JPH08220691A - Silver halide photographic sensitive material having rear adhesive layer - Google Patents

Abstract

PURPOSE: To provide a novel silver halide photographic sensitive material (photographic adhesive sheet) capable of being stably produced by cutting, without inhibiting development, causing no trouble in development and previously furnished with easy-to-use adhesive layer and releasable sheet. CONSTITUTION: The substrate of the releasable paper of a releasable sheet is resistant to water. The dynamic friction coefficient according to JIS P8147 between the surface of the releasable agent of the releasable sheet and the chloroprene rubber having 65±2 deg. Shore A hardness is controlled to >=0.21, the adhesive strength according to JIS Z1538 of the adhesive to a stainless steel sheet is adjusted to >=1,000g/25mm width and the silver halide photographic sensitive material (photographic adhesive sheet) has a rear adhesive layer with the adhesive layer of the releasable sheet adhered to the emulsion face on the opposite side of the substrate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material suitable for application of images to indoor and outdoor signs, advertising towers, wall decorations, identification cards, notebooks, albums and the like.

[0002]

2. Description of the Related Art Conventionally, a sticker print for sticking an image to a signboard wall decoration, a notebook, an album, etc. is one in which a paper portion of a support is peeled off after development processing, and the sticking layer and a release sheet are stuck before use. Are known and disclosed in JP-A-53-125823. That is, in this method, a photographic printing paper having a silver halide emulsion layer on the polyethylene layer of a polyethylene laminated photographic printing paper support is developed, and then the support paper is peeled off and the back surface of the polyethylene layer is separated. A double-sided pressure-sensitive adhesive tape with a mold sheet is attached, and an adhesive layer is provided on the back side of the polyethylene layer and a release sheet is further provided thereon. No. 60-41949 and No. 60-4
No. 1950 presents a method of reducing the thickness of a photographic printing paper, especially a paper support, and applying a pressure-sensitive adhesive layer and a release sheet without peeling off the paper support after development processing to form a seal print. ing.

[0003]

However, the work of providing the release sheet and the pressure-sensitive adhesive layer on the back surface after development of the photographic printing paper is very complicated and requires skill, especially in the case of a large area screen. Becomes very difficult. In order to avoid this complexity, a photographic support having an adhesive and a release sheet provided on the back surface of the support in advance is prepared, a silver halide emulsion layer is coated, and an adhesive layer and a release sheet are prepared. To prepare a silver halide photographic light-sensitive material (hereinafter referred to as a photographic pressure-sensitive adhesive sheet or seal print), and after cutting according to the application, after the photo-developing process, peel off the release sheet, A method of sticking to an adherend such as a signboard, notebook, album, etc. is considered, but when cutting according to the application, the slitter cutting blade, guillotine at the stage of performing slitting cutting processing, guillotine cutting processing, etc. Adhesive adheres to the cutting blade, etc., which significantly reduces the work efficiency of the cutting process, and the adhesive adhered to the blade transfers to the photographic adhesive sheet, causing development inhibition and developing an optimal image. To get Challenges that must be able to not or resolve the many. The photographic type pressure-sensitive adhesive sheet as used herein means a silver halide photographic light-sensitive material having a pressure-sensitive adhesive layer on the back surface, and this term may be used hereinafter.

On the other hand, since the photographic adhesive sheet is developed in the same manner as the ordinary photosensitive material for photographic printing paper, it is kept in contact with an aqueous solution in which various compounds are dissolved during the development processing, and the temperature of the solution is 25-. Be processed in the range of 40 ℃,
Since it is exposed to various photographic development processing conditions, such as processing under a wide range of pH of about 5 to 11 and drying at a high temperature of about 85 ° C, the adhesive strength of the adhesive decreases and processing In the process, the release sheet peels from the adhesive layer,
The adhesive may stick to the transport roller or the wall by peeling it from the photographic support, or the release paper may peel off, causing jamming, causing trouble, disrupting the development process, and taking important photos. It may cause a great nuisance to the customer that would ruin it. As described above, the photographic adhesive sheet cannot be easily realized, and a solution to this problem has been demanded.

The object of the present invention is to provide a novel halogenated product which can be manufactured stably by cutting, does not interfere with development, has no trouble in development, and is provided with an adhesive layer on the back side which is easy to use. Silver photographic light-sensitive material (photographic adhesive sheet)
Is to provide.

[0006]

SUMMARY OF THE INVENTION The present inventor has made a release paper substrate water resistant in a photographic pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is preliminarily provided on the non-emulsion layer side of the photographic support of a photographic paper photosensitive material. The release agent layer surface and Shore A hardness are 65 ± 2 °
By setting the dynamic friction coefficient according to JIS P 8147 to 0.21 or more with chloroprene rubber, the adhesive layer adheres to a stainless steel plate according to JIS Z 1538
The present invention has been achieved by setting the width to be g / 25 mm or more.

The present invention will be described in detail below.

The photographic pressure-sensitive adhesive sheet of the present invention refers to a silver halide photographic light-sensitive material having a structure composed of a silver halide photographic light-sensitive layer, a photographic support, an adhesive layer and a release paper, and is a conventional seal print. Such a material is distinguished from a material obtained by laminating a release sheet having a pressure-sensitive adhesive layer after developing such a silver halide photographic light-sensitive material.

The terms used in the present invention are explained below: Release paper substrate: Base of release paper; paper, paper structure having resin layers on both sides, sheet-like material such as plastic film Release paper: release Structure having release agent layers on both surfaces of the paper pattern substrate;
Release sheet that is peeled off at the time of use Release sheet: Adhesive structure having adhesive layer on release agent layer of release paper Adhesive layer: Adhesive layer adhered to target; Coating on one side of release paper Adhesive layer adhered to the back side of the photographic support Photographic support: Substrate on which the photographic photosensitive layer is coated; Paper structure having resin layer, or plastic film Photographic pressure-sensitive adhesive sheet: on one side A silver halide photographic light-sensitive material having a structure in which a pressure-sensitive adhesive layer of a release sheet is bonded to the other surface of a photographic support having a silver halide photographic light-sensitive layer.

Paper support: Paper as a core material of a photographic support or a release paper base paper structure. <Photographic Support Having Resin Layers on Both Sides of Paper Support><PaperSupport> The paper support (also referred to as base paper) used for the photographic support of the photographic adhesive sheet of the present invention is a photographic printing paper. A grade is used. Examples of the raw material for the base paper include natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, and various raw materials for laminated paper. As the natural pulp, softwood pulp, hardwood pulp, mixed pulp of softwood pulp and hardwood pulp, and the like are used. There are neutral paper, acid paper, etc. produced by the manufacturing method, but it does not depend on the type of the base paper according to the manufacturing method, and any other neutral paper, acid paper, etc. may be used. It is preferable to use a grade base paper. Particularly, photographic printing paper grade neutral paper is preferable. The thickness of the paper support is preferably 40-100 μm.

Since the above paper support is treated as a silver halide photographic light-sensitive material with a developing solution under conditions such as high pH and high temperature, the paper support itself is required to have water resistance. Although the processing liquid does not enter from the surface due to the resin layer, the so-called edge penetration occurs, in which the developing solution enters from the cutting surface to discolor the photographic print from the edge to yellow, and the quality is remarkably deteriorated. It is necessary to include a special paper waterproofing agent in the above. In this case, a mixture of additives such as a sizing agent, a fixing agent, a tension enhancer, a filler, an antistatic agent, a dye, an antifoggant and the like is used during papermaking.
Further, a surface sizing agent, a surface tension agent, an antistatic agent, or the like may be appropriately applied to the surface.

<< Photographic Support Having Resin Layer Laminated on Both Sides of Paper Support >> A photographic support having a resin support laminated on both sides of the paper support used in the present invention will be described.

A resin such as polyolefin or polyester is melt-extruded and coated on a paper support to be laminated. In this melt extrusion coating method, a resin composition is melted to a predetermined temperature in an extruder and is run on a paper support (at a coating position, the back side of the paper support is supported by a roll or a drum). Although it is melt-coated from the die slit,
The melt-applied resin composition layer may be a single layer applied from a single slit, or may be multiple layers from a plurality of slits. Its melt extrusion temperature is 20
Since it is carried out at 0 to 350 ° C., any resin that can be melted in this temperature range can be mixed and melted together to form a layer.

Examples of useful resins include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate, polyethylene naphthalate and modified polyester, polyether resins such as polyoxymethylene and polyoxypropylene, polyester urethanes and polyethers. Examples thereof include urethane resins such as system urethanes, polycarbonate resins, polystyrene resins and the like, which may be used alone or in combination. Preferable resins are polyethylene resin and polyester resin, which may be used alone in the resin layer, or may be used as a main component in a mixture with any other resin described above.

It is commonly used in the art to laminate or laminate the provision of the above resin layer on a photographic support on a paper support. It is stated in the Standard Chemistry Dictionary (Maruzen, edited by The Chemical Society of Japan) that polymer materials are laminated together or that polymer materials and different materials are laminated by adhesion or pressure bonding. In the present invention, the term "laminating" is used for the provision of the resin on the paper support or the provision of the resin.

The polyethylene resins useful in the present invention include low density polyethylene and high density polyethylene, both of which are preferably used, and these may be used alone or in combination.

The thickness of the polyethylene laminate layer is one side
If it is 10-40 μm, it will be water resistant.

A method of laminating a polyester resin in the same manner as a polyethylene laminated photographic support is described in, for example, JP-A-5-127309, JP-A-5127310, JP-A-5127311, JP-A-5-204091, and JP-A-5-04091. 5-265133, Dohei 5-323495, Dodai
6-3767, Dohei 6-3768, Dohei 6-3769, etc.

Examples of the polyester resin for laminating useful in the present invention include polyethylene terephthalate, polyethylene naphthalate, and modified polyester having polyethylene terephthalate as a main structure (hereinafter referred to as modified polyester). The modified polyester has polyethylene terephthalate as the main chain and comprises a polyester part and a modified part. The main chain constituent molecules of the modified part are terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and 2,7-naphthalene as dibasic acid of ester bond. Dicarboxylic acid, p-xylidene dicarboxylic acid,
1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, 5-alkali metal sulfo-isophthalic acid, 4-alkali metal sulfo-2,6-naphthalenedicarboxylic acid and the like, and also as ester bond glycol (diol) Ethylene glycol, propylene glycol, 1,4-butanediol, 1,4-hexylenediol, 1,4-benzenediol (hydroquinone), 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene Glycol, tetraethylene glycol, polyethylene glycol, (number average molecular weight 300
~ 30,000), polypropylene glycol (number average molecular weight
300 to 30,000), etc. Preferably, the dibasic acid is terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 5-metal sulfo-isophthalic acid, 4-metal sulfo-2,6-naphthalenedicarboxylic acid, etc. As the glycol, ethylene glycol, propylene glycol, 1,4-cyclohexanedimethanol, polyethylene glycol (number average molecular weight 300 to 30,000) and the like are used. The metal ion of the metal sulfo substituent is sodium, potassium, lithium, cesium, etc., preferably sodium.

The modified portion of the modified polyester useful in the present invention is 50 mol% or less based on the total polyester bonds, and when it exceeds 50 mol%, the physical properties as a support, such as mechanical strength, glass transition point, and water resistance. The properties are deteriorated and it becomes difficult to use as a support. It is preferably 40 mol% and particularly preferably 30 mol% or less.

The compound having an alkali metal sulfo group in the modified portion of the modified polyester is 2 for all ester bonds.
It is preferably contained in a proportion of from 10 to 10 mol%, and the adhesiveness between the emulsion layer and the photographic support is excellent. When this compound having an alkali metal sulfo group, such as 5-sodium sulfo-isophthalic acid, is 2 mol% or less, it is almost the same as polyethylene terephthalate, and the meaning of modification is weakened. Further, if it is 10 mol% or more, the water absorption rate becomes large, the adhesiveness between the paper support and the resin deteriorates, and there is a risk of peeling during the photographic processing. The problem comes out as a support. It is preferably 2 to 7 mol%, and particularly preferably 3 to 6 mol%.

For the modified portion of the modified polyester, it is also preferable to use polyethylene glycol and / or a saturated aliphatic dicarboxylic acid such as adipic acid together with the sulfo compound.

The modified polyester resin useful in the present invention can be synthesized by a conventionally known polyester production method. For example, in the esterification reaction, either an acid component can be directly esterified with a glycol component, or an acid component can be used as a dimethyl ester with glycol by a transesterification method. At this time, if necessary, a polyester can be polymerized and synthesized by using a transesterification reaction catalyst for esterification and a polymerization reaction catalyst such as antimony oxide in the polymerization reaction. Regarding the polyester constituent components and the synthetic method described above, for example, Polymer Experimental Science No. 5
Volume "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980) Nos. 103-136
Page or "Synthetic Polymer V" (Asakura Shoten, 1971) No. 1
It can be performed with reference to the description on pages 87 to 286.

Specific methods for synthesizing the modified polyester are described in US Pat. No. 4,217,441 and JP-A-5-210199, and the modified polyester useful in the present invention can be synthesized by these methods.

Polyesters (including modified polyesters) useful in the present invention should be of sufficiently high molecular weight. Generally, the molecular weight of a polymer compound such as polyester is represented as an intrinsic viscosity (for example, edited by The Chemical Society of Japan, Dictionary of Standard Chemistry, 224 pages, 1991, published by Maruzen), but the intrinsic viscosity of the polyester used in the present invention is 0.40 to 0.75
The preferable range is 0.45 to 0.65 as a range in which stable melt extrusion is possible. When the intrinsic viscosity of the polyester is less than the above, the resin becomes white and brittle after melt extrusion. Further, when melt-extruding while containing water, the intrinsic viscosity is extremely lowered, so that special attention must be paid to drying before melting, and even if the intrinsic viscosity is sufficiently high, hydrolysis may occur during melting. The resin chips are usually dried at about 150 ° C under a vacuum of about 10 ^-3 Torr.

If the thickness of the polyester laminate layer used in the present invention is 10 to 40 μm on one side, the water resistance function is achieved.

The resin layer on the side in contact with the photosensitive layer is a white resin layer mixed with a light-reflecting white pigment.

<< Photographic Support Having Electron Beam Curable Resin Layer >> A photographic support having an electron beam curable resin layer on at least one side of a paper support will be described below. recent years,
In place of the polyethylene laminated photographic support technology, a photographic support obtained by coating an electron beam curable resin on a paper support and irradiating it with an electron beam to cure it is disclosed in, for example, JP-A-57-2.
No. 7257, No. 57-49946, No. 61-262738, No. 62-61
No. 049 and the like.

As the electron beam curable compound of the electron beam curable resin, any compound can be used as long as it is a compound curable by electron beam irradiation. Examples of the compound curable by electron beam irradiation which can be used in the present invention include, for example, Japanese Patent Publication
60-17104, JP-A-60-126649, or JP-A-2-157
The electron beam curable compounds described in the specification of No. 747 and the like correspond to electron beam curable monomers or oligomers.

The curable monomer or oligomer used for the useful electron beam curable photographic support is 1
Unsaturated compounds containing two or more carbon-carbon double bonds in the molecule (eg acrylic or methacrylic oligomers, polyfunctional acrylic or methacrylic monomers)
An unsaturated compound containing at least one carbon-carbon double bond in one molecule (for example, a monofunctional acrylic monomer, a methacrylic monomer, a monomer used when the curable monomer is diluted and used). Vinyl monomers, etc.) are used.

Monomers having two or more of these unsaturated double bonds are radically polymerized by electron beam irradiation to form intermolecular,
A cross-linking bond is formed by a cross-linking reaction and cured to produce a cured resin. Examples thereof include acrylic acid or methacrylic acid ester of polyurethane, acrylic acid or methacrylic acid ester of polyether alcohol, bisphenol A or acrylic acid or methacrylic acid ester of bisphenol A or its epoxy condensate, 1,6-hexanediacrylate. Or methacrylate, neopentyl diacrylate or dimethacrylate, diethylene glycol diacrylate or dimethacrylate, butadiene acrylate or diacrylate, tetraethylene glycol diacrylate or dimethacrylate, glycerol triacrylate or trimethacrylate, polyethylene glycol (repeating unit n = 4 to 300) ) Diacrylate or dimethacrylate, 1,4-butanedioldia Relate or dimethacrylate, neopentyl glycol diacrylate or dimethacrylate, isocyanuric acid diacrylate or dimethacrylate, isocyanuric acid triacrylate or trimethacrylate, trimethylolpropane triacrylate or trimethacrylate, propylene oxide modified trimethylolpropane polyacrylate, 1, 2-bis (N, N-diepoxypropylaminomethyl) cyclohexane, trimethylolpropane triacrylate, pentaerythritol pentaacrylate, polyester maleic or fumaric acid ester, divalent or polyvalent organic acid such as adipic acid Condensation with dihydric or polyhydric alcohols such as ethylene glycol Poly or oligoesters or polyester diesters Or it can be given polyacrylate or methacrylate.

When it is necessary to adjust the viscosity of the composition liquid containing the crosslinkable monomer or oligomer, the unsaturated double bond which can be incorporated into the crosslinked polymer is 1
It is possible to use an individual diluting monomer, and as the diluting monomer, glycidyl acrylate or methacrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate,
(N or iso) -propyl acrylate or methacrylate, butyl acrylate or methacrylate, 2-hydroxyethyl acrylate or methacrylate, 2-hydroxypropyl acrylate or methacrylate, phenoxyethyl acrylate or methacrylate, cyclohexyl acrylate or methacrylate, benzyl acrylate or methacrylate,
N, N-dimethylaminoethyl acrylate or methacrylate, N, N-diethylaminoethyl acrylate or methacrylate, ethylene oxide-modified phenoxyphosphoric acid acrylate, styrene, polyoxyethylene phenyl alcohol acrylic ester, 2-ethylhexyl acrylate, etc. be able to.

In the electron beam curable composition useful in the present invention, an organic solvent may be used as a diluent, if necessary. In that case, these solvents are evaporated after coating and remain in the coating layer. It is preferable to irradiate with an electron beam after drying so as not to cause it. Examples of these are acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, ether, glycol monoethyl ether, dioxane,
Benzene, toluene, xylene, etc. can be used.

The method for applying the prepared coating solution onto the paper support includes roll coating, bar coating, air doctor coating, plate coating, squeeze coating,
Any of an air knife method, a reverse roll coating method, a transfer coating method and the like may be used. Also,
A fountain coater or slit orifice coater system can also be used.

As the electron beam accelerator for curing the electron beam curable resin composition applied to the paper support, a van de Graaff type scanning system, a double scanning system, a curtain beam system or the like is used. As electron beam characteristics, pressurization voltage is 100-1000KV, absorbed dose is 0.5-20
It is Megarad. The electron beam irradiation device used for the photographic support of the present invention is not particularly limited, and generally, as such an electron beam accelerator for electron beam irradiation, a curtain beam system which can obtain a large output at a relatively low cost. Are effectively used. Accelerating voltage during electron beam irradiation is 100 to 3
00kV is preferable, and the absorbed dose is 0.5-10M
It is preferably rad.

The photographic support having the electron beam curable resin layer of the present invention may contain a white pigment on the side of the photosensitive layer, and the back side may be substantially transparent. The back side may be an electron beam curable resin layer or may be laminated with the polyethylene. In this case, the polyethylene laminate may be applied before or after the application of the electron beam curable resin layer or the electron beam irradiation. However, the polyethylene layer of the back layer is laminated first, and the electron beam curable resin layer is applied and the electron beam irradiation is performed. It is preferable to carry out after the step in order to improve the smoothness of the surface on the photosensitive layer side.

The electron beam curable resin composition used in the present invention can fulfill the function of water resistance if the film thickness after curing is 3 to 40 μm, but it is preferably 5 to 30 μm. <White plastic film photographic support> Examples of the plastic film support used in the photographic support of the present invention include polyester films, polycarbonate films, polyvinyl chloride films, polypropylene films, polystyrene films and the like. Polyester is preferably used in terms of easiness of production, film properties, easiness of adhesion and the like.

The biaxially stretched white polyester film of the photographic support of the present invention is commercially available, for example, Crisper (trade name) from Toyobo Co., Ltd., or ICILi.
Melinex990 (brand name) etc. are on sale from mited. Any of them can be used in the present invention, but they can also be used by themselves.

As the resin for the white polyester film, the resin and the manufacturing method described for the polyester laminate support can be used as they are, but the film forming method is different. The film can be formed by a conventionally known method, for example, a polyethylene terephthalate film method.
For example, polyester resin and white pigment are kneaded with a kneader such as a kneader to block oxygen, and then the white resin is molded into chips, heat-vacuum-dried, melt-extruded, extruded into a sheet from a T die, and then statically extruded. An unstretched sheet is obtained by bringing it into close contact with a cooling drum by an electric application method or the like and cooling and solidifying. Then, the resulting unstretched sheet is heated within a range of Tg + 100 ° C. from the glass transition temperature (Tg) of polyester through a plurality of roll groups and / or a heating device such as an infrared heater,
Longitudinal stretching. In this case, the draw ratio is usually in the range of 2.0 times to 6.0 times, and it is necessary to set it in a range in which subsequent transverse stretching is possible.
When the sheet has a multi-layered structure, the stretching temperature is preferably set based on the highest Tg of Tg of the polyester of each constituent layer. Then, the polyester film uniaxially stretched in the machine direction obtained as described above is Tg to Tm-20 ° C (T
Within the temperature range of (m: melting point), transverse stretching is performed, and then heat setting is performed. The transverse stretching ratio is usually 2.0 to 3.0 times, and the ratio of the longitudinal stretching ratio to the transverse stretching ratio is appropriately adjusted so that the obtained biaxially stretched film has physical properties measured and has desirable characteristics. At this time, the temperature difference in the stretching region divided into two or more is 1 to 50 ° C.
When the film is transversely stretched while the temperature is sequentially raised in the range, the distribution of physical properties in the width direction can be reduced, which is preferable. Heat setting is usually 0.5 to 30 at a temperature higher than the final transverse stretching temperature and within a temperature range of Tm-20 ° C or lower.
Heat set for 0 seconds. At this time, it is preferable to heat-set while sequentially increasing the temperature difference in the range of 1 to 100 ° C. in the region divided into two or more. The heat-fixed film is usually cooled to Tg or lower, and the clip gripping portions on both ends of the film are cut and wound into a roll. At this time, it is preferable to perform a relaxation treatment in the width direction and / or the longitudinal direction by 0.1 to 10% within a temperature range not higher than the final heat setting temperature and not lower than Tg. In addition, cooling is performed from the final heat setting temperature to Tg at 100
It is preferable to perform gradual cooling at a cooling rate of ℃ or less. The means for cooling and relaxing treatment is not particularly limited, and any conventionally known means can be used.

The intrinsic viscosity of the polyester resin is 0.50-0.
85 is preferable, and 0.55 to 0.70 is particularly preferable. However, the intrinsic viscosity of modified polyester in the case of laminated film is 0.40 ~
Resin in the range of 0.60 is easy to handle.

The thickness of the film support as a photographic support used in the present invention is preferably 40 to 130 μm, but 50 to 100 μm is particularly preferable in terms of handling. The whole film of the plastic film photographic support used in the present invention may contain a white pigment, but only the surface layer may contain a white pigment. The laminated film of the surface white layer on the side in contact with the photosensitive layer can be formed by a usual laminated film forming technique.

Titanium oxide is preferably used as the white pigment in the white pigment-containing resin layer or white film on the photosensitive layer side of the photographic support used in the present invention, and white pigments such as zinc oxide, barium oxide and neodymium oxide. Can also be used as a mixture with titanium oxide. There are two types of titanium oxide, anatase type and rutile type. The anatase type is preferably used, but the rutile type is also used. Further, these titanium oxides may be mixed and used.

Further, tinting dyes or pigments such as cobalt blue, ultramarine blue, organic dyes (for example, phthalocyanine dyes) may be contained together with these white pigments, and the content thereof is preferably 0.0001 to 0.05% by weight. .

The titanium oxide may be untreated titanium oxide which is not surface-treated, but it may be hydrous aluminum oxide,
Surface treated titanium oxide with various inorganic compounds such as silicon dioxide, zirconium oxide and magnesium hydroxide, or titanium oxide treated with various organic compounds such as various alcohols, surfactants, siloxanes and silane coupling agents.
Further, titanium oxide or the like which has been subjected to both the inorganic surface treatment and the organic surface treatment can be used.

As a method of mixing the white pigment, in the polyethylene resin composition or the polyester resin composition, the resin chips obtained by heating the resin under high vacuum and drying are directly sprinkled with the white pigment so as to have a predetermined concentration. And then put it in an extruder, melt and mix the resin at a predetermined temperature within the range of 200 to 350 ° C, and apply it on the paper support, and melt the resin chips and white pigment beforehand with a kneader such as a kneader. There is a method in which mixed chips are taken out as colored chips, dried in vacuum, and then colored chips having a predetermined concentration are mixed as they are or with colorless chips so as to have a predetermined concentration and then melted (mixed) by an extruder. Either method is suitable for the photographic support resin composition of the present invention.

In the case of the electron beam curable resin composition,
In order to prepare a coating solution containing a white pigment, it is desirable to use a homomixer, a Cowles dissolver, an ultrasonic disperser, a roll mill, a ball mill or the like according to the properties of the coating solution. In order to uniformly disperse the white pigment in the liquid, it is preferable to use a white pigment, particularly titanium oxide whose surface is previously treated with a metal oxide such as aluminum hydroxide. The electron beam curable resin composition is preferably applied by coating with a curable monomer or oligomer solution containing a white pigment as it is, but when the viscosity is high, a diluting monomer may be additionally applied for coating. Depending on the case, the viscosity may be adjusted by mixing an ordinary diluent (solvent) not related to curing. For ease of coating, the concentration of the effective component of the coating liquid and the viscosity of the coating liquid may be set in consideration of the finished film thickness and the like.

The coating amount of the resin of the photographic support of the present invention is such that the concentration of the titanium oxide white pigment in the resin composition is 4 to 70.
In the range of%, an arbitrary range within the range may be selected depending on the thickness of the resin layer or the thickness of the plastic film. For example, the polyethylene resin composition has a titanium oxide content of 6 to
The coating amount is 40 to 130 g / m ² at 30% by weight, the titanium oxide content is 4 to 40% by weight in the polyester resin composition, the coating amount is 40 to 130 g / m ² , and the electron beam curable resin composition (electronic The amount after linear curing) is preferably 4 to 70% by weight, and the coating amount is preferably 5 to 60 g / m ² .

The photographic supports used in the present invention include the resin-laminated photographic supports, the electron beam curable resin photographic supports and the plastic film photographic supports as described above. Ease of handling varies depending on the thickness and rigidity of the photographic pressure-sensitive adhesive sheet after the sheet is peeled off. It is preferable that the photographic support is as thin and rigid as possible, and a photographic support is preferably a plastic film in the present invention. Above all, a polyester film is preferable as the photographic support.

<Undercoating and Undercoating Layer> In order to strengthen the adhesion of the light-sensitive layer as the silver halide photographic light-sensitive material of the present invention to the photographic support, surface treatment and coating of an undercoating layer, etc. Is generally done. Adhesion of the pressure-sensitive adhesive layer to the photographic support can be sufficiently performed without performing the undercoating treatment, but if necessary, the undercoating treatment may be performed to reinforce the adhesion of the pressure-sensitive adhesive layer. This surface treatment and provision of a so-called undercoat layer are collectively referred to as an undercoat treatment. The method of each support for the subbing treatment will be described below.

For the surface of the polyethylene laminate photographic support useful in the present invention on the side coated with the silver halide photosensitive layer, corona discharge treatment, flame treatment, glow discharge treatment, ultraviolet irradiation treatment, high frequency treatment, activity is performed. Plasma treatment,
Activation treatment such as laser treatment is applied, and this alone is sufficient for adhering the photosensitive layer, but the adhesion may be insufficient depending on the formulation of the photosensitive layer.In such a case, after the corona discharge treatment, A hydrophilic colloid solution such as gelatin may be applied. Also in the case of an electron beam curable resin, the undercoating treatment can be performed by applying the above-mentioned corona discharge treatment and the gelatin undercoating liquid.

The undercoat treatment of the photographic support laminated with the polyester resin useful in the present invention can be performed in the same manner as the former two. Further, the hydrophilic resins cited below (for example, maleic anhydride to
A solvent (for example, acetone) coating solution containing a vinyl acetate copolymer) can be coated on any surface with or without treatment such as corona discharge. Further, the same method as the subbing treatment of a usual stretched polyethylene terephthalate support can be used. That is, n-butyl methacrylate: t according to the method described in JP-A-55-67745, JP-A-59-19941 and the like.
-A quaternary copolymer latex consisting of butyl methacrylate, styrene and 2-hydroxyethyl methacrylate, a surface-active agent, and a water-based undercoating liquid consisting of a curing agent are applied, dried, and then treated again by corona discharge or the like. Although the drawing process is completed, the same undercoating process can be performed on both the resin layer surface on the side where the photosensitive layer is applied and the resin layer surface on the back side. Further, the back surface is subjected to the same treatment or an undercoat layer as the above, and then directly coated with an antistatic composition or with an antistatic layer binder such as cellulose diacetate in advance and then the antistatic composition. A desired photographic light-sensitive material can be finished by applying the product as an organic solvent system liquid. The modified polyester support of the present invention can be subbed in the same manner.

<Release Sheet><< Release Paper Substrate >> The release paper substrate used in the present invention cannot be treated with a developing solution and is peeled off from the paper used for ordinary seal prints and adhesive sheets. Occurs and cannot be used. In the present invention, a release paper substrate or a plastic film of a paper structure having a resin layer on both sides thereof is used in order to prevent troubles during development processing.

The paper support as the core material of the release paper substrate having resin layers on both sides used in the present invention may be a general paper support of release paper, but the internal additive is used in the beating step in the pulp paper making step. As the water resistance improver, the wet strength improver similar to the case of the paper support of the photographic printing paper support,
It is desirable to make the paper itself water resistant in order to prevent the invasion of the developing solution or the like from the cut surface by adding a strength improver or a filler.

The resin layer of the paper structure having resin layers on both sides of the release paper substrate of the present invention is the same as in the case of the photographic support.
There are those obtained by laminating polyolefin resin on both sides, and those obtained by applying an ultraviolet curable resin layer and curing by irradiating with an electron beam, both of which are made of the same material as the photographic support and by the manufacturing method. can get. As the polyolefin resin, polyethylene resin, polypropylene resin,
Poly (co-ethylene-co-propylene) resin and the like can be mentioned, but polyethylene resin is preferable from the viewpoint of easy handling in production. Further, the polyethylene resin can be used in either low density or high density without any problem.

Examples of the plastic film as the release paper substrate of the present invention include polyester films such as polyethylene terephthalate, polyethylene naphthalate and modified polyester, polyolefin films such as polyethylene and polypropylene, polystyrene films, polyvinyl chloride films and polycarbonate films. Both can be used.

The thickness of the release paper substrate used in the present invention is 20
It is preferably in the range of up to 100 μm.

<Release Agent> As the release agent according to the present invention, a known silicone resin in the release sheet industry is used. The release agent layer surface and chloroprene rubber having a Shore A hardness of 65 ± 2 ° are used. According to JIS P8147, a release agent satisfying the condition that the dynamic friction coefficient is 0.21 or more is preferable in the present invention, and the adhesive is preferable because it is difficult to adhere to a guillotine cutting blade, a rotor slitter blade or the like during cutting. Further, the coefficient of dynamic friction is particularly preferably in the range of 0.21 to 0.50. Specific examples of such a release agent include SD-7239, BY24-162, LTC-300B, and LTC-3 manufactured by Toray Dow Corning Silicone Co., Ltd.
50A, BY14-403, BY14-405, BY14-407, BY14-413, BY14-
414, BY-14-411, BY14-420, manufactured by Shin-Etsu Chemical Co., Ltd.
KS-845, KS-770, KNS-202A, KNS-305, KNS-316, KNS-31
9, KNS-320, X-62-1232, X-62-1233 and the like. The thickness of the release agent applied is preferably 0.4 to 2.0 g / m ² , and is especially 0.
6 to 1.3 g / m ² is preferred.

<< Measurement of dynamic friction coefficient >> According to JIS P 8147,
The average dynamic friction force between the surface of the release agent layer coated and dried on the release paper and chloroprene rubber (Shore A hardness 65 ± 2 °) is measured, and the dynamic friction coefficient is calculated according to the following formula.

Μ = Fμ ÷ F where: μ; dynamic friction coefficient Fμ; average dynamic friction force (g) F; vertical load by weight (g) << Adhesive layer >> When cutting the photographic adhesive sheet of the present invention, Adhesive does not adhere to rotary slitter cutting blades or guillotine cutting blades, has an appropriate adhesive force to release paper, and does not peel off during release cutting or during the photographic processing process. That the release sheet does not peel off when passing through the photographic development process, that it firmly adheres to the photographic support, and that it has sufficient adhesiveness to adhere to the adherend after peeling, etc. Is required. As a result of various investigations by the present inventor in response to such demands, a pressure-sensitive adhesive layer coated on a photographic support (for example, a polyester film) is a flat stainless steel whose surface is cleaned with a degreasing solvent such as alcohol. For the board, JI
It has been found that the above requirements are satisfied by having an adhesive strength equivalent to SZ 1538 of 1,000 g / 25 mm width or more. It's a crap, but of course the adhesive should not come off the photographic support.

The adhesive used in the present invention is known in the adhesive industry, for example, ethylene-vinyl acetate resin, acrylic emulsion resin, vinyl chloride resin, vinylidene chloride resin, synthetic rubber resin, natural rubber resin. Among them, resins satisfying the following conditions are used in the present invention.

Preferred adhesives for the present invention include Cybinol X-491-267E and X-491-26 manufactured by Saiden Chemical Co., Ltd.
8E, X-490-213E, X-490-229, Nikkazol TS-1413, TS-1436, TS-1446, TS144 manufactured by Nippon Carbide Co., Ltd.
8, Acronis K-0 made by Mitsubishi Petrochemical Badish Co., Ltd.
672, K-0611, I-0510, G-0412 and the like. Further, the acrylic latex described in JP-A-4-298586 and JP-A-3-6277 can also be used. The pressure-sensitive adhesives include solvent-type pressure-sensitive adhesives, emulsion-type pressure-sensitive adhesives, hot-melt pressure-sensitive adhesives, and the like, and as a device for applying these, a reverse roll coater, an air knife coater, a knife coater, a die coater or the like can be used.

The coating amount of the pressure-sensitive adhesive layer according to the present invention is 5 to 25.
range of g / m ² are preferred, cutting easiness, particularly preferably 10 to 20 g / m ² from the viewpoint of the stability of the adhesive strength after use.

<< Measurement of Adhesive Strength of Adhesive >> A commercially available polyethylene terephthalate film having a thickness of 100 μm prepared separately is coated with the above-mentioned adhesive so as to have a coating amount of 15 g / m ² and dried. × 500mm (coated area 25mm × 250mm)
The size of the adhesive tape is adhered to a 25 mm x 500 mm flat stainless steel plate that has been cleaned with alcohol under the conditions of 23 ° C and 55% RH. Align them so that they face each other, roll them 3 times back and forth with a 2 kg roller, press-bond them together, and after 24 hours, follow JIS Z 1538.
Under 23 ° C and 55% RH, one end of the stainless steel plate where the adhesive is not adhered is fixed by the clamp of the Instron tensile tester, while the other end of the polyethylene terephthalate film which is not adhered is hung downward. The end of the polyethylene terephthalate film is clamped in the lower clamp, and the load is measured when the polyethylene terephthalate film is pulled and peeled at a speed of 300 mm / min with an Instron type tensile tester in the direction of 180 °.

In the pressure-sensitive adhesive layer used in the present invention, pigments such as titanium oxide, calcium carbonate, barium sulfate, zinc oxide, silica, kaolin and clay, antistatic agents and preservatives are used to the extent that the above-mentioned adhesive properties are not impaired. Etc. can be added. Further, a water-soluble plasticizer described in JP-A-4-298586 may be added.

<Photographic pressure-sensitive adhesive sheet> The method for producing the support for the photographic-type pressure-sensitive adhesive sheet of the present invention is, for example, a method in which a release agent is applied to a release paper substrate and then an adhesive is applied thereon to release the release agent. Formed as a sheet, the pressure-sensitive adhesive layer surface of a release sheet is attached to another photographic support through a press roll, and the photosensitive layer is then applied to the photographic support, and the photographic support is provided on the non-emulsion side. A method in which the pressure-sensitive adhesive layer surface coated with the pressure-sensitive adhesive and the release agent layer surface of the release paper substrate coated with another release agent are pasted together through a press roll, and then the photosensitive layer is coated on the photographic support. There is. Any method can be used for producing the support for a photographic adhesive sheet of the present invention, but the method is not limited thereto. The former method of sticking the release sheet is preferable from the viewpoint of ease of production.

<Silver Halide Photosensitive Layer> The silver halide photographic photosensitive material of the photographic adhesive sheet of the present invention may be a color photographic photosensitive material or a black and white photosensitive material. Since color photographic light-sensitive materials are more common these days, color photographic light-sensitive materials will be described here.

The composition of the silver halide grains of the silver halide color photographic light-sensitive material used in the photographic type pressure-sensitive adhesive sheet of the present invention is such that all silver halide grains constituting the silver halide grains are
95 mol% or more is silver chloride, and it is necessary to consist essentially of silver iodobromide. The silver halide composition of the silver halide grains is preferably 97 mol% or more, more preferably 98 to 99.9% of the total silver halide constituting the silver halide.
9 mol% is silver chloride. This so-called high silver chloride emulsion having a high silver chloride content is suitable for accelerating the development processing and is one of the constitutional requirements in the present invention.

Here, the halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the grains having a uniform structure having the same composition in any part of the silver halide grains, the core inside the silver halide grains and the shell surrounding them ( Laminated structure particles with different halogen compositions with one or more layers of shells, or structures with non-layered parts with different halogen compositions inside or on the surface (edges, corners or surfaces of particles when on the particle surface) Particles having a structure in which portions having different compositions are bonded to each other can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is
It may be a clear boundary, an unclear boundary by forming a mixed crystal due to a difference in composition, or may be one which positively has a continuous structural change.

In the high silver chloride emulsion such as the silver halide photographic light-sensitive material of the present invention, the silver bromide localized phase is formed inside the silver halide grain and / or in the layered or non-layered form as described above.
Alternatively, a structure having a surface is preferable. These localized phases can be on the edges, corners or planes, but one preferred example is that epitaxially grown on the corners of the grains.

The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a (100) plane as a crystal surface.
Also, U.S. Pat.Nos. 4,183,756 and 4,225,666, JP-A-55
-26589, Japanese Patent Publication No. 55-42737 and The Journal of Photographic Science (J.Phot.Sci.) 21
Volume, page 39 (1973), etc.
Particles having a shape such as an octahedron, a tetradecahedron and a dodecahedron can be prepared and used. Further, grains having twin planes may be used.

The silver halide grains used in the present invention are
Particles having a single shape may be used, or particles having various shapes may be mixed.

The grain size of the silver halide grains used in the present invention is not particularly limited, but in view of other photographic performance such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm.
m, more preferably 0.2 to 1.0 μm. The particle diameter can be measured by various methods generally used in the technical field. A typical method is Loveland's "particle size analysis method" (ASTM
Symposium on Right Microscopy, 94
~ 122, (1955)) or "The Theory of Photographic Process
Third Edition "(Mies and James Co., Chapter 2, Macmillan, (1966)).

This particle size can be measured using the projected area of the particle or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The grain size distribution of the silver halide grains used in the present invention may be polydisperse or monodisperse.

Heavy metal ions can be incorporated into the silver halide emulsion used in the present invention. Examples of the heavy metal ions used include Group 8-10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt; Group 12 transition metals such as cadmium, zinc, and mercury; and lead, Rhenium, molybdenum,
Each of the ions of tungsten and chromium can be mentioned. Of these, transition metal ions of iron, iridium, platinum, ruthenium and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of salt or complex salt.

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion used in the present invention is
It may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but the one obtained by the simultaneous mixing method. Is preferred. As one form of the simultaneous mixing method, the pAg controlled double jet method described in JP-A-54-48521 can be used. If necessary, a silver halide solvent such as thioether is added, and a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye is added during the formation of silver halide grains or after the completion of grain formation. You may use it.

The silver halide emulsion used in the present invention is
A sensitization method using a sulfur compound, a sensitization method using a gold compound,
Then, it is possible to perform sensitization by using a sensitizing method in which a sulfur compound and a gold compound are used in combination. Examples of the sulfur sensitizer applied to the silver halide emulsion used in the present invention include thiosulfate, allylthiocarbamidourea, allylisothiocyanate, cystine, p-toluenethiosulfonic acid, rhodanine, and inorganic sulfur. . As the gold sensitizer applied to the silver halide emulsion used in the present invention, various gold complexes other than chloroauric acid, gold sulfide and the like and the above gold compounds can be preferably used.

The silver halide emulsion used in the present invention can prevent fog occurring during the process of preparing a silver halide color photographic light-sensitive material, reduce performance fluctuation during storage, and prevent fog occurring during development. Known antifoggants and stabilizers can be used for the purpose. As an example of a compound that can be used for such a purpose, JP-A 2-14
Examples thereof include compounds represented by the general formula (II) described in the lower column of page 6036 of the publication, and specific compounds thereof include ( _IIa- 1) to ( _IIa- 1) described on page 8 of the publication. (II _a-
8), compounds (II _b -1) to (II _b -7), compounds such as 1- (3-methoxyphenyl) -5-mercaptotetrazole, 1- (4-ethoxyphenyl) -5-mercaptotetrazole Can be mentioned. These compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, the end of the chemical sensitization step, and a coating solution preparation step depending on the purpose.

In the present invention, reducing the amount of silver per unit area of the silver halide color photographic light-sensitive material is
In speeding up the development process, it is necessary to speed up silver development and improve color development efficiency.
The amount of coated silver per unit area is 0.6g / m because of suitability for rapid processing.
² or less, preferably 0.57 g / m ² or less. 0.39g
/ M ² or less is not preferable from the viewpoint of photographic quality. Therefore, the silver amount per unit area of the silver halide color photographic light-sensitive material used in the present invention is particularly preferably 0.4 to 0.57 g / m 2.
²

In the silver halide color photographic light-sensitive material used in the present invention, a yellow coupler, a magenta coupler and a cyan coupler are combined with respective spectral sensitizing dyes to form a spectrum in a specific region of 400 to 900 nm. There are multiple layers containing sensitized silver halide emulsions. One sensitizing dye or a combination of two or more sensitizing dyes may be used in one silver halide emulsion.

Sensitizing dyes useful in the silver halide color photographic light-sensitive material used in the present invention include cyanine dyes,
Examples include merocyanine dyes and complex merocyanine dyes.

The coupler of the silver halide color photographic light-sensitive material used in the present invention forms a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidant of a color developing agent. Any compound that can be used can be used, but as a particularly typical one, it is a known coupler, but a wavelength range of 350 to 5
A yellow coupler having a spectral absorption maximum wavelength at 00 nm, a magenta coupler having a spectral absorption maximum wavelength at a wavelength range of 500 to 600 nm, and a cyan coupler having a spectral absorption maximum wavelength at a wavelength range of 600 to 750 nm are typically used. obtain.

In the silver halide color photographic light-sensitive material used in the present invention, various acylacetanilide type couplers are preferably used as yellow couplers. Of these, benzoylacetanilide couplers and pivaloylacetanilide couplers are advantageous. Further, as the magenta dye forming coupler, a 5-pyrazolone type coupler, a pyrazolobenzimidazole type coupler, a pyrazoloazole, a pyrazolotriazole type coupler and an open chain acylacetonitrile type coupler can be preferably used. As cyan dye-forming coupler,
A naphthol coupler, a phenol coupler, an imidazole coupler and the like can be used.

In addition to the couplers described in the examples of the silver halide color photographic light-sensitive material used in the present invention, yellow couplers preferably used include those represented by the general formula (Y-) described on page 8 of JP-A-4-114154. Examples thereof include couplers represented by I). In addition to this, U.S. Pat.
The fluorescent dye-releasing compounds described in No. 187 can also be used.

When the oil-in-water type emulsion dispersion method is used in the method of adding the coupler used in the silver halide color photographic light-sensitive material used in the present invention, the coupler is usually water-insoluble and has a high boiling point of 150 ° C. or higher. A method of dissolving in an organic solvent and optionally using a low boiling point and / or water-soluble organic solvent in combination, and emulsifying and dispersing this solution in a hydrophilic binder such as gelatin aqueous solution using a surfactant. Is taken. This dispersing means includes a stirrer, homogenizer, colloid mill, flow jet mixer,
An ultrasonic disperser or the like is used. After the dispersion, or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be performed.
High boiling organic solvents for dissolving and dispersing couplers include dibutyl phthalate, dinonyl phthalate, dioctyl phthalate, di-iso-decyl phthalate and other phthalates, triphenyl phosphate, diphenyl biphenyl phosphate and other phosphate esters. It is preferably used.

As a method which does not use a high boiling organic solvent, a method of emulsifying and dispersing a coupler and a water-insoluble polymer compound soluble in an organic solvent in a hydrophilic binder such as an aqueous gelatin solution using a surfactant is used. Yes, this method can be used. In this case, it may be dissolved in a low boiling point and / or water-soluble organic solvent, if necessary, and then similarly dispersed. Typical examples of the water-insoluble and organic solvent-soluble polymer include poly (Nt-butylacrylamide). For the dispersion of this method, various means similar to the above can be used.

In the emulsion layer of the silver halide color photographic light-sensitive material used in the present invention, in addition to the above compounds, various other photographic additives such as an ultraviolet absorber (eg, an ultraviolet absorber).
Benzophenone compounds, benzotriazole compounds, etc.), development accelerators (eg, 1-aryl-3-pyrazolidone compounds, etc.), surfactants (eg, alkylnaphthalene sulfonates, alkyl succinic acid sulfonates, etc.), Water-soluble irradiation prevention dyes (eg, azo compounds, styryl compounds, oxonol compounds, etc.), film physical property improvers (eg, liquid paraffin, polyalkylene glycols, etc.), color turbidity inhibitors (eg, diffusion-resistant hydroquinone) Compounds, etc.), color image stabilizers (eg, hydroquinone derivatives, gallic acid derivatives, etc.), water-soluble or oil-soluble fluorescent whitening agents, background color tone adjusting agents, and the like.

In addition to this, if necessary, a competitive coupler,
Fog agent, development inhibitor releasing coupler (so-called DIR
A coupler), a development inhibitor releasing compound and the like can be added.

The binder used in the silver halide emulsion layer of the silver halide color photographic light-sensitive material used in the present invention or in the non-light-sensitive layer such as the intermediate layer and the protective layer is mostly gelatin because of its excellent properties. However, if necessary, gelatin derivatives such as phthalated gelatin, gelatin graft polymers in which other polymers such as acrylic polymers are bound and dispersed with gelatin, proteins other than gelatin such as casein, and polysaccharides. Sugar derivatives, cellulose derivatives such as hydroxyethyl cellulose, vinylpyrrolidone, acrylic acid and its salts, methacrylic acid and its salts, vinylsulfonic acid and its salts, sulfopropyl acrylate and its salts, diethylaminoethyl methacrylate hydrochloride, etc. The parent of the copolymer A hydrophilic colloid such as sex synthetic polymer materials can be used in conjunction with gelatin. The gelatin may be lime-processed gelatin, acid-processed gelatin, or gelatin produced from any of cow bone, cow hide, pig skin, etc., but preferably cow bone or pig skin. It is a lime-treated or acid-treated gelatin.

The total amount of gelatin used in all the non-photosensitive layers such as the silver halide emulsion layer and the intermediate layer coated in the silver halide color photographic light-sensitive material used in the present invention depends on the suitability for rapid processing and in terms of sensitivity, also when considered in conjunction with the construction requirements of the other present invention, 7.5 g / m ² or less is preferred per unit area of the silver halide color photographic material, particularly preferably 5 to 7 g / m ^2.

Gelatin molecules, which mainly constitute the binder of the photographic emulsion layer and the non-photosensitive layer of the silver halide color photographic light-sensitive material used in the present invention, are cross-linked by a hardening agent and are treated in a processing solution such as a color developing solution. The degree of swelling is controlled, and various properties necessary for the silver halide color photographic light-sensitive material such as the developing rate, the spread of developed silver, the film strength when wet, and the drying rate are controlled. The degree of swelling is generally determined by the amount ratio of gelatin and hardener.

The swelling degree of a light-sensitive layer such as an emulsion layer of a silver halide color photographic light-sensitive material used in the present invention in a color developer is
80 to 160% is preferable.

In the silver halide color photographic light-sensitive material used in the present invention, when a hydrophilic colloid layer such as a silver halide emulsion layer and a gelatin layer is coated on a photographic support, a coating solution having a relatively low viscosity. A thickener may be added in order to improve the coating property of, and it may be used for controlling the viscosity. As a coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are useful.

The silver halide color photographic light-sensitive material of the present invention is a color photographic paper light-sensitive material, and an image can be formed by performing color development processing known in the art.

Known compounds can be used as the aromatic primary amine developing agent used in the color development processing of the silver halide color photographic light-sensitive material of the present invention. The following compounds may be mentioned as examples of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4-Amino-3-methyl-N-ethyl-N- (β-butoxyethyl) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) Aniline CD-6) 4-Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfone Amido CD-8) N, N-Dimethyl-p-phenylenediamine CD-9) 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10) 4-Amino-3-methyl-N- Ethyl-N- (β-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline.

The color developing agent used in the development processing of the silver halide color photographic light-sensitive material used in the present invention is usually used in the range of 1 × 10 ^-2 to 2 × 10 ^-1 mol per liter of the color developing solution. From the viewpoint of rapid processing, it is preferably used in the range of 1.5 × 10 ^-2 to 2 × 10 ^-1 mol per liter of color developer. The color developing agent may be used alone or in combination with other known p-phenylenediamine derivatives.

The color developing solution used in the silver halide color photographic light-sensitive material used in the present invention may contain the following color developing solution components in addition to the above components. As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, silicate or the like can be used alone or in combination, It can be used in combination within the range where no precipitation occurs and the pH stabilizing effect is maintained. In addition, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borate, etc. may be prepared for the purpose of preparation or for increasing the ionic strength. It can be used in a color developer.

Inorganic and organic antifoggants can be added as required. Further, for the purpose of suppressing development, a halide salt is often added to the color developing solution, but in order to finish development in a very short time,
It is preferable to mainly use chlorides such as potassium chloride and sodium chloride. The amount of these chlorides added is approximately 3.0 × 10 ^-2 mol or more, preferably 4.0 × 10 ^{-2 to} 5.0 × 10 ^-1 mol, per liter of the color developing solution. Bromide tends to suppress development, and it can be used as long as it is approximately 1.0 × 10 ⁻³ mol or less, preferably 5.0 × 10 ⁻⁴ or less per liter of the color developing solution. Furthermore, if necessary, a development accelerator can be added to the color developing solution. As the development accelerator, U.S. Pat.Nos. 2,648,604 and 3,671,247,
Various pyridinium compounds represented by the compounds described in JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine,
Neutral salts such as thallium nitrate, U.S. Pat.No. 2,533,990,
No. 2,531,832, No. 2,950,970, No. 2,577,127 and JP-B-44-9504 Nonionic compounds such as polyethylene glycol and its derivatives and polythioethers described in JP-B-44-9504, organic solvent described in JP-B-44-9509 And organic amine, ethanolamine, ethylenediamine, diethanolamine, triethanolamine and the like. Also,
Examples include phenethyl alcohol described in US Pat. No. 2,304,925 and acetylene glycol, methyl ethyl ketone, cyclohexanone, pyridine, ammonia, hydrazine, thioethers, amines, and the like.

Further, in the color developing solution, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin and other Japanese Patent Publication Nos. 47-33378 and 44-9509 are described. The compound can be used as an organic solvent for increasing the solubility of the color developing agent.

Further, an auxiliary developing agent may be used together with the color developing agent. As these auxiliary developers,
For example, N-methyl-p-aminophenol sulfate, phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N,
N ', N'-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually 0.01 to 1.0 g per liter of color developing solution.

Each component of the color developing solution can be prepared by sequentially adding and stirring to a fixed amount of water. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. Further, more generally, a color developing solution is prepared by adding a plurality of components, each of which can coexist stably, in a concentrated aqueous solution or in a small container prepared in advance in a solid state into water and stirring. You can also

In processing the silver halide color photographic light-sensitive material used in the present invention, the color developing solution can be used in an arbitrary pH range, but from the viewpoint of rapid processing, pH 9.6 to 13.
It is preferably 0, and more preferably used in the range of pH 9.8 to 12.0.

The color development processing temperature of the silver halide color photographic light-sensitive material used in the present invention is preferably 15 ° C. or higher and 45 ° C. or lower, and particularly preferably 20 ° C. or higher and 45 ° C. or lower. The color development time is conventionally about 3 minutes and 30 seconds, but the color development time of the rapid development in the present invention is 45 seconds or less, and further rapid development processing means color development.
It is done within 30 seconds.

When the silver halide photographic light-sensitive material used in the present invention is subjected to a running treatment (the treatment is continued while continuously replenishing a color developing solution), in order to reduce environmental pollution due to waste liquid disposal, color development is carried out. It is preferable that the overflow of the developing solution is reduced and the replenishing amount of the color developing solution is 20 to 150 ml per 1 m ² of the light-sensitive material. Further, it is more preferable that the amount of replenishment is such that waste liquid is not generated even if the liquid is substantially overflowed. As a concrete amount of replenishment, 20 to 60 ml per 1 m ² of the light-sensitive material is suitable and more preferable. Under such conditions, the performance of the silver halide photographic light-sensitive material is generally liable to change, but the silver halide color photographic light-sensitive material used in the present invention has no change in performance under such conditions. It can be used advantageously.

The silver halide color photographic light-sensitive material used in the present invention can be subjected to usual bleaching treatment and fixing treatment after color development, but the bleaching treatment may be conducted simultaneously with the fixing treatment. After the fixing process, a washing process is usually performed, but a stabilizing process may be performed as an alternative to the washing process.

The development processing apparatus used for the silver halide color photographic light-sensitive material used in the present invention is a roller transport type in which the light-sensitive material is sandwiched between rollers arranged in a processing tank and conveyed. An endless belt system may be used in which the sheet is fixed and conveyed. Further, the processing tank is formed in a slit shape, the processing solution is supplied to the processing tank and the photosensitive material is conveyed, the spray method for spraying the processing solution, and the contact with the carrier impregnated with the processing solution. It is also possible to use a web method according to the above, a method using a viscous treatment liquid, or the like.

The photographic adhesive sheet of the present invention is produced as described above, is developed, and is cut according to the purpose of use.
It can be pasted on the object. The cutting blade for cutting the photographic adhesive sheet of the present invention includes a slitter or a rotary cutter, a cross cutter or a guillotine cutter, a punching cutter, and a seal cutter which punches out only a release paper of a seal print, but these cutters are used. Even if cut, the adhesive does not spill out and adhere to the blade, which makes it difficult to work, or an excellent photographic image can be obtained without adhering to the photosensitive layer surface. Further, even in the production stage before development, when the product is cut into product sizes, it does not adhere to the photosensitive layer surface, and unexposed or undeveloped portions are not formed, so that the target product can be obtained in good yield.

The thus-obtained photographic adhesive sheet is easy to work with, requires no skill, and has outdoor signs, advertisements, decorations, interior decorations, identification cards, business cards, notebooks, albums, Photographic images can be attached to various items such as postcards, and can be easily provided at a lower cost than conventional products.

[0112]

EXAMPLES Examples of the present invention will be shown, but the present invention is not limited thereto.

A photographic adhesive sheet was prepared as follows.

<Preparation of Release Sheet><< Preparation of Release Paper Substrate >> (Release Paper Substrate-1) Tetron film (polyethylene terephthalate film) having a thickness of 75 μm manufactured by Teijin Ltd.
Is used as release paper substrate-1 (indicated as R-PET in Table 1).

(Release Paper Substrate-2) Polyethylene Laminated Paper A pulp formulation consisting of 30 parts of bleached softwood kraft pulp (NBKP) and 70 parts of bleached hardwood kraft pulp (LBKP) was added to the pulp as follows to prepare a stock. After the preparation, kraft paper with a basis weight of 60 g / m ² and a density of 1.0 g / m ² was made with a Fourdrinier paper machine. Next, polyethylene resin [density 0.95 g / cc, melt index (abbreviation MI) 8.0 g / 10 min] Chips were dried and put into an extruder, melted at 300 ° C, and adjusted to 30 g / m ² from the die slit. Extrusion coating of molten resin was applied to both sides of the paper support, and polyethylene laminated paper (in Table 1, R-
PE). Polyamide Polyaminoepichlorohydrin resin 0.82% Alkyl ketene dimer 0.45% Cationic starch 2.10% Anionic polyacrylamide resin 0.12%.

(Release Paper Substrate-3) Electron Beam Curable Resin Paper First, the following electron beam curable resin composition was dispersed in a ball mill for 20 hours.

Epoxy acrylate (NK ester EA800 manufactured by Shin-Nakamura Chemical) 20 parts by weight Polybutadiene (TEA-1000 manufactured by Nippon Soda) 15 parts by weight Triethylene glycol diacrylate 20 parts by weight Titanium oxide (anatase type average particle size 0.2 μm) 45 parts by weight Parts The composition thus obtained was separately coated on both sides of the paper support prepared by the above-mentioned release paper substrate-2 by the roll coating method so as to be 15 g / m ² , and the accelerating voltage: 175K.
The resin was cured by irradiating it with an electron beam under the conditions of V and absorbed dose: 2 Mrad. The cured resin surface was subjected to a corona discharge treatment of 8 w / m ² · min to prepare release paper substrate-3 (shown as R-UV in Table 1).

(Release Paper Substrate-4) Kraft Paper-Comparative Sample-The following was added per pulp to a pulp formulation consisting of 30 parts of unbleached softwood kraft pulp (NUKP) and 70 parts of bleached hardwood kraft pulp (LUKP). After preparing the paper stock with the paper, disperse the pulp slurry sufficiently and weigh 90 g with a Fourdrinier paper machine.
/ M ² and density 1.0g / m ² Kraft paper release paper substrate-2
(Indicated as R-KP in Table 1) was made into paper.

Polyamide polyaminoepichlorohydrin resin 0.82% Alkyl ketene dimer 0.45% Paraffin wax 1.00% Cationic starch 2.10% Anionic polyacrylamide resin 0.12% Aluminum sulfate 0.10%.

<< Releasing Agent Coating Processing >> The release paper substrate
A silicone release agent (types described in Table 1) was applied on both sides of 1, 2, 3 and 4 with a bar coater to a dry weight of 1.0 g / m ² , dried and wound to prepare release paper. . The dynamic friction coefficient of this release agent layer is shown in Table 1 (however, the method for measuring the dynamic friction coefficient of the release agent layer has been described above).

<< Adhesive Coating Process >> Next, an adhesive (type is shown in Table 1) is applied to the release agent layer surface on one side at a dry weight of 16-18.
It was coated with a reverse roll coater so as to be g / m ² and dried to form a pressure-sensitive adhesive layer, and another release paper of the same kind was wound on the pressure-sensitive adhesive layer surface and wound to prepare a release sheet. The adhesive strengths of these pressure-sensitive adhesives are shown in Table 1 (however, how to prepare a sample for measuring the adhesive strength and the measuring method of the adhesive strength have been described above).

<Preparation of Photographic Support> (Photographic Support-1) White PET White polyethylene terephthalate film with a thickness of 50 μm, manufactured by Toyobo Co., Ltd., CRISPER (trade name) is coated with the following undercoat. It was applied, and nothing was applied to the other side. Corona discharge is applied to the subbing surface at 8 W / min · m ² , and subbing liquid-1 is applied on it to 25 ml / m ² , and corona is again applied on this subbing layer-1. Discharge, 30 ml of subbing liquid-2
/ M ² was coated to prepare a photographic support-1 having one side undercoated (referred to as CRISPER in Table 1).

[Sub liquid-1] Butyl acrylate 30% by weight t-Butyl acrylate 25% by weight Styrene 25% by weight 2-Hydroxyethyl acrylate 25% by weight Copolymer latex (solid content 30%) 720 g Compound (C-6) 0.8 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Add water to make 1 liter.

[Sub liquid-2] Gelatin 10 g Compound (C-6) 0.2 g Compound (C-7) 0.2 g N, N ′, N ″ -trisacryloyl-1,3,5-trimethylenetriamine 0.1 g Silica particles (average particle size 0.3 μm) 0.1 g Water is added to make 1 liter.

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(Photographic support-2) In-line undercoat white
PET Commercially available polyethylene terephthalate resin chips (intrinsic viscosity 0.65) and 15% by weight of anatase type titanium dioxide were put into a rotary vacuum dryer and dried by sprinkling at 150 ° C for 8 hours and then into an extruder. Introduce the mixture, 28
Melt and knead at 5 ° C, extrude from a coat hanger die slit onto a rotary cooling drum at 50 ° C so that the film thickness after biaxial stretching will be 60 μm, and after cooling, peel from the drum, and at 85 ° C in the longitudinal direction 3.3 Stretching twice and applying in-line subbing liquid-3 containing the following aqueous copolyester before transverse stretching,
The film was stretched laterally 3.5 times at 95 ° C, heat-set at 220 ° C, and cooled to obtain a white polyethylene terephthalate film roll. Next, the undercoating surface was subjected to a corona discharge treatment of 8 W / m ² · min, and both surfaces were coated with undercoating liquid-4 with an air doctor coater and dried, and the undercoated photographic support-2 (Table 1
I labeled it as W-PET).

<< Synthesis of Aqueous Copolyester Subbing Agent >> 83 parts by weight of terephthalic acid, 41.5 parts by weight of isophthalic acid, and 77 parts by weight of ethylene glycol were added with 0.1 part by weight of calcium acetate monohydrate, and esterification reaction was carried out by a conventional method. I went. To the product obtained, 55 parts by weight of 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid was added as an ethylene glycol solution (concentration: 35% by weight), and 13 parts by weight of polyethylene glycol (average degree of polymerization of 2,000) and trioxide were added. Antimony 0.05
Parts by weight, tetramethylammonium hydroxide
0.15 part by weight and phosphoric acid trimethyl ester 0.13 part by weight were added. Next, gradually raise the temperature to 255 ° C and reduce the pressure to 280
Polymerization at ℃, 0.2mmHg for 1.5 hours, cooling, intrinsic viscosity
A copolyester resin CP having 0.52 was obtained. To use the resulting aqueous copolyester in an antistatic subbing liquid
The mixture was stirred in hot water at 95 ° C for 3 hours to give a 15% by weight aqueous solution.

<< Subbing Liquid-3 >> (In-line Subbing Liquid) The above aqueous copolyester liquid 540 g Compound (C-6) 0.6 g Compound (C-7) 0.2 g Silica particles having an average particle size of 3 μm 0.1 g Water 1 Finish to liters.

[Sub liquid-4] Gelatin 10 g Compound (C-6) 0.2 g Compound (C-7) 0.2 g N, N ', N "-trisacryloyl-1,3,5-trimethylenetriamine 0.1 g Average particle size 3 μm Silica particles 0.1 g Make up to 1 liter with water.

(Photographic Support-3) Laminated Polyester << Synthesis of Modified Polyester >> 100 parts by weight of terephthalic acid,
64 parts by weight of ethylene glycol and calcium acetate hydrate 0.
1 part by weight was added and the esterification reaction was carried out by a conventional method. The obtained product was 28 parts by weight of ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration 35% by weight) (5 mol% / total acid content), polyethylene glycol (number average molecular weight 3000). 8.1 parts by weight (7% by weight / polymer), 0.05 parts by weight of antimony trioxide and 0.13 parts by weight of phosphoric acid trimethyl ester were added.
Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain a modified polyester resin having an intrinsic viscosity of 0.57.

<< Preparation of Laminated Polyester Photographic Support >>
The modified polyester resin, the white PET resin mixture prepared with the photographic support-2, and the commercially available PET resin having an intrinsic viscosity of 0.65 were vacuum-dried at 150 ° C., respectively, and then three extruders were used.
Melt extrusion at ℃, modified polyester layer (M) in the center,
The surface layer on the photosensitive layer side is a white PET layer (WP), and the surface layer on the opposite side is an uncolored PET layer (PET). Pour into a drum and rapidly cool and solidify while adhering to the cooling drum by the electrostatic contact method.
A laminated unstretched film was obtained. At this time, the extruded amount of each molten resin is adjusted so that the thickness of the three layers is 65 μm and the thickness ratio is W.
P: M: P = 7: 10: 3. Then, it was stretched 3.5 times in the machine direction at 85 ° C. A photographic support to have a dry weight of 0.3 g / m ² on both sides of the longitudinal uniaxially stretched film.
The aqueous copolyester subbing liquid-3 synthesized in 2 was applied in the same manner, subsequently stretched 3.5 times in the transverse direction at 95 ° C, and then heat set at 210 ° C to be in-line subbed biaxially stretched film photographic support. -3 (labeled WP-M-PET in Table 1) was obtained. Further, when the above-mentioned laminated support is divided into two equal parts in the thickness direction, the respective laminated structures of the two divided halves are asymmetric because the thickness of the PET layer and the thickness of the modified polyester layer are different.

(Photographic Support-4) Polyethylene Laminated Paper << Preparation of Photographic Paper Support >> 40% photographic photographic paper grade bleached softwood pulp (NBSP) and 60% bisulfite bleached hardwood pulp (LBKP) And were mixed to form a pulp slurry having a concentration of 1.2%, and the following papermaking additives were added to the pulp at the following ratio with respect to the dry weight of the pulp, and the pH was adjusted to 7.6 with sodium hydroxide.

Polyamide Polyaminoepichlorohydrin resin 0.82% Alkyl ketene dimer 0.45% Cationic starch 2.10% Anionic polyacrylamide resin 0.12% After sufficiently dispersing this pulp slurry, weigh it with a paper machine.
A photographic paper support having a density of 70 g / m ² and a density of 1.0 g / m ² was prepared.

<< Polyethylene Laminated Photographic Support >>
Polyethylene resin [density 0.95 g / cc, melt index (abbreviation MI) 8.0
g / 10 minutes] The chips are dried, put into an extruder, melted at 300 ° C, and extrusion-coated with molten resin so that the amount becomes 30 g / m ² from the die slit, and then the remaining one surface on the photosensitive layer side. Polyethylene [Density 0.92g / cc, MI 5.0g / 10min]
A mixture of 90 parts by weight of anatase type titanium oxide added to 10 parts by weight is introduced into an extruder, and after kneading and melting, it is extruded from a die slit at 300 ° C. for coating, and a polyethylene laminate water-resistant photographic printing paper of 30 g / m ² is produced. A support was prepared. Subsequently, the surface of the photosensitive layer was subjected to a corona discharge treatment of 8 W / m ² · min, and 4.5 g of gelatin, 10 mg of sodium (2-ethylhexyl) sulfonate, and H-1 below
30 mg was mixed and dissolved in 100 ml of water, coated and dried to 40 mg / m ² to form an undercoat layer, and a photographic support-4 (in Table 1,
PE-P-PE) was prepared.

(Photographic support-5) Electron beam curable resin support << Preparation of electron beam curable resin photographic support >> This photographic support has a white electron beam curable resin layer on the photosensitive layer side. On the back side, a polyethylene resin layer is coated on both sides of the paper support. An electron beam curable resin composition coating liquid containing a white pigment having the following composition was prepared.

Epoxy acrylate (NK ester EA800 manufactured by Shin Nakamura Chemical) 20 parts by weight Polybutadiene (TEA-1000 manufactured by Nippon Soda) 15 parts by weight Triethylene glycol diacrylate 20 parts by weight Titanium oxide (anatase type average particle size 0.2 μm) 45 parts by weight Parts A mixture of the above components was dispersed in a ball mill for 20 hours.

The composition thus obtained was applied to the photosensitive layer side of the same paper support as used for the photographic support-3 by the roll coating method so that the composition became 15 g / m ² , and the accelerating voltage: The resin was cured by irradiating it with an electron beam under the conditions of 175 KV and absorbed dose: 2 Mrad. Next, a polyethylene resin layer was provided on the back side of the paper support in the same manner as the photographic support-4. Further, as with the photographic support-4, a corona discharge treatment and an undercoat layer were applied, and the photographic support-5 (indicated as UV-P-PE in Table 1).
Was produced.

<Preparation of Photographic Adhesive Sheet Support> While peeling off the release paper on one side of the release sheet, the exposed adhesive side and the antiphotosensitive layer side of the photographic supports 1 to 5 were brought into close contact with each other,
A photographic pressure-sensitive adhesive sheet support was produced by pressure bonding with a nip roll or a press roll.

<Preparation of Photographic Adhesive Sheet><< Preparation of Silver Halide Photosensitive Photosensitive Layer >> The following silver halide color photosensitive liquid was applied to the gelatin subbing surface of the photographic adhesive sheet support obtained above as follows. Multi-layer coating was performed to prepare a photographic adhesive sheet.

<< First Layer Coating Solution >> Yellow dye-forming coupler (YC-1) 23.4 g, dye image stabilizer (ST-1) 3.
34 g, dye image stabilizer (ST-2) 3.34 g, dye image stabilizer (ST-5) 3.34 g, stain inhibitor (HQ-1)
0.33 g, compound A 5.0 g and high boiling point solvent (DBP) 5.0 g
Ethyl acetate (60 cc) was added to and dissolved, and this solution was emulsified and dispersed in 220 cc of 10% gelatin aqueous solution containing 7 cc of 20% surfactant (SU-1) aqueous solution using an ultrasonic homogenizer to form a yellow dye forming coupler. A dispersion was prepared. This dispersion was mixed with a blue-sensitive silver halide prepared under the following conditions to prepare a coating solution for the first layer.

Further, each layer F-1 was added so that the total amount became 0.04 g / m ² . This dispersion was mixed with a blue-sensitive silver halide emulsion (Em-B) prepared under the following conditions to prepare a coating solution for the first layer. The ingredients and coating amount are shown below.

<< Second Layer to Seventh Layer Coating Liquid >> The components and coating amounts are shown below similarly to the above-mentioned first layer coating liquid. Each coating liquid was prepared so as to have such coating amount.

<< Photosensitive layer composition >> The components and the coating amount (g /
m ² unit). For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was prepared according to the following respective manufacturing methods.

First layer (blue-sensitive) Gelatin 1.50 Blue-sensitive silver chlorobromide emulsion (Em-B) 0.26 Yellow dye-forming coupler (YC-1) 0.70 Dye image stabilizer (ST-1) 0.10 Dye image stabilizer ( ST-2) 0.10 Dye image stabilizer (ST-5) 0.10 Anti-staining agent (HQ-1) 0.01 Compound A 0.15 DBP 0.15 Second layer (intermediate layer) Gelatin 1.20 AI-3 0.01 Anti-staining agent (HQ-2) 0.03 Anti-staining agent (HQ-3) 0.03 Anti-staining agent (HQ-4) 0.05 Anti-staining agent (HQ-5) 0.23 DIDP 0.06 Fluorescent whitening agent (W-1) 0.10 Third layer (green-sensitive layer) Gelatin 1.30 AI-1 0.01 Green-sensitive silver chlorobromide emulsion (Em-G) 0.17 Magenta dye-forming coupler (MC-10) 0.23 Dye image stabilizer (ST-3) 0.20 Dye image stabilizer (ST-4) 0.17 DIDP 0.13 DBP 0.13 4th layer (purple Line absorbing layer) Gelatin 1.00 Ultraviolet absorber (UV-1) 0.28 Ultraviolet absorber (UV-2) 0.09 Ultraviolet absorber (UV-3) 0.38 AI-2 0.02 Stain inhibitor (HQ-3) 0.10 Fifth Layer (Red-sensitive layer) Gelatin 1.30 Red-sensitive silver chlorobromide emulsion (Em-R) 0.21 Cyan dye-forming coupler (CC-2) 0.25 Cyan dye-forming coupler (CC-8) 0.08 Dye image stabilizer (ST-1) 0.18 Anti-stain (HQ-1) 0.004 DOP 0.34 6th layer (UV absorber layer) Gelatin 0.50 AI-2 0.01 UV absorber (UV-1) 0.12 UV absorber (UV-2) 0.04 UV absorber (UV) -3) 0.16 Anti-staining agent (HQ-5) 0.04 PVP 0.03 7th layer (protective layer) Gelatin 1.00 DIDP 0.005 Silicon dioxide 0.003 Hardener H-1 0.596 Hardener H-2 0.2
29 Here, the above abbreviations are shown below as compound names or structural formulas.

SU-1: sodium tri-i-propylnaphthalenesulfonate DBP: dibutylphthalate DOP: dioctylphthalate DIDP: di-i-decylphthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2 : 2,4-dichloro-6-hydroxy-s-triazine
Sodium Compound A: pt-octylphenol

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[0147]

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[0148]

[Chemical 4]

[0149]

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[0150]

[Chemical 6]

(Preparation of blue-sensitive silver halide emulsion) The following (A) was added to 1 liter of a 2% gelatin aqueous solution kept at 40 ° C.
30) while controlling the liquids) and (B liquid) to pAg = 7.3 and pH = 3.0
Simultaneously added over the course of minutes,
Simultaneous addition was carried out over 180 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, pAg = was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water added 200 cc (Solution B) Silver nitrate 10 g Water added 200 cc (Solution C) K ₂ IrCl ₆ 2 × 10 ^-8 mol / mol Ag Chloride Potassium 102.7g K ₄ Fe (CN) ₆ 1 × 10 ^-5 mol / mol Ag Potassium bromide 1.0g Water added 600cc (D liquid) Silver nitrate 300g Water added 600g After addition, Kao Atlas Demol N 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate were used for desalting, and then mixed with an aqueous solution of gelatin to obtain a single particle having an average particle size of 0.85 μm, a particle size distribution variation coefficient of 0.07, and a silver chloride content of 99.5 mol%. A dispersed cubic emulsion EMP-1 was obtained.

The above-mentioned EMP-1 was optimally chemically sensitized with the following compounds at 60 ° C. to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-3 8 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ^-4 mol / mol AgX (preparation of green-sensitive silver halide emulsion) (solution A) and solution B
The same as EMP-1, except that the addition time of (C liquid) and the addition time of (C liquid) and (D liquid) are changed, the average particle size is 0.43 μm, the variation coefficient of the particle size distribution is 0.08, and the silver chloride content is 99.5%. A dispersed cubic emulsion EKMP-2 was obtained.

The following compounds were added to EMP-2 at 55 ° C.
Was optimally chemically sensitized to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (preparation of red-sensitive silver halide emulsion) (solution A) and solution B
Of the average particle size of 0.50 μm, the variation coefficient of the particle size distribution of 0.08, and the silver chloride content of 99.5 mol% in the same manner as EMP-1 except that the addition time of (C liquid) and the addition time of (D liquid) are changed. A monodisperse cubic emulsion EMP-3 was obtained.

The following compounds were added to EMP-3 at 60 ° C.
Was optimally chemically sensitized to obtain a green-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX sensitizing dye RS-2 1 × 10 ^-4 mol / mol AgX STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1- Phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0159]

[Chemical 7]

<Evaluation Method><Development Processing Conveyance> Processing was performed under the following conditions using an automatic developing machine for color prints, and the presence or absence of peeling between the release layer and the adhesive layer of the photographic adhesive sheet after development processing. And the transport condition was visually judged.

<Development processing step> Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C 45 seconds 80cc Bleach fixing 35.0 ± 0.5 ° C 45 seconds 120cc Stabilization 30 to 34 ° C 60 seconds 150cc Dry 60 to 80 C. 30 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution replenisher pure water 800cc 800cc triethylenediamine 2g 3g diethylene glycol 10g 10g potassium bromide 0.01g-potassium chloride 3.5g-potassium sulfite 0.25g 0.5g N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g Diethylenetriamine pentaacetic acid sodium salt 2.0 g 2.0 g Fluorescence enhancement Whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to make the total volume 1 liter.
Adjust to 10 and replenisher to pH = 10.60.

Bleach-fixing solution Tank solution and replenishing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 cc 2-Amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 cc Add water to make the total volume 1 liter, and adjust to pH = 6.5 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenishing solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1.0 g Ammonia water (ammonium hydroxide 25 % Aqueous solution) 2.5 g Nitrilotriacetic acid / trisodium salt 1.5 g Add water to bring the total volume to 1 liter, and adjust to pH = 7.5 with sulfuric acid or aqueous ammonia.

<< Automatic developing machine transport test >> Using the automatic developing machine for color printing under the above-mentioned development prescription and conditions, peeling of the release layer from the adhesive layer of the photographic adhesive sheet during or after the development processing The presence or absence and the transportation status were visually evaluated in 4 ranks as follows: A: The peeling sheet was transported without any problem B: The edge of the release paper of the release sheet floated about 1 to 3 mm C: Peeling The release paper on the sheet was peeled from the edge to the middle, but it could be conveyed. D: The release paper on the release sheet was peeled off, and the adhesive surface of the photographic adhesive sheet stuck to the roll of the automatic developing machine, causing jamming, and the automatic developing machine. Stopped.

<< Cutting test with guillotine cutter >> Photographic adhesive sheet is cut into a length of 20 cm and a width of 15 cm, and 100 sheets are piled up, and a guillotine cutter tester CM-450 manufactured by Rokugo Seisakusho Co., Ltd.
(Product name) is cut 20 times continuously while shifting in the width direction by 2 to 3 mm, and the amount of the adhesive attached to the guillotine cutter blade and the cut surface of the cut sheet are visually evaluated as 4 ranks as follows. Yes: A: No adhesion of adhesive was found on the guillotine cutting blade, and the adhesive-like cut edge of the sheet was smooth. B: Adhesive became a small ball and was slightly stuck to the guillotine cutting blade. , The cross section of the adhesive layer was slightly flipped up at the cut edge C: Adhesive was considerably attached to the guillotine cutting blade, and the adhesive layer at the cut edge was almost flipped up D: Adhesive was sticking tightly to the guillotine cutting edge ,
It was difficult to cut, and the adhesive at the cut edge was protruding to the outside.

<< Rotary Cutter Slitting Test >> Photographic pressure-sensitive adhesive sheet was slitted with a rotary cutter over a total length of 10,000 m, and the amount of the adhesive agent adhering to the rotary blade and the slitting cross section of the sheet were visually observed as follows. Thus, the evaluation was performed with 4 ranks: A: No sticking of the adhesive was found on the rotary blade, and the cut edge of the sheet was smooth. B: The sticky adhesive was slightly attached to the rotary blade, and the adhesive layer was formed on the cut edge. The cross section was slightly flipped up C: Adhesive was quite attached to the rotary blade, and the cut edge was almost flipped up D: Adhesive was stuck to the rotary blade, cutting was difficult, and the adhesive on the cut was outside It was sticking out.

<< Ease of Sticking >> A photographic adhesive sheet of the size of a whole paper is exposed and developed, and the release sheet on the back side is peeled off. Yes: A: There was almost no curl, and it was easy to stick B: There was curl, but it was easy to stick C: There was curl, but it was a little difficult to stick, but there was no problem D: The curl was big and hard to stick. 《Quality after pasting》 Exposure and development of a photographic adhesive sheet of the size of all papers, peeling off the release sheet on the back side, and feel of thickness and flatness when touched on the object and visual evaluation Done: A: Very clean and well done B: Very well done C: A little thick and fluffy, but practically no problem D: Thick and flat It was a little inferior.

<Evaluation and Results>

[0170]

[Table 1]

The abbreviations are explained here: R-PET release paper substrate-1 polyethylene terephthalate film R-PE release paper substrate-2 polyethylene laminated paper R-UV release paper substrate-3 electron beam curable resin coated paper R- KP Release paper substrate-4 (Comparison) Kraft paper SD-7239 Release agent Silicon resin made by Toray Dow Corning Silicone Ltd. LTC-300B Release agent Same as above LTC-350A Release agent (Comparison) Same as BY24- 16 Release agent Same as above KS-845 Release agent Shin-Etsu Chemical Co., Ltd. KS-857 Release agent (comparison) Same as above X-2494 Release agent (comparative) Same as above X-62-2494 X-268E Adhesive Saiden Chemicals Co., Ltd. Cybinol X-491-268E X-269E Adhesive Saibinol X-491-269E X-213E Adhesive Saibinol X-490-213E X-279E Adhesive Saibinol X-491-279E L- 122 Adhesive (Comparison) Nikkale L-122 C-268 Adhesive (Comparison) (X-491-268E: Silicon) Oil, 10: 1 mixture) Crisper Photographic support-1 White polyethylene terephthalate film W-PET Photographic support-2 White polyethylene terephthalate film WP-M-PET Photographic support-3 laminated by Toyobo Co., Ltd. Polyester film PE-P-PE photographic support-4 polyethylene laminated paper UV-P-PE photographic support-5 electron beam curable resin / polyethylene laminated paper.

As can be seen from Table 1, the photographic adhesive sheet of the present invention was cut with a guillotine cutter and a rotary slitter, and as a result, no adhesion of adhesive was found on the guillotine cutting blade and the rotary blade. Further, in the transportability test with the automatic processor, the release sheet of the present invention could be transported without any problem. The comparative sample kraft paper of the release paper substrate could not be conveyed because the release paper peeled off during development.

[0173]

[Advantages of the Invention] An excellent photographic adhesive sheet which can be cut by a rotary slitter, cut by a guillotine cutter, etc., and which does not peel off while being conveyed by an automatic processor is obtained, and a photograph can be freely stuck anywhere. Is now possible.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09J 7/02 JKT C09J 7/02 JKT JKU JKU JKY JKY G03C 1/805 G03C 1/805

Claims (9)

[Claims] 1. A silver halide photographic light-sensitive material comprising a photographic support coated with a silver halide photographic light-sensitive layer, and a release sheet attached to the surface opposite to the light-sensitive layer via an adhesive layer. The release paper substrate of the release sheet has water resistance, and the dynamic friction coefficient between the surface of the release agent layer and chloroprene rubber having a Shore A hardness of 65 ± 2 ° in accordance with JIS P 8147 is 0.
21 or more and the adhesive layer is JI
A silver halide photographic light-sensitive material having a backside adhesive layer, which has an adhesive strength according to SZ 1538 of 1,000 g / 25 mm width or more. 2. The silver halide photographic light-sensitive material having a backside adhesive layer according to claim 1, wherein the release paper substrate is a plastic film. 3. A silver halide photographic light-sensitive material having a backside pressure-sensitive adhesive layer according to claim 1 or 2, wherein the release paper substrate is a polyester film. 4. The silver halide photographic light-sensitive material having a backside pressure-sensitive adhesive layer according to claim 1, wherein the release paper substrate has resin layers on both sides of a paper support which is a core material. 5. A silver halide photographic light-sensitive material having a backside pressure-sensitive adhesive layer according to claim 1 or 4, wherein the resin layer is a polyolefin layer and / or an ultraviolet curable resin layer. 6. The silver halide having a backside pressure-sensitive adhesive layer according to claim 1, wherein the photographic support has a resin layer on both sides of a paper support. Photographic material. 7. The backside pressure-sensitive adhesive layer according to claim 1, wherein the resin layer of the paper support is a polyolefin layer and / or an ultraviolet curable resin layer. A silver halide photographic light-sensitive material having 8. A silver halide photographic light-sensitive material having a backside pressure-sensitive adhesive layer according to claim 1, wherein the photographic support is a white polyester film. 9. The back surface according to claim 1, wherein the photographic support is a film in which white polyester, modified polyester and polyester are laminated. A silver halide photographic light-sensitive material having an adhesive layer.