JPH0345816B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing photographic cards using a photosensitive and heat-sensitive diazo type recording material which is a dry imaging system.

It is known in the art to photographically develop facial photographs on predetermined card substrates. For example, a) a method of obtaining a facial photograph by exposing a card substrate having a photosensitive layer consisting of a diazo compound and a coupler corresponding thereto to actinic rays and developing in an alkaline aqueous solution or ammonia atmosphere.

(b) After photo-curing with actinic rays on a card substrate having a photosensitive layer consisting of water-soluble colloidal substances such as gelatin, casein, polyvinyl alcohol, and dichromic acid or iron salts, etc., the unexposed areas are washed away with water; A method of obtaining facial photographs by staining the photocured relief area with dye.

c) A method of obtaining a facial photograph by exposing a card substrate having a photosensitive layer made of silver salt lactic acid to actinic rays, developing and fixing it.

d) A method in which a card substrate having a photosensitive layer comprising a photosensitive resin that can be developed with a slightly alkaline aqueous solution, a pigment, and a sensitizer is exposed to active light and developed to obtain a facial photograph.

etc. can be mentioned. All of the above-mentioned methods are wet imaging systems that require chemicals for processing, and also have disadvantages such as long processing times and waste liquid pollution caused by the recording material itself. In order to compensate for these shortcomings, dry imaging systems that do not use any chemicals at all and form photographic images physically or chemically using energy such as heat, light, magnetism, electricity, or pressure are attracting attention. There is.

The characteristics that dry imaging systems differ from wet imaging systems are: 1) The equipment is simple, so it is advantageous in terms of manufacturing costs and repair costs.

2) Easy to operate and anyone can use it.

3) Processing time is short and images can be obtained in a dry state.

4) There is no pollution problem as no treated waste liquid is used.

etc.

The required characteristics of photo cards using dry imaging systems with these excellent characteristics are that the image quality of the facial photo is high in resolution, contrast, and gradation because the facial photo information itself serves as a type of identification. It must also have excellent abrasion resistance, weather resistance, water resistance, and tamper resistance as a recording medium. On the other hand, when it is desired to record information other than facial photograph information, that is, character or pattern information, a system that can easily output the information recorded on a computer, etc., and that can record using a simple recording method is required. be done.

As a result of intensive research into a method for manufacturing face photo cards using a dry imaging system with the above-mentioned required characteristics, the inventors of the present invention have developed a recording layer made of a photosensitive and thermosensitive diazo type recording material, which is a dry imaging system. The company has developed a method for manufacturing photo cards.

The present invention exposes an image on the face photo information frame surface of a card substrate having a recording layer made of a light-sensitive heat-sensitive diazo type recording material, forms a latent image of a photographic image within the face photo information frame, and then applying thermal energy to develop the latent image of the facial photograph image or character or pattern information on the recording layer other than the facial photograph information frame, and finally irradiating the entire surface of the card substrate with light energy to fix it; This is a method for manufacturing photo cards characterized by forming a photo image and text or pattern information.

Photo cards manufactured in this way can be used for various purposes. Examples include credit cards, identification cards, employee ID cards, and commuter passes.

The reason why the present invention was achieved is that a photosensitive and heat-sensitive diazo type recording material was used. That is, in the image forming process using a light-sensitive and heat-sensitive diazo type recording material, one is to form an image using thermal energy;
A method of forming a permanent image using heat and light energy that is then fixed by irradiating the entire surface with light energy. Two other methods are possible: image exposure using light energy to form a latent image, and then developing by applying heat energy to the entire surface, forming a permanent image using light and heat energy. . The former is
Since a thermal image forming method is used, the resolution of the recorded image is somewhat poor, and the gradation depends on the mechanism of the recording method. On the other hand, since the latter optically forms a latent image, it has the characteristics of excellent resolution and gradation.

Recording using the photosensitive and heat-sensitive diazo type recording material used in the present invention is in a positive-positive mode, and the image forming process can be performed in two ways as described above. If you want to record information such as a face photo as an image, a method that optically forms a latent image is suitable because it has excellent resolution and gradation.On the other hand, if you want to record text or pattern information as an image, the positive-positive mode is suitable. Therefore, a thermal image forming method is advantageous because it can record sufficient character or pattern information as an image, although its resolution is inferior to that of an optical method.

As described above, the characteristics of the recording method using the photosensitive heat-sensitive diazo type recording material used in the present invention are as follows.
The characteristic that it is more suitable in the image forming process to use an optical method to record images that require resolution and gradation, and to use a thermal method to record images such as characters or patterns is that This is convenient for obtaining the required characteristics of photo cards using an imaging system. The reason is,
When you want to record character or pattern information, it is necessary to be able to easily output the recorded information to a computer, etc., and to record it using a recording method with a simple mechanism. One such recording method is thermal image recording. This is because the method is optimal.

Hereinafter, the method for producing photo cards of the present invention will be explained in detail with reference to the drawings.

In FIG. 1, 1 is a base made of a plastic sheet, and 2 is a recording layer coated on the upper surface of the base 1, which is both photosensitive and heat sensitive. Incidentally, a magnetic recording layer may be applied to the back surface of the substrate 1 using a magnetic paint commonly used for magnetic recording. Furthermore, predetermined characters or patterns may be applied on the recording layer 2 in advance. Here, as the substrate 1, a plastic sheet of polyethylene terephthalate, polyvinyl chloride, etc. is used. The recording layer 2 is made of a light- and heat-sensitive diazo-type recording material whose basic components are a diazonium salt, a coupling agent, an acid stabilizer, a thermal developer, and a polymeric binder. A known method can be used to apply the recording layer to the recording layer.

Specifically, a liquid in which a recording agent consisting of a diazonium salt, a coupling agent, an acid stabilizer, and a polymeric binder is dissolved in an organic solvent and a dispersion liquid containing a heat developer prepared in advance are uniformly mixed. The mixed coating solution is applied onto the substrate 1 using a wire bar/air knife coater, a roll coater, a gravure coater, etc., and dried at a low temperature of 80°C or less to form a recording layer made of a photosensitive/thermosensitive diazo type recording material. A card A having the following can be manufactured. Also,
When the recording layer has a two-layer structure, a coating liquid in which a thermal developer, a coupling agent, and a polymeric binder are uniformly dispersed in an organic solvent is coated on the substrate 1 using the above coating material. After drying, add diazonium salt on top of that layer.
A recording layer made of a light- and heat-sensitive diazo-type recording material is formed by coating a solution of a recording material consisting of an acid stabilizer and a polymeric binder dissolved in an organic solvent using the above-mentioned coating material and drying it. Card A can be manufactured.

Next, a card having a recording layer made of a photosensitive heat-sensitive diazo type recording material will be simply referred to as substrate A, and the manufacturing process of the photo card will be explained in detail with reference to FIGS. 2 to 4.

That is, in FIG. 2-1, a predetermined positive film B is closely exposed to the face photo information frame surface on the surface of the base 1 of the substrate A (FIG. 2-1 A), or a lens C is exposed using the positive film B. Projection exposure is performed through the photo frame (FIG. 2-1A') to form a positive mode latent image on the face photograph information frame surface.

Next, text or pattern information is applied to the recording layer 2 other than the latent image of the facial photograph image and the facial photograph information frame using a thermal printing medium to form an image (second
Finally, the entire surface of the substrate 1 is irradiated with light energy to fix it (FIG. 2-1 c), and a clear facial photograph and character or pattern information are formed on the substrate 1.

Or, as shown in FIG.
-2 Diagram A) or using positive film B, lens C
Projection exposure is performed through the substrate (FIG. 2-2A') to form a positive mode latent image on the surface of the substrate 1. Next, a heat roll is used to develop the surface of the substrate 1 on which the positive mode latent image is formed (2-2
A method of forming a clear photographic image on the substrate 1 using the method shown in FIG.

Incidentally, as the energy source used here, as light energy, a mercury lamp, a xenon lamp, a tungsten lamp, a xenon flash, etc. are used. In addition, as for heat energy, thermal head,
A thermal pen, a thermal roll, a laser beam as a thermal mode, etc. can be used. Further, the positive film used in the present invention can be either continuous tone or halftone positive depending on the purpose.

As another method, as shown in FIG. 3, a laser beam is scanned and exposed on the face photograph information frame surface on the surface of the substrate 1, and pixels are sequentially formed to form a latent image of a face photograph image. Regarding the subsequent manufacturing process, the substrate 1 is processed in the same manner as the process after the latent image of the face photograph in FIG.
A clear face photograph and text or pattern information are formed on the top. The laser recording system used here for recording a latent image of a facial photograph using a laser basically consists of a laser light source, a control unit, a modulator, a beam expander, a deflector, and a recording optical system. The recording unit can be combined with the reading unit and used for image duplication, and can also be used by organically combining it with various image systems such as facsimile, computer output, and OA equipment. However, as the laser light source used here, various lasers having oscillation wavelengths in the ultraviolet region, such as Ar laser, He-Cd laser, ZnSeTes laser, etc., are used.

Other methods for forming a latent image of a positive mode facial photograph image on the facial photograph information frame surface on the surface of the substrate 1 include, for example, a liquid crystal shutter, a combination of a shutter and an optical fiber, a dot matrix type light emitting element, etc. Examples include a method in which a latent image of a photographic image is formed by imagewise exposure using a photoreceptor.

On the thus obtained substrate 1, a clear photograph of the face, letters, or pattern information is formed on the photo card substrate, and then an overcoat or a thermoplastic film or the like is bonded using an adhesive to further impart wear resistance. Alternatively, it may be heat-compressed.

Next, the photosensitive and heat-sensitive diazo type recording material used in the present invention will be explained in detail.

The recording layer made of a photosensitive and heat-sensitive diazo type recording material must have storage stability at room temperature. (There is no pre-coupling development.) The color development sensitivity is compatible with the machine. Furthermore, since it is used as a photo card, it must have excellent weather resistance, water resistance, chemical resistance, and abrasion resistance. For this purpose, it is necessary that the recording composition exhibits hydrophobic properties and that the polymer binder is an organic solvent type thermoplastic resin. That is, an alkali precursor characterized by using diazonium borofluoride, a hydrophobic coupling agent, an acid stabilizer, an alkyl-substituted guanidine salt as a heat developer, and a solvent-type thermoplastic resin as a polymer binder. This is a photosensitive, heat-sensitive, diazo-type recording material.

More specifically, examples of the diazonium borofluoride used in the present invention include paraphenylenediamine N-N-substituted compounds (4-diazo-N-diethylaniline, etc.), aminohydroquinone ethers (4- Diazo-2-5-dibutoxy-N-diethylaniline, 4-diazo-2-
Chloro-5methoxy-N-benzoylaniline
etc), aminodiphenyl, aminodiphenylamine and similar compounds (4-diazo-2-5-4'-triethoxydiphenylamine etc), heterocyclic amine derivatives (4-diazo-2-5-dibutoxy-N - phenylmorpholine, etc.). The diazo compounds described above are used as organic solvent-soluble salts such as diazonium borofluoride.

Examples of the hydrophobic coupling agent used in the present invention include 2-hydroxynaphthalene-3-carbonylphenyl ester, 2-hydroxynaphthalene-3-carbonyl-substituted phenyl ester (as a substituent, a methyl group, methoxy group, ethoxy group, nitro group, halogen group, etc.), 2-hydroxynaphthalene-
3-carbonylanilide, 2-hydroxy-3-
Carbonyl-substituted anilide (however, substituents include methyl group, methoxy group, ethoxy group, nitro group, halogen group, etc.), 2,3-dihydroxynaphthalene-6-sulfonamide, 2-naphthol-
3,6-disulfonamide, 2,8-dihydroxynaphthalene-6-sulfonamide, 2,8-dihydroxynaphthalene-6-sulfonamide,
1,8-dihydroxynaphthalene-8-sulfonamide, 1,8-dihydroxynaphthalene-6-
sulfonamide, 2-hydroxy-3-naphthoic acid propylamide, etc., and yellow coupling agents include 1-hydroxynaphthalene-2-carbonyl-phenyl ester, 1-hydroxynaphthalene-2-carbonyl-substituted phenyl ester ( However, substituents include methyl group, methoxy group, ethoxy group, nitro group, halogen group, etc.)1
-Hydroxynaphthalene-2-carbonylanilide, 1-hydroxynaphthalene-2-carbonyl substituted anilide (however, substituents include methyl group, methoxy group, ethoxy group, nitro group, halogen group, etc.), 1-hydroxy-2-carbonylanilide -naphthoic acid propylamide, 2-acetoacetaminonaphthalene-6-sulfonamide, 1-acetoacetaminonaphthalene-4-sulfamide, 2,2'-4,
4'-tetrahydroxydiphenyl sulfide and the like.

Next, as a hydrophobic thermal developer, a polybasic acid with a first-order dissociation constant of 2×10 ^-1 to 1×10 ^-4 and a general formula (However, at least one of R ₁ and R ₂ is C _3
-C24 alkyl group, others are hydrogen atoms or _C1 or more alkyl groups) Salts with alkyl-substituted guanidines can be used.

Such a salt of alkyl-substituted guanidine has extremely low solubility in water, on the order of several mg or less per 100 ml of an aqueous solution. That is, guanidine compounds have more hydrophobic properties than hydrophilic properties. A polybasic acid having a first-order dissociation constant of 2×10 ⁻¹ to 1×10 ⁻⁴ can be selected as an acid capable of forming a suitable salt with such an alkyl-substituted guanidine exhibiting hydrophobicity.

More specifically, examples of the alkyl-substituted guanidine include octylguanidine, nonylguanidine, decylguanidine, undecylguanidine,
Laurylguanidine, tridecylguanidine, myristylguanidine, hexadecylguanidine,
Octadecylguanidine, icosylguanidine, docosylguanidine, dioctylguanidine, dioctadecylguanidine, N-methyl-N
-octadecylguanidine, N-methyl-N-decylguanidine, N,N-didecylguanidine,
etc. can be mentioned.

On the other hand, as a polybasic acid with a first-order dissociation constant of 2×10 ^-1 to 1×10 ^-4 that can form a salt with alkyl-substituted guanidine, for example, benzenesulfonic acid,
Trichloroacetic acid, oxalic acid, glycerophosphoric acid, maleic acid, phosphoric acid, citric acid, malonic acid, tartaric acid, malic acid, lactic acid, etc. are suitable.

Furthermore, the alkyl-substituted guanidine salt used in the present invention can be synthesized by a known method. That is, a solution of alkyl-substituted guanidine dissolved in a suitable solvent is heated to 50°C,
While stirring, add a stoichiometric amount of the dissolved solution dropwise. By continuing stirring for about 10 minutes after the completion of the dropwise addition, the product can be produced with a yield of approximately 100%.

Next, as the acid stabilizer used in the present invention, various known nonvolatile acids used for diazo type materials can be used. Examples include citric acid, gluconic acid, oxalic acid, tartaric acid, sulfamic acid, hydroxylamine hydrochloride, boric acid, phosphoric acid, and the like. Further, in order to improve the storage stability of the recording material after recording, thiourea, L-ascorbic acid, urea, allyl isothiocyanate, etc. may be used as an antioxidant.

Examples of solvent-type thermoplastic resins used in the present invention include polystyrene, polymethylstyrene, polyphenylstyrene, polychlorostyrene, polyxylene, polyvinyl butyral, cellulose acetate butyrate copolymer, polyethylene terephthalate, triacetylcellulose, and polyacrylate. , polyacrylonitrile,
Polymethyl methacrylate, polymethyl/butyl acrylate, isobutyl acrylate, butyl methacrylate, polychloromethyl acrylate, polyvinyl tert-butyl ether,
Polyvinyl chloride, hydrochloric acid bicopolymer, etc. can be used.

The present invention will be specifically described below with reference to Examples. In each example, "part" means "part by weight".

<Example 1> A dispersion liquid consisting of 5 parts of n-decylguanidine tartrate, 50 parts of methyl ethyl ketone, and 50 parts of toluene was uniformly dispersed using a disperser. P in the dispersion
-N,N-diethylaminobenzenediazonium borofluoride 1 part, 2-hydroxynaphthalene-3-
1 part carbonyl-2'-methylanilide, citric acid
A coating liquid was prepared by adding and dissolving 0.6 parts of polystyrene and 20 parts of polystyrene. The coating solution was applied using a gravure coater onto a 200μ polyester sheet that had a magnetic recording layer mainly composed of γ-Fe ₂ O ₃ on the back side.
A light and heat sensitive diazo recording layer (5μ) was applied on the polyester sheet by drying at 70°C. Next, basic characters and patterns necessary for a work pass were pre-printed on the recording layer, and punched out to a predetermined size.
Its external shape is as shown in Fig. 4-1. In FIG. 4-1, 4 is a magnetic recording layer containing γ-Fe ₂ O ₃ as a main component, 1 is a polyester film as a substrate, 2 is a photosensitive thermosensitive diazo recording layer obtained as described above,
3 indicates pre-printed characters or patterns, and A indicates a substrate having the above structure.

As shown in Fig. 4-2, a continuous-tone facial photo positive film with a mask applied on the six face photo information frames on the surface of the base 1 of the substrate A is closely exposed using a mercury lamp (exposure amount: 30 mJ/cm ² ). Then, a positive-positive mode latent image was formed on the six face photo information frames.

Next, the thermal head density is 6/mm, and the application conditions are
0.45W, 2.75ms, ON/OFF outputs the information previously recorded on the computer, and outputs the latent image of the face photo, job title, name, age, and common name as shown in Figure 4-2. Authentication identification information 7 such as expiry date, issue date, issue number, etc. was recorded. Next, the entire surface was irradiated with xenon flash (exposure energy: 600 joul) and fixed, thereby producing a work permit with a clear dark blue facial photograph and other authentication identification information attached on the substrate 1. Furthermore, even when the recorded image area of the work pass of this example was rubbed with gauze soaked in water, an aqueous solution of a neutral detergent, petroleum ether, or alcohol, no discoloration or fading of the image was observed.

As described above, we have been able to provide an excellent photo-containing work permit that has characteristics that can withstand practical use.

Furthermore, the method of forming a positive-positive mode latent image on the face photograph information frame surface of this embodiment was carried out by scanning exposure using a laser or the like instead of contact exposure through a positive film. That is, the facial photo information recorded in advance on a computer or the like is output on the six facial photo information frames on the surface of the substrate 1 of the substrate A, and scanning exposure (dot density) is performed using a He-Cd laser (441.6 nm). 300 dots/inch),
A positive-positive mode latent image was formed on the face photo information frame surface.

Thereafter, the process was carried out in the same manner as in the above-mentioned example to produce a work pass in which a clear dark blue image of the face and other authentication identification information were recorded on the substrate 1.

This manufacturing process is an example in which the recording unit, which is a laser beam and a thermal head, is combined with a reading unit and used for image duplication, and is also organically combined with various image systems such as computer output, facsimile, and OA equipment. There is also.

<Example 2> 2 parts of powdered silica and 4 parts of polyurethane resin on a 730μ white hard vinyl chloride sheet (card base)
parts, 1 part of salt vinyl acetate resin, 8 parts of methyl ethyl ketone,
A coating solution prepared by kneading a dispersion containing 2 parts of toluene overnight in a ball mill was applied using a roll coater, and dried to form a 20 μm silica layer as a porous solution-permeable layer. On the layer, 5 parts of myristylguanidine oxalate, 1 part of 2,3-dihydroxynaphthalene-6-sulfonamide, 80% ethanol.
A coating solution consisting of 30% was applied using a knife coater and allowed to penetrate and dry. Next, 4-morpholino-
1 part of 2,5-dibutoxybenzenediazonium borofluoride, 0.4 part of oxalic acid, 0.2 part of P-toluenesulfonic acid
A card substrate was prepared by applying a light-sensitive and heat-sensitive diazo layer on a white hard vinyl chloride seed on which a photosensitive solution consisting of 80 parts and 80 parts of methyl ethyl ketone was coated and permeated using a knife coater and dried at 70°C to form a layer permeated with the solution. . A positive face photo film was used as an original on the card substrate, and projection exposure was carried out using a mercury lamp (exposure amount: 20 mJ/cm ² ) to form a latent image of a face photo in positive-positive mode on the card substrate. Then, after developing with a heat roll (roll temperature 200℃),
75μ thick transparent vinyl chloride sheet cover films were layered together and heated at 130-140℃ using a flat plate heat press machine.
Heat and press for about 20 minutes at 5Kg/ ^cm2 , then slowly cool.
It was punched out to a predetermined size to obtain a photo card.
This photo card has excellent water resistance, solvent resistance, and weather resistance, and since the recording layer is covered with a cover film, it has excellent abrasion resistance, making it a photo card with properties that can withstand practical use. were able to provide the following.

Effects of the Invention As described above, according to the method for producing photo cards according to the present invention, a photographic image having gradation and excellent tamper resistance, and character or pattern information are developed in a dry imaging system at one time. and can be formed on a card by fusing.

[Brief explanation of drawings]

Each of the drawings shows one embodiment of the present invention.
The figure is an explanatory diagram of the card board used in the present invention.
FIG. 3 is an explanatory diagram of the manufacturing process of the photo card used in the present invention, and FIG. 4 is an explanatory diagram of the photo business card of the present invention. A...Substrate, B...Transparent positive film, C...Lens, D...Laser recording medium, 1...Base, 2...Recording layer, 3...Pre-printed characters or patterns, 4...Magnetic recording layer, 6...Face photo Information frame, 7...Authentication identification information.

Claims (1)

[Scope of Claims] 1. Surface image exposure is performed on the face photo information frame surface of a card substrate having a recording layer made of a photosensitive and heat-sensitive diazo type recording material to form a latent image of a photographic image within the face photo information frame. Then, heat energy is applied by a heating medium to develop the latent image of the photographic image or characters or pattern information on the recording layer other than the face photo information frame, and finally, the entire surface of the card substrate is irradiated with light energy. 1. A method for manufacturing photo cards, which comprises fixing the photo image and forming a photo image and character or pattern information. 2. Claims characterized in that the recording layer made of a photosensitive and heat-sensitive diazo type recording material is formed of a diazonium salt, a coupling agent, an acid stabilizer, a thermal developer, and a polymer binder. A method for producing photo cards as described in paragraph 1. 3. The method for manufacturing photo cards according to claims 1 and 2, wherein a latent image of a photographic image is formed on the face photo information frame surface by contact or projection exposure using a transparent positive film. 4 Scanning and exposing the face photo information frame surface with a laser,
3. A method for manufacturing photo cards according to claim 1, wherein pixels are sequentially formed to form a latent image of a photo image.