JPH07117367A - Image protecting transfer foil - Google Patents

Abstract

PURPOSE:To well protect an image by enhancing bonding strength and durability, in transfer foil wherein a release layer and an adhesive layer are successively laminated on a support, by adding a thermoplastic resin composed of a polystyrene/polyolefin block copolymer to the adhesive layer. CONSTITUTION:A thermal transfer image recording material is obtained by forming an image receiving layer 6 consisting of a molten image 9 and a sublimable image 10 on the surface of a support 7 for an ID card and forming a writing layer 8 on the rear surface thereof. A transfer foil 5 is obtained by successively laminating a release layer 2 and an adhesive layer 3 on the single surface of the support 1. The recording material 11 and the transfer foil 5 are bonded to be heated and pressed to bond the adhesive layer 3 and the image receiving layer 6 and the support 1 is peeled to form a protective layer 4 by the release layer 2 and the adhesive layer 3. Thereafter, an ultraviolet curable resin is applied and cured to form an ultraviolet cured resin layer 12. In this case, a thermoplastic resin composed of a polystyrene/polyolefin block copolymer is added to the adhesive layer 3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer foil for image protection, which has high adhesive strength and excellent durability. For more details,
In particular, the present invention relates to a transfer foil for image protection, which is suitable for protecting a sublimation and / or fusion heat transfer image without impairing the image quality.

[0002]

2. Description of the Related Art In recent years, licenses such as automobile licenses and various ID cards represented by identification cards, photo membership cards, authentication identification cards, photo business cards and the like have become popular. A face image is often formed on the surface of these ID cards for identification purposes. Since this face image has gradation, it is also called a gradation information containing image. Note that the gradation information-containing image is not limited to a face image, and is referred to as a gradation information-containing image as long as it contains an image having gradation. Further, in these ID cards, matters relating to the ID card holder and other necessary information are formed by characters, figures, symbols and the like. These characters, figures, symbols, etc. usually have no gradation and are formed in one color. Therefore, these images of characters, figures, symbols, etc. are referred to as character information containing images. Therefore, an image receiving layer is provided on a support, and a gradation information containing image is formed on this image receiving layer by a sublimation type thermal transfer recording method, and a character information containing image in which necessary information is described, for example, a heat melting type thermal transfer recording method Then, using a transfer foil having a protective layer composed of a release layer, an intermediate layer, an adhesive layer, etc. on the support on the surface of the image, the protective layer is heated and laminated under pressure. There has been proposed an image protecting method in which a protective layer is provided over the entire surface of the image receiving layer, and an ultraviolet curable resin is further applied and cured on the protective layer to provide an ultraviolet curable protective layer. However, the protective layer of the transfer foil that has been conventionally used is EV
A, styrene resin, acrylic resin, etc. have been used, but not only strong adhesion is not obtained, but also the bending resistance is not sufficient, and the thermal transfer recording material inside can be replaced, forgery or alteration There was a possibility of. Further, the fused image may be crushed by heating or pressing the transfer foil, or the sublimation image may be bleeding due to long-term storage. Furthermore, depending on the transfer conditions of the transfer foil, so-called burrs are often generated in which the protective layer is transferred even where the protective layer should not be transferred.

[0003]

The present invention has been made based on the above circumstances. That is, the object of the present invention is to prevent the collapse of the fused image by imparting an appropriate elasticity,
Further, the present invention provides a transfer foil for image protection which can prevent bleeding of a sublimated image due to long-term storage and further has a strong adhesive force. A second object is to provide a transfer foil for image protection which prevents cohesive failure of the entire protective layer and further improves bending resistance.
The third purpose is to prevent the formation of burrs. A fourth object is to provide a transfer foil for image protection, which has a stronger adhesive force while adequately permeating the ultraviolet curable resin into the release layer to sufficiently cure the ultraviolet curable resin.

[0004]

The above object of the present invention is to provide a transfer foil in which a release layer and an adhesive layer are provided in this order on a support, and a thermoplastic resin comprising a block polymer of polystyrene and polyolefin is contained in the adhesive layer. And a transfer foil for image protection.

More preferably, a tackifier is further contained in the adhesive layer. It is also preferable that the release layer of the transfer foil contains a polyvinyl acetal resin and / or a cellulosic resin, and it is also preferable to provide an intermediate layer between the release layer and the adhesive layer of the transfer foil.

In another embodiment, a transfer foil in which a release layer, an intermediate layer and an adhesive layer are provided on a support in this order is characterized in that the intermediate layer contains a thermoplastic resin composed of a block polymer of polystyrene and polyolefin. The above object of the present invention is achieved by the image protection transfer foil.
More preferably, the release layer of the transfer foil contains a polyvinyl acetal resin and / or a cellulosic resin.

A further object of the present invention is to apply a UV curable resin onto the transfer foil after transfer and cure the transfer foil to be used. In the transfer foil, the layer in contact with the UV curable resin has a solubility parameter and an SP value of 8 to 10. It can also be achieved by a transfer foil for image protection, which is characterized by containing 10% or more of a resin in the range of 12.

The present invention will be described in detail below.

The thermoplastic resin composed of a block polymer of polystyrene and polyolefin used in the present invention means a thermoplastic resin composed of a block of styrene and a linear or branched saturated alkyl having 10 or less carbon atoms (hereinafter referred to as thermoplastic resin S1. (Also called). In particular, styrene-butadiene-styrene (SB) which is a block polymer having a polystyrene phase and a hydrogenated phase of polyolefin.
S), styrene-isoprene-styrene (SIS), styrene-ethylene / butylene-styrene (SEBS),
Styrene-ethylene / propylene-styrene (SEP
S), styrene-ethylene / propylene (SEP) block polymers, and the like.

Specifically, they are Califlex TR / Clayton D and G series manufactured by Shell Chemical Co., Asahi Kasei Corporation, Tuftec H and M series, Kuraray manufactured and Septon series.

Next, an example of the present invention will be described with reference to the drawings.

FIG. 1 conceptually shows an ID card which is an example of a mode using the transfer foil for image protection of the present invention. The mode according to the present invention is not limited to the mode shown in FIG. FIG. 2 conceptually shows an example of a preferred embodiment of the transfer foil for image protection of the present invention.
The transfer foil for image protection of the present invention is not limited to the embodiment shown in FIG.

As shown in FIG. 1, a thermal transfer image recording body 11 of the present invention comprises an ID card support 7 and a sublimation dye formed on the surface of the ID card support 7 and by a sublimation type thermal transfer system. The image receiving layer 6 having the gradation information containing image 10 formed by the above and the character information containing image 9 formed by the heat fusion type transfer method or the sublimation type thermal transfer method, and the image receiving layer 6 of the ID card support 7 are Writing layer 8 formed on the opposite side
Composed of and. The transfer foil 5 is composed of the support 1, the peeling layer 2 and the adhesive layer 3. The thermal transfer image recording body 11 and the transfer foil 5 are adhered to each other, and by heating and pressurizing, the adhesive layer 3 and the image receiving layer 6 are closely adhered to each other, and then the support 1 of the transfer foil is peeled off and bonded to the peeling layer. The layer becomes the protective layer 4. Then, an ultraviolet curable resin is applied and irradiated with ultraviolet rays to be cured, whereby the ultraviolet curable protective layer 12 is formed, and the ID card is completed.

Image-Protecting Transfer Foil The image-protecting transfer foil of the present invention comprises an image-protecting transfer resin layer coated on one side of a support.

The transfer foil for image protection comprises at least an adhesive layer and a release layer, and it is preferable to provide an intermediate layer between the adhesive layer and the release layer. Further, the transfer foil for image protection may contain an ultraviolet absorber.

As the support for the transfer foil for image protection,
There is no particular limitation as long as it is a material having heat resistance and capable of laminating an image protection transfer foil, and various plastics such as vinyl chloride resin sheet, ABS resin sheet, polyethylene terephthalate base film, polyethylene naphthalate base film, etc. Examples thereof include a film or sheet and a film or sheet formed of various metals. The thickness of the film is usually 3 to 50
μm It is preferably 6 to 30 μm. The image-protecting transfer foil has at least an area necessary to cover the gradation image. The size of the area is appropriately determined according to the size of the transfer member.

The release layer has a solubility parameter, SP
It contains 10% by weight or more of a resin having a value in the range of 8-12.
By containing a resin having an SP value in this range, the UV-curable resin-containing coating liquid applied on the release layer can appropriately permeate, and the adhesion of the UV-curable protective layer after curing can be further strengthened. The curing does not become insufficient.
If the SP value is less than 8, the ultraviolet curable resin-containing coating liquid will not sufficiently penetrate into the release layer, and the compatibility will be insufficient, resulting in poor adhesiveness of the ultraviolet curable protective layer. If the SP value is greater than 12, it will penetrate too much and the ultraviolet-curing protective layer will be insufficiently cured, and its hardness will be insufficient, resulting in poor durability. The SP value here is the value described in "Kunio Goto, Polymer Blend, Nikkan Kogyo Shimbun" and "Saburo Akiyama, Takashi Inoue, Toshio Nishi, Polymer Blend-Compatibility and Interface-, CMC Corporation". Was referred to.

Further, it is preferable that the release layer contains a polyvinyl acetal resin and / or an ethyl cellulose resin. The content of these polyvinyl acetal resin and / or ethyl cellulose resin is usually 5 to 100%, preferably 20 to 100%. The thickness of the release layer is usually 0.2 to 3.0 μm, preferably 0.3 to 2.0 μm.

In the image-protecting transfer foil of the present invention, the resin layer to be transferred has a cushioning property to enhance the adhesiveness with the image-receiving layer at the time of transfer, the adhesiveness between the adhesive layer and the peeling layer, and the like. It is preferable to provide an intermediate layer for the above purpose. The film thickness is usually 0.2 to 3.0 μm, preferably 0.3 to 2.0 μm. The intermediate layer of the transfer foil for image protection of the present invention preferably contains a thermoplastic resin composed of a block polymer of polystyrene and polyolefin. More preferably, it contains the above-mentioned thermoplastic resin S1.

It is essential that the adhesive layer of the image-protecting transfer foil of the present invention contains a thermoplastic resin composed of a block polymer of polystyrene and polyolefin. In addition to this, for example, a composition constituting a hot-melt adhesive agent. (Including, for example, ethylene-vinyl chloride copolymer, wax, plasticizer, tackifier, antioxidant, filler, etc.), composition constituting polyvinyl acetate emulsion adhesive,
A composition that constitutes a chloroprene-based adhesive, a composition that constitutes an epoxy resin-based adhesive, and the like, if necessary, are formed by laminating the composition on an image-protecting transfer foil by a conventionally known coating method or the like. It Among these, it is preferable to contain a tackifier.

The addition amount of the thermoplastic resin S1 contained in the adhesive layer of the transfer foil for image protection of the present invention is usually 5% or more and 98% or less, preferably 10% or more and 95% or less. The addition amount of the tackifier added to the adhesive layer of the image-protecting transfer foil of the present invention is usually 1 to 80%, preferably 5 to 60%. All the above-mentioned addition amounts are weight%. Thickness is usually 0.2
˜4.0 μm, preferably 0.3 to 3.0 μm.

When the image-receiving layer of the heat-sensitive transfer image-receiving sheet contains a metal ion compound and the heat-sensitive transfer ink sheet contains a dye capable of chelating, when an image is formed by thermal transfer, the concentration of the heat-diffusible dye is higher on the surface of the image-receiving layer. It is often high, in which case there is also a heat diffusible dye that remains unchelated on the surface. In such a case, the formed dye image has insufficient image storability (for example, light resistance) and fixability. In many cases, the heat diffusible dye capable of forming a chelate has different color tones in the unchelated state and the chelated state, and when both are present in the formed image, color turbidity occurs and sufficient color reproducibility cannot be obtained.

Then, the image-protecting layer containing the compound containing a metal ion is thermally transferred onto the dye image formed on the image-receiving layer by using the transfer sheet for image-protecting layer described below, and the metal ion is added to the unchelated dye remaining on the image surface. It is also possible to supply the compound to be contained and use the heat at the time of transfer to advance the chelation reaction. This not only forms a completely chelated, stable, heat-diffusible dye image without color turbidity, but also improves the fixability and prevents bleeding and bleed-out of the dye due to light and heat. The light resistance storage stability and heat resistance storage stability are improved.

Transfer of the image-protecting transfer foil to the image-receiving layer by the transfer sheet is usually carried out by using a means such as a thermal head, a heat roller, a hot stamping machine or the like which can apply pressure while heating.

Method for producing heat-sensitive transfer image recording material (1) Image-receiving sheet for heat-sensitive transfer recording The image-receiving sheet for heat-sensitive transfer recording basically comprises a support and an image-receiving layer laminated on the support.

-Support-As the support, various papers such as paper, coated paper, and synthetic paper (polypropylene, polystyrene, or a composite material obtained by laminating them with paper), vinyl chloride resin sheet, ABS, etc. Various plastic films or sheets such as resin sheets, polyethylene terephthalate base film, polyethylene naphthalate base film,
Examples thereof include films or sheets formed of various metals, films or sheets formed of various ceramics, and the like. A white pigment such as titanium white, magnesium carbonate, zinc oxide, barium sulfate, silica, talc, clay or calcium carbonate is added to the support in order to enhance the sharpness of the image formed in the subsequent step. Is preferred. The thickness of the support is usually 20 ~
The thickness is 1000 μm, preferably 20 to 800 μm, and is appropriately selected from such a range.

-Image-Receiving Layer-The image-receiving layer contains the binder for the image-receiving layer as a basic component, and preferably a metal ion-containing compound and various additives can be added thereto, their kind, blending amount, and thickness of the image-receiving layer. Etc. may be appropriately selected according to the purpose.

1. Binder for image-receiving layer Generally, the binder for the image-receiving layer is, for example, polyvinyl chloride resin, a copolymer resin of vinyl chloride and another monomer (eg, alkyl vinyl ether, allyl glycidyl ether, vinyl propionate, etc.), polyvinylidene chloride-based resin. Resin, polyester resin, acrylic acid ester, methacrylic acid ester, epoxy resin, phenoxy resin,
Polyvinyl butyral, polyvinylpyrrolidone, polycarbonate, polysulfone, polyarylate, polyparabanic acid, cellulose triacetate, styrene acrylate resin, vinyl toluene acrylate resin, polyurethane resin, polyamide resin, urea resin, polycaprolactone resin, styrene-maleic anhydride resin, poly Acrylonitrile resin etc. can be mentioned. The binder for the image receiving layer used in the present invention is preferably a vinyl chloride resin, an epoxy resin, a phenoxy resin, or the like.

These resins may be used alone or in combination of two or more. The various resins described above may be newly synthesized and used, or commercially available products may be used.

In forming the image-receiving layer, the above-mentioned various resins utilize their reaction active points (if there are no reaction active points, they are imparted to the resin), and radiation, heat, moisture, a catalyst are used. You may bridge | crosslink or harden | cure by etc. In that case, a radiation-active monomer such as epoxy or acrylic, or a crosslinking agent such as isocyanate can be used.

If there are practical requirements for the image formed by the present invention (for example, the ID card to be issued is required to have a predetermined heat resistance), the binder is required to satisfy such requirements. It is necessary to consider the type or combination of. Taking heat resistance of an image as an example, if heat resistance of 60 ° C. or higher is required, it is preferable to use a binder having Tg of 60 ° C. or higher in consideration of bleeding of sublimable dye.

The choice of binder type is arbitrary,
Vinyl chloride resins are preferable in terms of image storability. Examples of the vinyl chloride resin include polyvinyl chloride resin and vinyl chloride copolymer. Examples of the vinyl chloride copolymer may include a copolymer of vinyl chloride containing vinyl chloride as a monomer unit in a proportion of 50 mol% or more and another comonomer.

Examples of the other comonomers include vinyl acetate, vinyl propylene oxide, vinyl esters of fatty acids such as vinyl acetate and vinyl beef tallow, acrylic acid, methacrylic acid, methyl acrylate, ethyl methacrylate,
Acrylic acid or methacrylic acid and its alkyl esters such as butyl acrylate, 2-hydroxyethyl methacrylate, 2-ethylhexyl acrylate, maleic acid, diethyl maleate, dibutyl maleate,
Examples thereof include maleic acid such as dioctyl maleate and its alkyl alkyl esters, alkyl vinyl ethers such as methyl vinyl ether, 2-ethylhexyl vinyl ether, lauryl vinyl ether, palmityl vinyl ether and stearyl vinyl ether. Further, as the comonomer, ethylene, propylene, acrylonitrile, methacrylonitrile, styrene, chlorostyrene, itaconic acid and its alkyl esters, crotonic acid and its alkyl esters, dichloroethylene, other halogenated olefins such as trifluoroethylene, cyclopentene. Examples thereof include cycloolefins, aconitic acid esters, vinyl benzoate, benzoyl vinyl ether, and the like.

The vinyl chloride copolymer may be a block copolymer, a graft copolymer, an alternating copolymer or a random copolymer. In some cases, it may be a copolymer with a compound having a peeling function such as a silicon compound.

In addition to the vinyl chloride resin, a polyester resin can be preferably used as an image receiving layer for sublimation type thermal transfer. Examples of polyester resins that can be used in the present invention include compounds described in JP-A-58-188695 and JP-A-62-244696. Further, a polycarbonate resin can also be used as a binder, for example, JP-A-62-169.
Various compounds described in 694 can be used.

Next, the heat-resistant resin has good heat resistance, is not a resin having an extremely low softening point or glass transition point (Tg), but is appropriately compatible with the vinyl chloride resin and is substantially colorless. As long as it is, various known heat resistant resins can be used. The term "heat resistance" as used herein means that the resin itself does not cause coloration such as yellowing when it is stored under heat, and the physical strength is not extremely deteriorated.

Examples of the heat-resistant resin satisfying the above conditions include phenol resin, melamine resin, urea resin and ketone resin, and among them, urea aldehyde resin and ketone resin are particularly preferable.

The urea aldehyde resin is obtained by condensation of urea and aldehydes (mainly formaldehyde), and the ketone resin is obtained by condensation reaction of ketone and formaldehyde. Various resins are known depending on the raw material ketone, and any of them can be used in the present invention.

Examples of the above-mentioned raw material ketones include methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, and methylcyclohexanone.

Examples of urea aldehyde resins that can be easily obtained include Laropearl A81 and Lalopearl A101 (manufactured by BASF), and ketone resins include Laropearl K80 (manufactured by BASF).

The binder selected from the above various resins in the present invention is for the purpose of improving physical properties such as increase of film strength of the image receiving layer, prevention of fusion of the sublimable dye during transfer, and prevention of bleeding of the sublimable dye. Curing with an isocyanate curing agent, curing with an ultraviolet curable resin or the like may be performed. Further, as a method for improving the physical properties of the image receiving layer, an appropriate additive may be added in addition to the curing agent.

2. Metal Ion-Containing Compound As the metal ion constituting the metal ion-containing compound, there may be mentioned divalent and polyvalent metals belonging to Groups I to VIII of the Periodic Table, among which Al, Co, Cr,
Cu, Fe, Mg, Mn, Mo, Ni, Sn, Ti and Zn are preferable, and Ni, Cu, Co, Cr and Zn are particularly preferable.

The compound containing these metal ions is preferably an inorganic or organic salt of the metal and a complex of the metal. Specific examples are Ni ²⁺ , Cu ²⁺ and Co.
A complex containing ²⁺ , Cr ²⁺ and Zn ²⁺ and represented by the following general formula is preferably used.

[M (Q ₁ ) _k (Q ₂ ) _m (Q ₃ ) _n ] ^{p +} p (L ⁻ ) where M represents a metal ion, and Q ₁ , Q ₂ and Q ₃ are each M. It represents a coordination compound capable of coordinatively binding with the metal ion, and these coordination compounds can be selected, for example, from the coordination compounds described in “Chelate Chemistry (5) (Nankodo)”. Particularly preferably, a coordination compound having at least one amino group that forms a coordinate bond with a metal can be mentioned, and more specifically, ethylenediamine and its derivatives, glycinamide and its derivatives, picolinamide and its derivatives can be mentioned. To be

L is a counter anion capable of forming a complex,
Examples thereof include inorganic compound anions such as Cr, SO ₄ , and ClO ₄ , and organic compound anions such as benzenesulfonic acid derivatives and alkylsulfonic acid derivatives. Particularly preferred are tetraphenylboron anion and its derivatives, and alkylbenzenesulfonic acid anion and its derivatives. It is a derivative.

K represents an integer of 1, 2 or 3, m represents 1, 2 or 0, and n represents 1 or 0. These are those in which the complex represented by the above general formula is tetradentate. , Hexadentate, or the number of ligands in Q ₁ , Q ₂ , Q ₃ . p represents 1, 2 or 3. Examples of this type of metal ion-containing compound include those exemplified in US Pat. No. 4,987,049.

The addition amount of the metal ion-containing compound, relative to the image receiving layer is preferably ^{0.5~20g / m 2, 1~15g / m} 2 is more preferable.

3. Additives A release agent, an antioxidant, a UV absorber, a light stabilizer, a filler (inorganic fine particles, organic resin particles), and a pigment may be added to the image receiving layer. Further, a plasticizer, a hot solvent or the like may be added as a sensitizer.

The release agent is for improving the releasability between the thermal transfer recording ink sheet and the thermal transfer recording image receiving sheet.

Examples of such a release agent include silicone oils (including those referred to as silicone resins); solid waxes such as polyethylene wax, amide wax, Teflon powder; fluorine-based and phosphoric ester-based surface active agents. Examples of the agent include silicone oil. This silicone oil is classified into a type that is simply added (simple addition type) and a type that is cured or reacted (curing reaction type).

In the case of the simple addition type, it is preferable to use a modified silicone oil (for example, polyester modified silicone resin, urethane modified silicone resin, acrylic modified silicone resin, etc.) in order to improve the compatibility with the binder.

The addition amount of these simple addition type silicone oils cannot be uniformly determined because it may vary depending on the type, but generally speaking, generally speaking, the binder for the image receiving layer is usually used. 0.1 to 50% by weight
And preferably 0.5 to 20% by weight.

As the curing reaction type silicone oil,
Examples thereof include a reaction curable type (for example, one obtained by reacting and curing an amino-modified silicone oil and an epoxy-modified silicone oil), a photocurable type, a catalyst curable type, and the like.

The amount of these curable silicone oils added is preferably 0.5 to 30% by weight of the binder for the image receiving layer.

A release agent layer may be provided on a part of the surface of the image-receiving layer by dissolving or dispersing the release agent in an appropriate solvent and applying it, followed by drying.

Next, as the above-mentioned antioxidant, JP-A-59-1 is used.
82785, 60-130735, JP-A-1-127387, and other antioxidants, and compounds known to improve the image durability of photographs and other image recording materials can be mentioned.

As the UV absorber and the light stabilizer,
JP-A-59-158287, 63-74686, 63-145089,
59-196292, 62-229594, 63-122596, 61-28
Examples thereof include compounds described in JP-A No. 3595 and JP-A No. 1-204788, and compounds known to improve image durability in photographs and other image recording materials.

Examples of the filler include inorganic fine particles and organic resin particles. Examples of the inorganic fine particles include silica gel, calcium carbonate, titanium oxide, acid clay, activated clay, alumina and the like, and organic fine particles include resin particles such as fluororesin particles, guanamine resin particles, acrylic resin particles, and silicon resin particles. Can be mentioned. These inorganic / organic resin particles are different depending on the specific gravity, but it is preferably added in an amount of 0 to 30% by weight.

Typical examples of the pigment include titanium white, calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, activated clay and acid clay.

As the plasticizer, phthalic acid esters,
Trimellitic acid esters, adipic acid esters, other saturated or unsaturated carboxylic acid esters, citric acid esters, epoxidized soybean oil, epoxidized linseed oil, epoxy stearic acid epoxys, orthophosphoric acid esters, phosphorous acid Examples thereof include esters and glycol esters.

As the hot solvent (heat-melting substance), alcohols such as terpineol, menthol, 1,4-cyclohexanediol and phenol, amides such as acetamide and benzamide, esters such as coumarin and benzyl cinnamate, etc. , Ethers such as diphenyl ether and crown ether, ketones such as camphor and p-methylacetophenone, aldehydes such as vanillin and dimethoxybenzaldehyde, hydrocarbons such as norbornene and stilbene, higher fatty acids such as margaric acid, higher fatty acids such as eicosanol Alcohol, higher fatty acid ester such as cetyl palmitate, higher fatty acid amide such as stearic acid amide, monomolecular compound represented by higher amine such as behenylamine, carnauba wax, beeswax, paraffin wax, ester wax Waxes such as montan wax and amide wax, rosin derivatives such as ester gum, rosin maleic acid resin, rosin phenol resin, phenol resin, ketone resin, epoxy resin, diallyl phthalate resin, terpene resin, aliphatic hydrocarbon resin, cyclopentadiene Examples thereof include resins, polyolefin-based resins, polymer compounds represented by polyolefin oxides such as polyethylene glycol and polypropylene glycol, and the like.

In the present invention, the total amount of the additives is usually 0.1 to 30% by weight based on the binder for the image receiving layer.
Is the range.

-Other Layers-In the ID card of the preferred embodiment of the present invention, a writing layer is usually formed on the surface of the support for the ID card opposite to the surface on which the image receiving layer is formed. When the ID card of the present invention is used as an automobile license or the like, it is particularly preferable to provide a writing layer. By forming the writing layer, it is convenient because various information can be written on the ID card.

For the description of the writing layer, see JP-A-1-2051.
The description of the "writing layer" from page 14, upper right column, line 14 to page 4, lower right column, line 2 of Japanese Patent Publication No. 55 will be replaced, and the detailed description thereof will be omitted.

In order to prevent fusion between the image receiving layer and the ink layer of the thermal transfer recording ink sheet more effectively, a release agent (the above-mentioned silicone resin, modified silicone resin,
A release layer containing a silicone oil film or a cured product thereof, a polyolefin resin, a modified polyolefin resin, various waxes) may be further laminated. The thickness of this release layer is usually 0.03 to 2.0 μm.

A cushion layer or a barrier layer may be provided between the ID card support and the image receiving layer. When the cushion layer is provided, noise can be reduced and an image corresponding to image information can be transferred and recorded with good reproducibility. Examples of the material forming the cushion layer include urethane resin, acrylic resin, ethylene resin, butadiene rubber, and epoxy resin. The thickness of the cushion layer is usually 1 to 50 μm, preferably 3 to 30 μm.

When the barrier layer is provided, the sublimation dye can be prevented from diffusing into the ID card support, and the dye can be prevented from bleeding in the ID card support. Examples of the material forming the barrier layer include hydrophilic binders such as gelatin and casein, and polymers having a high Tg.

(2) Production of image-receiving sheet for heat-sensitive transfer recording For the image-receiving sheet for heat-sensitive transfer recording, the components for forming the image-receiving layer are dispersed or dissolved in a solvent to prepare a coating liquid for forming the image-receiving layer. It can be formed by a coating method in which the surface of the support is coated with the coating liquid for forming and drying, or a laminating method in which the mixture having the components for forming the image receiving layer is melt extruded and laminated on the surface of the support.

Among these various methods, the coating method is preferable.

As the solvent used in the above coating method, water, alcohols (eg ethanol, propanol), cellosolves (eg methyl cellosolve, ethyl cellosolve), aromatics (eg toluene, xylene, chlorobenzene), ketones ( For example, acetone, methyl ethyl ketone), ester solvents (eg ethyl acetate, butyl acetate, etc.), ethers (eg tetrahydrofuran, dioxane), chlorine solvents (eg chloroform, trichloroethylene) and the like can be mentioned.

For the coating, conventionally known gravure roll coating methods, extrusion coating methods, wire bar coating methods, roll coating methods and the like can be adopted.

(3) Thermal Transfer Recording Ink Sheet The thermal transfer recording ink sheet basically comprises an ink layer laminated on a support.

-Support-As the support, any material may be used as long as it has good dimensional stability and can withstand heat during recording by a thermal head, but thin paper such as condenser paper, glassine paper, polyethylene terephthalate, Polyethylene naphthalate, polyamide, polyimide, polycarbonate, polysulfone,
A heat resistant plastic film such as polyvinyl alcohol cellophane or polystyrene can be used.

The thickness of the support is preferably 2 to 10 μm.

The shape of the support is not particularly limited,
For example, a wide sheet or film, a narrow tape or a card, or any other shape.

-Ink Layer- The ink layer contains a heat diffusing dye and a binder as essential components.

1. Thermal Diffusible Dye The thermal diffusible dye used in the present invention is, for example, JP-A-59-7.
8893, 59-109349, Japanese Patent Application No. 2-213303, 2-21471
Nos. 9 and 2-203742, cyan image-forming dyes (hereinafter referred to as cyan dyes) capable of forming a bidentate chelate with at least the above-mentioned metal ion-containing compound, and magenta image-forming dyes. (Hereinafter referred to as magenta dye) and yellow image forming dye (hereinafter referred to as yellow dye).

Preferred are dyes represented by the following general formula.

X ¹ -N = N-X ² -G wherein X ¹ is an aromatic carbocycle in which at least one ring is composed of 5 to 7 atoms, or a heterocycle. Represents a group of atoms necessary for, and at least one of the adjacent positions of the carbon atoms bonded to the azo bond is a nitrogen atom or a carbon atom substituted with a chelating group. X ²
Represents an aromatic heterocycle or an aromatic carbocycle in which at least one ring is composed of 5 to 7 atoms. G represents a chelating group.

The heat diffusing dye contained in the ink layer may be any of a yellow dye, a magenta dye and a cyan dye as long as the image to be formed is a single color.

Depending on the color tone of the image to be formed, any two or more of the above-mentioned three kinds of dyes or other heat-diffusible dyes may be contained.

The amount of the heat diffusible dye used is usually 0.1 to ²⁰ g, preferably 0.2 to 5 g, per 1 m ^{2 of} the support.

2. Binder As a binder for the ink layer, a cellulose addition compound,
Cellulose resins such as cellulose ester and cellulose ether; polyvinyl alcohol, polyvinyl formal, polyvinyl acetoacetal, polyvinyl butyral, and other polyvinyl acetal resins, polyvinylpyrrolidone, polyvinyl acetate, polyacrylamide, styrene resins, poly (meth) acrylic acid. Examples include vinyl-based resins such as ester-based esters, poly (meth) acrylic acid, and (meth) acrylic acid copolymers, rubber-based resins, ionomer resins, olefin-based resins, polyester resins, and the like.

Among these resins, polyvinyl butyral, polyvinyl acetoacetal, and cellulosic resins, which are excellent in preservability, are preferable.

One of the various binders may be used alone, or two or more thereof may be used in combination.

The weight ratio of the binder to the heat-diffusible dye is preferably 1:10 to 10: 1, particularly preferably 2: 8 to 7: 3.

3. Other optional components Further, various additives can be appropriately added to the ink layer.

As its additives, silicone resin, silicone oil (reaction hardening type is also acceptable), silicone modified resin, fluororesin, surfactant, and peelable compound such as wax, fine metal powder, silica gel, metal oxide. Substances, carbon black, fillers such as resin fine powder, and curing agents that can react with binder components (for example, radiation-active compounds such as isocyanates, acrylics, epoxies)
And so on.

Further, as an additive, a heat-melting substance for promoting transfer, for example, a compound described in JP-A-59-106997, such as wax or higher fatty acid ester, can be mentioned.

-Other Layers- The thermal transfer recording ink sheet is not limited to a two-layer structure comprising a support and an ink layer, and other layers may be formed.

For example, an overcoat layer may be provided on the surface of the ink layer for the purpose of preventing fusion with the image-receiving sheet for thermal transfer recording and settling (blocking) of the heat diffusing dye.

Further, the support may have an undercoat layer for the purpose of improving the adhesiveness with the binder and preventing the dye from being transferred to the support or dyeing.

Further, the back surface of the support (the side opposite to the ink layer)
Includes the fusion and sticking of the head to the support,
An anti-sticking layer may be provided for the purpose of preventing wrinkles on the thermal transfer recording ink sheet.

The thickness of the above-mentioned overcoat layer, subbing layer and anti-sticking layer is usually 0.1 to 1 μm.

(4) Production of Thermal Transfer Recording Ink Sheet For the thermal transfer recording ink sheet, an ink layer forming coating liquid is prepared by dispersing or dissolving the various components forming the ink layer in a solvent. , Coating this on the surface of the support,
It can be produced by drying.

The binder may be used alone or in combination of two or more in a solvent or dispersed in a latex form.

Examples of the solvent include water, ethanol, tetrahydrofuran, methyl ethyl ketone, toluene, xylene, chloroform, dioxane, acetone, cyclohexane, and normal butyl acetate.

For the coating, a conventionally known surface sequential coating method using a gravure roll, an extrusion coating method, a wire bar coating method, a roll coating method and the like can be adopted.

The ink layer may be formed on the entire surface or a part of the surface of the support as a layer containing a monochromatic heat diffusing dye, or a yellow ink layer containing a yellow dye and a magenta dye. The magenta ink layer containing the cyan ink layer and the cyan ink layer containing the cyan dye may be repeatedly formed along the plane direction.

Further, in addition to the three ink layers arranged along the plane direction, a black ink layer containing a black image forming substance may be interposed.

With respect to the black ink layer, a clear image can be obtained by either the diffusion transfer type or the melt transfer type.

The ink sheet for thermal transfer recording may be provided with detection marks or the like for forming perforations or detecting the positions of areas having different hues, so that it can be conveniently used.

(5) Image Formation (Thermal Transfer Recording) -Formation of Image Containing Gradation Information-The ink layer of the thermal transfer recording ink sheet and the image receiving layer of the thermal transfer recording image receiving sheet are superposed on each other. Apply imagewise thermal energy to the interface with the layers.
Then, the sublimable dye in the ink layer is vaporized or sublimated by an amount corresponding to the applied thermal energy, and is transferred to the image receiving layer side and received, so that an image containing gradation information is formed on the image receiving layer.

As a heat source for giving the heat energy,
A thermal head is generally used, but in addition to this, a conventionally known one such as a laser beam, an infrared flash, or a heating pen can be used. As a method of applying thermal energy, even if it is performed from the sublimation type thermal transfer recording ink sheet side,
It may be carried out from the side of the ID card support or from both sides, but it is desirable to carry out from the sublimation type thermal transfer recording ink sheet side if the effective utilization of heat energy is prioritized.

When a thermal head is used as a heat source for applying heat energy, the applied heat energy can be changed continuously or in multiple steps by modulating the voltage or pulse width applied to the thermal head.

When laser light is used as a heat source for giving heat energy, the heat energy to be given can be changed by changing the light amount of the laser light or the irradiation area.

In this case, in order to easily absorb the laser light, a laser light absorbing material (for example, carbon black or a near infrared absorbing substance in the case of a semiconductor laser) may be present in the ink layer or in the vicinity of the ink layer. .

When laser light is used, the thermal transfer recording ink sheet and the thermal transfer recording image receiving sheet are preferably brought into close contact with each other.

If a dot generator with a built-in acousto-optical element is used, it is possible to give heat energy according to the size of the halftone dot.

When an infrared flash lamp is used as a heat source for providing heat energy, it is preferable to heat the layer through a colored layer such as black as in the case of using laser light.

Alternatively, the heating may be carried out through a pattern or a halftone dot pattern in which the gradation of the image such as black is continuously expressed, or it corresponds to the negative of the above-mentioned pattern and a colored layer of one surface such as black. You may heat by combining a negative pattern.

The thermal energy may be applied from the thermal transfer recording ink sheet side, the thermal transfer recording image receiving sheet side, or both sides, but the effective use of thermal energy is prioritized. If you let
It is desirable to carry out from the thermal transfer recording ink sheet side.

By the above thermal transfer recording, an image of one color can be recorded on the image receiving layer of the image receiving sheet for thermal transfer recording, but according to the following method, a color photographic tone color image composed of a combination of the respective colors can be obtained. You can also

For example, yellow, magenta, cyan, and, if necessary, black heat-sensitive transfer recording sheets are sequentially replaced, and heat transfer is performed in accordance with each color, thereby obtaining a color photographic tone color image formed by combining each color. You can also

The following method is also effective.

That is, instead of using the heat-sensitive transfer recording ink sheet of each color as described above, a heat-sensitive transfer recording ink sheet having an area formed by separately coating each color is used.

Then, the yellow color-separated image is first thermally transferred using the yellow area, and then the magenta color-separated image is thermally transferred using the magenta area, and the following steps are sequentially repeated to repeat yellow, magenta, and cyan. , And, if necessary, a method of thermally transferring a black color separation image in order.

This method also makes it possible to obtain a color image having a color photographic tone, but more conveniently, this method has the advantage that the above-mentioned heat-sensitive transfer recording sheet need not be replaced. There is.

-Formation of Character Information-Containing Image-The character information-containing image is formed by imaging a conventionally known heat-melting type thermal transfer recording ink sheet having a heat-melting ink layer on a support with a laser or a thermal head. It can be formed by heating wisely and melt-transferring the heat-meltable ink to the image-receiving layer.

(6) Image protective layer and formation thereof The image protective layer and the image protective layer are formed and formed by the above-mentioned method.

(7) UV Curing Protective Layer and Formation Thereof In the ID card of the present invention, a substantially transparent UV curing protective layer formed by curing a UV curable resin by irradiation of ultraviolet rays is formed by using a transfer foil. Formed directly on the surface of the formed protective layer. For example, it can be formed by using various methods by using a coating agent for UV curing protective layer described later.

As a method for increasing the adhesive strength at the interface of the UV-curing protective layer, for example, a similar polymer which is easily heat-sealed is used, a compound having a polar group so as to form an ionic bond is used, and the layer is formed. Pressure when forming,
This can be achieved by adjusting conditions such as temperature and time, and by providing a structure that reacts with the functional group of the binder resin of the image receiving layer to form a covalent bond during UV irradiation.

The UV curing protective layer can also contain the following fine particles, for example. It is preferable to contain the fine particles because it is effective against forgery and alteration as compared with the case where the fine particles are not contained, and the card can be easily distinguished from other cards.

The material of the fine particles is not particularly limited,
Usually, inorganic fine particles and organic fine particles can be used.
Examples of the inorganic fine particles include powders of titanium white, magnesium carbonate, zinc oxide, barium sulfate, silica, talc, clay, brass and aluminum, and foils. As the organic fine particles, those which are not dissolved in a UV curable resin monomer or the like are preferable.

Further, in the present invention, the UV curing protective layer may contain a colorant. Examples of this colorant include dyes, pigments, fluorescent dyes, and infrared absorbing dyes.

When a coloring agent is contained in the UV curing protective layer,
Since the UV curing protective layer has a characteristic that it has a unique color tone, it is unlikely to be altered or forged as compared with the case where no colorant is contained, and it is easy to distinguish it from other cards. Is preferred.

Examples of the colorant include pigments, dyes, infrared absorbers and the like which are generally known in the field of synthetic resins. The amount of the colorant added is not particularly limited as long as it does not hinder the visual recognition of the recorded information on the transferred image, and various amounts can be selected.

The UV-curable protective layer may further have a pattern of irregularities formed on its surface. It is preferable to form unevenness of a specific pattern on the surface, for example, a mark of a certain kind, a pattern such as a fine pattern or a ground pattern, or the like because it can be distinguished from a counterfeit product or a modified product.

To make the surface of the UV curing protective layer uneven,
For example, the unevenness can be formed by a method of coating the UV-curable protective layer with a plate having a specific pattern of gravure, or a method of embossing when the UV-curable resin is semi-cured.

The UV-curable protective layer-forming coating agent can be formed from a composition containing a UV-curable prepolymer and / or monomer and a polymerization initiator as main components.

The UV-curable prepolymer and monomer include a type in which polymerization is caused by radical polymerization (mainly an acrylate type) and a type in which polymerization is caused by cationic polymerization (mainly an epoxy type),
For the purposes of this invention, the use of epoxy type is preferred.

Here, epoxy type UV-curable prepolymers and monomers are described. Examples of epoxy-based prepolymers and monomers include prepolymers containing two or more epoxy groups in one molecule. Examples of such prepolymers include alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, and polyglycidyl ethers of aromatic polyols. Examples thereof include hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds and epoxidized polybutadienes. One of these prepolymers may be used alone, or two or more thereof may be mixed and used.

The content of the prepolymer having two or more epoxy groups in one molecule in the coating composition for forming a UV curing protective layer is preferably 70% by weight or more.

A cationic polymerization initiator is preferable as the polymerization initiator, and specific examples thereof include aromatic onium salts.

As the aromatic onium salt, V.
Salts of Group a elements such as phosphonium salts (eg, triphenyl phenacylphosphonium hexafluorophosphate), salts of Group VIa elements such as sulfonium salts (eg, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, hexa) Examples thereof include tris (4-thiomethoxyphenyl) fluorophosphate, sulfonium and triphenylsulfonium hexisafluoroantimonate), and salts of Group VIIa elements such as iodonium salts (eg diphenyliodonium chloride).

The use of such an aromatic onium salt as a cationic polymerization initiator in the polymerization of an epoxy compound is disclosed in US Pat. Nos. 4,058,401, 4,069,055 and 4,10.
It is described in detail in 1,513 and 4,161,478.

Preferred cationic polymerization initiators are V
Examples thereof include sulfonium salts of Group Ia elements. Among these, from the viewpoint of UV curability and storage stability of the UV curable composition, triarylsulfonium hexafluoroantimonate is preferable.

The UV curing protective layer coating agent further contains a surfactant such as oils (particularly silicone oil) and silicone-alkylene oxide copolymers (for example, L-5410 commercially available from Union Carbide Co.). Agents, silicone oil-containing aliphatic epoxides, FO-171 and FO-430 commercially available from 3M Company, fluorocarbon surfactants such as Megafac F-141 commercially available from Dainippon Ink and Chemicals, etc. May be.

In the coating agent for the UV curing protective layer,
Further, vinyl monomers such as styrene, paramethylstyrene, methacrylic acid ester, acrylic acid ester and the like, cellulosic, thermoplastic polyester, phenyl glycidyl ether, silicon-containing monoepoxide, monoepoxide such as butyl glycidyl ether, and the like of the present invention can be used. You may contain in the range which does not inhibit the effect.

The UV curing protective layer coating agent contains dyes, pigments, thickeners, plasticizers, stabilizers, leveling agents, coupling agents, tackifiers and silicone groups as inactive ingredients. Activator, wetting improver such as fluorocarbon group-containing surfactant, various other additives, and acetone, methyl ethyl ketone, and methyl chloride that hardly react with the cationic polymerization initiator for the purpose of improving fluidity during coating of the coating agent. May be contained in a small amount of solvent such as.

UV in UV curing means light in the ultraviolet region (ultraviolet rays), and also includes light rays containing ultraviolet rays. Therefore, examples of the ultraviolet irradiation include irradiation with sunlight, irradiation with a low-pressure mercury lamp, irradiation with a high-pressure mercury lamp, irradiation with an ultra-high-pressure mercury lamp, irradiation with carbon arc, etc., irradiation with a metal halide lamp, and irradiation with a xenon lamp. In addition, a high energy beam such as an electron beam may be used depending on the case.

In curing, heating the coating film of the coating agent for the UV curing protective layer before or after irradiation with ultraviolet rays can shorten the curing time.

[0143]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following, "part" means "part by weight".

Example 1-Sublimation Thermal Transfer Ink Sheet-A coating liquid for forming an ink layer having the following composition on the surface of a polyethylene terephthalate film [Dia foil Hoechst K203E-6F] having a thickness of 6 μm as a support, which was subjected to easy adhesion treatment. By wire bar coating method, the thickness after drying is 1μm
Was applied and dried.

Further, a coating solution for forming a heat-resistant protective layer having the following composition is applied on the back side by a wire bar coating method so that the thickness after drying becomes 0.5 μm, and dried to obtain a thermal transfer recording ink sheet. It was

Coating liquid for forming Y ink layer; Y dye (Compound 1) 3.5 parts Polyvinyl acetoacetal (DENKI CHEMICAL INDUSTRIES, LTD., KY-24) 4.95 parts Styrene-acrylic resin (Toagosei Co., Ltd., Reseda GP) -200) 1.5 parts Silicone resin (Dainichi Seika Co., Ltd., SP-2105) 0.05 part (as solid content) Methyl ethyl ketone 60 parts Toluene 30 parts Coating solution for forming heat resistant protective layer; Silicone resin (Dainichi Seika Co., Ltd.) , SP-712) 5 parts (in terms of solid content) Methyl ethyl ketone 90 parts Cyclohexanone 5 parts M and C ink sheets were prepared in the same manner except that the dyes were changed to the following compounds 2 and 3, respectively.

-Fusion-type thermal transfer ink sheet-A polyethylene terephthalate base (Lumirror 6CF531 manufactured by Toray Industries, Inc.) on which the heat-resistant protective layer is not coated is coated with a release layer having the following formulation and a thermal transfer ink layer of 0.4 μm and 1.2, respectively. A fusion-type thermal transfer ink sheet was obtained by applying a gravure coating so as to have a thickness of μm and drying.

Coating liquid for hot-melt ink layer; (Release layer) Ethylene-vinyl acetate copolymer (Evaflex EV210, manufactured by Mitsui DuPont Polychemical Co., Ltd.) 0.3 part Carnauba wax 9.7 parts Solvent (methyl ethyl ketone: methyl isobutyl) Ketone = 1: 1) 90.0 parts (Color material layer) Ethylene-vinyl acetate copolymer (Mitsui DuPont Polychemical Co., Ltd., EVAflex EV40Y) 1 part Carbon black 8 parts Calcium carbonate (Okutama Industry Co., Ltd., Tamapearl TP) -123) 4 parts Phenolic resin (manufactured by Arakawa Chemical Industry Co., Ltd., Tamanor 526) 7 parts Methyl ethyl ketone 80 parts-Thermal transfer image recording material-Supporting material: Polyethylene terephthalate resin sheet of 350 μm thickness (ICI Melinex 226) White polypropylene resin with a thickness of 50 μm on both sides (Narita Corporation) Ren FL25
-HA) was heat-welded to obtain a composite resin sheet having a thickness of 450 μm. 25W on one side of the obtained composite resin sheet
Corona discharge treatment was performed at / (m ² · min).

Writing layer: A coating layer-forming coating solution having the following composition was applied to the surface of the support opposite to the corona discharge-treated surface and dried to form a writing layer having a thickness of 40 μm.

Colloidal silica 2.5 parts Gelatin 7 parts Hardener (Compound 4) 0.2 parts Water 90 parts Image receiving layer; The following adhesive layer forming coating liquid is applied to the corona discharge treated surface of the above support to give a thickness of 0.8. A μm adhesive layer is formed, and the following coating solution for forming the underlayer is successively applied onto this adhesive layer by a wire bar coating method and dried to form a 3 μm thick underlayer. The forming coating liquid was applied in the same manner to form an upper layer having a thickness of 0.5 μm. Further, by cutting this sheet, a card size image receptor of 54.0 × 85.5 mm in length and width was manufactured.

Coating liquid for forming an adhesive layer: polyvinyl acetoacetal (manufactured by Sekisui Chemical Co., Ltd., S-REC BL-1) 9 parts Isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HX) 1 part Methyl ethyl ketone 80 parts Acetic acid n-Butyl 10 parts Coating liquid for forming lower layer; polyvinyl butyral resin (BX-1 manufactured by Sekisui Chemical Co., Ltd.) 6 parts Metal ion-containing compound (Compound 5) 4 parts Methyl ethyl ketone 80 parts n-Butyl acetate 10 parts Upper layer Coating liquid for forming; urethane-modified ethylene-acrylic acid ester copolymer (25% solid content) (manufactured by Toho Chemical Industry Co., Ltd., Hitec S6254) 8 parts polyethylene resin emulsion (35% solid content) (Toho Chemical Industry ( Ltd., Hi-Tech E1000) 23 parts Water 69 parts

[0152]

[Chemical 1]

-Transfer Foil- Polyethylene terephthalate (S-25) manufactured by DIAFOIL Hoechst Co., Ltd. has a release layer, an intermediate layer and an adhesive layer having the following formulations, each having a thickness of 1.0 μm, 1.0 μm and 2.0 μm. In this way, the wire bar coating was applied and dried to obtain a transparent protective layer transfer sheet.

(Release layer) Film thickness 1 μm A: Ethyl cellulose (SP value: 10.3) (Shin-Etsu Chemical Co., Ltd., 10 cps) 5 parts Polyvinyl acetoacetal (SP value: 9.4) (Sekisui Chemical Co., Ltd., KS-1) ) 5 parts Methyl ethyl ketone 40 parts Toluene 50 parts B: Acrylic resin (SP value: 9.3) (Mitsubishi Rayon Co., Ltd., Dinal BR-77) 5 parts Polyvinyl acetoacetal (SP value: 9.4) (Sekisui Chemical Co., Ltd.) , KS-1) 5 parts Methyl ethyl ketone 40 parts Toluene 50 parts C: Acrylic resin (SP value: 9.3) (Mitsubishi Rayon Co., Ltd., Dianal BR-87) 9 parts Silicone resin fine particles (Toshiba Silicone Co., Ltd., Tospearl 120) 1 part Methyl ethyl ketone 40 parts Toluene 50 parts D: Polyamide resin (SP value: 12.7 to 13.6) (SANWA CHEMICAL INDUSTRIES, LTD., Sunmide) 50) 10 parts Toluene 60 parts IPA 30 parts E: Polyethylene resin emulsion (SP value: 7.9) (35% solid content) (Toho Chemical Industry Co., Ltd., Hitec E1000) 100 parts (intermediate layer) Film thickness 1 μm i: Styrene resin (Kuraray Co., Septon 2006) 5 parts Polyvinyl butyral resin (Sekisui Chemical Co., Ltd., BL-S) 5 parts Toluene 90 parts b: Styrene resin (Asahi Kasei Co., Tuftec M-1953) 5 Part Polyvinyl butyral resin (Sekisui Chemical Co., Ltd., BL-S) 5 parts Toluene 90 parts C: Polyvinyl butyral resin (Sekisui Chemical Co., Ltd., BL-S) 10 parts Toluene 90 parts (adhesive layer) Film thickness 2 μm (1 ): Styrene-based resin (Shell Chemical Co., Ltd., Clayton G-1726) 9 parts Hydrogenated petroleum resin (Tonex Co., Escoletz 5320HC) 1 part Torr 90 parts (2): Styrene-based resin (Asahi Kasei Co., Ltd., Tuftec M-1953) 6 parts Alicyclic saturated hydrocarbon resin (Arakawa Chemical Co., Ltd., Alcon P100) 3.5 parts Calcium carbonate (Okutama Industry Co., Ltd.) , Tamapearl TP-123) 0.5 part Toluene 90 part (3): Styrene resin (Asahi Kasei Co., Ltd., Tuftec M-1953) 5.5 parts Alkylphenol resin (Arakawa Chemical Co., Ltd., Tamanor 526) 3.5 parts Silicon resin particles (Toshiba Silicone Co., Ltd., Tospar 120) 1 part Toluene 90 parts (4): Styrene resin (Kuraray Co., Septon 2006) 6.5 parts Alkylphenol resin (Arakawa Chemical Co., Ltd., Tamanor 526) 2.5 parts Silicone resin particles (Toshiba Silicone Co., Ltd., Tospar 120) 1 part Toluene 90 parts (5) Styrene resin (Asahi Kasei Co., Ltd., Tuftec M-1953) 4.5 parts Alkylphenol resin (Arakawa Chemical Co., Ltd., Tamanor 526) 2.5 parts Metal ion-containing compound (Compound 5) 2 parts Silicone resin particles (Toshiba Silicone Co., Ltd. Tospar 120) 1 part Toluene 90 parts (6): Ethylene vinyl acetate-maleic anhydride modified resin (Mitsui DuPont Polychemical Co., Ltd., VR-103) 10 parts Toluene 90 parts (7): Styrene resin (Idemitsu Chemical Co., Ltd., GP-US300) 10 parts Toluene 90 parts With respect to the release layer, the intermediate layer, and the adhesive layer having the above-mentioned compositions, each Example and Comparative Example transfer foil composed of the combinations shown in Table 1 were prepared.

-Ultraviolet Curing Protective Layer- An ultraviolet curable resin-containing coating liquid having the following composition was prepared.

Side chain type bisphenol A glycidyl ether 15 parts 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carbosylate 70 parts trimethylolpropane triglycidyl ether 15 parts aromatic sulfonium salt-based UV initiator 6 parts The sublimation type thermal transfer recording ink sheet and the image receiving body are superposed so that the former ink layer surface and the latter image receiving layer surface are in contact with each other, and the thermal head is used to output 0.06 from the support side of the thermal transfer recording ink sheet. W / dot,
A human image with gradation was recorded by heating under the conditions of the thermal head cycle = 10 msec, energization time = 0 to 6 msec, and dot density of 16 dots / mm.

Next, the melting type thermal recording ink sheet and the image receiving body are superposed so that the former ink layer surface and the latter image receiving layer surface are in contact with each other, and the thermal transfer recording ink sheet is thermally transferred from the support side. Output 0.11W using head
/ Dot, thermal head cycle = 2.4 msec, energization time = 0.8
Character information was recorded at msec and a dot density of 16 dots / mm.

Further, the transfer foil described in each of Examples and Comparative Examples having the transparent protective layer having the above-mentioned structure on the image receptor on which images and characters were recorded was heated to a surface temperature of 200 ° C.
Using a heat roller with a rubber hardness of 85 and a diameter of 5 cm, the pressure is 150k.
Transfer was performed by applying heat for 1.2 seconds at g / cm ² .

On the image receptor to which the transfer foil was transferred, the ultraviolet-curable resin-containing coating liquid was applied by a gravure roll coater having a specific background pattern so that the coating amount was 20 g / m ² , and the following curing was performed. The ultraviolet curable resin-containing coating liquid was cured under the conditions to form an ultraviolet curable protective layer.

Curing conditions Light irradiation source 60 w / cm ² high pressure mercury lamp Irradiation distance 10 cm Irradiation mode 3 cm / sec Optical scanning evaluation method Each sample prepared by the above method was evaluated by the following method.

Adhesiveness: The adhesiveness was evaluated by peeling the tape.

Cellophane adhesive tape (manufactured by Nichiban) was strongly adhered to the surface of the cured protective layer, and the cellophane adhesive tape was rapidly peeled from the surface.
Evaluation was performed according to the method specified by the 5400 cross-cut tape method.

Use a sharp knife such as a knife on the surface of the protective layer 30
It was cut at an angle of ° to make 100 grids (10 × 10) of 1 mm or 1.5 mm that reach the substrate, and the number of grids of the coating film that remained without peeling at this time was measured. If the coating film has good adhesiveness as a whole, after making a grid, stick a cellophane tape on the surface, peel off the tape and measure the number of peeled parts in the thickness direction. Evaluated.

The evaluation was performed by the following evaluation score method.

Evaluation score of cross-cut test Evaluation score Scratch condition 10 Each cut is thin and smooth on both sides, and it cannot be peeled off at a straight line at the intersection of cuts.

[0166] 8 There was slight peeling at the intersection of the cuts, there was no peeling at every square, and the area of the defect was within 5% of the total square area.

6 There was peeling on both sides of the cut and the intersection, and the area of the defect was 5 to 15% of the total square area.

4 The width of peeling due to cuts is wide, and the area of the defective portion is 15 to 35% of the total square area.

2 The width of peeling due to cuts is wider than 4 points, and the area of the defect is 35 to 65% of the total square area.

The area of 0 peeling is 65% or more of the total square area.

Flex resistance: evaluated by a folding test.

According to JIS K6772, using a Scott type operation tester, a sample having a length of 80 mm and a width of 30 mm is bent at a bending cycle of 120 times / min, a bending stroke of 50 mm, a gripping distance of 10 mm, and a gripping opening of a free end of 3.0 mm. , 500 at room temperature
A bending test was conducted to examine the adhesiveness, peeling, cracks, folds, etc. of the UV-curable protective layer.

The evaluation was carried out in the following three stages.

⊚: No abnormality was observed ◯: Slight abnormality was observed Δ: Slight abnormality was observed ×: Abnormality was observed Character crushing: Characters printed with molten ink were visually observed and evaluated. .

◯: Character crushing is not observed Δ: Character crushing is slightly recognized ×: Character crushing is recognized Bleeding: An image sample provided with an ultraviolet curing protective layer was stored at 100 ° C. for 12 hours, and then Bleeding of the sublimation image was visually evaluated.

A: No bleeding is visually observed.

◯: Slight bleeding but no problem in practical use Δ: Bleeding is recognized and slightly problematic in practical use ×: Bleeding is clearly recognized and practically problematic Burr: Burr during transfer foil transfer The occurrence situation was observed and evaluated.

◯: No burr is generated. Δ: Slight burr is generated. X: Burr is generated. Hardness: The pencil hardness of the image sample provided up to the UV-curing protective layer was measured according to the pencil scratch test described in JIS5400. It was measured.

[0179]

[Table 1]

It can be seen from Table 1 that the samples of the present invention have moderate elasticity as compared with the comparative examples, can prevent collapse of fused images, can prevent bleeding of sublimation images due to long-term storage, and have a strong adhesive force. It can be seen that it is a transfer foil for image protection having.
Furthermore, a transfer foil for image protection that prevents cohesive failure of the entire protective layer, further improves bending resistance, has no burr, and has a stronger adhesive force while sufficiently curing the UV curable resin. It turns out that it can be obtained.

[0181]

According to the present invention, a transfer foil for image protection which has appropriate elasticity, prevents crushing of a fused image, prevents bleeding of a sublimated image due to long-term storage, and has a strong adhesive force is provided. Was obtained. Furthermore, a transfer foil for image protection that prevents cohesive failure of the entire protective layer, further improves bending resistance, has no burr, and has a stronger adhesive force while sufficiently curing the UV curable resin. A transfer foil for image protection was obtained which was able to prevent the melted image from collapsing due to the obtained moderate elasticity and to prevent the sublimation image from bleeding due to long-term storage, and further having a strong adhesive force.

[Brief description of drawings]

FIG. 1 is a scheme showing an example of producing an ID card from the image-protecting transfer foil of the present invention.

FIG. 2 shows another embodiment of the transfer foil for image protection of the present invention.

[Explanation of symbols]

 1 Support 2 Release Layer 3 Adhesive Layer 4 Protective Layer 5 Transfer Foil 6 Image Receiving Layer 7 ID Card Support 8 Writing Layer 9 Writing Layer 9 Melt Image 10 Sublimation Image 11 Thermal Transfer Image Recording Body 12 UV Curable Resin Layer

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 27, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

Polyurethane grafted with polyurethane
The latex of the tin is specifically manufactured by Toho Chemical Industry Co., Ltd.
High Tech S series can be mentioned
It is preferable that the shift ratio is 40 mol% or more. Also, polyurethane
Specifically, the Tex is a high-tech product manufactured by Toho Chemical Industry Co., Ltd.
The Ku U series can be mentioned. Dry these latex
The film thickness is preferably 0.1 to 1.0 μm. This top layer makes it more resistant
The durability is further improved. Next, an example of the present invention will be described with reference to the drawings.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0180

[Correction method] Change

[Correction content]

It can be seen from Table 1 that the samples of the present invention have moderate elasticity as compared with the comparative examples, can prevent collapse of fused images, can prevent bleeding of sublimation images due to long-term storage, and have a strong adhesive force. It can be seen that it is a transfer foil for image protection having.
Furthermore, a transfer foil for image protection that prevents cohesive failure of the entire protective layer, further improves bending resistance, has no burr, and has a stronger adhesive force while sufficiently curing the UV curable resin. It turns out that it can be obtained. Example 2 Polyurethane is used as the uppermost layer of the foil No. 1 of Example 1.
Rafted polyolefin latex [Toho Chemical Industry
Hitec S-8529 (Grafting rate 100 mol%)
Or Hitec S-6254 manufactured by the same company (grafting rate: 40 mol
%) And polyurethane latex (Hitech U-66 manufactured by the same company)
The mixture with the weight ratio of 7: 3 of 16) was dried to a thickness of 0.3μ.
Two types of transfer foil provided were prepared. Cross-cut test of Example 1
As a result, the score of 8 was improved to 10.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B42D 15/10 501 A 9121-2H B41M 5/26 E 9121-2H 101 F (72) Inventor Kawamura Tomoki Konica Stock Association, 1 Sakura-cho, Hino-shi, Tokyo In-house

Claims (7)

[Claims] 1. A transfer foil for image protection, comprising a support and a release layer and an adhesive layer provided in this order, wherein the adhesive layer contains a thermoplastic resin composed of a block polymer of polystyrene and polyolefin. . 2. The transfer foil for image protection according to claim 1, wherein the adhesive layer further contains a tackifier. 3. The transfer foil for image protection according to claim 1, wherein the release layer of the transfer foil contains a polyvinyl acetal resin and / or a cellulosic resin. 4. The transfer foil for image protection according to claim 1, wherein an intermediate layer is provided between the peeling layer and the adhesive layer of the transfer foil. 5. A transfer foil in which a release layer, an intermediate layer and an adhesive layer are provided in this order on a support, wherein the intermediate layer contains a thermoplastic resin composed of a block polymer of polystyrene and polyolefin. Transfer foil. 6. The transfer foil for image protection according to claim 5, wherein the release layer of the transfer foil contains a polyvinyl acetal resin and / or a cellulosic resin. 7. A transfer foil, which is used by applying and curing an ultraviolet curable resin on a transfer foil after transfer, has a solubility parameter and an SP value of 8 to 8 in a layer in contact with the ultraviolet curable resin of the transfer foil.
A transfer foil for image protection, which contains 10% or more of resin in the range of 12.