JP2549846B2 - Transfer sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a transfer sheet.

[Conventional technology]

2. Description of the Related Art Conventionally, attempts have been made to form an image composed of a dye transferred to the surface of a heat-transferred sheet by heating the heat-transfer sheet in spots by a thermal head or the like according to an image signal.

In image formation by such thermal transfer, conventionally, a thermal transfer sheet having a dye layer containing a sublimable disperse dye or the like and a thermal transfer sheet such as resin-coated paper have been used.

[Problems to be solved by the invention]

In the case of the conventional image formation of this type, a heat transferable sheet is always used, and it is difficult to form an image on ordinary paper or the like.

When heat transfer is performed on plain paper using a conventional heat transfer sheet, the dye is transferred to the normal paper but the coloring of the dye is hardly or not at all, and as a result, the color of the transferred image is extremely light, It was virtually impossible to form.

For this reason, conventionally, resin-coated paper, plastic, etc. are used as the heat transfer sheet, but such a method is suitable for transferring a large amount, but a small amount, especially a large number. When the small amount of paper is transferred to each type of paper, the workability and the economical efficiency are extremely poor.

The present invention has been made in view of the above drawbacks of the prior art, and an object of the present invention is to provide a transfer sheet capable of forming an excellent image on ordinary paper.

[Means for solving problems]

In order to solve the above problems, the transfer sheet of the present invention comprises a transfer dye layer comprising a synthetic resin and a transfer dye layer containing, on a base material sheet, a dye which is melted or sublimated and transferred by heating in a resin binder. It has a constitution in which a receiving layer for receiving the dye to maintain the image formed and an adhesive layer for adhering the receiving layer to the transfer target are sequentially laminated.

In the present invention, as the substrate sheet, condenser paper, polyester film, polyethylene naphthalate film, polystyrene film, polysulfone film, polyimide film, polyvinyl alcohol film, cellophane, aramid (aromatic polyamide)
A plastic film such as a film is used and has a thickness of 2 to 50 μm, preferably 2 to 12 μm. These plastic films are preferable because they have a smooth surface and high mechanical strength, and it is preferable to use a polyester film or an aramid film.

In the present invention, for the purpose of the invention, the sheet-shaped substrate is mainly a plastic film, but in addition to this, when importance is attached to the price of the sheet itself and the heat resistance of the sheet itself, paper such as condenser paper is also used. Can be used.

In the present invention, the transfer dye layer is composed of a dye and a binder which are melted or sublimated by heating to be transferred.

The dye is preferably a sublimable disperse dye, a sublimable oil-soluble dye, or a sublimable basic dye, and has a molecular weight of 150 to 800, preferably 350 to 700. These dyes are selected in consideration of sublimation temperature, hue, weather resistance, solubility in ink or binder resin and the like, for example, as follows.

CI (abbreviation of chemical index, the same applies below) Yellow 51, Same 3, Same 54, Same 79, Same 69, Same 23, Same 7, Same 141, CI Disperse Blue 24, Same 56, Same 14, 14,
Same 301, Same 334, Same 165, Same 19, Same 72, Same 87, Same 287, Same 15
4, the same 26, CI Disperse Red 135, the same 146, the same 59,
The same 1, the same 73, the same 60, the same 167, CI Disperse Violet 4, the same 13, the same 36, the same 56, the same 31, CI Solvent Violet 13, CI Solvent Black 3, CI Solvent Green 3, CI Solvent Yellow 56 , Ibid 14, ibid 1
6, 29, CI Full Vent Blue 70, 35, 63, 3
6, 50, 49, 111, 105, 97, 11, CI Solvent Red 135, 81, 18, 25, 19, 23, 2
4, 143, 146, 182.

Further, as the binder, ethyl cellulose,
Cellulose resins such as hydroxyethyl ellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, polyvinyl resins such as polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, polyester, polyvinyl acetate, polyacrylamide, etc. Can be used.

As an example of a more preferable binder, the molecular weight is not 60,000 to 20,000, instead of the above-mentioned usual vinyl butyl resin.
0, a special polyvinyl butyral resin having a weight% of vinyl alcohol portion of 10 to 40%, preferably 15 to 30% in a polyvinyl butyral resin and a glass transition point of 60 to 110 ° C, preferably 70 to 110 ° C. If the molecular weight is less than 60,000, the binding force as a binder is insufficient, and if it exceeds 200,000, the viscosity at the time of coating becomes too high, which hinders coating. If the vinyl alcohol portion is less than 10%, the stability of the transfer dye layer over time will be insufficient, and therefore aggregation of the dye or the like is unavoidable. On the other hand, if it exceeds 40%, the sublimation of the dye is hindered due to the compatibility of the polyvinyl alcohol portion with the dye, and the printing density is lowered.

The weight ratio of the dye to the binder in the transfer dye layer is dye /
The binder content is preferably 0.3 or more, and when it is less than 0.3, the print density and thermal sensitivity are insufficient. On the other hand, if the dye / binder exceeds 2.3, the retention of the dye in the binder becomes insufficient and the storage stability of the transfer sheet is deteriorated. Therefore, the dye / binder is preferably 0.3 to 2.3, more preferably 0.55 to 1.5.

The dye is preferably dissolved in the binder of the transfer dye layer.

The transfer dye layer may be formed by selecting a dye so that a desired hue can be transferred when printed, and if necessary, two or more transfer dye layers having different dyes are arranged side by side on one transfer sheet. For example, when repeating the printing of each color according to the color separation signal to form an image like a natural color photograph,
The hue when printed is preferably cyan, magenta and yellow, and three transfer dye layers containing a dye giving such hue are arranged. Alternatively, in addition to cyan, magenta, and yellow, a transfer dye layer containing a dye that imparts a hue of black may be added. In addition, when forming the transfer dye layer, it is preferable to provide a mark for position detection at the same time when any of the transfer dye layers is formed, because an ink or a printing step different from the transfer dye layer formation is not required.

In the present invention, the material constituting the receiving layer is for receiving the dye transferred from the transfer dye layer and maintaining the image formed by the receiving. For example,
The synthetic resin (e) can be used alone or as a mixture of two or more kinds.

(A) Those having an ester bond.

Polyester resin, polyacrylic ester resin, polycarbonate resin, polyvinyl acetate resin, styrene acrylate resin, vinyl toluene acrylate resin, etc.

(B) Those having a urethane bond.

 Polyurethane resin and the like.

(C) Those having an amide bond.

 Polyamide resin (nylon).

(D) Those having a urea bond.

 Urine resin, etc.

(E) Others having a highly polar bond.

Polycaprolactone resin, polystyrene resin, polyvinyl chloride resin, polyacrylonitrile resin, etc.

Alternatively, the receiving layer is composed of a mixed resin of saturated polyester and vinyl chloride-vinyl acetate copolymer. Examples of the saturated polyester include Byron 200 and Byron 29
0, Byron 600 and the like (above, Toyobo), KA-1038C (Arakawa Kagaku), TP200, TP235 (above, Nippon Synthetic) and the like are used. The vinyl chloride-vinyl acetate copolymer preferably has a vinyl chloride content of 85 to 97 wt% and a degree of polymerization of about 200 to 800. The vinyl chloride-vinyl acetate copolymer is not necessarily limited to a copolymer of only a vinyl chloride component and a vinyl acetate component, but includes a vinyl alcohol component, a maleic acid component, and the like within a range not to impair the object of the present invention. There may be.

The receiving layer may also be composed of a polystyrene resin, for example, a styrene monomer, for example, a polystyrene resin composed of styrene, α-methylstyrene, or a homopolymer of vinyltoluene, or the styrene monomer. And other monomers such as acrylic acid ester, methacrylic acid ester, acrylonitrile, methacrylonitrile, or other acrylic or methacrylic monomer or a styrene copolymer resin which is a copolymer with maleic anhydride.

Further, the whiteness of the receiving layer is improved to enhance the sharpness of the transferred image and at the same time, the writing property is imparted to the transferred receiving layer surface,
A white pigment may be added to the receiving layer for the purpose of preventing retransfer of the transferred image. As the white pigment, titanium oxide, zinc oxide, kaolin clay, calcium carbonate, fine powder silica and the like are used, and two or more kinds of them can be mixed and used. Further, in order to enhance the light resistance of the transferred image, an ultraviolet absorber and / or a light stabilizer can be added to the image receiving layer. The amount of these ultraviolet absorbers and light stabilizers added is preferably 0.05 to 10 parts by weight and 0.5 to 3 parts by weight, respectively, with respect to 100 parts by weight of the resin constituting the image receiving layer.

In the present invention, the adhesive layer is formed on the surface of the receptive layer and is used for adhering the receptive layer to the transferred material to be transferred.
The adhesive layer may be of any type as long as it can adhere the receptor layer and the transferred material, and it may be polyester-based, polyacrylic ester-based, polyurethane-based, polyvinyl chloride-based, polyolefin-based, ethylene-vinyl acetate copolymer, synthetic. A rubber-based organic solvent solution or emulsion can be used. The adhesive layer may be a heat adhesive type or a room temperature adhesive type. In the case of the heat-bonding type, heat-bonding with a hot-melt type adhesive such as wax, ethylene / vinyl acetate copolymer resin, polyolefin, petroleum resin, or lamination with an extrusion film such as a polyolefin film may be used.

The transfer sheet of the present invention may contain a releasing agent in the receptive layer in order to improve the releasability between the transfer dye layer and the receptive layer after the transfer to the transferred material. Examples of the release agent include solid waxes such as polyethylene wax, amide wax and Teflon powder, fluorine-based and phosphoric acid ester-based surfactants, and silicone oil, with silicone oil being preferred.

As the silicone oil, oily ones can be used, but curable ones are preferable. Examples of the curable silicone oil include a reaction curable type, a photocurable type and a catalyst curable type, and a reaction curable type silicone oil is particularly preferable. The reaction-curable silicone oil is preferably a reaction-cured amino-modified silicone oil and an epoxy-modified silicone oil, and the amino-modified silicone oil is KF-393, KF-857, KF-858, X.
-22-3680, X-22-3801C (above, Shin-Etsu Chemical Co., Ltd.)
Manufactured by Shin-Etsu Chemical Co., Ltd. and the like. Examples of the epoxy-modified silicone oil include KF-100T, KF-101, KF-60-164, KF-103 (above, Shin-Etsu Chemical Co., Ltd.). KS-705F, KS-770 (catalyst-curable silicone oil: Shin-Etsu Chemical Co., Ltd.)
Manufactured by Shin-Etsu Chemical Co., Ltd., and the like. The addition amount of these curable silicone oils is preferably 0.5 to 30 wt% of the resin constituting the receiving layer.

Further, as a more preferable catalyst, a release layer can be provided between the receptor layer and the transfer dye layer by dissolving or dispersing the above-mentioned release agent in an appropriate solvent and applying the solution, followed by drying. As the release agent constituting the release layer, a reaction cured product of the amino-modified silicone oil and the epoxy-modified silicone oil described above is particularly preferable. The thickness of the release layer is
The thickness is preferably 0.01 to 5 μm, more preferably 0.05 to 2 μm.

The receptor layer can be formed by a known coating or printing method using a receptor layer-forming composition obtained by dissolving or dispersing a material for forming the receptor layer on the surface of a transfer dye layer or a release layer. .

The transfer sheet according to the present invention basically has the above configuration, but may be subjected to the following additional processing.
First, a primer layer may be provided between the transfer dye layer and the substrate sheet in order to improve the adhesive force of each layer. As the primer layer, known ones can be used. For example, if a primer layer of acrylic resin, polyester resin, polyol and diisocyanate is used, the adhesiveness of both layers is particularly improved when polyester is used as the base sheet. Be improved.

Instead of forming the primer layer, the base sheet may be subjected to corona discharge treatment. Further, the primer layer may be formed after the corona treatment.

Further, it is possible to provide an intermediate layer between the receiving layer and the adhesive layer.

The intermediate layer is either a cushioning layer or a porous layer, depending on the constituent material, or may also serve as an adhesive in some cases.

The cushioning layer is mainly composed of a resin having a 100% modulus of 100 kg / cm ² or less specified in JIS-K-6301. Here, if the 100% modulus exceeds 100 kg / cm ² , the rigidity is increased. It is not preferable because it is too expensive. Also, the above 100
The lower limit of% modulus is practically about 0.5 kg / cm ² .

Examples of resins that meet the above conditions include the following.

Polyurethane resin Polyester resin Polybutadiene resin Polyacrylic ester resin Epoxy resin Polyamide resin Rosin-modified phenol resin Terpene phenol resin Ethylene / vinyl acetate copolymer resin The above resins may be used alone or in combination of two or more. Since the above resins are relatively sticky, inorganic additives such as silica, alumina, clay, calcium carbonate, etc., or amides such as stearic acid amide, etc. can be used when there is a problem during processing. A system substance may be added.

The cushioning layer can be formed by kneading the above-mentioned resin with a solvent, a diluent, etc. together with a large number of additives as necessary to prepare a paint or ink, and drying the film as a coating film by a known coating method or printing method. , Its thickness is
The thickness is 0.5 to 50 μm, more preferably 2 to 20 μm.
When the thickness is 0.5 μm, it cannot absorb the roughness of the surface of the transfer target, which is the transfer target, and therefore it is not effective.
If it exceeds, not only the effect is not improved, but also the receptive layer portion becomes too thick and protrudes, which hinders winding and stacking, and is not economical.

It is considered that the formation of such an intermediate layer improves the adhesion between the transfer sheet and the transfer target because the intermediate layer itself has low rigidity and thus is deformed by the pressure during printing. Such a resin usually has a low glass transition point and a softening point, and it is presumed that it contributes to the fact that the thermal energy applied during printing further lowers the rigidity and makes it easier to deform than at room temperature. .

The porosity is 1) a synthetic resin emulsion such as polyurethane, a layer in which a synthetic rubber latex such as methylmethacrylate-butadiene series is bubbled by mechanical stirring is applied on the receiving layer and dried, 2) the above synthetic resin emulsion, A layer obtained by applying a liquid obtained by mixing a foaming agent to the synthetic resin rubber latex onto the receiving layer and drying the mixture, 3) a synthetic resin such as vinyl chloride plastisol or polyurethane, or a synthetic rubber such as styrene-butadiene system, and the foaming agent. Layer which is foamed by applying the above liquid on the receiving layer and heating, 4) compatibility with a solution in which a thermoplastic resin or synthetic rubber is dissolved in an organic solvent, which is less likely to evaporate than the organic solvent Which is mixed with a non-solvent (including one having water as a main component) which has a solubility in a thermoplastic resin or a synthetic rubber and which is not soluble in the thermoplastic resin or the synthetic rubber, is coated on the receiving layer. Microporous layer or the like by forming a flocculated film microscopically form is used by 燥.

Most preferably, the microporous layer of 4) above is provided as the porous layer.

Examples of the thermoplastic resin used in forming the microporous layer include saturated polyester, polyurethane, vinyl chloride vinyl acetate copolymer, cellulose acetopropionate, and the like, and the synthetic rubber used in the same manner is styrene. -Butadiene-based, isoprene-based, urethane-based, and the like. Various organic solvents and non-solvents can be used as the organic solvent and non-solvent used in the formation of the microporous layer, but hydrophilic solvents such as methyl ethyl ketone and alcohol are usually used as the organic solvent, and water is used as the non-solvent. Used.

The thickness of the porous layer in the present invention is preferably 3 μm or more, particularly preferably 5 to 20 μm. When the thickness of the porous layer is less than 3 μm, the cushioning and heat insulating effects are not exhibited.

Further, an antistatic agent may be contained in the receiving layer or on the surface of the receiving layer in order to suppress generation of static electricity during the process of processing the transfer sheet or during running in the printer. Antistatic agents include surfactants such as cationic surfactants (eg, quaternary ammonium salts, polyamine derivatives, etc.), anionic surfactants (eg, alkyl phosphates, etc.) zwitterionic surfactants or nonionic surfactants. Surfactants may be mentioned.

The antistatic agent may be applied and formed on the surface of the receiving layer by gravure coating, bar coating or the like, or may be kneaded into the resin for the receiving layer and transferred to the surface of the receiving layer during coating and drying of the receiving layer.

A cationic acrylic polymer can also be used as the antistatic agent mixed with the receptor layer resin.

Hereinafter, the transfer sheet of the present invention will be described in more detail with reference to the drawings.

The transfer sheet 1 of the present invention has, for example, as shown in FIG. 1, a transfer dye layer 3, a receiving layer 4 and an adhesive layer 5 on the surface of a base material sheet 2.
Are sequentially laminated, and a peeling layer 6 is provided between the transfer dye layer 3 and the receiving layer 4.

As shown in FIG. 2 (a), the transfer sheet 1 configured as described above is abutted so that the transfer layer 7 made of normal paper or the like and the adhesive layer 5 are in close contact with each other. To transfer the dye of the transfer dye layer 3 to the receiving layer 4 and heat the transfer sheet 1 and the transfer target 7 together to form the adhesive layer 5.
Glued by. Thereafter, as shown in FIG. 2B, the base sheet 2 and the transfer dye layer 3 are peeled from the peeling layer 6, and an image is formed on the transferred body 7.

〔Example〕

 Hereinafter, the present invention will be described in detail with reference to examples.

Example An ink composition for forming a transfer dye layer having the following composition was prepared on a polyethylene terephthalate film having a thickness of 6 μm, coated with a wire bar No. 10 (coating amount: about 1.2 g / m ² ) and dried with warm air. A transfer dye layer was formed.

Ink composition for forming a transfer dye layer Disperse dye 4 parts by weight (Nippon Kayaku: Kayaset Blue 714) Polyvinyl butyral resin 4.3 parts by weight (ESREC BX-1) Toluene 40 parts by weight Methyl ethyl ketone 40 parts by weight Isobutanol 10 parts by weight Next On the transfer dye layer, a solution of amino-modified silicone and epoxy-modified silicone dissolved in a solvent in a ratio of 1: 1 was applied with a wire bar and dried to form a release layer having a thickness of 1 μm after drying.

Next, a receptive layer-forming composition of the following composition is applied and dried using a wire bar on the release layer, and the coating amount when dried is 5 g.
A receiving layer of / m ² was provided.

Composition for forming receptive layer Vinyl chloride-Vinyl acetate 10 parts by weight (Vinyl VYHH manufactured by Union Carbide) Calcium carbonate 3 parts by weight Solvent 87 parts by weight (toluene / methyl ethyl ketone = 1: 1) Next, EVA adhesive is applied to the wire bar. Was coated on the surface of the receiving layer to form an adhesive layer to obtain a transfer sheet.

The obtained transfer sheet and high-quality paper are faced to each other and a thermal transfer printer is used to heat the transfer sheet from the back side of the transfer sheet so that the maximum image density can be obtained by a thermal head and transfer the dye from the transfer dye layer to the receiving layer The transfer sheet and high-quality paper were bonded together. Thereafter, the base sheet and the transfer dye layer were peeled off in the peeling layer to form an image.

 The obtained image had extremely good sharpness.

〔The invention's effect〕

As described above, the transfer sheet of the present invention comprises a transfer dye layer containing a dye which is melted or sublimated and transferred by heating in a resin binder on a base sheet, and a receiving layer which receives the dye of the transfer dye layer. Since the adhesive layer is sequentially laminated, a clear image can be easily transferred to plain paper which is not surface-treated.

In particular, when transfer is performed on many types of transferees, surface transfer is not performed on each transferee, so that workability is improved and transfer can be performed at low cost. Further, the transfer sheet of the present invention comprises a receiving layer made of a synthetic resin for maintaining the image formed by receiving the dye of the transfer dye layer, and an adhesive layer for adhering the receiving layer to the transferred material. Since it is formed on the surface, it is possible to select the most suitable material for the receiving layer and the adhesive layer. The receiving layer improves the recording characteristics by excellent image reproducibility, and the adhesive layer ensures the above-mentioned receiving layer. Can be glued to.

[Brief description of drawings]

The drawings show the embodiments of the present invention. FIG. 1 is a longitudinal sectional view of an essential part showing an embodiment of the transfer sheet of the present invention, and FIG. 2 is an explanatory view showing a state in which the transfer sheet of the present invention is used. . 1 ... Transfer sheet 2 ... Base sheet 3 ... Transfer dye layer 4 ... Receiving layer 5 ... Adhesive layer

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-60-145891 (JP, A) JP-A-59-106997 (JP, A) JP-A-60-222267 (JP, A) JP-A-61- 11295 (JP, A) JP 61-199997 (JP, A) JP 59-165688 (JP, A) JP 63-17086 (JP, A)

Claims (2)

(57) [Claims] 1. A transfer sheet formed on a base sheet, the transfer dye layer containing a dye which is melted or sublimated to be transferred by heating in a resin binder; and a synthetic resin which is formed by receiving the dye in the transfer dye layer. A transfer sheet comprising a receptive layer for maintaining an image and an adhesive layer for adhering the receptive layer to a transferred material, which are sequentially laminated. 2. The transfer sheet according to claim 1, wherein a release layer is provided between the transfer dye layer and the receiving layer.