JPH05330258A - Photographic thermal transfer material - Google Patents

Abstract

PURPOSE:To provide a photographic thermal transfer material capable of forming a thermal transfer image excellent in durability, especially, water resistance on a photograph without especially performing protective processing. CONSTITUTION:In a photographic thermal transfer material having a thermal transfer layer obtaining a thermal transfer image by a thermal transfer system using a photograph obtained from a silver halide photographic photosensitive material as a manuscript, a gelatin curing agent is added to the thermal transfer layer. Further, it is pref. that the gelatin curing agent is an aziridine compd. and added to the uppermost layer of the thermal transfer layer and a resin having an amino group and/or a carboxyl group is added to the uppermost layer of the thermal transfer layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic heat-sensitive transfer material for obtaining a heat-transferred image by a heat-transfer method using a photograph obtained from a silver halide photographic light-sensitive material as an original. More specifically, it is excellent in durability, particularly water resistance. The present invention relates to a photographic heat-sensitive transfer material which gives a heat-transfer image.

[0002]

2. Description of the Related Art Conventionally, there has been known a method of printing an image on a photographic printing paper from a negative film and also printing characters and illustration images by using a mask material for image formation to make a photographic print. The mask material for use must be prepared in advance by computer typesetting, and a special device is required for printing on photographic paper, which is troublesome at present.

A method for forming an image by thermally transferring characters and illustrations to a developed photograph using a heat-sensitive transfer material
4-109244 and Japanese Patent Application No. 2-141019. However, the durability of the thermal transfer image formed on the photograph was poor. Therefore, Japanese Patent Application No. 2-138679 discloses a method of coating a thermal transfer image with an ultraviolet curable resin and ultraviolet curing, and Japanese Patent Application No. 2-132944 discloses a method of laminating a thermal transfer image. It required special equipment and spoiled the appearance of the photograph. Further, as a thermal transfer material, JP-A-3-31989 describes that a polyester resin having a hydrophilic group is contained in the thermal transfer layer, and the oil resistance and scratch resistance of the transferred image are satisfactory, It was extremely inferior in water resistance.

[0004]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a photographic heat-sensitive transfer material capable of forming on a photographic image a heat-transfer image which is excellent in durability, particularly in water resistance, even without protective processing.

[0005]

The above object of the present invention is to provide a photographic heat-sensitive transfer material having a heat transfer layer for forming a heat transfer image on a photographic original obtained from a silver halide photographic light-sensitive material by a heat transfer method. This is achieved by a photographic heat-sensitive transfer material containing a gelatin hardening agent in the heat transfer layer. In addition, the uppermost layer of the thermal transfer layer contains a gelatin hardener, the gelatin hardener is an aziridine compound,
The inclusion of a resin having an amino group and / or a carboxyl group in the uppermost layer of the thermal transfer layer is a preferred embodiment because the effect of the present invention can be more exerted.

The present invention will be described in more detail below.

The photographic heat-sensitive transfer material of the present invention basically has a heat transfer layer (also referred to as "color material layer" or "ink layer") provided on a support. The anti-fusion layer, the peeling layer between the support and the thermal transfer layer, the thermal transfer layer being divided into two or more layers, and the metal vapor deposition layer can be provided therein. When the thermal transfer layer is divided into two or more layers, each layer does not necessarily need to contain a coloring material.

Examples of the support include various papers such as paper, coated paper, synthetic paper (polypropylene, polystyrene or a composite material obtained by laminating them with paper), vinyl chloride resin sheet, ABS resin sheet, polyethylene terephthalate. Various plastic films or sheets such as base film and polyethylene naphthalate base film,
Examples thereof include a film or sheet formed of various metals, a film or sheet formed of various ceramics, and the like. The thickness of the support is usually in the range of 1 to 10 μm.

The thermal transfer layer comprises a coloring material, a binder and, if necessary, various additives (antistatic agent, plasticizer, heat-fusible substance,
However, when the thermal transfer layer is divided into two or more layers, the coloring material may not necessarily be contained.

Examples of the coloring material include pigments such as inorganic pigments and organic pigments, and dyes.

Examples of the inorganic pigments include titanium dioxide, carbon black, zinc oxide, Prussian blue, cadmium sulfide, iron oxide and chromates of lead, zinc, barium and calcium.

The organic pigments include azo, thioindigo, anthraquinone, anthanthrone, triphendioxazine pigments, vat dye pigments, phthalocyanine pigments (eg copper phthalocyanine) and their derivatives,
Examples include quinacridone pigment.

Examples of organic dyes include acid dyes, direct dyes, disperse dyes, oil-soluble dyes, and metal-containing oil-soluble dyes.

The content of the coloring material in the thermal transfer layer is not particularly limited, but is usually in the range of 5 to 70% by weight, preferably 10 to 60% by weight.

A thermoplastic resin is preferably used as the binder.

Examples of the thermoplastic resin include ethylene-based copolymers, polyamide-based resins, polyester-based resins, polyurethane-based resins, polyolefin-based resins, acrylic-based resins,
Vinyl chloride resin, cellulose resin, rosin resin,
Polyvinyl alcohol resin, polyvinyl acetal resin, ionomer resin, petroleum resin and other resins; natural rubber, styrene butadiene rubber, isoprene rubber, chloroprene rubber, diene copolymers and other elastomers; ester gum, rosin maleic acid resin, Rosin derivatives such as rosin phenol resin and hydrogenated rosin; phenol resin, terpene resin, cyclopentadiene resin,
Examples thereof include polymer compounds such as aromatic hydrocarbon resins. Among these resins, a resin having an amino group and / or a carboxyl group is preferable in order to further exert the effect of the gelatin hardening agent.

By appropriately selecting these thermoplastic substances, a thermal transfer layer having a desired thermal softening point or thermal melting point can be formed.

Next, the gelatin hardening agent added to the thermal transfer layer will be described.

As a gelatin hardening agent, an aziridine-based agent,
Used in the photographic industry such as epoxy type, vinyl sulfone type, acryloyl type, chlorotriazine type, methane sulfonate type, isocyanate type, carbodiimide type, maleide type, aldehyde type, ketone type, polymer type and inorganic compound type. Are listed, Research Disclosure No.17643,26
No. 18716, pp. 651 and The Theory of the Photogra
Phic Process 3rd. Ed. 54 pages (published by Macmillan). Among these, the aziridine-based curing agent
It is particularly preferable because the heat transfer image does not require post-heating (to accelerate the hardening reaction of gelatin).

Further, polyester, polyimine, polythioether, polyamide, polyacetal, polysiloxane, polyanhydride, polycarbonate, polyurethane,
Polyurea, polyolefin, phenolic resin, cellulose, polyamine, starch, polyvinyl (polyvinyl chloride,
Resins such as polystyrin, polymethylmethacrylate, polyacrylonitrile, polyvinyl alcohol, etc., having an aziridine group introduced therein may be used. The resin containing an aziridine group may be copolymerized with another resin. The addition amount of the curing agent is appropriately 5 to 100% by weight of the thermal transfer layer, and in the case of the resin type curing agent, the addition itself can also serve as the binder.

Typical specific examples of the aziridine type and other curing agents are shown below, but the invention is not limited thereto.

[0022]

[Chemical 1]

[0023]

[Chemical 2]

[0024]

[Chemical 3]

In the case of post-heating, the temperature is preferably 100 ° C. or lower so as not to deteriorate the photograph.

Of the various additives used as necessary,
As the antistatic agent, carbon black, aluminum, iron and the like can be used. As the surfactant, known anionic, cationic, amphoteric and nonionic surfactants can be used.

Examples of the plasticizer include phthalic acid esters (dimethyl phthalate, dioctyl phthalate, didecyl phthalate, etc.), trimellitic acid esters (octyl trimellitic acid, trimellitic acid-i-nonyl, trimellitic acid-). i-
Decyl etc.), pyromellitic acid esters (octyl pyromellitic acid), adipic acid esters (dioctyl adipate, methyl lauryl adipate, etc.), other oleic acid esters, succinic acid esters, maleic acid esters, sebacine Acid esters, oxalic acid esters, epoxidized soybean oil, epoxidized linseed oil, epoxystearic acid epoxys, and further phosphoric acid esters (triphenyl phosphate, tricresyl phosphate, etc.), phosphorous acid esters (triphenyl phosphite) , Tridecyl phosphite, dibutyl hydrogen phosphite, etc.) and glycol esters (ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate) and the like.

As the heat-fusible substance, vegetable waxes such as carnauba wax, wood wax, auricurie wax and espal wax; beeswax,
Animal waxes such as insect wax, shellac wax and whale wax; petroleum waxes such as paraffin wax, microcrystalline wax, polyethylene wax, ester wax and acid wax; and waxes such as mineral wax such as montan wax, ozokerite and ceresin. In addition to these waxes, higher fatty acids such as palmitic acid, stearic acid, margaric acid and behenic acid; palmityl alcohol, stearyl alcohol, behenyl alcohol, marganyl alcohol, myricyl alcohol, eicosanol and the like. Higher alcohols; higher fatty acid esters such as cetyl palmitate, myricyl palmitate, cetyl stearate, myricyl stearate; acetamide, propionamide, palmitamide, stearamide, amide wax Amides; and stearylamine, behenylamine, like higher amines such as palmityl amine.

Examples of mat materials include titanium white, calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, activated clay and acid clay.

As the metal fine particles (filler), inorganic fine particles (silica gel, calcium carbonate, titanium oxide,
Acid clay, alumina, etc.) and organic resin particles (fluorine resin particles, guanamine resin particles, acrylic resin particles, silicon resin particles, etc.).

The thickness of the thermal transfer layer containing these is 0.5 to 5.0 μm.
m is preferable, and more preferably 1.0 to 3.0 μm.

The fusion preventing layer, which is preferably provided on the back surface of the support, improves the heat resistance when it comes into contact with the thermal head, and its material is silicone resin, fluorine resin, polyimide resin, epoxy resin, phenol resin, Melamine resin, acrylic resin, nitrocellulose and the like are suitable. The anti-fusing layer preferably has a thickness of about 0.1 to 1.0 μm, more preferably 0.2 to 0.5 μm.

Next, the peeling layer which is preferably provided between the support and the thermal transfer layer will be described.

The peeling layer is a layer provided on the peeling layer when heated by a heating mechanism such as a thermal head during image formation (generally a thermal transfer layer in which at least one layer contains a coloring material). ) Is provided for the purpose of rapid peeling and transfer, and contains a heat-meltable substance suitable for achieving this purpose, and is a layer in which the attributes of the heat-meltable substance are dominant, particularly a layer having excellent peelability. Configured as.

The release layer may be composed of the heat-melting substance itself, but is usually composed of the heat-melting substance and / or a binder resin such as a thermoplastic resin (described above as the binder for the heat transfer layer). Is preferred. Furthermore, a silicone compound having releasability, for example, polyester modified silicone resin (or silicone modified polyester resin), acrylic modified silicone resin (or silicone modified acrylic resin), urethane modified silicone resin (or silicon modified urethane resin), cellulose modified silicone resin (Or silicon modified cellulose resin), alkyd modified silicone resin (or silicon modified alkyd resin), epoxy modified silicone resin (or silicon modified epoxy resin), and the like.

The thickness of the release layer is preferably 0.1 to 2.0 μm,
More preferably, it is 0.3 to 1.0 μm.

Each of the above layers can be applied by a known application method such as gravure application, wire bar application or curtain application.

The heat-melt transfer method using the heat-sensitive transfer material of the present invention is not different from the usual heat-transfer recording method, but the case of using the most typical thermal head as the heat source will be described as an example. .

First, the heat transfer layer of the heat-sensitive transfer material and the photographic surface are brought into close contact with each other, and if necessary, a heat pulse is applied from the back surface of the photo by a platen while applying a heat pulse with a platen to obtain a desired printing or transfer pattern. The corresponding thermal transfer layer is locally heated. As a result, the heated portion of the thermal transfer layer rises in temperature and is quickly softened and transferred to the photographic surface.

[0040]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of heat-sensitive transfer material) Anti-fusion layer (30 parts by weight of nitrocellulose, 70 parts by weight of acrylic silicone resin, film thickness) on the back surface
0.2 μm) provided on a PET support having a thickness of 5 μm, a release layer (0.5 μm) and a thermal transfer coloring material layer (1.5 μm) shown in Table 1 are laminated and coated by a gravure coating method (solvent dispersion) to form a thermal transfer material. Created. (Ratio of materials is parts by weight)

[0042]

[Table 1]

[0043]

[Chemical 4]

Printing was performed on a developed print photograph (Konica Color Type QA: manufactured by Konica Co., Ltd.) using each thermal transfer material with Lupo JW88F (word processor manufactured by Toshiba Corporation).

Each printed matter was subjected to a heat treatment (60 ° C.) after printing in addition to the evaluation of water resistance described below immediately after printing.
-Water resistance after 3 hours) was evaluated. The evaluation results are shown in Table 2.

<Evaluation of Water Resistance> Each printed matter was immersed in water at 23 ° C.
After dipping for 1 second, 1 minute, 1 hour, and 24 hours, the printed surface was rubbed with a cloth and evaluated in 3 levels.

◯: The printed matter does not fall off. Δ: The printed matter does not fall off, but the cloth is slightly soiled. X: The printed matter falls off.

[0048]

[Table 2]

As is clear from Table 2, the water resistance of the thermal transfer image was remarkably improved by including the gelatin hardening agent in the thermal transfer layer of the thermal transfer material. In particular, it is effective to add a gelatin hardening agent to the uppermost layer of the thermal transfer layer, to eliminate the need for post-heating by using an aziridine-based gelatin hardening agent, and to make the uppermost resin of the thermal transfer layer have a carboxyl group or an amino group. Met.

The thermal transfer image of the present invention was also excellent in oil resistance and scratch resistance.

Example 2 In the heat-sensitive transfer material 4 of Example 1, H-14, H-15 and H- were used instead of the gelatin hardening agent H-17 of the heat transfer color material layer.
A heat-sensitive transfer material was prepared in the same manner except that 16, H-18 and H-19 were added, and the same evaluation as in Example 1 was carried out. As a result, the effect of the present invention was obtained.

[0052]

By using the heat-sensitive transfer material for photography of the present invention, a heat transfer image having excellent water resistance, oil resistance and scratch resistance can be combined on a normal photograph.

Claims (4)

[Claims] 1. A photographic heat-sensitive transfer material having a heat transfer layer for forming a heat transfer image on a photographic original obtained from a silver halide photographic light-sensitive material by a heat transfer method, wherein a gelatin hardening agent is added to the heat transfer layer. A heat-sensitive transfer material for photographs, characterized by containing. 2. The heat-sensitive transfer material for photographs according to claim 1, wherein a gelatin hardening agent is contained in the uppermost layer of the heat transfer layer. 3. The heat-sensitive transfer material for photographs according to claim 1, wherein the gelatin hardening agent is an aziridine compound. 4. The heat-sensitive transfer material for photographs according to claim 1, wherein the uppermost layer of the heat-transfer layer contains a resin having an amino group and / or a carboxyl group.