JP3401698B2 - Photographic recording medium and method for producing photographic image recording medium - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a photographic image-containing recording material in which a photographic image is recorded in a thermoplastic resin, and a method for producing a photographic image-containing recording material for recording a stable photographic image in the thermoplastic resin. . More specifically, the present invention relates to a photographic image-containing recording material which is easy to manufacture and has good image stability, and a method for producing a photographic image-containing recording material for the recording material. The photographic image-containing recording material of the present invention can be particularly favorably used, for example, for an authentication identification card (ID card).

[0002]

2. Description of the Related Art Conventionally, as an identification card such as an employee ID card, a credit card, a driver's license, or a pass permit, a predetermined necessary information such as an address, a name, or a number is printed on a supporting plate surface such as paper or plastic. It is generally used that such bibliographical items (information) are filled in by printing or the like, and confirmation information such as a photograph for confirming the person is affixed and a tally mark is applied.

However, this conventional type has a problem that it is easy to tamper with forgery or alteration. Further, these are weak in durability against friction and the like, and are often contaminated or damaged while being always carried. In order to improve such defects, recently, a light-sensitive material in which a support plate is coated with a light-sensitive emulsion such as a silver halide emulsion is used, and bibliographic information is printed on the light-sensitive material and a facial photograph of a person is printed. It has been used, and the surface of such a card is covered with a resin film and heat-sealed,
It is known that the card is laminated on both sides with a resin film and variously modified to prevent tampering.

However, in the method using these photosensitive materials, the processing for forming an image is liquid processing,
It has the drawback of being complicated and the size of the apparatus for forming the image being large. As a method for improving these drawbacks, Japanese Patent Application Nos. 63-131939 and 63-29397.
No. 7 proposes a method of forming an image in a thermoplastic resin by a thermal transfer method or a heat development method and laminating this resin with an appropriate laminating material to form an image, particularly an image for an ID card. ing.

[0005]

According to this method, it is possible to obtain an image by a simple and dry process, but there is a problem in storage stability and sharpness of the obtained image. In particular, the deterioration of sharpness is presumed to be due to the heating during lamination.

Further, the adhesiveness between the thermoplastic resin of the obtained recording material and the laminating material is not sufficient, and there is a problem in terms of storability and tampering prevention of the recording material.

This problem tends to be exacerbated by changing the laminating temperature or the laminating material in order to improve the sharpness deterioration.

[0008] Further, in issuing various certificates such as ID cards and booklets, the applicant desires that the submission of the application form to the issuance of the certificate be carried out in a short time. Has been required to process a large amount of processing within a certain period of time, and it has been required to reduce the issuing time for one sheet as much as possible.

The present invention has been made in view of the above problems.

A first object of the present invention is to provide a good photographic image-containing recording material for an ID card or the like which can be obtained by a simple method, and a method for producing a photographic image-containing recording material for this recording material. .

A second object of the present invention is to provide a photographic image-containing recording material improved in image storability and sharpness and a method for producing a photographic image-containing recording material for this recording material.

A third object of the present invention is to provide a photographic image-containing recording material excellent in tampering resistance and a method for producing a photographic image-containing recording material for the recording material.

A fourth object of the present invention is to provide a recording medium containing an image excellent in image storability and sharpness quickly and at low cost.

[0014]

In order to solve the above-mentioned problems, the invention of a recording material containing a photographic image according to claim 1 has a thermoplastic resin layer having a photographic image on a support, and The furthest layer has 2 epoxy groups in one molecule.
It is characterized in that it has a protective layer formed by irradiating an active energy ray-curable composition containing a compound containing one or more of them with an active energy ray.

Further, the invention of the method for producing a recording material containing a photographic image according to claim 2 provides an image with a dye and / or pigment for a photographic image on a recording material having a thermoplastic resin layer on a support based on image information. After recording, an active energy ray-curable composition containing a compound containing two or more epoxy groups in one molecule is coated on the thermoplastic resin layer, and then irradiated with active energy rays to form a photographic image. It is characterized in that a protective layer is formed on the thermoplastic resin layer.

Further, the invention of a recording material containing a photographic image according to a third aspect is an image recorded on a recording material having a thermoplastic resin layer on a support with a dye and / or a pigment for a photographic image based on image information. And a part or all of the symbol and / or the character image is melt-type thermally transferred, and the active energy ray-curable composition contains a compound containing two or more epoxy groups in one molecule on the thermoplastic resin layer. It is characterized by having a protective layer formed on the thermoplastic resin layer on which a photographic image is formed by irradiating an object with an active energy ray.

Further, in the invention of the method for producing a recording body containing a photographic image according to claim 4, an image formed by a dye and / or a pigment for a photographic image is formed on a recording body having a thermoplastic resin layer on a support based on image information. It is recorded, and then a part or all of the symbol and / or character image is transferred by using the melt-type thermal transfer method, and further, epoxy groups are formed on the thermoplastic resin in an amount of 2 per molecule.
The invention is characterized in that after coating an active energy ray-curable composition containing a compound containing one or more of them, the composition is irradiated with an active energy ray to form a protective layer on the thermoplastic resin on which a photographic image is formed.

As a result of earnest research, the present inventors have found that the objects of the present invention can be achieved by the inventions of claims 1 to 4, and have completed the invention. Hereinafter, the present invention will be described in more detail.

The photographic image of the present invention means an image having 32 or more gradations.

The symbol of the present invention means an optically readable symbol such as a bar code or an OMR symbol, a stamp pattern, or a simple pattern such as a mark expressing the issuer.

The support of the present invention includes a transparent support,
Although any of opaque supports and the like may be used, for example, polyethylene terephthalate, polycarbonate, polystyrene, polyvinyl chloride, polyethylene, films such as polypropylene and titanium oxide in these supports,
Supports containing pigments such as barium sulfide, calcium carbonate, talc, baryta paper, RC papers laminated with a thermoplastic resin containing pigments on paper, cloths, glasses, metals such as aluminum, and the like. Examples of the support include a support obtained by coating and curing an electron beam curable resin composition containing a pigment on a support, and a support having a coating layer containing a pigment provided on these supports. Further, JP-A-62-283333
The cast-coated paper described in No. 1 is also useful as a support.

A preferable support is a white plastic film support (for example, polyethylene terephthalate, polycarbonate, polyvinyl chloride), and a polyvinyl chloride support is particularly preferable.

Further, an IC device or a magnetic recording layer may be provided in the support or between the support and the thermoplastic resin. Further, paper may be laminated on the back surface of the support to give the writing property.

Examples of the binder for the thermoplastic resin layer of the present invention include polyvinyl chloride resins, copolymer resins of vinyl chloride and other monomers (eg, vinyl chloride / vinyl acetate copolymer resins, ethylene / vinyl chloride copolymers). Union), polyester resin (eg polyethylene terezotalate), acrylic ester, chlorinated polyethylene, ethylene, vinyl acetate copolymer, ketone resin, alkyd resin, polyvinylpyrrolidone, polycarbonates (eg bisphenol A, polycarbonate), triacetic acid Cellulose, polyacrylate resin, styrene acrylate resin, vinyl toluene acrylate resin, polyurethane resin, polyamide resin, urea resin, polycaprolactone resin, styrene, maleic anhydride resin, acrylonitrile resin, polystyrene, polyvinyl Nilbutyral and the like can be mentioned. These polymers can be used also as a support, in which case the support may be formed of a single layer or a plurality of layers. Among them, vinyl chloride-vinyl acetate copolymer resin, polyester resin, polyvinyl chloride resin and the like are preferable. These may be used alone or in combination of two or more.

The above-mentioned various resins may be newly synthesized and used, or commercially available products may be used. For example,
Commercially available polyester resins include Byron 200, Byron 290, Byron 600, etc. (above, Toyobo Co., Ltd.), K
A1038C (manufactured by Arakawa Chemical Co., Ltd.), TP220, TP235 (all manufactured by Nippon Gosei Co., Ltd.) can be used.

The vinyl chloride / vinyl acetate copolymer resin preferably has a vinyl chloride component content of 50 to 100% by weight and a degree of polymerization of about 50 to 2,500. The vinyl chloride-vinyl acetate copolymer resin preferably used in the present invention does not necessarily have to be composed only of a vinyl chloride component and a vinyl acetate component, and a vinyl alcohol component and maleic acid are used as long as the object of the present invention is not impaired. It may contain components and the like. Examples of such vinyl chloride-vinyl acetate copolymers include S-REC A, S-REC C, S-REC M (above, Sekisui Chemical Co., Ltd.), Vinylite VACH, Vinylite VYHH, and Vinylite VMC.
H, Vinyl Light VYHD, Vinyl Light VYLF, Vinyl Light VYNS, Vinyl Light VMCC, Vinyl Light VMC
A, Vinylite VACD, Vinylite VERR, Vinylite VROH (above, Union Carbide), Denka Vinyl 1000GKT, Denka Vinyl 1000L, Denka Vinyl 1000CK, Denka Vinyl 1000A, Denka Vinyl 1000L
K2, Denka Vinyl 1000AS, Denka Vinyl 1000MT
2, Denka Vinyl 1000 CSK, Denka Vinyl 1000 CS,
Examples include Denka vinyl 1000GK, Denka vinyl 1000GSK, Denka vinyl 1000GS, Denka vinyl 1000LT3, Denka vinyl 1000D, Denka vinyl 1000W (all manufactured by Denki Kagaku Kogyo Co., Ltd.).

In any case, from the viewpoint of physical properties, as the binder for the thermoplastic resin layer, a resin having a glass transition point (Tg) in the range of 20 to 250 ° C., particularly 3
A resin in the range of 0 to 240 ° C. is preferable, and in terms of molecular weight, a resin in which the Mw is in the range of 2000 to 100,000 is preferable. When 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).
It may be crosslinked or cured by radiation, heat, moisture, a catalyst or the like.

In that case, a radiation-active monomer such as epoxy or acrylic or a crosslinking agent such as isocyanate can be used.

A release agent, an antioxidant, a UV absorber, a light stabilizer, a filler (inorganic fine particles, organic resin particles, a pigment may be added to the thermoplastic resin layer. Further, a plasticizer as a sensitizer may be added. Or a heat solvent may be added, and these are appropriately used in consideration of compatibility with the binder, image storability, and the like.

The release agent can improve the releasability between the recording ink sheet and the thermal transfer recording image receptor when sublimation type thermal transfer is used for forming a photographic image.

Examples of such a release agent include solid waxes such as silicone oil, polyethylene wax, amide wax, and Teflon powder; fluorine-based and phosphoric acid ester-based surfactants, among which silicone oil is preferred. 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 as the silicone oil in order to improve the compatibility with the binder.

As the modified silicone oil, polyester modified silicone resin (or silicone modified polyester resin), acrylic modified silicone resin (or
Silicon modified acrylic resin), urethane modified silicone resin (or silicone modified urethane resin), cellulose modified silicone resin (or silicone modified cellulose resin), alkyd modified silicone resin (or,
Silicon modified alkyd resin), epoxy modified silicone resin (or silicon modified epoxy resin) and the like can be mentioned.

That is, a polyester-modified silicone resin containing a polysiloxane resin in the main chain and copolymerizing polyester in a block form, and a silicon-modified polyester resin having a dimethylpolysiloxane moiety as a side chain bonded to the polyester main chain. A block copolymer of dimethylpolysiloxane and polyester, an alternating copolymer, a graft copolymer, a random copolymer and the like can also be used as the modified silicone oil or resin.

Particularly in the present invention, it is preferable to add a polyester-modified silicone resin.

A typical polyester-modified silicone resin is, for example, a block copolymer of dimethylpolysiloxane and a polyester which is a ring-opening polymer of diol and dibasic acid or a ring-opening polymer of caprolactone. (Including a copolymer in which one end or one end is blocked with the above polyester portion, or conversely, the above polyester is blocked with dimethylpolysiloxane), or (dimethyl) polysiloxane having a side chain with the above polyester as a main chain It is possible to increase the copolymer in which

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, it is generally for the image receiving layer. It is 0.5 to 50% by weight, preferably 1 to 20% by weight, based on the binder.

Examples of the hardening reaction type silicone oil include reaction hardening type, light hardening type and catalyst hardening type.

As the reaction hardening type silicone oil, there is a reaction hardening type of amino modified silicone oil and epoxy modified silicone oil.

As the catalyst-curable or photocurable silicone oil, KS 705 FPS, KS 705 F
PS 1, KS 770 PL 3 (Catalyst hardening type silicone oil: manufactured by Shin-Etsu Chemical Co., Ltd.), KS 720
, KS 774 PL 3 (all are photocurable silicone oils: manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. The addition amount of these curable silicone oils 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 the solution, followed by drying.

Next, as the above-mentioned antioxidant, Japanese Patent Laid-Open No.
The compounds described in JP-A No. 9-182785, JP-A No. 1-127387, and compounds known to improve image durability in photographs and other image recording materials can be mentioned.

Examples of the UV absorber and the light stabilizer include JP-A-59-158287 and 59-182785,
63-74686, 63-145089, 5
9-196292, 60-130735, 61
-118748, 61-153638, 61-
159644, 62-229594, 63-1
22596, 61-283595, JP-A 1-2
Examples thereof include compounds described in JP-A-04788 and compounds known to improve the image durability of 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 fluorine resin particles, guanamine resin particles, acrylic resin particles, silicon resin particles. Resin particles such as These inorganic / organic resin particles differ depending on the specific gravity, but
Addition of 1 to 70% by weight is preferred.

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

Examples of the plasticizers and heat solvents include phthalic acid esters (eg, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, didecyl phthalate, etc.), adipic acid esters (dioctyl adipate, methyl lauryl adipate). , Di-2-ethylhexyl adipate,
Ethyl lauryl adipate, etc.), other oleic acid esters, succinic acid esters, maleic acid esters,
Sebacate esters, citric acid esters, epoxy stearic acid epoxies, and further phosphoric acid esters such as triphenyl phosphate and tricresyl phosphate, glycol esters such as ethylphthalylethyl glycolate and butylphthalylbutyl glycolate. And the like.

In the present invention, the total amount of the additives is usually 0.1 to 50% by weight based on the binder for the image receiving layer.

An overcoat layer may be laminated on the surface of the thermoplastic resin layer for the purpose of preventing fusion, improving image storage and the like. This layer can be formed by an ordinary coating process or laminating method. The thickness of this layer is usually 0.05 to 5 μm. Further, a cushion layer can be provided between the base material and the image receiving layer of the thermal transfer recording image receiving sheet in order to reduce noise and transfer-record an image corresponding to image information 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 preferably 5 to 25 μm.

As the active energy ray curable composition for forming the protective layer of the present invention, for example, an ultraviolet curable composition can be used. The UV-curable protective composition that can be used is not particularly limited, but an epoxy group may be used.
It is preferable that the composition is composed mainly of a prepolymer containing two or more molecules in the molecule and an aromatic onium salt as a cationic polymerization initiator. Further, preferably, a prepolymer containing two or more epoxy groups in one molecule is 70
It is present in a weight percentage or more. Any prepolymer containing two or more epoxy groups in one molecule can be used, and any known one can be used. For example, alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, polyglycidyl ethers of aromatic polyols, polyglycidyl of aromatic polyols. Examples thereof include hydrogenated compounds of ethers, urethane polyepoxy compounds and epoxidized polybutadienes. These prepolymers may be used as a blend of two or more. As the cationic polymerization initiator, an aromatic onium salt is preferable, and a salt of a Group Va element of the periodic table, for example, a phosphonium salt (for example, triphenylphenacylphosphonium hexafluorophosphate), a salt of a Group VIa element, For example, sulfonium salts (eg, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, tris (4-thiomethoxyphenyl) hexafluorophosphate, sulfonium and triphenylsulfonium hexafluoroantimonate) and Group VIIa elements Salts such as iodonium salts (eg diphenyliodonium chloride) and the like are included.

The use of an aromatic onium salt as a cationic polymerization initiator in the polymerization of an epoxy compound is described in US Pat. Nos. 4,058,401, 4,069,055 and 4,101,513.
And Nos. 4,161,478.

The preferred cationic polymerization initiator is
Examples thereof include sulfonium salts of Group VIa elements. Among them, triarylsulfonium hexafluoroantimonate is preferable from the viewpoint of ultraviolet curability and storage stability of the ultraviolet curable composition.

The amount of the above cationic polymerization initiator used is preferably 3 to 20% by weight, and more preferably 5 to 12% by weight based on the total weight of the ultraviolet curable composition containing the prepolymer.
% By weight.

When the amount of the cationic polymerization initiator does not exceed 1% by weight based on the total weight of the ultraviolet curable composition, the curing speed upon irradiation with ultraviolet rays becomes extremely slow.

The UV-curable composition used in the present invention further includes oils (particularly silicone oil) and silicone-
Surfactants such as alkylene oxide copolymers (eg L-5410 commercially available from Union Carbide), silicone oil containing aliphatic epoxide groups, FO-171 commercially available from 3M and also 3M. Commercially available from FO
-430, Megafac F commercially available from Dainippon Ink and Chemicals
Fluorocarbon surfactants such as -141 may be included.

The UV-curable composition used in the present invention may further contain inert components such as fillers such as talc, calcium carbonate, alumina, silica, mica, barium sulfate, magnesium carbonate and glass powder, dyes and pigments. , Thickener, plasticizer, stabilizer, leveling agent, coupling agent,
A tackifier, a silicone group-containing activator, a wetting improver such as a fluorocarbon group-containing surfactant, various other additives, and the above cationic polymerization initiator for the purpose of improving the fluidity of the composition during coating. It is also possible to add a small amount of a solvent such as acetone, methyl ethyl ketone, or methyl chloride, which hardly reacts with.

Further, the ultraviolet-curable composition used in the present invention further includes, for example, vinyl monomers such as styrene, paramethylstyrene, methacrylic acid esters, acrylic acid esters and the like, cellulosics, thermoplastic polyesters,
Phenyl glycidyl ether, silicon-containing monoepoxide, monoepoxide such as butyl glycidyl ether, etc. may be used within a range that does not impair the effects of the present invention.

The ultraviolet curable composition used in the present invention is
It is cured by irradiation with light in the ultraviolet region, but the irradiation light source used in the ultraviolet region (hereinafter also simply referred to as "ultraviolet ray") is sunlight, low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon. There are lamps, etc.

The atmosphere for irradiating the ultraviolet rays may be air or an inert gas such as nitrogen gas or carbon dioxide gas.

The irradiation time of ultraviolet rays to the ultraviolet curable composition used in the present invention varies depending on the kind of the irradiation light source in the above-mentioned ultraviolet region, but is generally 0.5 seconds to 5 minutes, preferably 3 seconds to 2 minutes. Is.

Usually, when the irradiation time is short, a large light source having a high irradiation intensity is required, and when the irradiation time is long, a light source having a low irradiation intensity can be used. It is a disadvantage. However, according to the present invention, it is possible to use an ultraviolet ray generating lamp of 200 W or less,
It is advantageous that the purpose can be reached by irradiation for 2 seconds to 2 minutes.

During curing, heating can be performed before or after irradiation with ultraviolet rays to further shorten the curing time.

When heating, the heating temperature is 30 to
80 ° C. is preferred. Before UV irradiation, the heating time may be short or long as long as the temperature of the UV-curable composition layer reaches this temperature, and after UV irradiation, the heating time is preferably 1 to 120 minutes.

Although the UV curable resin composition has been described above as an example, other active energy ray curable resin compositions may be used in the same manner as above according to the properties of each active energy ray and composition. it can.

Such a resin composition can be applied as a liquid resin material to a support, for example, an outermost layer (for example, an image forming layer) on a belt-shaped support. To apply the liquid resin material to the layer surface, this material solution can be used by a usual method such as a double roll coater, a slit coater, an air knife coater, a wire per coater, a slide hopper, and spray coating. It can be easily applied to the card surface. The appropriate coating thickness at this time is about 0.1 to 30 μm. Preferably 1 to 15 μ
Is.

In the present invention, the heat-sensitive transfer material is used for recording an image with the melt-type heat transfer ink. This heat-sensitive transfer material has a support and an ink layer, and on this support, for example, as a thin film base for an ink ribbon support, materials: polyester, polyamide, polyimide, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, Polyacrylic ester, polyolefin, polycarbonate, polystyrene, phenol resin, cellulose triacetate, condenser paper, glassine paper, film thickness: 3 to 12 μm, etc. may be used, and a back coat (BC) layer may be provided, and melt transfer is also possible. In addition to the ink layer, the layer may include, for example, an intermediate layer, an overcoat (OC) layer, or the like.

The melt transfer layer should have the property of being melted by heat and exhibiting adhesiveness to the substrate, but it is generally composed of the following materials.

Dyes and pigments, alkaline earth metal carbonates, TiO2, MgO, ZnO, alumina, silica, carbon black, nigrosine dye, Sudan black S
M, First Yellow G, Benzidine Yellow,
Pigment Yellow, Oil Yellow GG, Zapon First Yellow CG, G, Sumiplast Yellow G
G, India First Orange, Sumiplast Orange G, Pigment Orange R, Zapon First Orange GG, Irgadine Red, Paranitroaniline Red, Toluidine Red, Resole Red 2G, Lake Red O, Oil Scarlet, The Pont First Scarlet Use all known dye pigments such as OG, Eisenspiron Red BEH, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Fast Gen Blue 5007, Victoria Blue F4R, Sudan Blue, Oil Peacock Blue, Brilliant Green B, Phthalocyanine Green. You can

As waxes, carnauba wax, montan wax, beeswax, rice wax, candelilla wax, lanolin wax, paraffin wax,
Examples include microcrystalline wax, polyethylene wax, sazol wax, oxide wax, amide wax, and silicon wax.

As the thermoplastic resin, polyamide resin (nylon etc.), polyester resin, poly (meth) acrylic acid ester type resin (polymethyl methacrylate, polyethyl acrylate etc.), polyurethane resin, polyvinyl chloride resin, polyvinylidene chloride resin , Polystyrene resin, polyvinyl acetate resin, polyvinyl chloride-vinyl acetate resin, polystyrene-acrylic resin, polyethylene-vinyl acetate resin, polyethylene resin, polypropylene resin, polybutadiene resin, polyvinyl alcohol resin,
Phenol resin, cellulosic resin (methyl cellulose,
(Ethyl cellulose, carboxymethyl cellulose, nitrocellulose, acetyl cellulose, etc.), polyvinyl ether resin, polyvinyl pyrrolidone resin, polyvinyl aniline resin, polysulfone resin, polycarbonate resin, ionomer resin, polysiloxane resin, acetal resin (polyvinyl butyral, polyvinyl acetal, polyvinyl formal) Etc.), petroleum resin, rosin resin, chroman-indene resin, terbene resin, styrene-butadiene rubber, isobrene rubber, nitro rubber, etc.

As additives, various surfactants, higher fatty acids (stearic acid, palmitic acid, lauric acid, etc.), long-chain alcohols (stearyl alcohol, etc.),
There are metal salts of long-chain fatty acids (alcium stearate, zinc palmitate, etc.), antioxidants, various plasticizers, silicone oil and the like.

The preferable composition ratio of each of these materials is completely different depending on the layer structure used. The ink layer may have a multi-layered structure for efficient thermal transfer by heating, and for example, the following layers may be laminated in order on the material.
However, it is not limited to this.

Release Layer, Color Material Layer Release Layer, Color Material Layer, Adhesive Layer Color Material Layer, Adhesive Layer In the present invention, all the images to be expressed use a sublimation type heat transfer system or a heat development system. However, from the viewpoint of reducing running cost and manufacturing time, it is preferable to use a fusion type thermal transfer method for a monotone image portion which does not require fine gradation expression such as characters and symbols.

In the invention of the recording material containing a photographic image according to the first aspect, a thermoplastic resin layer having a photographic image is provided on a support, and an epoxy group is included in one molecule as a layer farthest from the support. It has a protective layer formed by irradiating an active energy ray-curable composition containing a compound containing two or more of the above with an active energy ray, and has excellent image storability and sharpness, and further has tamperproof property. It is a recording material containing a photographic image which is excellent and suitable for ID cards.

Further, in the invention of the method for producing a photographic image-containing recording material according to claim 2, a photographic image-containing recording material having excellent image storability and sharpness, excellent tamperproof property, and good for an ID card is provided. It can be obtained by a simple method.

Further, in the invention of the recording material containing a photographic image according to claim 3 and the production method thereof according to claim 4, there is provided a thermoplastic resin layer having a photographic image on a support, and an epoxy group is contained. It has a protective layer formed by irradiating an active energy ray-curable composition containing a compound containing two or more compounds in one molecule with an active energy ray, and is excellent in image storability and sharpness. It is possible to obtain a photographic image-containing recording material which is excellent in tamperproof property and is suitable for ID cards and the like quickly, at low cost, and by a simple method.

[0077]

BEST MODE FOR CARRYING OUT THE INVENTION A specific example of an image forming method based on the image forming apparatus shown in FIGS. 1 and 2 will be described below.

FIG. 1 shows the case where a sublimation type thermal transfer system is used for transfer image formation of a photographic image. Reference numeral 1 represents an ink ribbon supply unit, and the ink ribbon is brought into close contact with the card P conveyed from the card supply unit 2 by the photographic image recording unit 3,
The thermal head 4 is heated according to the photographic image information and the dye is transferred to the thermoplastic resin layer on the card P. Subsequently, in the character image recording unit 5, the melt type thermal transfer ink ribbon conveyed from the melt type thermal transfer ink ribbon supply unit 6 is brought into close contact with the card P, and is heated by the thermal head 7 according to the character image information. Characters are transferred to the upper thermoplastic resin layer.

Next, the card P is conveyed to the active energy ray-curable composition coating section 8 and coated with the active energy ray-curable composition containing substantially no solvent. The application method is appropriately selected from the methods described above. Then, after being conveyed to the ultraviolet ray irradiating section 9 and irradiated with ultraviolet rays for 10 to 20 seconds, it is conveyed to the card receiving section 10 and a photographic image-containing recording medium is produced.

FIG. 2 shows the case where the thermal development system is used for transfer photographic image formation.

Reference numeral 11 is a photothermographic material supply section,
The photothermographic material is supplied from the roll of photothermographic material to the image exposure section 12 and exposed with a laser beam for a photographic image. The exposure method is not limited to laser exposure, but CR
A method using a light source such as T, FOT, or a light emitting diode may be used. The photosensitive layer surface of the exposed photothermographic material and the thermoplastic resin surface of the card P supplied from the card supply unit 13 are brought into close contact with each other and conveyed between the heating rollers of the heat development unit 14 to form an image on the card P. It is formed. The heating time is 20 seconds ~
2 minutes is preferred.

Subsequently, in the character image recording section 15,
The ink ribbon for melt type thermal transfer conveyed from the melt type thermal transfer ink ribbon supply unit 16 is brought into close contact with the card P, heated by the thermal head 17 according to the character image information, and the character is transferred onto the card P.

Next, the card P is conveyed to the protective layer forming section 18 which also serves as an active energy ray-curable composition coating section and an ultraviolet ray irradiating section, and a protective layer is formed by irradiation with coating light to form a card receiving section. It is conveyed to 19 and a recording material containing a photographic image is produced.

In the above description, the case where the thermoplastic resin is previously formed on the card-shaped support has been described. However, after the image is formed in the thermoplastic resin, the card-shaped support and the resin are formed. You may make it stick.

Specific examples of the photothermographic material used in the present invention are JP-A-64-52147 and JP-A-1.
-114844, etc. and the Journal of the Photographic Society of Japan 52,
Pp. 167-171 (1989).

FIG. 3 and FIG. 4 are a side view and a plan view of a specific example of a recording medium containing a photographic image.

Reference numeral 21 is a support, which is made of 0.7 mm white polyvinyl chloride. Reference numeral 22 denotes a thermoplastic resin layer, which is coated with a coating liquid for forming an image receiving layer having the following composition by a wire bar coating method, and is temporarily dried with a dryer, and then dried in an oven at a temperature of 100 ° C. for 1 hour to have a thickness. An image receiving layer having a thickness of 5 μm was formed.

Coating Liquid for Forming Image Receiving Layer Vinyl Chloride-Vinyl Acetate Copolymer (trade name VYHH: manufactured by Union Carbide Co., Ltd.) 10 parts Methyl ethyl ketone 90 parts Photographic image 24 and symbols and character images 2 on this resin layer
5, 27, 28 are recorded. 26 is a magnetic recording layer.

For No. 23, the following coating compositions 1 to 3 were applied at a coating amount of 10 g / m ² and irradiated under a high pressure mercury lamp of 62 W / cm ² at a speed of 3 m / min from a distance of 10 cm. It is a protective layer obtained by curing the coating composition, and the recording material obtained corresponding to the protective layer of each composition is A1.
~ A3. Coating composition 1. Bis (3,4 epoxy-6 methylcyclohexylmethyl) adipate (UCL, ERL-4299) 70 parts by weight Bisphenol A diglycidyl ether (Toto Kasei Co., Ltd., Epototo YD 8124) 10 parts by weight 1.4-butane Diol diglycidyl ether (RD-2 manufactured by Ciba-Geigy) 11 parts by weight Triarylsulfonium hexafluoroantimony solution 9 parts by weight Coating composition 2. Hydrogenated bisphenol A diglycidyl ether (Adeka Resin EP 4080 manufactured by Asahi Denka Co., Ltd.) 30 parts by weight diglycidyl hexahydrophthalate manufactured by Ciba Geigy, Araldite CY 183 22 parts by weight epoxidized polybutadiene (manufactured by Idemitsu Petrochemical Co., Ltd.) Poly bd R-45 EP7) 40 parts by weight triphenylsulfonium hexafluoroantimony solution (GE, UVE-1014) 8 parts by weight Composition for coating 2. Pentaerythritol acrylate (Osaka Organic Chemical Industry Co., Ltd., Viscoat 300) 53.5 parts by weight r-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM 503) 12.5 parts by weight p- (3,4 Epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM 303) 14.0 parts by weight 1,4 butanediol diglycidyl ether 11.0 parts by weight 4,4 ′ bischloromethylbenzophenol 4.0 parts by weight Triarylsulfonium hexafluoroantimony solution (manufactured by GE, UVE1014) 5 parts by weight As a comparative example, the recording material A4 and the protective layer excluding the protective layers of the recording materials A1 to A3 were changed to polyvinyl chloride (on the thermoplastic resin layer). Put a polyvinyl chloride sheet on top of it and heat it for 10 seconds (140 ℃) The vinyl layers were provided) was recorded body A5 was produced.

Photographic image recording was performed by a sublimation type thermal transfer system, and symbol and character image recording was performed by a fusion type thermal transfer. Specific examples of each heat-sensitive transfer material are shown below.

Symbols and characters Images used Melt-type heat transfer material Support 4.5 μm thick PET film (Toray) Heat resistant protective layer 0.2 μm Nitrocellulose 30 parts by weight Acrylic silicone resin 70 parts by weight Release layer Thickness 0 2.9 μm EV-210 (Mitsui DuPont Chemical) 5 parts by weight Paraffin wax (Nippon Seiwa) 95 parts by weight Coloring material layer 1.0 μm carbon black 20 parts by weight Tamanor 526 75 parts by weight EV-40Y 5 parts by weight For photographic images As a sublimation-type heat-sensitive transfer material support, a corona-treated surface of a polyethylene terephthalate film having a thickness of 6 μm (manufactured by Toray Industries, Inc.) was dried by a wire bar coating method with an ink layer-forming coating solution having the following composition. Is coated and dried to a thickness of 1 μm, and silicone oil is applied to the back surface that is not corona-treated. Yue Silicone Co., Ltd., X-4
One or two drops of 14003 A) were dripped on the spot and spread over the entire surface, and a back surface treatment code was applied to obtain an ink sheet for thermal transfer recording of three colors of yellow, magenta and cyan.

Ink layer forming coating liquid Disperse dye 1. Yellow MS Yellow Mitsui Toatsu Dye 3 parts by weight 2. Magenta MS Mazena Mitsui Toatsu Dye 5 parts by weight 3. Cyan Kayaset Blue 136 Nippon Kayaku Co., Ltd. 4 parts by weight Polyvinyl butyral [Polymerization degree 1700, Sekisui Chemical Co., Ltd., trade name BX-1] 5 parts by weight Methyl ethyl ketone 90 parts by weight Cyclohexanone 5 parts by weight Further, thermoplasticity The resin layer 22 is added with an image stabilizer such as silicon oil as a desiliconizer and a UV absorber (described below).

UV absorber

[0094]

When the sharpness of the images of the obtained recording materials A1 to A5, especially the photographic image, was visually evaluated, only the recording material A5 showed color blur due to the diffusion of the dye. Further, when the recording materials A1 to A5 were overlapped with plain paper for an electrophotographic copying machine and stored at a temperature of 80 ° C. for 3 days, the recording materials A4
It was found that some of the image forming dyes were transferred to plain paper. Further, in the recording materials A4 and A5, deterioration of sharpness was observed after storage.

When the recording material A5 was prepared, the recording material A6 was prepared by changing the thermocompression bonding condition to 120 ° C./5 seconds. In recording body A6, deterioration of sharpness was not observed, but peeling between protective layer 23 and thermoplastic resin layer 22 was observed only in recording body 6 when stored at a relative temperature of 80% and a temperature of 50 ° C. That is, the recording body A6 does not have a sufficient tampering protection function.

As another embodiment, the recording material A1
The same results were obtained when the recording materials B1 to B6 subjected to the same post-processing as the recording materials A1 to A6 were evaluated in the same manner for the sample B in which the symbol and character images were formed by the same sublimation type thermal transfer method as the photographic image. was gotten. Further, when the cost and the manufacturing time required to manufacture the recording bodies A1 and B1 were compared, the cost of the recording body A1 was about half that of the recording body B1 and the manufacturing time was about 2/3. .

[0098]

As described above, according to the first and second aspects of the present invention, a photographic image-containing recording medium which does not require complicated processing such as liquid development, and has high image quality and excellent tamperproof property can be obtained. Is obtained.

According to the third and fourth aspects of the present invention, similarly, a complicated recording process is not required, and a photographic image-containing recording material having high image quality and excellent tamperproof property can be easily obtained at low cost. To be

Even if the heat development method is used for image recording,
The effect of the present invention is exhibited, and a higher quality image can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic diagram of an image forming apparatus.

FIG. 2 is a schematic diagram of an image forming apparatus.

FIG. 3 is a side view showing a specific example of a recording body containing a photographic image.

FIG. 4 is a plan view showing a specific example of a recording medium containing a photographic image.

[Explanation of symbols]

1 Ink ribbon supply section 2 Card supply section 3 Photo image recording section 5 character image recording section 6 Melting type thermal transfer ink ribbon supply section 8 Active energy ray curable composition coating part 9 UV irradiation part 10 Card receiving part 11 Photothermographic material supply unit 12 Photographic exposure unit 13 Card supply department 14 Thermal development section 15 Character image recording section 16 Melting type thermal transfer ink ribbon supply section 21 Support 22 thermoplastic resin layer 23 Protective layer 24 portrait image 25 character image 26 magnetic recording layer 27 barcode 28 company name logo

Front page continued (72) Inventor Tomoki Kawamura 1 Sakura-cho, Hino-shi, Tokyo Konica stock company (72) Inventor Sota Kawakami 1 Sakura-cho, Hino-shi, Tokyo Konica stock company (72) Inventor Takayuki Sugaiwa 1 Sakura-cho, Hino-shi, Tokyo Konica Co., Ltd. (72) Inventor Takahiro Ogawa 1 Sakura-cho, Hino-shi, Tokyo Konica Co., Ltd. (56) Reference JP-A-2-269097 (JP, 269097) A) Japanese Unexamined Patent Publication No. 1-195096 (JP, A) Japanese Unexamined Patent Publication No. 2-310096 (JP, A) Japanese Unexamined Patent Publication No. 1-195449 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) ) B42D 5/00-15/10

Claims (4)

(57) [Claims] 1. An active energy ray-curable composition having a thermoplastic resin layer having a photographic image on a support and containing a compound having two or more epoxy groups in one molecule as a layer farthest from the support. A recording material containing a photographic image, which has a protective layer formed by irradiating the composition with active energy rays. 2. An image with a dye and / or a pigment for a photographic image is recorded on a recording medium having a thermoplastic resin layer on a support based on image information, and then an epoxy group in one molecule is formed on the thermoplastic resin layer. Characterized in that the protective layer is formed on the thermoplastic resin layer on which a photographic image is formed by applying an active energy ray-curable composition containing a compound containing two or more of the above and irradiating with an active energy ray. A method for producing a recording material containing a photographic image. 3. A recording material having a thermoplastic resin layer on a support, which has an image recorded with a dye and / or a pigment for a photographic image based on image information, and further has a part of a symbol and / or character image. Alternatively, a photographic image was formed by irradiating an active energy ray-curable composition containing a compound containing two or more epoxy groups in one molecule on this thermoplastic resin layer by melt-type thermal transfer. A recording medium containing a photographic image, which has a protective layer formed on a thermoplastic resin layer. 4. An image with a dye and / or pigment for a photographic image is recorded on a recording medium having a thermoplastic resin layer on a support based on image information, and then a part or all of the symbol and / or character image is recorded. Transfer is performed by using a fusion thermal transfer method, and then an active energy ray-curable composition containing a compound containing two or more epoxy groups in one molecule is applied on a thermoplastic resin, and then irradiated with active energy rays. And forming a protective layer on the thermoplastic resin on which the photographic image is formed.