JP2001030639A - Heat transfer image receiving sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat transfer image receiving sheet, capable of forming an image having a high dye dying property through high-speed printing and provided with a sufficient separating property without being welded to a heat transfer sheet through thermal fusion upon forming the image. SOLUTION: A receptive layer is formed on at least one surface of a substrate sheet and at least phenoxy resin and more than one of plasticizers are contained in the receptive layer whereby recording sensitivity is improved nd an image, high in dying property, can be obtained through high-speed printing since the phenoxy resin is provided with a high compatibility with respect to the plasticizer. Further, at least one of parting agent is contained in the receptive layer whereby a heat transfer image receiving sheet will not adhere to the heat transfer sheet through thermal fusion welding upon forming the image. Further, a protective layer is transferred on an imaging part in order to improve the resistance to light and fingerprint of a printed matter while a parting agent is added so as to eliminated troubles in bonding to the protective layer whereby the printed matter, having excellent separating performance upon heat transferring through a heat transfer sheet and having no oozing due to the plasticizer, can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer image-receiving sheet, and more particularly to a thermal transfer recording method using a sublimable dye. The present invention relates to a thermal transfer image receiving sheet which has sufficient peelability without being thermally fused with the thermal transfer sheet during image formation.

[0002]

2. Description of the Related Art Conventionally, various thermal transfer methods are known. Among them, a sublimation transfer dye is used as a recording material, and a sublimation dye is used from a thermal transfer sheet in which this is carried on a base sheet such as a polyester film. There has been proposed a method in which a sublimation transfer dye is thermally transferred onto an image receiving sheet having a receiving layer formed thereon on a transferable material such as paper or a plastic film to form various full-color images. In this case, a thermal head of a printer is used as a heating means, and a large number of three or four color heating-adjusted color dots are transferred to the image receiving sheet by heating in a very short time, and the multi-color heating is performed. It reproduces the full color of the original using color dots. The image formed in this way is very clear because the coloring material used is a dye, and
Because of its excellent transparency, the resulting image is excellent in reproducibility and gradation of intermediate colors, similar to images by conventional offset printing or gravure printing, and high-quality images comparable to full-color photographic images Can be formed.

[0003]

In order to effectively carry out the thermal transfer method as described above, the structure of the thermal transfer sheet is, of course, required.
The structure of the image receiving sheet for forming an image is also important. As a conventional technology of an image receiving sheet, Japanese Patent Application Laid-Open No.
No. 69370, No. 57-207250, No. 60-25
No. 793, etc., the receiving layer is formed by using a vinyl resin such as a polyvinyl chloride resin, a polyvinyl butyral resin, an acrylic resin, a cellulose resin, an olefin resin, a polystyrene resin, a polyester resin, and a polycarbonate resin. A formed resin is disclosed.
Japanese Patent Application Laid-Open No. 62-152897 discloses a heat-transferable image-receiving sheet having excellent storage stability even at high temperature and high humidity by using a phenoxy resin as a resin having a bisphenol skeleton and forming a receptor layer. Have been.

In Japanese Patent Application Laid-Open No. 02-106393, a receptor layer is formed by using a phenoxy resin modified with a partial hydrolyzate of a polyfunctional silane coupling agent.
A heat-transferable image-receiving sheet excellent in storage stability without heat fusing is disclosed. JP-A-06-155932 discloses that a hydroxyl group of a phenoxy resin is an ester group,
A heat transfer image-receiving sheet excellent in light resistance by forming a receptor layer using a modified phenoxy resin blocked with an amide group, an ether group or a silyl ether group is disclosed. In recent years, an improvement in printing speed (high-speed printing) has been demanded in order to reduce the printout time per sheet. For high-speed printing, the conventional thermal transfer image receiving sheet as described above has a problem that a sufficient print density cannot be obtained. In order to obtain a sufficient printing density, a method of increasing the amount of the dye for the binder holding the dye of the thermal transfer sheet or performing thermal transfer with high energy is conceivable.

[0005] However, when the amount of the dye is increased, the dye moves to the back side during winding of the thermal transfer sheet, and
The thermal head is contaminated due to the concentration drop over time or the back surface is contaminated with time, causing a problem that the life of the thermal head is shortened or the normal printing is hindered. There has been a problem that heat fusion occurs between the layers to cause abnormal transfer. Further, when thermal transfer is performed with high energy, there is a problem in that thermal fusion occurs between the thermal transfer sheet and the thermal transfer image receiving sheet during thermal transfer, causing abnormal transfer. As a method for solving the above problems, JP-A-60-191138, JP-A-04-284292, JP-A-05-193279, polycarbonate, polyvinyl chloride, a curable resin, such as A method of adding a plasticizer to a small resin is disclosed, but since these resins originally have low dyeing properties, they are equivalent to vinyl chloride-vinyl acetate copolymers which are resins having high dyeing properties, and polyester resins. It is a degree that can obtain a printing density of, a resin with high dyeing properties, for example,
If a plasticizer is added to the vinyl chloride-vinyl acetate copolymer or polyester resin so that it has sufficient dyeing power for high-speed printing, the dye receiving layer cannot retain the dye and the image bleeds, or the thermal transfer sheet and thermal transfer during thermal transfer There is a problem that heat fusion occurs between the image receiving sheets and abnormal transfer occurs.

As a method for solving the above-mentioned problem of the plasticizer, there is a method in which a receiving layer is formed into a multilayer structure and a layer containing a plasticizer is set as a lower layer (substrate side). The dyeing power of the dye is small, so that the dye cannot be diffused to the lower layer in high-speed printing, resulting in a low concentration, or the multi-layer structure has a problem that the production is complicated and the production cost is increased. Therefore, the present invention solves the above-mentioned problems, and an image having high dye-dyeability is formed at high-speed printing, and the thermal transfer image-receiving sheet is sufficiently peelable without heat fusion with the thermal transfer sheet for image formation. It is an object of the present invention to provide a thermal transfer image receiving sheet having the following.

[0007]

Means for Solving the Problems According to the present invention, as a result of intensive studies to achieve the above object, a thermal transfer image-receiving sheet having a receiving layer formed on at least one surface of a substrate sheet is described. The above problem was successfully solved by allowing the receiving layer to contain at least a phenoxy resin and one or more plasticizers. Preferably, the plasticizer comprises at least one selected from phthalic acid plasticizers, phosphate ester plasticizers, polycaprolactone, and polyester plasticizers. Further, the receiving layer desirably contains at least one or more release agents. A seal-like form in which a release sheet is releasably laminated on the surface of the base material opposite to the surface on which the receiving layer is formed via an adhesive layer can be used. Further, in a printed matter in which a dye image is formed on the receiving layer of the thermal transfer image-receiving sheet, it is preferable that a protective layer is transferred to at least a part of the dye image.

[0008]

The thermal transfer image-receiving sheet of the present invention has a receiving layer formed on at least one surface of a base sheet, and the receiving layer contains at least a phenoxy resin and one or more plasticizers. By adding a plasticizer having high compatibility with the phenoxy resin of the layer resin, the recording sensitivity is improved, and an image having high dye-dyeing property can be obtained at high-speed printing. In addition, when the receiving layer contains at least one or more release agents, sufficient releasability can be obtained without thermal fusion of the thermal transfer image-receiving sheet to the thermal transfer sheet during image formation. For the purpose of improving the light resistance of the print, the fingerprint resistance and the plasticizer resistance, a protective layer is transferred to the image portion after image formation, but a phenoxy resin having heat resistance,
By the combination of the phenoxy resin and the plasticizer having high compatibility, furthermore, at the time of transfer of the protective layer, a release agent is added so as not to hinder the adhesion with the protective layer, and excellent at the time of thermal transfer with the thermal transfer sheet. A print having peeling performance and no bleeding due to a plasticizer can be obtained.

[0009]

Embodiments of the present invention will be described below. (Substrate sheet) The substrate sheet has a role of holding the receiving layer and is preferably applied with heat at the time of thermal transfer. Therefore, it is preferable that the substrate sheet has a mechanical strength that does not hinder handling even in a heated state.

[0010] The material of such a base sheet is not particularly limited. For example, condenser paper, glassine paper, parchment paper, or high-size paper, synthetic paper (polyolefin-based, polystyrene-based, etc.), high-quality paper , Art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper, paperboard, etc., cellulose fiber paper, or polyester, polyacrylate, polycarbonate, Polyurethane, polyimide, polyetherimide, cellulose derivative, polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polystyrene, acrylic, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, Lisulfone, polyether sulfone, tetrafluoroethylene / perfluoroalkyl vinyl ether, polyvinyl fluoride, tetrafluoroethylene / ethylene, tetrafluoroethylene / hexafluoropropylene, polychlorotrifluoroethylene, various plastic films such as polyvinylidene fluoride or A sheet can be used, and a white opaque film formed by adding a white pigment or a filler to these synthetic resins or a foamed foamed sheet can be used, and is not particularly limited.

Further, a laminate formed by combining any of the above-mentioned base sheets can also be used. As an example of a typical laminated body, a laminated synthetic paper of cellulose fiber paper and a synthetic film or a plastic film or sheet is exemplified. Such a laminated synthetic paper may be a two-layer body,
It may be a three-layer body or a laminate of three or more layers in which synthetic paper or a plastic film is stuck on both sides in order to obtain the texture and texture of the base material. The lamination method is not limited to dry lamination, wet lamination, extrusion, and other techniques. Further, an adhesive layer is provided in the middle of the laminate of any combination of the above base sheets so as to be peelable, and a layer having a desired glossiness can be formed in a seal form or to control the gloss of the obtained image receiving sheet. In order to transfer the receiving layer after forming the receiving layer on the base material or to transfer the receiving layer after printing to an arbitrary support (a card or a curved support), the receiving layer is peeled off so that the receiving layer can be peeled off. It can also be provided on the material sheet. The thickness of these base sheets may be arbitrary, and is generally about 10 to 300 μm.
Further, when the base sheet as described above has a poor adhesion to a layer formed on the surface, it is preferable to subject the surface to various primer treatments or corona discharge treatment.

(Receiving Layer) The receiving layer formed on the surface of the base sheet is for receiving the sublimable dye migrating from the thermal transfer sheet and maintaining the formed screen, and at least one surface. In a thermal transfer image-receiving sheet having a receiving layer formed thereon, the receiving layer is formed by having at least a phenoxy resin and one or more plasticizers. The phenoxy resin used in the present invention is a phenoxy resin derived from epichlorohydrin and bisphenol A. The phenoxy resin is modified with a partial hydrolyzate of a polyfunctional silane coupling agent disclosed in JP-A-02-106393. A modified phenoxy resin in which the hydroxyl group of a resin or a phenoxy resin disclosed in JP-A-06-155932 is blocked with an ester group, an amide group, an ether group, or a silyl ether group can also be used.

In addition, other thermoplastic resins other than the phenoxy resin may be blended within a compatible range. The ratio of the resin to be blended is 0 to 100 parts by weight of the phenoxy resin.
If the amount exceeds 100 parts by weight, the density does not correspond to high-speed printing. Thermoplastic resins that can be blended include halogenated polymers such as polyvinyl chloride and polyvinylidene chloride, polyvinyl acetate, ethylene-
Vinyl resins such as vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyacrylester, polystyrene and polystyrene acryl; acetal resins such as polyvinyl formal, polyvinyl butyral and polyvinyl acetal; and various saturated and unsaturated polyesters Resin,
Examples thereof include a polycarbonate resin, a cellulose resin such as cellulose acetate, a polyolefin resin, and a polyamide resin such as a urea resin, a melamine resin, and a benzoguanamine resin.

The plasticizer used in the present invention includes a phthalic acid plasticizer, a phosphate ester plasticizer, a polycaprolactone, and a polyster plasticizer. The addition amount of the plasticizer depends on the plasticizer, but is preferably 20 to 60 to 70 parts by weight based on 100 parts by weight of the phenoxy resin.
If the amount of the plasticizer is less than 20 parts by weight, there is no density capable of coping with high-speed printing. As a result, a clear image cannot be obtained. In order to obtain sufficient dyeing properties, at least one selected from phthalic acid plasticizers, phosphate ester plasticizers, polycaprolactone, and polyester plasticizers is added to the phenoxy resin.

At present, the thermal transfer recording material described in the present application has a market need of 50% both before and after printing due to the temperature history during product transportation and the storage environment after printing (in a car in summer, etc.). It is required to have a heat resistance of 60C to 60C. Considering the temporal change in recording sensitivity before printing and the bleeding of the image over time during storage after recording, phthalic acid plasticizer, phosphate ester plasticizer, polycaprolactone, melting point of polyester plasticizer, or The freezing point is desirably 60 ° C. or higher.

The phthalic acid plasticizer is represented by the following general formula 3.

Embedded image (However, R ₄ and R ₅ in the formula each represent either an alkyl group or an aryl group.)

Specific examples of the phthalic acid plasticizer include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (= 2-ethylhexyl phthalate),
Dicyclohexyl phthalate (DCHP), diphenyl phthalate and the like can be mentioned, and DCHP is particularly preferably used.

Next, as the phosphate plasticizer, non-halogen phosphates and non-halogen condensed phosphates represented by the following general formulas 4 and 5 are preferable.

Embedded image [In the above formula 4, R ₁ and R ₂ represent hydrogen, an alkyl group such as a methyl group, or a substituted alkyl group. ]

[0019]

Embedded image [In the above formula 5, R ₁ and R ₂ represent hydrogen, an alkyl group such as a methyl group, or a substituted alkyl group. ]

Regarding polycaprolactone, the number average molecular weight is 2,000 in consideration of bleeding during high-temperature storage after printing.
0 to 100,000, particularly preferably 10,000 to 7
000 is preferred. If the molecular weight is 2,000 or less, it tends to spread over time after recording, and if it is 100,000 or more, there is a problem in the production stability of polycaprolactone itself and the compatibility with the phenoxy resin of the present invention. Further, the polyester plasticizer does not contain polycaprolactone and means a low molecular weight one, and examples thereof include adipic acid polyester and azelaic acid polyester.Diol adipate is particularly effective in improving fingerprint resistance, plasticizer resistance, and the like. Is preferred.

As the release agent used in the present invention, an existing release agent can be used, but a fluorine-based surfactant, silicone oil and / or a cured product thereof are particularly preferred. Fluorosurfactants include Fluorad FC-43
0, FC-431 (3M), and various modified silicone oils as described in "Silicone Handbook" Nikkan Kogyo Shimbun and cured products thereof can be used as the silicone oil. When the protective layer is transferred and bonded, a fluorine-based surfactant or an uncured silicone oil is preferable so that the protective layer can be bonded.

In addition to the above-mentioned release agents, a conventionally used release agent may be used in combination, and even when a plurality of release agents are used, the total amount of the release agent is 0 to the receiving layer resin. .5-
10% by weight is preferred. Various other additives can be added to the receiving layer as needed. In order to improve the whiteness of the receiving layer and further enhance the sharpness of the transferred image,
Pigments and fillers such as titanium oxide, zinc oxide, kaolin, clay, calcium carbonate, and finely divided silica can be added. However, when transparency is required, such as for OHP applications, the amount of the pigment or additive should be such that the required transparency is not lost. In addition, known additives such as a plasticizer, an ultraviolet absorber, a light stabilizer, an antioxidant, a fluorescent brightener, and an antistatic agent can be added to the receiving layer as needed.

The thermal transfer image-receiving sheet of the present invention uses a phenoxy resin as described above on at least one surface of the above-mentioned base sheet, and is preferably a phthalic acid plasticizer, a phosphate ester plasticizer, polycaprolactone, or polyester. At least one selected from among the plasticizers is added, and other necessary additives such as a releasing agent, a cross-linking agent, a curing agent, a catalyst, an ultraviolet absorber, an antioxidant, and a light stabilizer. Is appropriately dissolved or dispersed in an appropriate organic solvent, and coated and dried by a forming means such as a gravure printing method, a screen printing method, or a reverse roll coating method using a gravure plate to form a dye-receiving layer. Obtained by: Coating of an intermediate layer, a back surface layer, an easy-adhesion layer, and an antistatic layer, which will be described later, is also performed in the same manner as the above-described means for forming the receiving layer. In order to impart antistatic properties, the following antistatic agents can be kneaded into the coating liquid for the receiving layer. Antistatic agents; fatty acid esters, sulfates, phosphates, amides, quaternary ammonium salts, betaines, amino acids, acrylic resins, ethylene oxide adducts and the like. The addition amount of the antistatic agent is 0.1 to
2.0% by weight is preferred.

In the thermal transfer image-receiving sheet of the present invention, the coating amount of the receiving layer is 0.5 g / m ^{2 to} 4.0 g / m ^{2 in} dry weight.
It is preferably ² . Coating amount is 0.5 by dry weight
If it is less than g / m ² , for example, when the receiving layer is provided directly on the base sheet, the image of the highlight portion is rough due to insufficient adhesion to the thermal head due to factors such as the rigidity of the base sheet. Problem. This problem can be avoided by providing an intermediate layer that imparts cushioning properties, but it is more vulnerable to damage to the receiving layer. Also,
Roughness of the surface when high energy is applied tends to become relatively poor when the coating amount of the receiving layer increases,
If the coating amount exceeds 4.0 g / m ² in dry weight, for example, it becomes slightly dark at a high density portion during OHP projection. The coating amount (or coating amount) of the present invention below
Is a dry weight and a solid content value, unless otherwise specified.

(Intermediate Layer) An intermediate layer may be provided as a component between the receiving layer and the substrate formed on the substrate sheet. The intermediate layer refers to all layers between the base material and the receiving layer, and may have a multilayer structure. The functions of the intermediate layer include solvent resistance, barrier performance, adhesion performance,
Although the hiding performance and the like can be mentioned, all conventionally known intermediate layers can be used without being limited thereto. Solvent resistance performance,
In order to have barrier performance, it is preferable to use a water-soluble resin.

Examples of the water-soluble resin include cellulosic resins (especially carboxymethylcellulose), polysaccharide resins such as starch, proteins (especially casein), gelatin, agar,
Further, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, vinyl acetate (meth) acrylic copolymer, vinyl acetate veova copolymer, (meth) acrylic resin, styrene (meth) ) Acrylic copolymers, vinyl resins such as styrene resins, polyamide resins such as melamine resins, urea resins, benzoguanamine resins, polyesters, polyurethanes and the like. The water-soluble resin referred to here means a complete dissolution (particle size of 0.01 μm or less) or a colloidal dispersion (0.01 to 0.1 μm) in a solvent mainly composed of water.
m), or an emulsion (0.1 to 1 μm) or a slurry (1 μm or more).

Among these water-soluble resins, particularly preferred are hexane, cyclohexane, acetone, methyl ethyl ketone, xylene, ethyl acetate, butyl acetate, toluene, methanol, ethanol, alcohols such as IPA, and other general-purpose solvents. Needless to say, it is a resin that does not even swell. In this sense, a resin that completely dissolves in a solvent mainly composed of water is most preferable. In particular, a polyvinyl alcohol resin and a cellulose resin are mentioned. The adhesion performance varies depending on the type of the base material and its surface treatment, but urethane-based resins and polyolefin-based resins are generally used. or,
When a thermoplastic resin having active hydrogen and a curing agent such as an isocyanate compound are used in combination, good adhesiveness can be obtained.

As the whitening agent, any of the conventionally known compounds can be used as the fluorescent whitening agent. Examples thereof include stilbene, distilbene, benzoxazole, styryl-oxazole, pyrene-oxazole, coumarin, and aminocoumarin. , Imidazole, benzimidazole, pyrazoline, and distyryl-biphenyl fluorescent brighteners. The degree of whiteness can be adjusted by the type and amount of the fluorescent whitening agent. As a method for adding the fluorescent whitening agent, any method can be used. That is, a method of adding by dissolving in water, a method of pulverizing and dispersing by a ball mill or a colloid mill,
There are a method of dissolving in a high boiling point solvent, mixing with a hydrophilic colloid solution, and adding it as an oil-in-water dispersion, and a method of impregnating and adding the polymer latex.

Further, if titanium oxide is added to the intermediate layer in order to conceal glare and unevenness of the base material, the degree of freedom in selecting the base material may be further increased. Titanium oxide has two types, rutile-type titanium oxide and anatase-type titanium oxide. Considering the whiteness and the effect of a fluorescent whitening agent, the absorption of ultraviolet light is shorter on the shorter wavelength side than the rutile type. Certain anatase titanium oxides are preferred. If the intermediate layer binder resin is water-based and the titanium oxide is difficult to disperse, use a titanium oxide whose surface has been subjected to hydrophilic treatment,
Alternatively, it can be dispersed by a known dispersant such as a surfactant and ethylene glycol. The amount of titanium oxide added was 1 part by weight of solid titanium oxide to 100 parts by weight of resin solids.
0 to 400 parts by weight is preferred.

(Back Side Layer) On the back side of the thermal transfer image receiving sheet,
A back surface layer can be provided for improving the mechanical transportability of the sheet, preventing curling, preventing charging, and the like. In order to improve the transportability, it is preferable to add an appropriate amount of an organic or inorganic filler to the binder resin, or to use a resin having high lubricity such as a polyolefin resin or a cellulose resin. Also, in order to obtain an antistatic function, conductive resins and fillers such as acrylic resins, furthermore, fatty acid esters, sulfate esters,
Various antistatic agents such as phosphates, amides, quaternary ammonium salts, betaines, aminos, and ethylene oxide adducts may be added, or an antistatic layer on the back surface or between the back layer and the substrate May be provided.

The amount of the antistatic agent varies depending on the layer to which the antistatic agent is added and the type of the antistatic agent. In any case, the surface electric resistance of the thermal transfer image-receiving sheet is 1%.
0 ¹³ Ω / cm ² or less is preferable. Surface electric resistance value is 1
If it exceeds 0 ¹³ Ω / cm ² , the thermal transfer image-receiving sheets stick to each other due to electrostatic contact, causing a paper feeding trouble. The amount is preferably 0.01 to 3.0 g / m ² . If the amount of the antistatic agent used is less than 0.01 g / m ² , the antistatic effect is insufficient, while 3.0 g / m 2
^{If it is} more than ² , the amount used is too large, which is uneconomical and may cause problems such as stickiness.

(Easy Adhesion Layer) An easy adhesion layer made of an adhesive resin such as an acrylate resin, a polyurethane resin or a polyester resin may be applied to the front and / or back surface of the base sheet. In addition, without providing the coating layer described above, the front surface and / or the back surface of the base sheet is subjected to a corona discharge treatment or a plasma treatment to enhance the adhesion between the base sheet and the layer provided thereon. Can be.

(Antistatic layer) The surface of the substrate sheet and / or
Alternatively, an antistatic layer may be provided on the back surface, or on the image receiving surface or the back surface of the thermal transfer image receiving sheet or on the outermost surface of both surfaces. The antistatic layer is composed of an antistatic agent such as fatty acid ester, sulfate ester, phosphate ester, amides,
It can be formed by coating and dissolving or dispersing a quaternary ammonium salt, betaines, amino acids, acrylic resin, ethylene oxide adduct, and the like in a solvent. The coating amount is preferably from 0.001 g / m ^{2 to} 0.1 g / m ² . As described above, the thermal transfer image-receiving sheet provided with the antistatic layer on the outermost surface has excellent antistatic properties before printing, and thus can prevent poor feeding such as double feed. Further, it is possible to prevent troubles such as missing prints caused by attracting dust or the like.

In the present invention, in the printed matter having the dye image formed on the receiving layer of the thermal transfer image receiving sheet described above,
It is preferable to transfer and provide a protective layer on at least a part of the dye image. Specifically, an image is formed by thermally transferring a sublimation dye from a thermal transfer sheet having a dye layer formed on a base material to the receiving layer of the thermal transfer image receiving sheet, and the base material is formed on at least a part of the image. Using a protective layer transfer sheet provided with a transferable resin layer (protective layer) thereon, the transferable resin layer is thermally transferred to transfer and form the protective layer. As the thermal transfer sheet having the dye layer and the protective layer transfer sheet, conventionally known ones can be used and are not limited. Incidentally, it is also possible to use a thermal transfer sheet provided with a dye layer of yellow, magenta, cyan or the like and a transferable protective layer in a plane-sequential manner.

A seal type heat transfer image receiving sheet having a receiving layer provided on one side of a base sheet, and an adhesive layer using an adhesive or the like and a release paper provided in this order on the other side of the base sheet. Also, the present invention can be applied. The means for forming the adhesive layer is performed in the same manner as the means for forming the receiving layer. Further, the present invention can be applied to a receiving layer in a receiving layer transfer sheet in which a dye receiving layer is formed on a substrate so as to be peelable. Further, first, the dye sublimation dye is transferred from the thermal transfer sheet having the dye layer formed on the base material to the receiving layer of the intermediate transfer recording medium in which the dye receiving layer is provided releasably on the base material to form an image. The present invention can also be applied to a method in which an intermediate transfer recording medium is thereafter heated to transfer the image-formed receiving layer onto a transfer-receiving member.

[0036]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following description, parts and% are based on weight unless otherwise specified. Example 1 A 150 μm thick synthetic paper (YUPOFPG # 150, manufactured by Oji Yuka Co., Ltd.) was used as a base sheet, and a receiving layer coating liquid 1 having the following composition was coated on one surface of the base sheet by a wire bar method. The receiving layer was formed by applying and drying (110 ° C., 30 seconds) at a rate of 4.0 g / m ² at the time of drying to form a receiving layer, and allowed to stand at room temperature for 12 hours or more. Obtained.

Receptive layer coating liquid 1 Phenoxy resin (PKHC: manufactured by Union Carbide) 80 parts Plasticizer (diphenylphthalate) 20 parts Release agent (fluorinated surfactant) 3 parts (Fluorad FC-431: manufactured by 3M) ) Methyl ethyl ketone / toluene = 1/1 (weight ratio) 400 parts

Example 2 A thermal transfer image-receiving sheet of Example 2 was obtained in the same manner as in Example 1 except that the coating liquid for the receiving layer in Example 1 was changed to a coating liquid 2 for the receiving layer having the following composition. . Receptive layer coating liquid 2 Phenoxy resin (PKHH: manufactured by Union Carbide) 70 parts Plasticizer 30 parts (tetrakis (2,6 xylenol resorcinol) diphosphate)

Embedded image Release agent (fluorinated surfactant) 3 parts (Fluorad FC-431: manufactured by 3M) Methyl ethyl ketone / toluene = 1/1 (weight ratio) 400 parts

Example 3 A thermal transfer image-receiving sheet of Example 3 was obtained in the same manner as in Example 1 except that the coating liquid for the receiving layer in Example 1 was changed to the coating liquid 3 for the receiving layer having the following composition. . Receptive layer coating liquid 3 Phenoxy resin (PKHJ: manufactured by Union Carbide Co., Ltd.) 60 parts Plasticizer (caprolactone) 40 parts (Placcel H1P: manufactured by Daicel Chemical Industries, Ltd.) Release agent (fluorinated surfactant) 3 parts ( (Fluorad FC-431: manufactured by 3M) Methyl ethyl ketone / toluene = 1/1 (weight ratio) 400 parts

Example 4 The thermal transfer image-receiving sheet of Example 4 was obtained in the same manner as in Example 1 except that the coating liquid for the receiving layer in Example 1 was changed to the coating liquid 4 for the receiving layer having the following composition. . Receptive layer coating liquid 4 Phenoxy resin (PKHH: manufactured by Union Carbide) 70 parts Plasticizer (polyester-based plasticizer) 30 parts (BAA-15: manufactured by Daihachi Chemical Industry Co., Ltd.) Release agent (fluorinated surfactant) Agent) 3 parts (Fluorad FC-431: manufactured by 3M) Methyl ethyl ketone / toluene = 1/1 (weight ratio) 400 parts

Example 5 A thermal transfer image-receiving sheet of Example 5 was obtained in the same manner as in Example 1 except that the coating liquid for the receiving layer in Example 1 was changed to the coating liquid 5 for the receiving layer having the following composition. . Receptive layer coating liquid 5 Phenoxy resin (PKHH: manufactured by Union Carbide) 60 parts Polystyrene (GP550-51: manufactured by Mitsui Chemicals, Inc.) 10 parts Plasticizer (diphenylphthalate) 30 parts Release agent (fluorinated surfactant) 3 parts (Fluorad FC-431: manufactured by 3M) Methyl ethyl ketone / toluene = 1/1 (weight ratio) 400 parts

Example 6 A thermal transfer image-receiving sheet of Example 6 was obtained in the same manner as in Example 1 except that the coating liquid for the receiving layer in Example 1 was changed to the coating liquid 6 for the receiving layer having the following composition. . Receptive layer coating solution 6 Phenoxy resin (PKHH: manufactured by Union Carbide) 50 parts Polyester (Byron 200: manufactured by Toyobo Co., Ltd.) 20 parts Plasticizer (caprolactone) 30 parts (Placcel H1P: manufactured by Daicel Chemical Industries, Ltd.) Release agent (fluorinated surfactant) 5 parts (Fluorad FC-431: manufactured by 3M) Methyl ethyl ketone / toluene = 1/1 (weight ratio) 400 parts

Example 7 A thermal transfer image-receiving sheet of Example 7 was obtained in the same manner as in Example 1 except that the coating liquid for the receiving layer in Example 1 was changed to the coating liquid 7 for the receiving layer having the following composition. . Receptive layer coating liquid 7 Phenoxy resin (PKHH: manufactured by Union Carbide) 35 parts Polyvinyl butyral (BX-200: manufactured by Sekisui Chemical Co., Ltd.) 35 parts Plasticizer (caprolactone) 30 parts (Placel H1P: Daicel Chemical Industries, Ltd.) Release agent (fluorinated surfactant) 5 parts (Fluorad FC-431: manufactured by 3M) Methyl ethyl ketone / toluene = 1/1 (weight ratio) 400 parts

Example 8 A thermal transfer image-receiving sheet of Example 8 was obtained in the same manner as in Example 1 except that the coating liquid for the receiving layer in Example 1 was changed to the coating liquid 8 for the receiving layer having the following composition. . Receptive layer coating liquid 8 Propionic acid-modified phenoxy resin A 70 parts (prepared so that 50% of the hydroxyl groups of the phenoxy resin are calculated values and propionic acid esterification was performed, propionic acid was ester-modified, and propionic acid-modified phenoxy resin A was used. In the IR measurement, the hydroxyl group peak was smaller than that of the phenoxy resin.) 30 parts of plasticizer (caprolactone) (Placcel H1P: manufactured by Daicel Chemical Industries, Ltd.) Release agent (fluorinated surfactant) 5 parts (Fluorad FC-431: manufactured by 3M) Methyl ethyl ketone / toluene = 1/1 (weight ratio) 400 parts

Example 9 A thermal transfer image-receiving sheet of Example 9 was obtained in the same manner as in Example 1 except that the coating liquid for the receiving layer in Example 1 was changed to the coating liquid 9 for the receiving layer having the following composition. . Receptive layer coating liquid 9 Propionic acid-modified phenoxy resin B 35 parts (100% of the hydroxyl groups of the phenoxy resin were calculated so that propionic acid esterification was performed, and propionic acid was ester-modified to form propionic acid-modified phenoxy resin B. According to IR measurement values, peaks of hydroxyl groups were reduced in propionic acid-modified phenoxy resin A, but all hydroxyl groups could not be completely esterified.) Polyvinyl butyral (BX-200: Sekisui Chemical Co., Ltd.) 35 parts Plasticizer (caprolactone) 30 parts (Placcel H1P: manufactured by Daicel Chemical Industries, Ltd.) Release agent (fluorinated surfactant) 5 parts (Fluorad FC-431: manufactured by 3M) Methyl ethyl ketone / Toluene = 1/1 (weight ratio) 400 parts

(Comparative Example 1) A thermal transfer image-receiving sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that the receiving layer coating liquid in Example 1 was changed to the receiving layer coating liquid 10 having the following composition. Receptive layer coating liquid 10 Phenoxy resin (PKHH: manufactured by Union Carbide) 100 parts Release agent (fluorinated surfactant) 3 parts (Fluorad FC-431: manufactured by 3M) Methyl ethyl ketone / toluene = 1/1 (weight ratio) ) 400 copies

(Comparative Example 2) A thermal transfer image-receiving sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that the receiving layer coating liquid in Example 1 was changed to the receiving layer coating liquid 11 having the following composition. Receptive layer coating liquid 11 Propionic acid modified phenoxy resin B 100 parts (same as propionic acid modified phenoxy resin synthesized in Example 9) Release agent (fluorinated surfactant) 3 parts (Fluorad FC-431: manufactured by 3M Company) ) Methyl ethyl ketone / toluene = 1/1 (weight ratio) 400 parts

Comparative Example 3 A thermal transfer image-receiving sheet of Comparative Example 3 was obtained in the same manner as in Example 1 except that the receiving layer coating liquid in Example 1 was changed to the receiving layer coating liquid 12 having the following composition. Receptive layer coating liquid 12 Polycarbonate resin 60 parts (same as polycarbonate used in protective layer coating liquid for protective layer transfer sheet) Plasticizer (caprolactone) 40 parts (Placcel H1P: manufactured by Daicel Chemical Industries, Ltd.) Release agent (Fluorosurfactant) 5 parts (Fluorad FC-431: manufactured by 3M) Methyl ethyl ketone / toluene = 1/1 (weight ratio) 400 parts

(Comparative Example 4) A thermal transfer image-receiving sheet of Comparative Example 4 was obtained in the same manner as in Example 1 except that the receiving layer coating liquid in Example 1 was changed to the receiving layer coating liquid 13 having the following composition. Receptive layer coating liquid 13 polyester (Byron 200: manufactured by Toyobo Co., Ltd.) 100 parts Release agent (fluorinated surfactant) 5 parts (Fluorad FC-431: manufactured by 3M) Methyl ethyl ketone / toluene = 1/1 ( 400 parts by weight)

Comparative Example 5 A thermal transfer image-receiving sheet of Comparative Example 5 was obtained in the same manner as in Example 1 except that the coating liquid for the receiving layer in Example 1 was changed to the coating liquid 14 for the receiving layer having the following composition. Receptive layer coating liquid 14 Polyester (Byron 200: manufactured by Toyobo Co., Ltd.) 60 parts Plasticizer (caprolactone) 40 parts (Placcel H1P: manufactured by Daicel Chemical Industries, Ltd.) Release agent (fluorinated surfactant) 5 Part (Fluorad FC-431: manufactured by 3M) Methyl ethyl ketone / toluene = 1/1 (weight ratio) 400 parts

(Thermal Transfer Sheet) On the other hand, a coating solution for forming a dye layer having the following composition was prepared, and the back surface was heat-treated to 6 μm.
A thick polyethylene terephthalate film was coated and dried with a wire bar so that the dry coating amount was 1.0 g / m ² to form a dye layer, thereby obtaining a thermal transfer sheet. Dye layer coating liquid 6 parts of cyan dye represented by the following chemical formula

Embedded image Cellulose resin 4 parts (CAB-381-20: manufactured by Eastman Kodak Co.) Methyl ethyl ketone / toluene = 1/1 (weight ratio) 90 parts

The dye-receiving layer of the thus-obtained thermal transfer image-receiving sheet and the dye layer of the above-mentioned thermal transfer sheet are superposed on each other so as to face each other, and thermal transfer recording is performed from the back of the thermal transfer sheet using a thermal head under the following conditions. The following various evaluations were performed. (Printing conditions) Thermal head; KGT-217-12MPL20 (manufactured by Kyocera Corporation) Heating element average resistance value: 3195 (Ω) Printing density in main scanning direction; 300 dpi Printing density in sub-scanning direction; 300 dpi Applied power; 0.1 ( w / dot) 1 line cycle; 5 (msec.) Printing start temperature; 40 (° C)

Applied pulse; gradation printing: The number of divided pulses having a pulse length obtained by equally dividing one line cycle into 256 in one line cycle is from 0 to 25.
Using a multi-pulse type test printer capable of changing up to five pulses, the duty ratio of each divided pulse is fixed at 60%, and the number of pulses per line cycle is 0 in one step, 31 in two steps, and 3 depending on the gradation. In the step, 59 steps and 0 to 255 steps are sequentially incremented every 28 steps, so that 10 steps from 1 step to 10 steps are performed.
The gradation was controlled. Protective layer transfer: A multi-pulse type test printer capable of varying the number of divided pulses having a pulse length obtained by equally dividing one line cycle into 256 in one line cycle from 0 to 255 is used, and the duty of each divided pulse is used.
The ratio is fixed at 60% and the number of pulses per line cycle is 2
Ten pieces were fixed, solid printing was performed, and the protective layer was transferred to the entire printing screen.

(Protective layer transfer sheet) For the above protective layer transfer, the following protective layer transfer sheet was used. A 6 μm-thick polyethylene terephthalate film having a heat-resistant treatment on the back side was prepared with a coating liquid for forming a release layer having the following composition,
After coating and drying (110 ° C., 60 seconds) by a gravure coating method so that the dry coating amount becomes 0.5 g / m ² , a release layer is formed, and then a coating liquid for forming a protective layer having the following composition Is adjusted on the release layer by a gravure coating method so that the dry coating amount is 2.0 g / m ² , and then dried (1).
(10 ° C., 60 seconds) to form a protective layer to obtain a protective layer transfer sheet.

Release layer coating liquid Alkyl vinyl ether / maleic anhydride copolymer derivative 10 parts (VEMA; manufactured by Daicel Chemical Industries, Ltd.) Polyvinyl alcohol resin (manufactured by Kuraray Co., Ltd.) 2 parts Water / ethanol = 2/3 (Weight ratio) 100 parts

Protective layer coating liquid 15 parts polycarbonate resin (Polycarbonate resin which is a random copolymer containing 20 mol% of a structural unit represented by the following general formula 8 and 80 mol% of a structural unit represented by the following general formula 9) , Glass transition temperature 127.1 ° C.) UV absorber acrylic copolymer 5 parts (UVA635L; manufactured by BASF Japan Ltd.) UV absorber (Tinuvin 320; manufactured by CIBA-GEIGY) 10 parts (represented by the following chemical formula 10) .) Methyl ethyl ketone / toluene = 1/1 (weight ratio) 400 parts

[0057]

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[0058]

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[0059]

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(Print Density) The thermal transfer image-receiving sheets of Examples and Comparative Examples were subjected to thermal transfer recording on the thermal transfer sheet under the printing conditions of the gradation printing described above, and the optical reflection density of the obtained printed matter was obtained. Was measured, and the evaluation of print density was determined based on the following criteria. ；: The highest concentration was O. D. = 2.00 or more. ×: The highest concentration was O.D. D. = Less than 2.00.

(Releasability) The thermal transfer image-receiving sheets of Examples and Comparative Examples were subjected to thermal transfer recording on the thermal transfer sheet under the printing conditions of the gradation printing, and the thermal transfer image-receiving sheet was peeled off from the thermal transfer sheet. The property was determined based on the following criteria. ；: The thermal transfer image-receiving sheet and the thermal transfer sheet were easily peeled off, no abnormal transfer occurred, and the peelability was good. ×: fusion of the thermal transfer image-receiving sheet and the thermal transfer sheet,
The receiving layer is taken on the thermal transfer sheet side, or the dye layer binder is taken on the image receiving sheet side, abnormal transfer occurs,
The peelability is poor.

(Background Soil) The thermal transfer image-receiving sheets of Examples and Comparative Examples were subjected to thermal transfer recording on the thermal transfer sheet under the printing conditions of the gradation printing, and the non-printed area of the obtained printed matter was obtained. Was visually observed, and judged based on the following criteria. ；: No soiling is observed. X: Background dirt is observed.

(Bleeding) The thermal transfer image-receiving sheets of Examples and Comparative Examples were subjected to thermal transfer recording on the thermal transfer sheet under the printing conditions of gradation printing described above, and the obtained printed matter was heated at 60 ° C./200° C. The printed matter was stored in a dark place for a certain period of time, and the bleeding of each printed matter was visually observed, and judged based on the following criteria. ；: No bleeding was observed. Δ: No bleeding was observed with the naked eye, but bleeding was observed with a loupe. X: Bleeding is observed with the naked eye.

(Lightfastness) The thermal transfer image-receiving sheets of Examples and Comparative Examples were subjected to thermal transfer recording on the thermal transfer sheet under the printing conditions of the gradation printing and the protective layer transfer, and a print with a protective layer was obtained. Were subjected to a light resistance test using a xenon fade meter under the following conditions. Irradiation tester; Atlas Ci35 light source; Xenon lamp filter; Inside ... IR filter, Outside ... Soda lime glass Black panel temperature: 45 ° C Irradiation intensity: 1.2 (w / m ² ) ・ ・ ・ 420 nm Measurement energy at irradiation energy: 400 (KJ / m ² ) ··· 420 n
Integrated value in m

Optical densitometer (Macbeth RD, manufactured by Macbeth)
Using -918), the optical reflection density of the Cy component is measured with a red filter, and the change in the optical density before and after the irradiation is measured for the step where the optical reflection density before the irradiation is around 1.0. , And the residual ratio was calculated. Residual rate (%) = ([optical reflection density after irradiation] / [optical reflection density before irradiation]) × 100 Based on the residual rate of not less than 100, light resistance was determined according to the following criteria. ；: The residual ratio is 70% or more, and the light resistance is excellent. Δ: The residual ratio is 40% or more and less than 70%, and the light resistance is almost good. X: The residual ratio is less than 40%, and the light resistance is poor.

(Evaluation Results) The evaluation results are shown in Table 1 below.

[Table 1] * 1 and * 2 in the above table are evaluations of light resistance when the protective layer was not transferred.

The print density of Comparative Examples 1 to 4 such as a conventionally used medium is expressed by “applied power: 0.12 (w /
dot), the printing density (OD = about 2.10 to 2.30) achieved by the embodiment can be achieved, but the required power is increased by 20%. According to the present invention, a sufficient print density can be obtained with lower energy than conventional media (such as a comparative example). It can print at high speed. Formula; energy (mJ / dot) = power (W) × printing speed (msec / dot)

[0068]

According to the present invention, as described above,
In a thermal transfer image-receiving sheet having a receiving layer formed on at least one surface of a substrate sheet, the receiving layer is characterized by having at least a phenoxy resin and one or more plasticizers, so that the dye can be printed at high speed. It is possible to provide a thermal transfer image receiving sheet on which an image having high dyeing properties is formed, which has excellent peeling performance, and which is free from bleeding by a plasticizer. Further, after forming an image on the image-receiving surface of the thermal transfer image-receiving sheet, by transferring the protective layer to the image-forming surface, it is possible to provide a print having high light resistance and no bleeding.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshihiko Tamura 1-1-1, Ichigaya-Kaga-cho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (72) Inventor Masahiro Hanmura 1-1-1, Ichigaga-cho, Shinjuku-ku, Tokyo No. 1 Dai Nippon Printing Co., Ltd. F term (reference) 2H111 AA01 AA27 AA52 CA03 CA05 CA30 CA33 CA41 4J038 DD002 DF061 DL032 JA61 JC24 KA06 KA11 PA18 PB11 PC10

Claims (10)

[Claims] 1. A thermal transfer image-receiving sheet having a receiving layer formed on at least one surface of a substrate sheet, wherein the receiving layer contains at least a phenoxy resin and at least one plasticizer. Thermal transfer image receiving sheet. 2. The method according to claim 1, wherein the plasticizer comprises at least one selected from phthalic plasticizers, phosphate plasticizers, polycaprolactone, and polyester plasticizers. 2. The thermal transfer image-receiving sheet according to item 1. 3. The thermal transfer image-receiving sheet according to claim 2, wherein the phthalic acid-based plasticizer is diphenyl phthalate. 4. The thermal transfer image-receiving sheet according to claim 2, wherein the phosphate plasticizer is a non-halogen phosphate and / or a non-halogen condensed phosphate. 5. The thermal transfer image-receiving sheet according to claim 4, wherein the phosphate plasticizer is a non-halogen phosphate represented by the following general formula 1. Embedded image [Wherein R ₁ and R ₂ represent hydrogen, an alkyl group such as a methyl group, or a substituted alkyl group] 6. The thermal transfer image-receiving sheet according to claim 4, wherein the phosphate plasticizer is a non-halogen condensed phosphate represented by the following general formula 2. Embedded image [Wherein R ₁ and R ₂ represent hydrogen, an alkyl group such as a methyl group, or a substituted alkyl group] 7. A method according to claim 1, wherein said receiving layer contains at least one or more release agents.
The thermal transfer image-receiving sheet described in any one of the above. 8. The method according to claim 7, wherein the release agent is one or both of a modified silicone oil and / or a cured product thereof, and a fluorine type surfactant. Thermal transfer image receiving sheet. 9. A seal-like form in which a release sheet is releasably laminated via a pressure-sensitive adhesive layer on a surface of the substrate opposite to the surface on which the receiving layer is formed. The thermal transfer image-receiving sheet according to claim 1. 10. A printed matter in which a dye image is formed on a receiving layer of the thermal transfer image-receiving sheet according to any one of claims 1 to 9, wherein a protective layer is transferred onto at least a part of the dye image. Prints characterized by being made.