JP5697013B2 - Photographic image transfer method - Google Patents

Description

  The present invention relates to a method for producing a photographic image transfer product.

  The silver salt black and white photographic image has a structure in which silver fine particles are dispersed in a gelatin film on a substrate. The use of gelatin as a support material is an epoch-making invention in the history of photographic image formation, and gelatin has been considered essential as a support material in photographic images because of its excellent properties.

  However, the gelatin film and silver fine particles constituting this photographic image are not sufficiently stable and change in quality with time, so deterioration of the image during storage cannot be avoided, which is an important problem in storage of photographic images. For example, silver fine particles undergo oxidation and sulfurization reactions due to oxygen and moisture in the air and residual components of the fixing solution, and change to silver oxide and silver sulfide, causing discoloration, changes in gradation and tone, contamination and discoloration. Degradation of the image such as the occurrence of Gelatin causes mold generation, stickiness, adhesion to others, and the like in a wet state, and cracks and peeling due to drying of the film in a dry state. These all cause photographic image damage. In addition, the gelatin film has insufficient mechanical strength, and has problems such as peeling or scratching due to scraping or friction.

  In order to improve the storability of a photographic image, a technique called toning has been used for a long time to prevent silver alteration by replacing silver particles constituting the image with other noble metals. However, in this technique, a new process of toning must be added after a normal development process, and the process becomes complicated. Further, this technique may cause the photographic image to deteriorate due to unevenness due to non-uniformity of the toning process, contamination of the image due to the remaining toning process liquid, and the like. Furthermore, this technique has no effect on the defects of the gelatin film.

  In contrast to such a technique, for example, Patent Document 1 below discloses a technique for exposing and baking a photographic photosensitive material in which a photographic emulsion containing gelatin and silver halide grains is coated on a heat-resistant substrate.

JP 2005-317885 A

  However, since the technique described in Patent Document 1 includes a baking process at several hundred degrees in the manufacturing process, the substrate needs to have heat resistance. Therefore, a specially prepared heat-sensitive substrate photographic photosensitive material must be used, and the type, shape, size, etc. of the heat-resistant substrate are greatly restricted due to limitations of equipment such as a dark room and a dryer. There is. Furthermore, since the heat-resistant substrate is usually hard and inflexible, the photographic material cannot be rolled up and is difficult to handle.

  Therefore, in view of the above problems, the present invention relaxes the restriction that the substrate of the photographic photosensitive material must have heat resistance, and includes a variety of photographic photosensitive materials including commercially available products, including three-dimensional shaped objects. Another object of the present invention is to provide a method capable of producing various kinds of photographic image transfer products.

  A method for producing a photographic image transfer product according to a first aspect for solving the above-mentioned problems is as follows: (1) At least a photographic light-sensitive material obtained by coating a photographic emulsion containing silver halide grains and gelatin on a flammable substrate. A step of partially exposing, (2) a step of depositing noble metal fine particles on an exposed portion of a photographic image, (3) a step of attaching the photographic photosensitive material to a heat resistant substrate, and (3) burning and removing the photographic photosensitive material. The process of carrying out.

  According to the present invention, the restriction of using a heat-resistant substrate is relaxed, and various photographic image transfer materials including three-dimensional objects are easily produced using various photographic photosensitive materials including commercially available photographic printing paper. It becomes a method that can be done.

It is a schematic process drawing of the preparation method of the photographic image transfer thing concerning an embodiment. It is a figure which shows the photographic image transcription | transfer material produced by the Example.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention can be implemented in many different forms, and is not limited only to the description of the following embodiments and examples.

  FIG. 1 is a diagram showing an outline of the steps of a method for producing a photographic image transfer product according to this embodiment (hereinafter referred to as “the present method”). As shown in this figure, this method comprises the steps of (1) exposing at least a part of a photographic photosensitive material 1 coated with a photographic emulsion 13 containing silver halide grains 11 and gelatin 12 on a combustible substrate 14. (2) depositing the noble metal fine particles 15 on the exposed portion of the photographic photosensitive material, (3) attaching the photographic photosensitive material 1 to the heat resistant substrate 16, and (4) burning and removing the photographic photosensitive material. Have.

  (1) The step of exposing at least a part of the photographic light-sensitive material 1 in which a photographic emulsion 13 containing silver halide grains 11 and gelatin 12 is coated on a flammable substrate 14 is performed by exposing the silver halide grains on the silver halide grains. In this step, the latent image nucleus 17 is formed (see FIG. 1A). The latent image nuclei are silver fine particles generated by exposure. The silver fine particles are very small and cannot be observed. In general, it is not possible to see an image composed of the latent image nuclei only by this step.

  In this step, the photographic emulsion 13 contains silver halide fine grains 11 and gelatin 12. The silver halide grains 11 are preferably at least one of silver chloride and silver bromide, and a small amount of silver iodide can be contained therein, but is not limited thereto.

  In this step, the photographic emulsion 13 is coated on a combustible substrate 14. The combustible base material 14 is removed by a step of burning and removing a photographic photosensitive material described later, and is not limited to this, but is preferably a flexible film-like organic substance. More preferred is paper. By being composed of a film-like organic substance, it is easy to remove by combustion and easy to handle, and this effect is particularly remarkable with paper. Commercially available photographic paper or the like can also be used. In the case of photographic paper, baryta photographic paper using barium sulfate as a surface coating agent is a preferred example. However, when a metal oxide powder such as titanium oxide is included as a surface coating agent, it is melt-fixed by firing and is a heat resistant substrate. When a metal oxide is included, it is preferable to use a metal oxide that does not change depending on the combustion temperature of the combustible base material and gelatin, and barium sulfate may be included. It is preferable to remove titanium oxide that is denatured at a temperature lower than the combustion temperature from organic substances as much as possible.

  The step of exposing at least a part of the photographic light-sensitive material includes a step of performing so-called photography. A latent image nucleus 17 composed of silver fine particles is formed in the exposed portion, and a latent image nucleus is not formed in the unexposed portion. The amount of latent image nuclei varies depending on the exposure amount and exposure intensity. Thereby, the shading in the photographic image can be formed.

  (2) The step of depositing the noble metal fine particles 15 on the exposed portion of the photographic light-sensitive material deposits noble metal atoms in the photographic emulsion 13 film using the latent image nucleus 17 formed by the step (1) as a catalyst. This process is also called a development process (FIG. 1B). This step can be realized by immersing the photographic photosensitive material in which the latent image nuclei are formed in a processing solution containing noble metal ions. In this step, the formed latent image nuclei act as a catalyst for the oxidation-reduction reaction, and noble metal fine particles are deposited corresponding to the distribution of the latent image nuclei to form a photographic image. In the present specification, an image composed of a noble metal on a substrate is expressed as a photographic image.

  In this case, the noble metal used in the treatment liquid is not limited as long as it can be precipitated using silver fine particles as a catalyst and is not oxidized and removed by subsequent combustion, but at least gold and platinum group elements. Either can be mentioned. The platinum group element is not particularly limited, but preferably contains at least one of platinum, ruthenium, rhodium, palladium, osmium and iridium.

  In the treatment liquid of the present embodiment, the noble metal is preferably present as an ion, and more preferably present as a complex in which a ligand is coordinated to deposit the noble metal more stably. This is preferable. Although it is not necessarily limited in this case, it is a preferable example that it is a complex. For example, a complex containing at least one of a thiosulfuric acid complex, a thiourea complex, a thiocyanic acid complex, etc. is used as a complex. It is more preferable from the point that can be achieved.

  Moreover, it is preferable that the treatment liquid of this embodiment contains a halide in order to adjust the concentration of silver ions in the liquid and prevent dissolution of silver halide. Examples of the halide include, but are not limited to, those containing at least one of potassium bromide, potassium chloride, and sodium bromide. When potassium bromide is included, it is useful to include potassium iodide at a lower concentration than this potassium bromide, since the concentration of precious metals, particularly gold, can be increased.

  Moreover, it is also preferable that the treatment liquid of this embodiment contains a reducing agent for reducing noble metal ions. By doing in this way, there exists an advantage that precipitation of a noble metal atom can be accelerated | stimulated. In addition, although it does not necessarily limit as this reducing agent, For example, it is preferable that it contains at least any one of ascorbic acid, malonic acid, and a citric acid.

  In this step, it is preferable to treat with a photographic fixing solution. In this way, the silver halide in the photographic emulsion is removed and only the noble metal fine particles can be left in the gelatin. As the photographic fixing solution, a commercially available solution can be used as long as it has this function, and it is not limited, but includes, for example, at least one of sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, and the like. It is preferable.

  Further, in this step, it is preferable to appropriately perform a treatment such as washing between the step of processing with the photographic fixing solution and the step of processing with the processing solution.

(3) The step of attaching the photographic photosensitive material 1 to the heat resistant substrate 16 is more specifically a step of attaching the photographic emulsion film side of the photographic photosensitive material to the heat resistant substrate 16. Since the moistened photographic emulsion film has viscosity, it can be easily attached to a heat-resistant substrate, and the flammable base material is generally flexible, so that the heat-resistant substrate is formed with unevenness and curvature. Even if it is a case, it can affix with high sufficient adhesiveness.

  The heat-resistant substrate according to the present embodiment is not limited as long as it remains unburned when the gelatin and the flammable base material in the photographic light-sensitive material described later are burned and removed. For example, glass, stone, Various things such as metal and earthenware can be used, and there are no restrictions on the size, shape, etc. as long as they can be put into a combustion furnace.

(4) The step of burning and removing the photographic light-sensitive material 1 is specifically performed by burning and removing the gelatin 12 and the flammable base material 14 in the photographic light-sensitive material, and the noble metal particles in the gelatin on the heat-resistant substrate 18. It is a process to fix as.

  This step is not limited as long as gelatin and the flammable base material can be burned and removed, but it is preferably 400 ° C. or higher, more preferably 480 ° C. or higher. It is the range below the possible temperature. When the temperature is 300 ° C. or higher, a black carbon film of gelatin is formed. However, when the temperature is 400 ° C. or higher, it can be reliably removed by combustion. Further, by making the temperature lower than the heat-resistant temperature of the substrate, it is possible to prevent photographic image damage (image deterioration) due to deformation and deterioration of the substrate. According to this process, the gelatin film and the flammable base material burn out after carbonization, and the noble metal fine particles agglomerate in the direction perpendicular to the substrate and melt and adhere to the heat-resistant substrate. By removing, a photographic image transfer product in which a photographic image is formed as shown in FIG. 1D can be produced.

  The photographic image transfer product obtained in this embodiment comprises a heat-resistant substrate and a noble metal layer 18 formed thereon, both of which are chemically extremely stable, and mechanical strength is obtained by fixing the noble metal film to the substrate. Will also be very high. In addition, since gelatin is not contained, there is little possibility that the gelatin film will be chemically altered during storage or biological alteration such as mold. Therefore, this photographic image transfer product has the advantage of having very high storage stability.

  In this step, since a flexible material can be used as the combustible base material, the photographic photosensitive material can be attached to a heat-resistant substrate having unevenness and curvature. Therefore, there exists an advantage that a three-dimensional photographic image modeling thing can be produced.

  Furthermore, the preparation of the light-sensitive material is not easy because it requires equipment such as a dark room and it is difficult to obtain a photographic emulsion. In the present embodiment, since a photosensitive material such as commercially available photographic paper can be used, there is an advantage that the photosensitive material does not necessarily have to be manufactured by itself and can be used in a wide range.

  As described above, according to this embodiment, since a flammable and flexible base material can be used, it is generally unnecessary to use a hard heat-resistant substrate, and photographic photosensitive material preparation becomes easy. A variety of photographic light-sensitive materials including commercially available photographic printing paper can be used, and more various photographic image transfer materials including three-dimensional objects can be produced.

  Note that the photographic image transfer material created by the method for producing a photographic image transfer material according to the present embodiment is formed using a noble metal, and the noble metal layer has good electrical conductivity. It can be applied to the production of printed circuit boards and the like.

  Hereinafter, the production work was actually performed on the photographic image transfer product according to the above embodiment, and the effect was confirmed.

(Example 1: Barita photographic paper)
First, baryta photographic paper (Azo photographic paper, manufactured by Kodak Co.) was used as a photographic photosensitive material, and a negative image was exposed to this.

Next, this photographic light-sensitive material was subjected to gold deposition at 25 ° C. under the conditions shown in Table 2 below using a processing solution having the composition shown in Table 1 below. In the fixing operation, an F5 fixing solution generally used as a fixing solution was used.

Next, a photographic photosensitive material on which the gold was deposited was attached using a decorative tile (manufactured by INAX, white decorative tile, 10 cm × 10 cm) as a heat resistant substrate, and baked in two stages in an electric furnace. The firing conditions were as shown in Table 3 below.

  As a result, the barium sulfate contained in the white base of the photographic paper formed a thin film on the tile, but it was in the form of a white powder and could be easily removed. It was confirmed that a glossy image can be formed. The obtained tile is shown in FIG.

(Reference example: RC paper)
In this example, the same procedure as in Example 1 was performed except that the combustible base material was resin-coated photographic paper RC paper (manufactured by Fujifilm, Fujibro).

  As a result, a photographic image transfer product having a gold film on the tile surface could be obtained, but the titanium oxide contained in the white base of the photographic paper was thinned and could not be easily removed. Further, since the film was formed in a mottled shape, and this film caused light interference, the interference light concealed the gold film image, and a clear image could not be obtained.

  As described above, the effectiveness of the present invention was confirmed by the examples.

  The present invention has industrial applicability as a method for producing a photographic image transfer product.

Claims (1)

A step of exposing a photographic emulsion containing silver halide grains and gelatin onto at least a part of a photographic photosensitive material coated on a flammable substrate made of an organic material not containing titanium oxide ;
Depositing noble metal fine particles comprising gold, a platinum group element or a mixture thereof on the exposed portion of the photographic material;
Attaching the photographic emulsion side of the photographic material to a heat-resistant substrate,
A method for producing a photographic image transfer product, comprising a step of burning off the photographic light-sensitive material.