JPS5928151A - Post activation type dry type silver salt photosensitive material - Google Patents

Abstract

PURPOSE:To prevent halation and to enhance stability of a raw film, by coating the side of a support reverse to a photosensitive layer with a strippable colored layer. CONSTITUTION:Any transparent film or sheet, such as polyethylene, cellulose acetate, or polyester, can be used for a support. As a dye used for the colored layer, a dye absorbing radiation in the wavelength region to which a photosensitive compd. in the photosensitive layer is sensitive and being stable enough to retain >=1/4 of the initial optical density before the exposure to 20,000 luces white fluorescent light for 5hr can be used. A polymer having softening point within 0-150 deg.C is preferable for the binder of the colored layer. It is necessary for the colored layer to have an adhesive strength fastly adhering to the prescribed position of the support during the operations before the exposure, such as storage conveyance, preheating, etc. of the raw film, and when it is stripped after the exposure or development, it must have tensile strength enough to be stripped fully at one time.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a post-activated dry type silver salt photographic material which prevents halaying and improves the stability of a raw film.

Although various types of dry silver salt photosensitive materials have been proposed in the past, the ones actually used are so-called ordinary photosensitive dry silver salt photosensitive materials.

The dry silver salt photosensitive material provided here by the present inventors is called a post-activated dry silver salt photosensitive material, and is non-photosensitive under normal light, but can be made photosensitive by heating. It is a dry image forming material that can be imparted with the following properties and that can form an image only by dry processing.

There are also points in the post-activated dry type silver salt photosensitive materials that require various improvements in practical terms. In other words, 1. One problem was that an image with clear outlines could not be obtained.

Regarding this point, in conventional conventional photosensitive dry silver salt photosensitive materials, a method of providing a halayone prevention layer has been known. (Japanese Patent Publication No. 48-33692, Japanese Patent Publication No. 5
(No. 7-68831) However, it is very difficult to apply this method to post-activated dry type silver salt photosensitive materials.

This is because the post-activated dry silver salt photosensitive dye is characterized by the photostability of the raw film. Therefore, the antihalation layer is naturally required to have a certain degree of photostability. Therefore, both the binder and the dye constituting the antihalation layer must have excellent photostability. On the other hand, conventional photosensitive dry silver salt photosensitive materials are not exposed to harmful light prior to image forming operations, and therefore, photostability fg: is not required for the halayone prevention layer. Therefore, the concept of conventional photosensitive dry-type silver salt photosensitive materials cannot be directly applied to post-activation type dry-type silver salt photosensitive materials.

In order to obtain practical sensitivity, if the sensitivity is increased using a sensitizer, etc., the stability of the raw film decreases, and if the stability of the p raw film is improved using a stabilizer, etc., the sensitivity decreases. There was an essential problem. For this reason, it was extremely rare to obtain a film that had both practical sensitivity and raw film stability.

As a result of intensive research to solve the above problems, the inventors of the present invention have found that a strippable colored layer is coated on the opposite side of the photosensitive layer of the support to prevent halation and to prevent raw film. The present inventors have discovered that the stability of the compound can be improved, and have completed the present invention.

That is, the present invention provides a post-activated dry silver salt photosensitive layer, which is characterized in that a post-activated dry silver salt photosensitive layer is provided on one side of the support, and a colored layer that can be peeled off after exposure is provided on the other side. It is interest.

The post-activated dry type silver salt photosensitive materials used in the present invention are disclosed in Japanese Patent Publication No. 51-29819, Japanese Patent Publication No. 41967-1982, Japanese Patent Application Laid-open No. 54-21326, and Japanese Patent Publication No. 54-1.
As described in Japanese Patent Application Laid-open No. 24721 and Japanese Patent Application Laid-open No. 153937/1987, it is non-photosensitive under normal light, but can become photosensitized by heating.
In addition, it is a photosensitive material that allows images to be obtained only by dry processing. For example, (1) a silver halide that is reducible to free silver by light irradiation and that contains silver iodide (may contain other silver halides, but always contains iodide #!) , silver iodobromide) and (11) a redox reaction composition that can initiate a reaction and produce a visible change by heating in the presence of free silver [e.g. silver behenate and 2,2'-
Methylenebis(4-ethyl-6-+-butylphenol)] and (iii) have the effect of oxidizing free silver, but they themselves become photosensitized by heating, and the effect on free silver by light irradiation after heating. An oxidizing agent for free iron (for example, a divalent mercury ion compound) that suppresses the oxidation action and also has a catalytic action to promote the redox reaction of the redox reaction composition, and (1v) reduction as the free silver is oxidized. A post-activated dry silver salt photosensitive material containing a photoreactive oxidizing agent (for example, tetrazolomobutane) for restoring the free iron oxidizing agent to its original state under light irradiation. I can list them. It is also possible to use a photosensitive dye that is spectrally sensitized by adding a photosensitive dye (such as melonanine type or cyanine type).

The support used in the present invention may be of polyethylene, cellulose acetate, polyester, etc., as long as the film material is sorted and transparent.

The dye in the colored layer absorbs radiation in at least the same wavelength range to which the photosensitive means in the photosensitive layer is sensitive, and
After 5 hours of irradiation with 20,000 lux of white fluorescent light, a dye that is more stable than the pre-test optical density can be used.

The analogy is Bengara and lead tan.

Cadmium red, cobalt purple 2 ultramarine blue, cobalt evening.

Emerald green, Carzen black, Hansa yellow, Toluidine rhet, Phthalonanine blue, Phthalocyanine green, Auramine lake, Pigment scarlet, Lake red.

Eosin Rake, Rhodamine Rake 1 Victoria
Pigments such as blue lake, anrad green lake, malachite green lake, naphthol, etc.
Yellow S, Oil Yellow AB, Congo Red, Auramine 0. Malachite Clean, Erythrone, Methylene Blue, Inziza, Alizarin Blue Black B.

Dyes such as aniline blue can be used.

The Nonon inder used in the colored layer has a softening point (Tg
) is preferably 0° C. to 150° C. Other polymers may be used as long as they have the same physical properties as the composition by mixing additives and the like. For example, polyvinyl butyral, polyvinyl formal.

Polystyrene, polyvinyl alcohol, polymethyl methacrylate, gelatin, polyvinyl chloride.

Styrene-acrylonitrile copolymer, styrene-acrylate copolymer, styrene-butanoene-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinylidene chloride-acrylonitrile copolymer,
Vinylidene chloride-vinyl acetate copolymer and the like can be used. If the binder has a softening point below 0°C, the raw film will adhere to the upper and lower films during storage, and stripping will not be possible at once. Also, the softening point is 15
Non-inders with temperatures of 0'C or higher pose practical problems because the halayon prevention layer may partially peel off from the support or crack entirely during storage of the raw film.

The colored layer must have enough adhesive strength to remain firmly in place on the support during pre-exposure operations such as storage, transportation, and preheating of the raw film, and must have sufficient adhesion to remain firmly in place on the support after exposure (or after development). )
When stripping, there must be enough tensile strength to strip cleanly at one time. Therefore, in order to control the adhesion, it is desirable to mix an adhesive or a softener with the above-mentioned inder to increase the adhesion, and to reduce the adhesion, use an inert agent or a softener to reduce the adhesion. It is preferable to add powders, oily substances, etc. It is also desirable to control the thickness in order to control the tensile strength of the core.

For coating the photosensitive layer and the halayon prevention layer on the support,
It doesn't matter which method you use. The coating thickness is preferably 2 to 50 microns.

...The anti-ration layer is provided on the opposite side of the photosensitive layer.

This is because after forming a 0 image, a clear image can be obtained by removing it by a stripping process. ■Providing a Rayon prevention layer between the photosensitive layer and the support poses difficulties in selecting binders, dyes, and bath mediums, and in particular limits the type and concentration of dyes, so that sufficient effects cannot be obtained. difficult to obtain.

The light-sensitive material according to the present invention can be used as any type of photographic material. For example, roll microfuge
Can be used for 1lum making machine, roll type slide making machine, etc. Further, the stripping of the halayone prevention layer from the support may be carried out at any time after the exposure is completed.

By adopting the above structure, the light-sensitive material of the present invention has the effect that not only halation is prevented, but also the stability of the raw film is significantly improved. Note that by storing the raw film in layers, the stability of the raw film can be further improved.

Example 1 A solution was prepared by adding the compounds shown below with stirring as described below. Spread this solution to a thickness of 127 μm.
;1? It was coated on a ``Lyester Film'' to a wet thickness of 1007 mm and dried at room temperature to form an anti-haline layer.

Methyl ethyl ketone 7ft toluene
3i polyvinyl butyral
1g-It A L 910 black ink (manufactured by Tokyo Ink) 27.Meanwhile, 8.55r- of behenic acid was added to ethanol.
#150 ml VC was dissolved while heating and stirring, and while continuing to heat and stir, an aqueous sodium hydroxide solution obtained by dissolving 1y- of sodium hydroxide in 100 parts of water was added dropwise to this to prepare sodium behenate. did. Next, 200 d of hot water is added to this, and when heating and stirring are continued, the sodium behenate is completely dissolved. Next, an acidic nitric acid aqueous solution containing an equimolar amount of silver nitrate to the charged behenic acid was added dropwise to the solution while stirring with heating. The dissolved sodium behenate was converted into silver behenate and insolubilized. This is f
After filtering, it was washed repeatedly with hot water and hot ethanol, and then dried and used.

Next, 79 parts by weight of a 2:s mixed solvent of methyl ethyl ketone and toluene and 21 parts by weight of the above-mentioned silver behenate were milled for 16 hours+lξ-luminescence to give behene rI1. A silver dispersion was prepared. Next, a solution of polyvinyl butyral in methyl ethyl ketone (11% by weight) was added to this silver behenate dispersion 207.
30 g was added and stirred. Next, while stirring, add 3d of methanol solution of mercuric acetate (4 parts by weight), iodine i0
．． 27, toluene solution of diphenylzolomethane (1
0.6 parts by weight) and 0.67 parts by weight of antipyrine were added in this order and stirred to prepare an emulsion. This emulsion was applied to the opposite side (on the support) of the above-mentioned halayone prevention layer at a thickness of 100 μm when wet.
Apply to a thickness of 100 mL and air dry for 5 minutes at room temperature. Next, a solution of polymethyl methacrylate in methyl ethyl ketone (10 MM
Part) A solution containing 0.45 ii' of phthalazinone 0,147.2.6-methylenebis(2-hydroxy-3-+-butyl-5-methylenyl)-4-methylphenol in 10t was added to a thickness of 100μ when wet. Top coated and dried at room temperature.

The obtained sheet was preheated at 100° C. for 5 seconds under a red safety lamp, then loaded into a camera, an original image consisting of fine lines was photographed on a reduced scale, and then developed at 120° C. for 5 seconds. Next, the anti-halation layer was removed 7 times, resulting in an image with clear outlines and no halation.

Comparative Example 1 An image obtained by performing the same operations as in Example 1 except that the antihalation layer of Example 1 was omitted had unclear outlines.

FIG. 1 shows 1001. The optical density distribution of the line image of /ltrm is shown.

Examples 2 to 5 (and Comparative Examples 2 to 3) The composition of the anti-harrayon layer was changed, and the MTF at this time was
(Modulation transfer function) is shown in Table 1 including Example 1 and J7 Comparative Example 1. At this time, components other than the anti-nolation layer and all operations related to fine formation of images were carried out in the same manner as in Example 1.

Table 1 Note 1 In Comparative Example 2, cracks occurred in the halayone prevention layer during the process from preheating to exposure, and stripping after development was not completed at once.

Note 2 In Comparative Example 3, stripping was not easy, the adhesive strength was stronger than the tensile strength, and several treatments were required.

Note 3 Pigment column C3■ indicates color index Example 6 Examples 1 to 5. Comparative Example 1 to 30 month samples were stacked in 10 sheets for each sample and heated under the conditions of 23°C and 50% It H.
When I took out the sample υ that had been saved by Chizuki, the following changes had occurred.

The Sansols of Examples 1 to 5 and Comparative Example 1 had no abnormalities.

In the case of Sansol of Comparative Example 2, the anti-rain coating layer was partially peeled off from the support and was cracked throughout.

In the case of Comparative Example 3, since the anti-reflection layer was sticky, some of the 10 sheets of Sansol adhered to each other, making it impossible to form an image.

Example 7 The samples of Examples 1 to 5 and Comparative Example 1 were heated at 40°0°80
%I:LH The back side of the photosensitive layer of the support was irradiated with 10,000 lux from a white fluorescent lamp (Toshiba PR, TOW) to observe the decrease in sensitivity, and it was found that the initial sensitivity was 2. The following differences were found in the time it takes to reach +0.3 in l ()'og g.

Examples 1 to 5 2 4-hour comparative example 1: 1-hour example; 3 The same test as in Example 7 was conducted by stacking 10 samples for each sample, and the sensitivity of the fifth sample from the top was the initial sensitivity. When I looked at the time it took to reach 1/2 of that, I found the difference as shown below.

Examples 1-5: 42 hour comparative example = 2 hours Example 9 Examples 1-5. Each of the films of Comparative Examples 1 to 3 had a width of about 40 mm.
The films were cut into pieces with a length of 1.51 mm and a length of 1.51 nm, preheated at about 100° C. for 5 seconds, loaded into a still camera, and the handling properties of each film were examined.

The films of Examples 1 to 5 and Comparative Example 1 had smooth film feeding and did not cause any problems in handling.

On the other hand, in the film of Comparative Example 2, as the roll film was being transported, cracks occurred in the lateral direction in the anti-fine layer as the film was flexed and stretched, and a portion of the film peeled off in small pieces. In addition, the sample of Comparative Example 3 had some drawbacks, such as a part of the roll film adhered to the roll and peeled off from that part during handling.

Example 10 A test as described in F was conducted for the preheated, exposed, and developed one-shot sols of Examples 1 to 5 and Comparative Examples 2 and 3 for practicality comparison.

First, each sample was cut into a size of 1 cm in length and 20 ounces in length using a cutter, and placed on an office desk with the anti-polishing layer facing up, evenly over the entire surface with double-sided tape. Next, one end of each sample was lightly held with cellophane tape and gently peeled off, and the entire antihalation layer of the samples of Examples 1 to 5 was peeled off cleanly at once. On the other hand, in Comparative Example 2, even when I tried to peel it off, it was so brittle that I could only peel off the part that was covered with cellophane tape. In Comparative Example 3, the antihalation layer was broken during peeling, and it was impossible to remove the entire surface cleanly in one operation.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the optical density distribution at 100 t/rtvn of the sheet materials obtained in Example 1 and Comparative Example 1. Patent applicant Asahi Kasei Kogyo Co., Ltd. Figure 1 ■ 111111 Shokei 1111

Claims (3)

[Claims] (1) Post-activated dry-type silver characterized in that a post-activated dry-type silver salt photosensitive layer is provided on one side of the support, and a colored layer for preventing halation that can be removed after exposure is provided on the other side. salt photosensitive material (2) The post-activated dry silver salt photosensitive layer reacts with (1) silver halide, which is reducible to free silver by light irradiation and contains silver iodide, and (11) by heating in the presence of free silver. and (iii) a redox reaction composition capable of initiating a visible change.
) It has the effect of oxidizing free silver, but it itself becomes photosensitized by heating, and the oxidizing effect on free silver is suppressed by light irradiation after heating, and the redox reaction of the redox reaction composition is suppressed. and (iv) a photoreactive oxidation agent for restoring the free silver oxidizing agent, which is reduced as the free silver is oxidized, to its original state under light irradiation. A post-activated dry type silver salt photographic material according to claim 1, characterized in that it contains an agent. (3) In the antihalation colored layer, a polymer in which l1g of Nononinder is between 0°C and 150°C,
H before testing after 5 hours of irradiation with white fluorescent light at 20,000 lux
A post-activated dry type silver salt photographic material according to claim 1, characterized in that it is a dye that is stable enough to maintain an optical density of