JPH06250332A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a highly versatile silver halide color photographic sensitive material for the transmission photo display excellent in picture quality by the light transmitted from the rear. CONSTITUTION:A hydrophilic polymer and a polyolefin resin layer are successively laminated on a base paper, and a substrate with the peel strength between the base paper and the polyolefin layer controlled to 30-160g/inch is coated with at least one silver halide emulsion layer to constitute the silver halide color photographic sensitive material. In the material, (1) 14-30wt.% of white pigment is incorporated into the polyolefin layer, (2) a white pigment layer is provided between the polyolefin layer and the silver halide emulsion layer closest to the base paper, or (3) a colored layer is furnished between the polyolefin layer and a silver halide emulsion layer closest to the base paper, and the maximum color transmittance density of the silver halide photographic sensitive material is controlled to >=2.0.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material for a transmission type photo display which is excellent in image quality due to transmitted light from the back surface and has high versatility (hereinafter , "Color photosensitive material" or "color sensitive material" may be abbreviated).

[0002]

2. Description of the Related Art In recent years, displays using color photographs have been increasing in department stores, subway platforms, restaurants, hotel lobbies and the like. As a display method for these photo displays, under a specific condition such as in a dark room or outdoors at night, a transmissive method of viewing with light emitted from the back side of the image is generally used. used.

The support of such a transmissive display light-sensitive material is usually limited to a method of putting the light-sensitive material in an existing light box and viewing it with light from the back surface as a display method. For this reason, it has been desired to develop a transmissive display light-sensitive material having a more versatile display method. In particular, from the viewpoint of versatility, it has been desired to develop a support which replaces the polyethylene terephthalate base which is usually used in a transmissive display light-sensitive material.

[0004]

The inventors of the present invention have studied various supports, but the general-purpose base paper support does not allow light from the back surface to pass therethrough, and thus can be used as a support for a transparent display light-sensitive material. Can not. On the other hand, we also examined the use of a thin base paper support, but compared to general-purpose base paper, although the image quality due to the transmitted light from the back side was good, it was not clear enough as compared to polyethylene terephthalate base, and it was There was a defect that the curl characteristics before and after the treatment were poor during transport and during the treatment.

On the other hand, a peelable color paper is known. In the peelable color paper, the base paper and the polyolefin resin layer are easily peeled off, and after peeling, it can be attached to a shutter or a telephone card, but the maximum density is insufficient for use as a transmissive display.
Further, the sharpness and white background were insufficient.

Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material for a transmission type photo display which is excellent in image quality and versatility. More specifically, it is excellent in image quality due to transmitted light from the back surface and is versatile. The object is to provide a silver halide color photographic light-sensitive material for a transmissive photo display having high property.

[0007]

The above object of the present invention is achieved by the following constitution.

(1) A hydrophilic polymer and a polyolefin resin layer are laminated in this order on a base paper, and at least one layer of silver halide is formed on a support having a peel strength of 30 to 160 g / inch between the base paper and the polyolefin resin layer. In the silver halide color photographic light-sensitive material coated with an emulsion layer, the polyolefin resin layer contains a white pigment in a density of 14 to 30% by weight, and the maximum color transmission density of the silver halide photographic light-sensitive material is 2.0.
The above is a silver halide color photographic light-sensitive material.

(2) A hydrophilic polymer and a polyolefin resin layer are laminated in this order on the base paper, and at least one layer of silver halide is formed on a support having a peel strength between the base paper and the polyolefin resin layer of 30 to 160 g / inch. In a silver halide color photographic light-sensitive material coated with an emulsion layer, a white pigment layer is provided between the polyolefin resin layer and the silver halide emulsion layer closest to the base paper, and the maximum silver halide photographic light-sensitive material A silver halide color photographic light-sensitive material having a color transmission density of 2.0 or more.

(3) A hydrophilic polymer and a polyolefin resin layer are laminated in this order on a base paper, and at least one layer of silver halide is provided on a support having a peel strength between the base paper and the polyolefin resin layer of 30 to 160 g / inch. A silver halide color photographic light-sensitive material coated with an emulsion layer, which has a coloring layer between the polyolefin resin layer and the silver halide emulsion layer closest to the base paper, and has the maximum color development of the silver halide photographic light-sensitive material. A silver halide color photographic light-sensitive material having a transmission density of 2.0 or more.

In (1), (2) or (3), it is a preferred embodiment that the total silver coverage of the light-sensitive material is 1.0 g / m ² or more, because the effects of the present invention can be more exerted. .

The present invention will be described in more detail below.

The support according to the present invention is based on a base paper, a hydrophilic polymer is coated on the base paper on which the silver halide emulsion layer is coated, and then both surfaces of the base paper are laminated with a polyolefin resin to give a halogenated product. This facilitates peeling of the base paper from the polyolefin resin on the silver emulsion layer side.

The peel strength between the polyolefin resin and the base paper is 30 to 160 g / inch. Peel strength is measured by the American Materials Sample Association "ASTM" D-903 measurement method. The upper limit of peel strength is the easiness of peeling when affixed to a transfer target after photographic processing, and the lower limit is the processing step. It is set in consideration of prevention of peeling, and is preferably 40 to 120 g / inch.

As the hydrophilic polymer used as the release agent of the present invention, generally used hydrophilic polymers can be used, but the following polymers are preferable.

(1) Polymer compound containing cellulose as a constituent (2) Polymer compound containing vinyl acetate as a constituent (3) Polymer compound containing vinyl alcohol as a constituent (4) Acrylic acid or maleic acid High molecular compound contained in the constituent requirements regarding the hydrophilic polymer containing cellulose as a constituent is preferably a weight body having a molecular weight of 100 to 100,000 of cellulose ether or cellulose ester, for example, methyl cellulose, ethyl cellulose, benzyl cellulose, carboxymethyl cellulose, acetyl cellulose, sulfuric acid. Examples include cellulose and cellulose phthalate.

Regarding the polymer compound containing vinyl acetate as a constituent, the copolymerization partner may be any as long as it copolymerizes with vinyl acetate. These are usually used in the form of so-called emulsions dispersed in water. Generally, the molecular weight of these is preferably 100 to 100,000.
If the molecular weight is 1000 or less, the adhesive strength will be extremely weak,
When the molecular weight is 1,000,000 or more, the coating suitability is extremely deteriorated and it is difficult to put it into practical use. Specific examples of the polymeric substance containing vinyl acetate as a constituent element include polyvinyl acetate, ethylene / vinyl acetate copolymer, carboxy-modified ethylene / vinyl acetate copolymer, vinyl acetate / vinyl chloride copolymer, vinyl acetate. -Acrylic acid copolymer and vinyl acetate-maleic acid copolymer are mentioned.

As the polymer compound containing vinyl alcohol as a constituent, polyvinyl alcohol alone,
Alternatively, a copolymer of vinyl alcohol and another monomer can be used. The molecular weight thereof is not particularly limited, but generally 100 to 100,000 is preferable. Specific examples of the polymer compound containing vinyl alcohol as a constituent include polyvinyl alcohol and ethylene / vinyl alcohol copolymer.

Regarding the polymer compound composed of a polymer of acrylic acid or maleic acid, specific examples thereof include polyacrylic acid, sodium polyacrylate, polyacrylic acid methyl ester, polymaleic acid, polymaleic acid methyl ester, sulfone / maleic acid. There are copolymers and the like.

The molecular weight of these is not particularly limited, but is preferably 10 to 100,000.

Of the above-mentioned release agents, preferred examples are carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol and ethylene vinyl alcohol copolymer.

The release agent described above is applied to the surface of photographic paper (0.
5 ~ 1.5g / m ² ) Coated. As a coating method, a usual gravure coat, bar coat, air knife coat, curtain coat or the like can be applied.

The base paper of the present invention can be selected from the raw materials generally used for photographic printing paper. Examples thereof include natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, and various raw materials for paper making. In general, natural pulp mainly composed of softwood pulp, hardwood pulp, mixed pulp of softwood pulp and hardwood pulp, etc. can be widely used.

Further, the support may contain additives such as a sizing agent, an anchoring agent, a toughening agent, a filler antistatic agent and a dye, which are generally used in papermaking, and a surface size. An agent, a surface-strengthening agent, an antistatic agent, etc. may be appropriately applied to the surface.

As the support, one having a smooth surface having a weight of 50 to 300 g / m ² is usually used, and the release agent is coated on at least one surface and then both surfaces are laminated with a polyolefin resin. The polyolefin resin can be selected from ethylene, α-olefins, homopolymers such as polypropylene, at least two copolymers of the above olefins, or a mixture of at least two of these various polymers. Particularly preferred polyolefin resins are low density polyethylene, high density polyethylene or mixtures thereof.

The molecular weight of the above-mentioned polyolefin resin is not particularly limited, but one having a range of 20,000 to 200,000 is usually used.

The polyolefin resin layer of the support according to the present invention on the side on which the photographic emulsion is coated has a thickness of 25 to 50 μm, preferably 25 to 35 μm.

The polyolefin used to laminate the back side of the support (opposite the side on which the emulsion layer is provided) is usually a melt-laminated mixture of low and high density polyethylene. And this layer is often matted.

In the polyolefin resin used for laminating the support surface (the surface on which the emulsion layer is provided) according to the present invention, 14 to 30% by weight of a white pigment is dispersed and mixed. Especially 14
It is preferably about 20% by weight on a white background.

As the white pigment, inorganic and / or organic white pigments can be used, preferably inorganic white pigments. Examples of such white pigments include sulfates of alkaline earth metals such as barium sulfate. , Calcium carbonate and other alkaline earth metal carbonates, finely divided silicic acid, synthetic silicate silica, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like.

Of these, preferably barium sulfate,
Calcium carbonate and titanium oxide, more preferably barium sulfate and titanium oxide.

Titanium oxide may be of the rutile type or the anatase type, and the one whose surface is coated with a metal oxide such as hydrous alumina oxide or hydrous ferrite is also used.

In the present invention, the coefficient of variation of the occupied area ratio (%) of the fine particles of the pigment in the waterproof resin is preferably 0.20 or less, more preferably 0.15 or less, and particularly preferably 0.10 or less.

The dispersibility of the titanium oxide fine particles in the resin layer is determined by exposing the surface of the resin to a thickness of about 0.1 μm, preferably about 500 Å by the ion sputtering method by glow discharge and scattering the resin on the surface to expose the pigment. The fine particles of (1) are observed with an electron microscope, the area occupied by the image capturing is obtained, and it can be evaluated by the coefficient of variation of the occupied area ratio (%). Ion Sputtering Method is based on Yoichi Murayama and Kunihiro Kashiwagi "Surface Treatment Technology Using Plasma": Machinery Research, Vol. 33, No. 6 (19
1981) and so on.

In order to control the variation coefficient of the white pigment particles to 0.20 or less, it is preferable to sufficiently knead the white pigment in the presence of a surfactant, and the surface of the pigment particles should be 2 as described above. It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (%) of the white pigment fine particles per defined unit area is most typically divided into unit areas of 6 μm × 6 μm which are adjacent to each other, and Occupied area ratio of projected particles (%)
It can be determined by measuring (Ri). The coefficient of variation of the occupied area ratio (%) is Ri with respect to the average value (Rm) of Ri.
It can be obtained by the ratio S / Rm of the standard deviation S of. The number (n) of the target unit areas is preferably 6 or more.

Various additives such as colored pigments, optical brighteners and antioxidants may be added to the water resistant resin.

The photographic material of the present invention preferably has a white pigment layer between the peelable polyolefin resin layer and the silver halide emulsion layer closest to the base paper.

As the white pigment used in the white pigment layer, those conventionally used for concealing photographic printing paper or proposed can be used.
For example, titanium oxide, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, lithopone, white alumina,
Examples thereof include zinc oxide, silica, antimony trioxide, titanium phosphate, talc and clay. These can be used alone or in combination.

Of these, barium sulfate, calcium carbonate, titanium oxide and zinc sulfide are preferable, and titanium oxide is particularly preferable because it has good whiteness, dispersibility and stability, and has a large hiding power. Titanium oxide may be rutile type or anatase type, and may be used alone or in combination. Moreover, the thing made by the sulfuric acid method and the thing made by the chlorine method may be used. Titanium oxide is hydrated alumina treated, hydrous silicon oxide treated or surface treated with an inorganic substance such as zinc oxide, trimethylolmethane,
Trimethylolethane, trimethylolpropane, 2,4-
It is possible to appropriately use those which are surface-coated with an organic physical property such as dihydroxy-2-methylpentane, or those which are treated with siloxane such as polydimethylsiloxane. The particle size of titanium oxide is not particularly limited, but the average particle size is preferably 0.1 to 0.5 μm. The filling amount of the white pigment in the white pigment layer is not particularly limited and varies depending on the type of white pigment used and the thickness of the white pigment layer, but is preferably selected in the range of 0.01 to 10 g / m ² , It is preferably 0.01 to 5 g / m ² . The thickness of the white pigment layer is not particularly limited, but is usually about 5 to 80 μm, preferably about 5 to 60 μm.

The light-sensitive material of the present invention has a white pigment layer and a non-emulsion layer such as a gelatin layer between the peelable polyolefin resin layer and the silver halide emulsion layer closest to the base paper. Good.

The color light-sensitive material of the present invention is preferably provided with a colored layer containing a substance that absorbs light between the peelable polyolefin resin layer and the silver halide emulsion layer closest to the base paper. . This colored layer has a function of preventing halation by absorbing light.

The term "colored layer" as used herein means that the light-sensitive material is colored before development processing. Preferably,
From the standpoint of white background, it is preferably colorless after the development processing.

The colored layer of the present invention has wavelengths of 450 nm, 550 nm,
All reflection densities at 690 nm are 0.1 or more, preferably 0.1 to 1.4, more preferably 0.2 to 1.2. The reflection density mentioned here is the density of only the colored layer.

As the above-mentioned light absorbing substance, various inorganic substances and dyes exhibiting this action can be used. As the inorganic substance, for example, colloidal metal can be used. As the organic substance, for example, a substance in which various dyes are bound to a polymer or the like to be fixed (so-called moldant) so as not to be eluted in a color developing solution can be used. When an antihalation dye is used by fixing it with a polymer mordant as described above, it is not always easy to make the coating uniform, or if it is difficult to remove the light absorbing substance after color development, decolorization is necessary. Therefore, it is preferable to take measures against them.

Colloidal silver, colloidal manganese, and the like are preferable as the inorganic compound used in the practice of the present invention, and colloidal silver is particularly preferable. Since these have good decolorizing properties, they are also effective for application to color light-sensitive materials. As colloidal silver, for example, gray colloidal silver is prepared by setting silver nitrate by reducing silver nitrate in gelatin in the presence of a reducing agent such as hydroquinone, phenidone, ascorbic acid, pyrogallol or dextrin, and then neutralizing and cooling. Then, the reducing agent and unnecessary salts are removed by a noodle washing method. When reducing with alkaline, azaindene compound,
When making colloidal silver particles in the presence of mercapto compounds,
A colloidal silver dispersion of uniform particles can be obtained.

Further, the dye has a good spectral absorption characteristic according to the purpose of use, is completely decolorized in a photographic processing solution, and is easily eluted from the light-sensitive material to remain after the development process. It must satisfy various conditions such as no contamination, no adverse effects such as fog and desensitization on the photographic emulsion, and excellent stability over time in a solution or in a light-sensitive material without discoloration. .

As long as the above conditions are satisfied, any of the known compounds can be used. Particularly, as dyes having absorption in the visible region, see JP-A-3-251840, page 30, lower left column to lower right column. The dyes AI-1 to 11 are preferably used, and the infrared absorbing dyes are represented by the general formulas (I), (II) and (III) described in JP-A 1-280750, page 2, lower left orchid. The compounds are preferable because they have preferable spectral characteristics, have no influence on the photographic characteristics of the photographic emulsion, and have no stain due to residual color. Specific examples of preferable compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column.

When forming a laminate on the front and back of the support,
In general, in order to improve the flatness of the developed photographic paper in a normal environment, means such as slightly increasing the density of the resin layer on the front side than the back side or increasing the laminating amount on the back side rather than the front side is used.

In general, the front and back surfaces of the support can be laminated by melt extrusion coating of the polyolefin resin composition onto the support. In order to carry out this melt extrusion coating method, usually, a polyolefin resin composition is melt extrusion coated on a running support from a slit die of an extruder into a single-layer or multi-layer film form. Usually, the melt extrusion temperature is preferably 200 to 350 ° C. Further, it is preferable that the support is subjected to activation treatment such as corona discharge treatment and flame treatment.

Further, the surface of the support or, if necessary, both front and back surfaces can be subjected to activation treatment such as corona discharge treatment and flame treatment. Further, if necessary, on the surface of the surface laminate layer, a subcoat layer for improving the adhesiveness with the photographic emulsion, or on the backside laminate layer, a backcoat layer for improving the printing writability and antistatic property. Etc. may be provided.

The thickness of this support is preferably 200 μm or more, more preferably 210 μm or more.

The maximum color transmission density of the color light-sensitive material of the present invention is 2.0 or more. The maximum color transmission density of 2.0 or more referred to here means that the light-sensitive material was exposed to light by exposure and then color-developed, and the obtained sample was coated with an emulsion layer using PDA-65 (manufactured by Konica Corporation). It means that the B, G, R densities were measured with the side facing the detector, and the B, G, R densities obtained by subtracting the densities of the unexposed portions from the measured values were all 2.0 or more.

In the case of a transmissive display light-sensitive material, the maximum color transmission density is 2.0 because it is viewed by the light transmitted from the back surface.
In the following cases, the image becomes thin and it is difficult to use it as a transmissive display light-sensitive material. The maximum color transmission density is preferably 2.2 or more.

The total silver coverage of the light-sensitive material of the present invention is 1.0 g / m ^2.
That is all. The total silver coating amount here means the total silver coating amount on the emulsion layer side. When the total silver coating amount is lower than 1.0 g / m ^2, it is difficult to obtain the maximum color transmission density of 2.0 or more, and more preferably 1.2 g / m ² or more.

The silver halide used in the silver halide emulsion layer according to the present invention includes silver chloride, silver bromide, silver iodide,
Any silver halide such as silver chlorobromide, silver iodobromide and silver chloroiodide can be used.

The silver halide grains preferably used are
A silver halide grain mainly comprising silver chloride containing at least 80 mol% of silver chloride, more preferably a silver chloride content of 90 mol% or more, particularly preferably 95 mol% or more, and a silver bromide content of 5 mol. %, And the silver iodide content is preferably 0.5 mol% or less. More preferably, the silver bromide content is
It is 0.1 to 2 mol% of silver chlorobromide.

The silver halide grains may be used alone or in combination with other silver halide grains having different compositions. Further, it may be used as a mixture with silver halide grains having a silver chloride content of 80 mol% or less.

In a silver halide emulsion layer containing silver halide grains having a silver chloride content of 80 mol% or more, the silver chloride content in all silver halide grains contained in the emulsion layer. The proportion of silver halide grains of 95 mol% or more is 60 wt% or more, preferably 80 wt% or more.

The composition of silver halide grains may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. When the composition inside and outside the particle is different, the composition may continuously change or may be discontinuous.

The silver halide grains may have any shape. One preferable example is a cube having a (100) plane as a crystal surface.

The grain size of the silver halide grain is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm, more preferably 0.2 to 1.2 μm.
It is in the range of 1.0 μm. The grain size distribution of the silver halide grains used in the present invention may be polydisperse or monodisperse. Preferably, the coefficient of variation is 0.22 or less,
More preferably, it is a monodisperse silver halide grain of 0.15 or less. Here, the coefficient of variation is a coefficient representing the breadth of the particle size distribution and is defined by the following equation.

Coefficient of variation = S / R (S is the standard deviation of the grain size distribution, R is the average grain size) The grain size referred to here is the diameter of spherical silver halide grains, or the cube. In the case of particles having a shape other than or spherical, it represents the diameter when the projected image is converted into a circular image having the same area.

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

The silver halide emulsion 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 producing the seed particles and the method for growing the seed particles may be the same or different. The method of reacting the soluble silver salt and the soluble halide salt may be any one of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof and the like, but a method obtained by the simultaneous mixing method is preferable. Further, as a form of the simultaneous mixing method, JP-A-54-485
The pAg-controlled double jet method described in No. 21 etc. can also be used.

Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added and used during the formation of silver halide grains or after the completion of grain formation.

A known method can be used for reduction-sensitizing the silver halide emulsion. For example, a method of adding various reducing agents can be used, or a method of aging under conditions of high silver ion concentration or a method of aging under conditions of high pH can be used.

Examples of the reducing agent used for reduction sensitization include stannous salts such as stannous chloride, boranes such as tri-t-butylamine borane, sulfites such as sodium sulfite and potassium sulfite, and reductones such as ascorbic acid. Examples thereof include thiourea dioxide and the like. Among these, thiourea dioxide, ascorbic acid and its derivatives, and sulfite can be preferably used. Compared with the case where reduction sensitization is performed by controlling the silver ion concentration and pH during ripening, the method using a reducing agent as described above is excellent in reproducibility and is preferable.

After the reduction sensitization, a small amount of an oxidizing agent may be used to modify the reduction sensitizing nucleus or deactivate the remaining reducing agent. Examples of the compound used for such purpose include
Examples thereof include potassium hexacyanoferrate (III), bromosuccinimide, p-quinone, potassium perchlorate, and hydrogen peroxide solution.

The silver halide emulsion used in the present invention can be reduction-sensitized and combined with a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer. As the chalcogen sensitizer, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, but the sulfur sensitizer is preferable. As the sulfur sensitizer, thiosulfate,
Examples include allyl thiocarbamide, thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine and the like.

As the gold sensitizer, various gold complexes such as chloroauric acid, gold sulfide, gold thiosulfate and the like can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanate, mercaptotetrazole,
Examples thereof include mercaptotriazole.

The silver halide emulsion contains a known antifoggant for the purpose of preventing fog during the process of preparing a light-sensitive material, reducing performance fluctuation during storage, and preventing fog during development. Stabilizers can be used. As an example of a compound used for such a purpose, the compound represented by the general formula (II) described in JP-A-2-146036, page 7, lower column
Compounds represented by the formula (IIa-1) to (IIa-1) described on page 8 of the same publication are listed.
-8), compounds (IIb-1) to (IIb-7), 1- (3-methoxyphenyl) -5-mercaptotetrazole, and the like.

The color light-sensitive material of the present invention has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength range of 400 to 900 nm in combination with a yellow coupler, a magenta coupler and a cyan coupler. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

Any known compound can be used as the spectral sensitizing dye, but as the blue-sensitive sensitizing dye, BS-described in JP-A-3-251840, page 28, upper right column to lower left column, can be used. 1 to 8 can be preferably used alone or in combination. As a green-sensitizing sensitizing dye, the same publication 28
GS-1 to 5 described in the lower right column on the page are preferably used, and RS-1 to 8 described in the upper left column to the upper right column on page 29 of the same publication are preferably used as the red photosensitive sensitizing dye.

When the color light-sensitive material of the present invention is exposed by a printer using a semiconductor laser, it is necessary to use a sensitizing dye having infrared sensitivity. As the infrared-sensitive sensitizing dye, The dyes of IRS-1 to 11 described in JP-A-4-285950, pages 6 to 8 are preferably used. or,
Supersensitizers SS-1 to 9 described on pages 8 to 9 of the same publication are preferably used in combination with these dyes.

When the light-sensitive material of the present invention is subjected to laser exposure, it is advantageous to use an exposure device using a semiconductor laser in terms of downsizing of the device.

Dyes having absorption in various wavelength regions can be used in the light-sensitive material according to the present invention for the purpose of preventing irradiation and halation. Any known compound can be used, but as the dye having absorption in the visible region and infrared region, the compounds described in JP-A-3-251840 and 1-280750 are preferable.

As the coupler used in the color light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by a coupling reaction with an oxidant of a color developing agent. Can also be used, yellow coupler having a spectral absorption maximum wavelength in the wavelength range 350 ~ 500 nm, magenta coupler having a spectral absorption maximum wavelength in the wavelength range 500 ~ 600 nm, wavelength range 600 ~ 7
The one known as a cyan coupler having a spectral absorption maximum wavelength at 50 nm is typical.

Examples of yellow couplers which can be preferably used in the present invention include couplers represented by the general formula [Y-1] described in JP-A-4-114154, page 3, upper right column. Examples of the compounds include those described as YC-1 to 9 in the same publication, page 3, lower left column to page 4, upper left column. Among them, YC described in the upper left column on page 4 of the same publication
-8 and YC-9 are preferable because they can reproduce a preferable yellow color.

Examples of the magenta coupler include couplers represented by the general formulas (M-I) and (M-II) described on page 12 of the above. Specific compounds include those described as MC-1 to 11 on pages 13 to 16 of the same specification. Among them, MC-8 to 11 described on pages 15 to 16 of the same specification are preferable because they are excellent in the reproduction of colors ranging from blue to purple and red and are also excellent in the depiction of details.

Examples of the cyan coupler include couplers represented by the general formulas (C-I) and (C-II) described on page 17 of the above. Specific compounds are described in the same specification.
The compounds described as CC-1 to 9 on pages 18 to 21 can be mentioned.

When the oil-in-water type emulsion dispersion method is used to add the coupler, it is usually added to a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher and, if necessary, a low-boiling point and / or water-soluble organic solvent. Are dissolved together and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. A step of removing the low boiling point organic solvent may be added after or at the same time as the dispersion. As the high boiling point organic solvent that can be used for dissolving and dispersing the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

In place of the method using a high-boiling point organic solvent, the coupler and the water-insoluble and organic solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. A method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder can also be adopted. Examples of the water-insoluble organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

[0084] The coating amount of the coupler is not particularly limited if it can obtain a sufficiently high concentration, preferably 1 mol of silver halide per 1 × 10 ^-3 to 5 mol, more preferably, 1 × 10 ^- It is used in the range of ² to 1 mol.

In the present invention, it is preferable to add an oil-soluble dye. The oil-soluble dye means an organic dye having a solubility in water at 20 ° C. of 0.01% by weight or less, and a compound having a molecular absorption coefficient of 20000 or more at a maximum absorption wavelength at a wavelength of 400 nm or more is preferable. Preferred compounds include compounds of the general formulas (II) and (III) shown in JP-A-2-842, page 7, lower right column to page 8, upper right column. Specific examples of preferable compounds include compounds 1 to 27 described in the same publication, page 8, lower left column to page 9, upper right column. Among these, compounds 4 and 9 are particularly preferable.

The oil-soluble dye is preferably added to the non-photosensitive layer, and is preferably added in an amount of 0.05 to 5 mg / m ² .

In the light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives. Also, hydrophilic colloids such as cellulose derivatives and synthetic hydrophilic polymer substances such as homopolymers or copolymers can be used.

The coating amount of gelatin is preferably 8.0 g / m ² or more in order to suppress the generation of stain and further enhance the effect of the present invention.

At the time of coating the light-sensitive material, a thickener may be used to improve coatability. The coating method is 2
Extrusion coatings and curtain coatings, which allow for the simultaneous application of more than one layer, are particularly useful.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can be mentioned as an example 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- (N-ethyl-N- (β-hydroxyethylamino) aniline CD-5: 3-methyl-4- (N-ethyl-N- (β-hydroxyethylamino) aniline CD-6: 4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline CD-7: N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide 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-ethoxy Ethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N- (β-butoxyethyl) aniline Among these, (CD-5), ( D-6), (CD-
9) is preferred.

The color developing agent used for color image formation may be used alone or in combination with a known p-phenylenediamine derivative.

The color developing agent is usually used in the range of 1 × 10 ^-2 to 2 × 10 ^-1 mol per liter of developing solution, and from the viewpoint of rapid processing, it is 1.5 × 10 2 per liter of color developing solution.
A range of ^{−2 to} 2 × 10 ⁻¹ mol is preferable.

The developing solution used in the present invention preferably contains substantially no benzyl alcohol. Here, the term "substantially free of" means that benzyl alcohol is 2 cc / liter or less, and it is most preferred that no benzyl alcohol is contained.

In the present invention, it is preferable that the color developing solution contains chlorine ions in an amount of 2.5 × 10 ^{-2 to} 5 × 10 ^-1 mol / liter. In addition, bromide ion is 2.0 × 10 ^-5 ~ 2.0
It is preferable to contain ^{x10 -2} mol / liter.

Chloride ions and bromine ions may be added directly to the developing solution, or may be eluted from the light-sensitive material into the developing solution during the development processing. When added directly to the color developing solution, sodium chloride, potassium chloride, ammonium chloride, lithium chloride,
Nickel chloride, magnesium chloride, manganese chloride, calcium chloride, cadmium chloride and the like can be mentioned, with preference given to sodium chloride and potassium chloride. Further, it may be supplied from an optical brightener added to the developing solution.

As the bromine ion supplying substance, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, nickel bromide, magnesium bromide, manganese bromide,
Calcium bromide, cadmium bromide, cerium bromide, thallium bromide and the like can be mentioned, with preference given to sodium bromide and potassium bromide.

When it is eluted from the light-sensitive material during the development processing,
Both chlorine ion and bromine ion may be supplied from the emulsion, or may be supplied from other than the emulsion.

Further, in the color developing solution, instead of hydroxylamine which has been conventionally used as a preservative, JP-A-63-1 is used.
46043, 63-146042, 63-146041, 63-146040
Nos. 63-135938 and 63-118748, and hydroxylamine derivatives described in JP-A-64-62639, JP-A-1-303438, etc., hydroxamic acids, hydrazines, hydrazides, phenols, α -Hydroxyketones, α-aminoketones, saccharides, monoamines, diamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, etc. as organic preservatives It is preferably used. It is also possible to use these compounds in combination with the conventionally used hydroxylamine and the above organic preservative,
It is preferable not to use hydroxylamine from the viewpoint of developing characteristics.

Further, a development accelerator can be used if necessary. In addition, depending on the situation, stain inhibitors,
Various additives such as an anti-sludge agent and a multi-layer effect accelerator can be used.

The sulfite concentration in the color developer used in the present invention is preferably 1 × 10 ^-2 mol / liter or less. Especially 0
To 7-× is good during 10 ^-3 mole / liter or less, especially preferably not more than 0 to 5 × 10 ^-3 mol / liter.

The above color developing solution can be used in any pH range, but from the viewpoint of rapid processing, it is preferably pH 9.5 to 13.0, more preferably 9.8 to 12.0.

The processing temperature for color development is preferably 25 to 70 ° C. The higher the temperature, the shorter the treatment is possible, which is preferable, but it is preferable that the temperature is not too high from the stability of the treatment liquid.
Treatment at 25 to 50 ° C is preferred. Color development time is 50
It is preferably 120 seconds. If it is shorter than 50 seconds, the maximum density becomes unstable, and if it is longer than 140 seconds, fog tends to occur.

The replenishing amount of the color developing solution is preferably 500 cc or less, and more preferably 50 to 400 cc per 1 m ² of the light-sensitive material.

The processing steps consist essentially of a color development step, a bleach-fixing step, and a water washing step (including a stabilizing treatment as an alternative to water washing), but steps may be added or equivalent to the extent that the effects of the present invention are not impaired. It can be replaced with a meaningful process. For example, the bleach-fixing step can be separated into a bleaching step and a fixing step, or a bleaching step can be placed before the bleach-fixing step. The processing steps used in the present invention include:
It is preferable to provide a bleach-fixing step immediately after the color development step.

The bleaching agent used in the bleach-fixing solution is not limited, but is preferably a metal complex salt of an organic acid. The complex salt is obtained by coordinating an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid, and citric acid with a metal ion such as iron, cobalt and copper. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid or an aminopolycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific examples of these compounds are described in JP-A-1-
The compounds [2] to [20] described in No. 205262, pages 58 to 59 can be mentioned.

As the bleach-fixing solution, a solution containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, in addition to the ethylenediaminetetraacetic acid iron (III) salt bleaching agent and the above-mentioned silver halide fixing agent, a bleach-fixing solution having a composition in which a large amount of a halide such as ammonium bromide is added, and further ethylenediaminetetraacetic acid iron (III) ) A special bleach-fixing solution having a composition comprising a combination of a salt bleach and a large amount of a halide such as ammonium bromide can be used.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which reacts with silver halide as used in ordinary fixing processing to form a water-soluble complex salt, for example, potassium thiosulfate or sodium thiosulfate. Typical examples thereof include thiosulfates such as ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether.

The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used in the range of 4.0 to 9.5, preferably 4.
Used in 5-8.5. Most preferably, it is in the range of 5.0 to 8.5.

The processing temperature for bleach-fixing is 80 ° C. or lower, preferably 55 ° C. or lower, and evaporation is suppressed before use. Processing time is 12
0 second or less is preferable.

In the developing process, a washing process is carried out subsequent to the color developing and bleach-fixing steps. A preferred embodiment of the washing process will be described below.

As the compound preferably used in the washing solution, a chelating agent having a chelate stabilizing constant for iron ions of 8 or more is preferable. Here, the chelate stabilization constants are the Stability Constants by LG Sillen and AEMartell.
of Metalion Complexes '', The Chemical Society, Lond
on (1964), S.Chaberek, AEMartell "Organic Sequ"
“Estering Agents”, Wiley (1959), etc. mean the constants generally known.

Examples of the chelating agent having a chelate stability constant of 8 or more with respect to iron ions, which is preferably used in the washing solution, include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. In addition, the said iron ion means a ferric ion. Specific examples of the chelating agent having a chelate stability constant with ferric ion of 8 or more are described in JP-A-1-2051
The compounds described in No. 62, page 63, line 15 to page 64, line 17 can be mentioned.

Further, as a compound to be added to the washing solution, an ammonium compound is particularly preferable. These are supplied by ammonium salts of various inorganic compounds, and specific examples thereof include compounds described in JP-A 1-205162, page 65, line 5 to page 66, line 11. Further, it is desirable that the washing solution contains sulfite within the range where bacteria are not generated. The sulfite to be contained in the washing liquid may be any one such as an organic substance or an inorganic substance as long as it releases a sulfite ion, but is preferably an inorganic salt, and preferable specific compounds include sodium sulfite, potassium sulfite and ammonium sulfite. , Ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite, cartaraldehyde sodium sodium bisulfite, succinic aldehyde bis sodium bisulfite and the like. To be

The washing solution used in the present invention preferably contains a mildew-proofing agent, which can prevent sulfuration and improve image storability.

Antifungal agents that can be used include sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guadinine compounds, morpholine compounds, quaternary phosphonium compounds,
They are ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, pyronone compounds and amino compounds. Specific compounds include JP-A 1-205162, page 68, 10
Lines to page 72 line 16 compounds. Among these compounds, thiazole compounds, sulfamide compounds, and pyronone compounds are particularly preferably used.

Ion exchange water treated with an ion exchange resin may be used as the washing water.

The pH of the wash water is in the range of 5.5 to 10.0. Applicable pH adjusters are generally known alkaline agents,
Any of the acid agents can be used. The washing temperature is preferably 15 to 60 ° C, more preferably 20 to 45 ° C. The processing time is preferably 240 seconds or less. When washing with water in multiple tanks, perform the treatment in a shorter time than the previous tank,
It is preferable that the treatment time is longer in the later tank. Especially in the front tank
It is preferable to carry out the treatment sequentially with treatment times of 20 to 50% increase.

The washing water amount is 0.1 to 50 of the carry-in amount of the pre-bath (usually a bleach-fixing solution or a fixing solution) per unit area of the light-sensitive material.
It is preferably doubled, and particularly preferably 0.5 to 30 times.

The washing tank in the washing treatment is preferably 1 to 5 tanks, and more preferably 1 to 3 tanks.

As the developing processing apparatus for the photosensitive material used in the present invention, any known apparatus may be used. In the present invention, a large amount of light-sensitive materials are processed and run in these color development-drying steps to elute components from the light-sensitive materials into the processing liquid, contamination between processing tanks, and evaporation of the processing liquid are saturated and constant. The effect is particularly exerted when it is treated later.

[0123]

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

Example 1 Sample 1 was prepared by coating a silver halide emulsion in the following layer structure on a transparent polyethylene terephthalate film (BASE-1) having a thickness of 180 μm. The silver halide emulsion and colloidal silver are in terms of silver.

Layer composition Addition amount (g / m ² ) 7th layer (protective layer) Gelatin 1.0 Anti-staining agent (HQ-2) 0.002 Anti-staining agent (HQ-3) 0.002 Anti-staining agent (HQ-4) 0.004 Anti-staining agent (HQ-5) 0.02 Compounds B, C, D and E 2 × 10 ^-5 DIDP 0.005 Hardener (H-1) 0.08 Antifungal agent (F-1) 0.002 6th layer (UV absorbing layer) ) Gelatin 0.4 Anti-irradiation dye (AI-2) 0.02 Anti-irradiation dye (AI-4) 0.01 UV absorber (UV-1) 0.1 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Anti-staining agent (HQ-5) 0.04 Compound E 2 × 10 ^-4 Compounds F, G 0.03 PVP 5th layer (red sensitive layer) Gelatin 4.0 Red sensitive silver chlorobromide emulsion (Em-R) 0.43 Cyan coupler (C) -1) 0.35 Cyan coupler (C-2) 0.5 Color image stabilizer (S -1) 0.4 Anti-staining agent (HQ-1) 0.02 Compound 1 0.00 HBS-1 0.4 DOP 0.6 Fourth layer (UV absorbing layer) Gelatin 2.0 UV absorbing agent (UV-1) 0.2 UV absorbing agent (UV-2) 0.2 UV absorber (UV-3) 0.4 Anti-staining agent (HQ-5) 0.1 Compound E 1 × 10 ^-3 Third layer (green sensitive layer) Gelatin 3.0 Irradiation preventing dye (AI-1) 0.01 Green sensitive chlorobromide Silver emulsion (Em-G) 0.52 Magenta coupler (M-1) 0.7 Color image stabilizer (ST-3) 0.4 Color image stabilizer (ST-4) 0.2 Color image stabilizer (ST-5) 0.2 Stain Inhibitor (HQ-2) 0.02 DOP 0.6 Second layer (intermediate layer) Gelatin 1.2 Anti-irradiation dye (AI-3) 0.02 Anti-stain agent (HQ-2) 0.03 Anti-stain agent (HQ-3) 0.03 Anti-stain agent (HQ-4) 0.05 Stain inhibitor HQ-5) 0.23 Compound B, C, D, E each 3 × 10 ^-4 DIDP 0.06 Fluorescent brightening agent (W-1) 0.1 fungicide (F-1) 0.02 The first layer (blue-sensitive layer) Gelatin 2.6 Blue-sensitive silver chlorobromide emulsion (Em-B) 0.61 Yellow coupler (Y-1) 1.6 Color image stabilizer (ST-1) 0.6 Color image stabilizer (ST-2) 0.4 Anti-stain (HQ-1) ) 0.4 Compound A 4 × 10 ^-4 DNP 0.4 0 G layer Gelatin 1.5 Surfactant (SU-3) 0.03 Hardener (H-1) 0.05 White pigment layer Gelatin 2.0 Rutile titanium oxide 4.5 Surfactant (SF-1) ) 0.03 Support (transparent polyethylene terephthalate) First back layer Gelatin 3.0 UV absorber (UV-1) 0.2 UV absorber (UV-2) 0.1 UV absorber (UV-3) 0.4 Colloidal silver 0.1 Second back layer ( Protective layer) Gelatin 2.0 Colloidal silver 0.05 Hardener (H-2) 0.06 each The structural formula of the compounds used in the following.

HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonylbutyl) hydroquinone Compound A: Quinone derivative of HQ-1 Compound B: HQ -2 quinone compound C: HQ-3 quinone compound D: HQ-4 quinone compound E: HQ-5 quinone compound F: 1-hydroxy-2-bromo-4-aminoanthraquinone compound G: 2,4-Di (butylamino) anthraquinone DIDP: Diisodecylphthalate DOP: Dioctylphthalate DNP: Dinonylphthalate PVP: Polyvinylpyrrolidone HBS-1: 4-{(4-dodecylphenyl) sulfamoyl}
Toluene ST-1: 2 ', 4'-di-t-amylphenyl-3,5-di-t-butyl-4-hydroxybenzoate ST-2: 2,4-di-t-amyl-diethylcarbamoylmethoxybenzene ST-3: 2,5-di-t-amyl hydroquinone dioctyl ether ST-4: Methylenebis (2-t-butyl-4-methylphenol) ST-5: 2,5-di-t-butyl hydroquinone dibutyl ether SU -1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Sodium di (2-ethylhexyl) sulfosuccinate SU-3: Di (1,1,2,2,3,3,4,4) sulfo succinate -Octafluorobutyl) sodium H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium

[0127]

[Chemical 1]

[0128]

[Chemical 2]

[0129]

[Chemical 3]

(Preparation of blue-sensitive silver halide emulsion) In 1000 cc of a 2% gelatin aqueous solution kept at 40 ° C., the following (A solution) and (B solution) were taken for 30 minutes while controlling pAg = 6.5 and pH = 3.0. At the same time, and then add the following (solution C) and (solution D) to pAg
= 7.3, pH = 5.5, and simultaneous addition was performed over 180 minutes. 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 0.07 g Water to make 200 cc (Solution B) Silver nitrate 10 g Water to make 200 cc (Solution C) Sodium chloride 102.7 g Potassium bromide 2.10 g Water To 300 cc (D solution) 300 g of silver nitrate Add water to 600 cc After completion of the addition, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate. A monodisperse cubic emulsion EMP-1 having an average particle size of 0.85 μm, a coefficient of variation of 0.07 and a silver chloride content of 99.0 mol% was obtained by mixing with an aqueous gelatin solution.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound 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-1 6 × 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 method of green-sensitive silver halide emulsion) (solution A) and (B
(Liquid) and the addition time of (C liquid) and (D liquid) are changed in the same manner as EMP-1, except that the average particle size is 0.43 μm.
A monodisperse cubic emulsion EMP-2 having m, a coefficient of variation of 0.07 and a silver chloride content of 99.0 mol% was obtained.

For EMP-2, the following compounds were used.
Chemical ripening was carried out at 120 ° C. for 120 minutes 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 sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (red Method for Preparing Sensitive Silver Halide Emulsion) Addition Time of Solution A and Solution B and Solution C and Solution D
In the same manner as EMP-1 except that the addition time of
A monodisperse cubic emulsion EMP-3 having an average grain size of 0.50 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.0 mol% was obtained.

The following compounds were used for EMP-3:
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-R) was obtained.

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

[0138]

[Chemical 4]

The first back layer, the second back layer, the white pigment layer, and the 0G layer of Sample 1 were removed, and the support and silver coverage were shown in Table 1.
Samples 2 to 12 were prepared in the same manner as the sample 1 except that it was changed as shown in FIG.

(Preparation of BASE-2) Canadian Standard Freeness (JIS P-8121-76) 250 by refiner
20% bleached softwood sulfite pulp (NBSP) beaten to cc
Was mixed with 80% of softwood bleached sulfuric acid pulp (LBKP) beaten to the same freeness of 280 cc to prepare a papermaking raw material.

Add the papermaking additive to the pulp dry weight,
It was used in the following amounts.

Cationized starch 2.0% Alkyl ketene dimer resin 0.4% Anionic polyacrylamide resin 0.1% Polyamide polyamine epichlorhydrin resin 0.7% Sodium hydroxide Adjusted to pH 7.5 Papermaking raw material containing the above additives is used in a Fourdrinier machine. Papermaking, size press and mamin calender were applied, and the rice basis weight was 17
A base paper with 0 g / m ² , a tightness of 1.0 and a water content of 8% was produced.

As a size press treatment agent, a 5% size liquid prepared by dissolving carboxyl-modified PVA and sodium chloride in water at a ratio of 2: 1 was used, and 2.2 g / m ² was applied to both sides of the base paper. The amount applied. Then, carboxymethyl cellulose (molecular weight 300,000) was coated as a release agent on the silver halide emulsion layer coating layer side.

Corona discharge was applied to both the front and back sides of the obtained base paper, and high density polyethylene containing anatase type titanium oxide of 10% (specific gravity: 0.
94, MI = 6.8) to form a 35 μm thick resin coating layer, and the back surface of the layer is made of polyethylene containing no titanium oxide at 280 ° C. by a coextrusion coating method.
A polyethylene resin coating layer having an upper and lower two-layer structure was formed, and the obtained laminate was pressed against a cleaning roll having a matte surface at 20 ° C. with a linear pressure of 20 kg / cm to produce a support for photographic printing paper. The peel strength was 74 g / inch.

The thickness of this support was 230 μm.

Similar to BASE-2, BA having different peel strength or different titanium oxide concentration in the polyethylene resin coating layer was used.
SE-2 to 10 were created.

These samples were continuously processed according to the following processing steps, and evaluated by the evaluation method described later.

(Processing step) Processing step Processing temperature Time Replenishment amount Color development 35.0 ± 0.3 ℃ 110 seconds 377cc / m ² Bleach-fixing 35.0 ± 0.5 ℃ 110 seconds 215cc / m ² Water wash 30-34 ℃ 3 minutes 40 seconds 248cc / m ² dry 60 to 80 ° C 150 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution replenisher Pure water 800cc 800cc Potassium bromide 20mg Potassium chloride 3.0g Potassium sulfite 0.25g 0.5g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl -4-Aminoaniline sulfate 4.5g 9.2g N, N-diethylhydroxylamine 5.0g 9.0g Triethanolamine 10.0g 15.0g Diethylenetriaminepentaacetic acid sodium salt 2.0g 2.0g Disulfonic acid ethylhydroxylamine 2.0g 3.0g Fluorescent brightening Agent (4,4'-diaminostilbene sulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 27 g 30 g Add water to bring the total volume to 1 liter.
0, pH of replenisher is adjusted to 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 5-Amino-1,3,4-thiadiazole-2-thiol 2.0 g Ammonium sulfite (40% aqueous solution) 27.5cc Add water to make the total volume 1 liter, and adjust to pH = 6.5 with potassium carbonate or glacial acetic acid.

Washing liquid Tank liquid and replenishing liquid Orthophenylphenol 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 Fluorescence enhancement Whitening agent (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 (polyvinylpyrrolidone) 1.0 g Ammonia water (hydroxide Ammonium 25% aqueous solution) 2.5 g Nitrilotriacetic acid trisodium salt 1.5 g Water is added to bring the total volume to 1 liter, and pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

[Evaluation Method] <Maximum Color Transmission Density and Dmin> After each sample was exposed to white light by irradiation, the sample was treated according to the treatment process.
The DA-65 was used to measure the transmission densities of yellow, magenta, and cyan, and from the obtained values, the minimum densities (Dmi
n) was subtracted.

<Transparent viewing image quality> Each sample was cut into 254 mm x 305 mm, printed imagewise, processed according to the above-mentioned processing steps, and the obtained print was visually evaluated with Ilmix II (manufactured by Eastman Kodak Company). .

X ... Poor Δ ... Good ○ ... Excellent <General versatility> After each sample was processed, it was attached to a tent, paper or the like with an adhesive to evaluate general versatility.

Samples 3 to 10 using BASE-3
Was tested by peeling off the polyolefin layer on the emulsion layer side and the base paper.

X: Difficult to attach ○: Easy to attach <Peel strength> 610 mm wide sample was cut into 1 inch width and all samples were measured by American Society for Testing Materials “ASTM” D-903 Averaged. Peel strength of less than 40 g / inch, when handling samples,
It has been confirmed that it peels off when peeling is not necessary, and it is difficult to peel off at 160 g / inch or more, and it stretches or breaks, which is a practical problem.

<Sharpness> Each sample was cut into a size of 254 mm × 305 mm, imagewise exposed, and the print obtained by processing in the above-mentioned processing step was visually evaluated for sharpness with Ilmix II (supra).

∘: Very sharp image with excellent sharpness ∘: Excellent sharpness Δ: Blurred image appears blurred ×: Image is blurred, resulting in poor sharpness Collectively shown in Table 1.

[0159]

[Table 1]

However, the maximum color transmission density of Samples 2 to 12,
The transparent viewing image quality and the sharpness are both evaluated after peeling.

As is clear from the results of Table 1, the comparison B
The sample 1 using ASE-1 and the samples 9 to 11 whose peel strength is outside the scope of the present invention are not versatile.

Further, in Sample 2, in which the concentration of titanium oxide in the polyethylene resin layer is lower than that of the present invention, Dmin is too low, so that the transmission image quality is poor and the sharpness is also poor. Furthermore, Sample 7 in which the concentration of titanium oxide in the polyethylene resin layer is higher than that of the present invention
, The transmission image quality is poor because Dmin is too high. Further, the sample 12 having the maximum color density outside the scope of the present invention is inferior because the transmission image quality is too thin.

On the other hand, the peeling strength, the titanium oxide concentration, and the maximum color density of Samples 4 to 6 of the present invention are
The sharpness and versatility are excellent, and particularly, the samples 5 and 6 are very excellent in sharpness.

Example 2 In the same manner as in Example 1, the yellow couplers Y-2 to Y-7, the magenta coupler M-2 to M-7 and the cyan cyan cyan dye were used in the structures of Samples 1 to 12 of Example 1. Coupler C-3 to C-
The same evaluation as in Example 1 was performed by substituting 10

As a result, the effect of the present invention was obtained even when the yellow coupler, the magenta coupler and the cyan coupler were replaced.

[0166]

[Chemical 5]

[0167]

[Chemical 6]

[0168]

[Chemical 7]

[0169]

[Chemical 8]

[0170]

[Chemical 9]

Example 3 Example 1 up to the preparation of Photosensitive Material Sample 1 and BASE-2
BASE-3 to 7 were prepared in the same manner as above, but the peel strength or the titanium oxide concentration in the polyethylene resin coating was changed.

Same as Sample 1 except that the first back layer and the second back layer of Sample 1 were removed and the amounts of titanium oxide and silver content in the support and the white pigment layer were changed as shown in Table 2. Samples 2 to 13 were prepared. These samples were processed in the same manner as in Example 1 and evaluated in the same manner. The results are shown below.

[0173]

[Table 2]

However, the maximum color density, transmission viewing image quality, and sharpness of Samples 2 to 13 are all evaluated after peeling.

As is clear from the results of Table 2, the comparison B
Sample 1 using ASE-1 and Samples 10 to 12 whose peel strength is outside the scope of the present invention have poor versatility. Further, the sample 2 not coated with the titanium oxide layer has a too low Dmin, so that the transmission image quality and the freshness are both inferior. Further, in Sample 7, in which the concentration of titanium oxide in the polyethylene resin layer is higher than that of the present invention, the transmission image quality is poor because Dmin is too high.

On the other hand, Samples 3 to 9 having the titanium oxide layer and satisfying the peel strength and the maximum color density of the present invention are excellent in transmission image quality, sharpness and versatility.

Example 4 In the same manner as in Example 3, the yellow couplers Y-2 to Y-7, the magenta coupler M-2 to M-7 and the cyan cyan cyan dye were used in the constructions of Samples 1 to 12 of Example 3. Coupler C-3 to C-
The same evaluation as in Example 3 was carried out by substituting 10 and the effect of the present invention was obtained even when each coupler was replaced.

Example 5 Example 1 up to the preparation of Photosensitive Material Sample 1 and BASE-2
In the same manner as described above, BASE-3 to 5 having different peel strengths or different titanium oxide concentrations in the polyethylene resin coating were prepared.

The first back layer, the second back layer, the white pigment layer and the 0G layer of Sample 1 were removed, a colored layer was provided between the support and the first layer (blue sensitive layer), and the support and silver were attached. Sample 2 was prepared in the same manner as Sample 1 except that the amount was changed as shown in Table 3.
Twelve created. These samples were processed in the same manner as in Example 1 and evaluated in the same manner. The results are shown below.

[0180]

[Table 3]

However, the composition of the colored layer in the table is as follows.

AHU-1 added amount (g / m ² ) AHU-2 added amount (g / m ² ) Gelatin 1.5 Gelatin 1.5 AI-1 0.01 AI-1 0.02 AI-2 0.02 AI-2 0.04 AI-3 0.01 AI -3 0.02 AI-4 0.01 AI-4 0.02 SU-3 0.03 SU-3 0.03 AHU-3 addition amount (g / m ² ) AHU-4 addition amount (g / m ² ) Gelatin 1.5 Gelatin 1.5 Colloidal silver 0.05 Colloidal silver 0.10 SU-3 0.03 SU-3 0.03 Further, the maximum color density of Samples 2 to 12, transmission viewing image quality, and sharpness are all evaluated after peeling.

As is clear from the results of Table 3, the comparison B
The sample 1 using ASE-1 and the samples 9 to 11 whose peel strength is outside the scope of the present invention are not versatile. In addition, Sample 2 in which the titanium oxide concentration of the polyethylene resin layer is lower than that of the present invention is
Is too low, resulting in poor transmitted image quality and poor freshness. Furthermore,
In Sample 7, in which the titanium oxide concentration in the polyethylene resin layer is higher than that of the present invention, the transmission image quality is poor because Dmin is too high. Further, the sample 12 having the maximum color density other than the present invention is not good because the transmission image quality is too thin.

On the other hand, Samples 3 to 8 having the peel strength, titanium oxide concentration, and maximum color density of the present invention are excellent in transmission image quality, sharpness, and versatility, and particularly, Samples 5 and 6 are preferable.
Has markedly improved sharpness.

Example 6 In the same manner as in Example 3, the yellow couplers Y-2 to Y-7, the magenta coupler M-2 to M-7 and the cyan cyan cyan dye were used in the configurations of Samples 1 to 12 of Example 3. Coupler C-3 to C-
The same evaluation as in Example 3 was carried out by substituting 10 and the effect of the present invention was obtained even when each coupler was replaced.

[0186]

By using the color light-sensitive material of the present invention,
We were able to provide a highly versatile transmissive photo display with excellent image quality when viewed with transmitted light from the back side.

Claims (4)

[Claims] 1. A silver halide emulsion comprising at least one layer of a hydrophilic polymer and a polyolefin resin layer, which are laminated on a base paper in this order, and the peel strength between the base paper and the polyolefin resin layer is 30 to 160 g / inch. In the silver halide color photographic light-sensitive material coated with a layer, a white pigment is contained in the polyolefin resin layer at a density of 14 to 30% by weight, and the maximum color transmission density of the silver halide photographic light-sensitive material is 2.0 or more. A silver halide color photographic light-sensitive material characterized by being present. 2. A silver halide emulsion comprising at least one layer of a hydrophilic polymer and a polyolefin resin layer, which are laminated in this order on a base paper, and the peel strength between the base paper and the polyolefin resin layer is 30 to 160 g / inch. In a silver halide color photographic light-sensitive material coated with a layer, a white pigment layer is provided between the polyolefin resin layer and the silver halide emulsion layer closest to the base paper, and the maximum color development of the silver halide photographic light-sensitive material is achieved. A silver halide color photographic light-sensitive material having a transmission density of 2.0 or more. 3. A hydrophilic polymer and a polyolefin resin layer are laminated in this order on a base paper, and at least one layer of a silver halide emulsion is provided on a support having a peel strength between the base paper and the polyolefin resin layer of 30 to 160 g / inch. In a silver halide color photographic light-sensitive material coated with a layer, a coloring layer is provided between the polyolefin resin layer and the silver halide emulsion layer closest to the base paper, and the maximum color transmission of the silver halide photographic light-sensitive material is obtained. A silver halide color photographic light-sensitive material having a density of 2.0 or more. 4. The total silver coating amount of the silver halide photographic light-sensitive material is
4. The silver halide color photographic light-sensitive material according to claim 1, which has a content of 1.0 g / m ² or more.