 parts (PZ-33, manufactured by Nippon Shokubai Co., Ltd.)

(Example 6)
In the thermal transfer image receiving sheet prepared in Example 1, the thermal transfer image receiving sheet of Example 6 was obtained in the same manner as in Example 1 except that the dye receiving layer was a dye receiving layer coating agent-6 having the following composition.

<Dye Receptive Layer Coating Agent-6>
100 parts of vinyl chloride copolymer emulsion (in terms of solid content)
(Viniblanc 701, manufactured by Nissin Chemical Industry Co., Ltd.)
Non-reactive silicone oil 1 part (KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.)
2 parts of reactive silicone oil (X-22-3701E, manufactured by Shin-Etsu Chemical Co., Ltd.)
Aziridine-based cross-linking agent 7 parts (PZ-33, manufactured by Nippon Shokubai Co., Ltd.)

(Example 7)
In the thermal transfer image receiving sheet prepared in Example 1, the thermal transfer image receiving sheet of Example 7 was obtained in the same manner as in Example 1 except that the dye receiving layer was a dye receiving layer coating agent-7 having the following composition.

<Dye Receptive Layer Coating Agent-7>
100 parts of vinyl chloride copolymer emulsion (in terms of solid content)
(Viniblanc 701, manufactured by Nissin Chemical Industry Co., Ltd.)
Non-reactive silicone oil 3 parts (KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Reactive Silicone Oil Part 1 (X-22-3701E, manufactured by Shin-Etsu Chemical Co., Ltd.)
Aziridine-based cross-linking agent 7 parts (PZ-33, manufactured by Nippon Shokubai Co., Ltd.)

(Example 8)
In the thermal transfer image receiving sheet prepared in Example 1, the thermal transfer image receiving sheet of Example 8 was obtained in the same manner as in Example 1 except that the dye receiving layer was a dye receiving layer coating agent-8 having the following composition.

<Dye Receptive Layer Coating Agent-8>
100 parts of vinyl chloride copolymer emulsion (in terms of solid content)
(Viniblanc 701, manufactured by Nissin Chemical Industry Co., Ltd.)
5 parts of non-reactive silicone oil (KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Reactive silicone oil 0.5 part (X-22-3701E, manufactured by Shin-Etsu Chemical Co., Ltd.)
Aziridine-based cross-linking agent 7 parts (PZ-33, manufactured by Nippon Shokubai Co., Ltd.)

(Example 9)
In the thermal transfer image receiving sheet prepared in Example 1, the thermal transfer image receiving sheet of Example 9 was obtained in the same manner as in Example 1 except that the dye receiving layer was a dye receiving layer coating agent-9 having the following composition.

<Dye image receiving layer coating agent-9>
100 parts of vinyl chloride copolymer emulsion (in terms of solid content)
(Viniblanc 701, manufactured by Nissin Chemical Industry Co., Ltd.)
7 parts of non-reactive silicone oil (KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Reactive Silicone Oil 0.1 Part (X-22-3701E, manufactured by Shin-Etsu Chemical Co., Ltd.)
Aziridine-based cross-linking agent 7 parts (PZ-33, manufactured by Nippon Shokubai Co., Ltd.)

(Example 10)
In the thermal transfer sheet produced in Example 1, a thermal transfer image receiving sheet of Example 10 was obtained in the same manner as in Example 1 except that the dye receiving layer was a dye receiving layer coating agent-10 having the following composition.

<Dye image receiving layer coating agent-10>
100 parts of vinyl chloride copolymer (in terms of solid content)
(Solvine A, manufactured by Nissin Chemical Industry Co., Ltd.)
5 parts of non-reactive silicone oil (KF-6020, manufactured by Shin-Etsu Chemical Co., Ltd.)
Reactive Silicone Oil 0.1 Part (X-22-3939A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Isocyanate compound 3 parts (DN-950, manufactured by DIC Corporation)

(Example 11)
In the thermal transfer sheet produced in Example 1, a thermal transfer image receiving sheet of Example 11 was obtained in the same manner as in Example 1 except that the dye receiving layer was a dye receiving layer coating agent-11 having the following composition.

<Dye Receptive Layer Coating Agent-11>
100 parts of vinyl chloride copolymer emulsion (in terms of solid content)
(Viniblanc 701, manufactured by Nissin Chemical Industry Co., Ltd.)
5 parts of non-reactive silicone oil (KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Reactive silicone oil 0.5 part (X-22-3939A, manufactured by Shin-Etsu Chemical Co., Ltd.)
15 parts of aziridine-based cross-linking agent (PZ-33, manufactured by Nippon Shokubai Co., Ltd.)

(Example 12)
In the thermal transfer sheet produced in Example 1, a thermal transfer image receiving sheet of Example 12 was obtained in the same manner as in Example 1 except that the dye receiving layer was a dye receiving layer coating agent-12 having the following composition.

<Dye Receptive Layer Coating Agent-12>
100 parts of vinyl chloride copolymer emulsion (in terms of solid content)
(Viniblanc 701, manufactured by Nissin Chemical Industry Co., Ltd.)
5 parts of non-reactive silicone oil (KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Reactive silicone oil 0.5 part (X-22-3939A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Aziridine-based cross-linking agent 2 parts (PZ-33, manufactured by Nippon Shokubai Co., Ltd.)

(Comparative Example 1)
In the thermal transfer image receiving sheet prepared in Example 1, the thermal transfer image receiving sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that the dye receiving layer was a dye receiving layer coating agent-13 having the following composition.

<Dye Receptive Layer Coating Agent-13>
100 parts of vinyl chloride copolymer emulsion (in terms of solid content)
(Viniblanc 701, manufactured by Nissin Chemical Industry Co., Ltd.)
Non-reactive silicone oil 0 parts Reactive silicone oil 0 parts Aziridine-based cross-linking agent 7 parts (PZ-33, manufactured by Nippon Shokubai Co., Ltd.)

(Comparative Example 2)
In the thermal transfer image receiving sheet prepared in Example 1, the thermal transfer image receiving sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that the dye receiving layer was a dye receiving layer coating agent-14 having the following composition.

<Dye Receptive Layer Coating Agent-14>
100 parts of vinyl chloride copolymer emulsion (in terms of solid content)
(Viniblanc 701, manufactured by Nissin Chemical Industry Co., Ltd.)
0.5 parts of non-reactive silicone oil (KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.)
2 parts of reactive silicone oil (X-22-3939A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Aziridine-based cross-linking agent 7 parts (PZ-33, manufactured by Nippon Shokubai Co., Ltd.)

(Comparative Example 3)
In the thermal transfer image receiving sheet prepared in Example 1, the thermal transfer image receiving sheet of Comparative Example 3 was obtained in the same manner as in Example 1 except that the dye receiving layer was a dye receiving layer coating agent-15 having the following composition.

<Dye Receptive Layer Coating Agent-15>
100 parts of vinyl chloride copolymer emulsion (in terms of solid content)
(Viniblanc 701, manufactured by Nissin Chemical Industry Co., Ltd.)
10 parts of non-reactive silicone oil (KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Reactive Silicone Oil 0.1 Part (X-22-3939A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Aziridine-based cross-linking agent 7 parts (PZ-33, manufactured by Nippon Shokubai Co., Ltd.)

(Comparative Example 4)
In the thermal transfer image receiving sheet prepared in Example 1, the thermal transfer image receiving sheet of Comparative Example 4 was obtained in the same manner as in Example 1 except that the dye receiving layer was a dye receiving layer coating agent-16 having the following composition.

<Dye Receptive Layer Coating Agent-16>
100 parts of vinyl chloride copolymer emulsion (in terms of solid content)
(Viniblanc 701, manufactured by Nissin Chemical Industry Co., Ltd.)
7 parts of non-reactive silicone oil (KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Reactive Silicone Oil 0.05 Parts (X-22-3939A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Aziridine-based cross-linking agent 7 parts (PZ-33, manufactured by Nippon Shokubai Co., Ltd.)

(Comparative Example 5)
In the thermal transfer image receiving sheet prepared in Example 1, the thermal transfer image receiving sheet of Comparative Example 5 was obtained in the same manner as in Example 1 except that the dye receiving layer was a dye receiving layer coating agent-17 having the following composition.

<Dye Receptive Layer Coating Agent-17>
100 parts of vinyl chloride copolymer emulsion (in terms of solid content)
(Viniblanc 701, manufactured by Nissin Chemical Industry Co., Ltd.)
2 parts of non-reactive silicone oil (KF-352A, manufactured by Shin-Etsu Chemical Co., Ltd.)
5 parts of reactive silicone oil (X-22-3939A, manufactured by Shin-Etsu Chemical Co., Ltd.)
Aziridine-based cross-linking agent 7 parts (PZ-33, manufactured by Nippon Shokubai Co., Ltd.)

[Preparation of thermal transfer sheet]
In order to carry out the print evaluation of each of the prototype thermal transfer image receiving sheets, a thermal transfer sheet as shown in FIG. 2 was prepared as follows.

A polyester film having a thickness of 4.5 μm was used as the base material 21, and an ink for forming a heat-resistant slip layer was used on one surface to form a heat-resistant slip layer 22 with a dry film thickness of 1.3 μm.

On the other surface, yellow ink for forming a sublimation dye layer, magenta ink for forming a sublimation dye layer, and cyan ink for forming a sublimation dye layer, which are prepared at predetermined positions by the gravure coating method, are used. The sublimation dye layer 23 was formed in a surface-sequential manner with a thickness of 0.8 μm to obtain each sublimation dye layer 23.

Further, after forming the release layer 27 with a dry film thickness of 0.5 μm using the release layer forming ink, for forming a release layer in order to form the thermal transferable protective layer 24 on the release layer 27. By forming the release layer 26 with a dry film thickness of 0.6 μm using ink, and further forming the adhesive layer 25 with a dry film thickness of 0.8 μm on the release layer 26 using the adhesive layer forming ink. , A sublimable thermal transfer sheet 20 was obtained.

<Ink for forming a heat-resistant slippery layer>
Acrylic polyol resin 15.0 parts Zinc stearate 1.5 parts Polyoxyalkylene alkyl ether 1.5 parts Talk 1.0 parts 2,6-tolylene diisocyanate 5.0 parts Toluene 50.0 parts Methyl ethyl ketone 20.0 parts Acetic acid 6.0 parts of ethyl

<Yellow ink for sublimation dye layer formation>
C. I. Solvent Yellow 93 0.6 part C.I. I. Solvent Yellow 16 3.6 parts Polyvinyl butyral resin 5.4 parts Silicone oil 0.4 parts Methyl ethyl ketone 60.0 parts Toluene 30.0 parts

<Magenta ink for sublimation dye layer formation>
C. I. Disperse thread 60 6.0 parts C.I. I. Disperse Violet 26 1.0 parts Polyvinyl butyral resin 5.0 parts Silicone oil 0.5 parts Methyl ethyl ketone 58.5 parts Toluene 29.0 parts

<Cyan ink for sublimation dye layer formation>
C. I. Solvent Blue 36 6.9 copies C.I. I. Solvent Blue 63 2.5 parts Polyvinyl butyral resin 5.0 parts Silicone oil 0.6 parts Methyl ethyl ketone 57.0 parts

<Ink for forming a release layer>
Cellulose acetate 20.0 parts Methyl ethyl ketone 80.0 parts

<Ink for forming a release layer>
Acrylic resin 19.0 parts Silicone oil 1.0 parts Toluene 40.0 parts Methyl ethyl ketone 40.0 parts

<Ink for forming an adhesive layer>
Acrylic resin 20.0 parts Methyl ethyl ketone 80.0 parts

〔Evaluation method〕
Using the thermal transfer image receiving sheet and the thermal transfer sheet prepared above, (1) abnormal transferability evaluation, (2) protective layer transferability evaluation, (3) maximum concentration evaluation, (4) environmental load evaluation, (5) set-off Evaluation was carried out.

(1) Evaluation of abnormal transferability With respect to the thermal transfer image receiving sheet and the thermal transfer sheet produced above, gradation images are continuously produced in an environment of 40 ° C., 80% RH and 23 ° C., 80% RH using an evaluation thermal printer. The printing was performed, and it was visually confirmed whether or not abnormal transfer had occurred on the printed material.
◯: No abnormal transfer occurred on the printed matter.
Δ: Very slight abnormal transfer occurred on the printed matter.
X: Abnormal transfer occurred on the entire surface of the printed matter.
-: Could not print.
In this evaluation, if it is Δ or higher, there is no problem in actual operation.

(2) Evaluation of Protective Layer Transferability For the thermal transfer image receiving sheet and thermal transfer sheet produced above, a black solid image and a white solid image are printed using an evaluation thermal printer, the thermal transfer protective layer is transferred, and then under black light. It was visually confirmed whether or not the thermal transferable protective layer transferred in 1 had a transfer defect, and evaluation was performed based on the following evaluation criteria.
◯: No transfer failure has occurred.
Δ: Transfer failure with a length of less than 1 mm occurred.
X: A transfer defect having a length of 1 mm or more occurred.
-: Could not print.
In this evaluation, if it is Δ or higher, there is no problem in actual operation.

(3) Maximum density evaluation The thermal transfer image receiving sheet and the thermal transfer sheet produced above are printed with a solid black image using an evaluation thermal printer, and the maximum reflection density is printed using a spectroscopic densitometer (X-Rite 528 manufactured by SDG Co., Ltd.). Was measured.
◯: The maximum concentration was 1.8 or more.
Δ: The maximum concentration was 1.7 or more.
X: The maximum concentration was less than 1.7.
-: Could not print.
In this evaluation, if it is Δ or higher, there is no problem in actual operation.

(4) Environmental load evaluation From the viewpoint of environmental consideration, the mass% of the organic solvent contained in the paint solvent was compared.
◯: The mass% of the organic solvent is less than 20%.
Δ: The mass% of the organic solvent is 20% or more.

(5) Set-off evaluation The thermal transfer image receiving sheet prepared above was stored for 7 days in an environment of 23 ° C. and 50% RH while a load of ^{3.6 kg / cm 2 was applied, and the image received before storage.} The amount of surface silicone of the layer and the amount of surface silicone of the image receiving layer after storage were measured using a PHI 5000 VersaProbe III (manufactured by ULVAC PFI Co., Ltd.), which is an X-ray photoelectron spectroscopy analyzer. From the obtained measurement results, the set-off amount (atomic%) was calculated by Equation 2 and compared.
Set-off amount = Surface silicone amount before storage − Surface silicone amount after storage… Equation 2
◯: The amount of set-off was less than 1 atomic%.
Δ: The amount of set-off was 1 atomic% or more and less than 2.5 atomic%.
X: The amount of set-off was 2.5 atomic% or more.
In this evaluation, if it is Δ or higher, there is no problem in actual operation.

The results of each of the above evaluations are shown in Table 2.

From the results in Table 2, it can be seen from Comparative Example 1 that even printing cannot be performed when the cross-linking agent and the modified silicone are not added to the dye receiving layer of the thermal transfer image receiving sheet.

Further, from the result of Comparative Example 2, when the mass ratio A / B of the non-reactive silicone oil (A) and the reactive silicone oil (B) is less than 0.5, the mold is released by the modified silicone oil. It can be seen that the sexual effect is not sufficiently exhibited and abnormal transfer occurs on the entire surface of the printed matter.

From the results of Comparative Example 3, when the amount of the non-reactive silicone oil added is more than 7 parts by mass with respect to the binder resin, the effect of releasability is too strong, and therefore, when transferring the thermal transferable protective layer 24, In addition, it can be seen that transfer defects have occurred.

Further, from the result of Comparative Example 4, even when the amount of the non-reactive silicone oil (A) added is 7 parts by mass or less with respect to the binder resin, the mass ratio A / B is larger than 70. Due to insufficient addition of the reactive silicone oil (B), abnormal transfer occurs on the front surface of the printed matter.

From the results of Comparative Example 5, when the amount of the reactive silicone oil (B) added is more than 2 parts by mass with respect to the binder resin and the mass ratio A / B is smaller than 0.5, Due to the excessive addition of the reactive silicone oil (B), abnormal transfer occurs on the entire surface of the printed matter.

It is considered that this is because, as described above, the crosslink density of the binder resin was lowered by adding a large amount of the reactive silicone oil.

Further, when the solvent-based dye receiving layer coating agent of Example 10 is used, no functional problem is found at the time of printing, but since the solvent is used, water is used from the viewpoint of environmental load. It can be said that it is desirable to use a dispersive dye receiving layer coating agent.

From Examples 5 and 9, it was found that when the amount of the non-reactive silicone oil (A) added is large, transfer defects tend to occur when the thermal transferable protective layer 24 is transferred. It can be seen that the amount of the non-reactive silicone oil (A) added is preferably 7 parts by mass or less with respect to the binder resin.

From the results of Example 11, when the amount of the cross-linking agent added is increased, the dye acceptability is slightly lowered as the cross-linking density of the binder resin is increased, so that the maximum concentration is evaluated although it is within the permissible range. It can be seen that it is lower than that of.

Further, from the results of Example 12, it can be seen that when the amount of the cross-linking agent added is reduced, the cross-linking density of the binder resin is lowered and the adhesiveness to the resin on the thermal transfer sheet side begins to be exhibited. As a result, a slight tendency for abnormal transcription has begun to appear.

Further, regarding the set-off of the modified silicone oil, it can be seen from Comparative Example 3 and Comparative Example 4 that the amount of set-off is high when the mass ratio A / B is larger than 70.

It is considered that this is because the amount of set-off is large because the non-reactive silicone oil that is not fixed is excessively added to the reactive silicone oil that is fixed to the binder resin. ..

As described above, by using the thermal transfer image receiving sheet of the present invention, abnormal transfer such as sticking at the time of printing is suppressed, and even when the thermal transfer image receiving sheet is wound into a roll, it does not set off. It is possible to provide a thermal transfer image receiving sheet capable of obtaining a sufficient printing density.

10… Thermal transfer image receiving sheet 11… Base sheet 12… Back layer 13… Porous layer 14… Underlayer 15… Dye receiving layer 20… Thermal transfer sheet 21… Base material 22… Heat-resistant slippery layer 23… Sublimation dye layer 24… Thermal transfer protective layer 25… Adhesive layer 26… Peeling layer 27… Release layer

Claims (3)

At least, a thermal transfer image receiving sheet in which a back layer, a base sheet, a porous layer, and a dye receiving layer are laminated.
The dye receiving layer contains a vinyl chloride resin, a cross-linking agent, and a modified silicone oil, and the modified silicone oil does not have a reactive functional group in the side chain or the terminal. Non-reactive silicone oil (A) And a mixture of one or more reactive silicone oils (B) each having a reactive functional group.
The mass ratio of the non-reactive silicone oil (A) and the reactive silicone oil (B) is, meets the equation 1, and,
The modified silicone oil contained in the dye receiving layer is
The non-reactive silicone oil (A) is in the range of 1 to 7 parts by mass and the reactive silicone oil (B) is in the range of 0.1 to 2 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. thermal transfer image-receiving sheet according to claim.
0.5 ≤ A / B ≤ 70 ... Equation 1 The thermal transfer image receiving sheet according to claim 1, wherein the vinyl chloride resin is an aqueous dispersion type vinyl chloride resin. The cross-linking agent contained in the dye receiving layer is an aziridine-based compound.
The thermal transfer image receiving sheet according to claim 1 or 2, wherein the vinyl chloride resin is blended in a range of 3 to 12 parts by mass with respect to 100 parts by mass.

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