JP2000352797A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material enhanced in rigidity and restrained from the occurrence of a pressure fog and scratches in conveyance in minilaboratories and capable of using regenerated pulp for a paper base support. SOLUTION: Resin coating layers on both sides of a paper base support are composed of each one oriented polymer sheet and each adhesive layer is formed between each oriented polymer sheet and each paper base, and (1) and antistatic layer is formed on the resin coating layer on the paper base support on the side reverse to the side of an silver halide emulsion layer. (2) A nonphotosensitive hydrophilic colloidal layer farthest apart from the support contains an fluorine-containing surfactant and (3) an organopolysiloxane, and (4) the regenerated pulp made of used paper is used in an amount of >=10 weight % of the total pulp for constituting the paper base, and (5) the oriented polymer sheet contains an antioxidant.

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, and more particularly to a silver halide photographic light-sensitive material which has excellent stiffness, is hardly damaged by pressure fog and scratches when transported in a minilab, and makes it easy to count the number of prints accumulated after the minilab processing. The present invention relates to a silver halide photographic light-sensitive material comprising a paper support capable of improving a white background over time after forming a print and further containing recycled pulp in a base paper.

[0002]

2. Description of the Related Art In silver halide photographic light-sensitive materials,
With the spread of color photographic light-sensitive materials, color development processing has been increasingly simplified and accelerated, and it is desired that processing can be performed quickly and that the processing is stable.

[0003] With the recent spread of minilabs in color photographic paper, the processing speed from development to drying of exposed prints has become extremely high, and photosensitive materials suitable for this rapid processing have been demanded.

[0004] For speeding up, improvement of the support has been studied. In recent years, as a support for a color print photosensitive material, a water-resistant support (hereinafter referred to as R) in which a polyethylene resin is laminated on both sides of a base paper in order to speed up development processing.
C), and a white pigment such as titanium oxide is dispersed in the polyethylene layer on the photographic emulsion side for sharpness and a white background.

The base paper of the RC base paper is mainly composed of natural pulp, and virgin pulp is usually used as the natural pulp. In recent years, papers included in municipal waste together with resource conservation have been particularly highlighted. And paper from households and offices has spurred the increase in municipal waste. Therefore, it is desired to collect such waste paper and use it as a raw material. Recycled pulp is recycled from waste paper,
Almost no original pulp manufacturing process is required, and energy can be saved. However, a silver halide photographic material using RC base paper using recycled pulp made of waste paper as a base paper has a higher rigidity than a silver halide photographic material using RC base paper using virgin pulp. When the unexposed silver halide photographic light-sensitive material is aged at room temperature or higher, fogging, which is a serious problem of the silver halide photographic light-sensitive material, is likely to occur. It has been difficult to put the base paper into practical use as a silver halide photographic light-sensitive material.

[0006] A photographic print is usually viewed by a person who picks it up. If the waist of the photographic print, that is, the rigidity is low, there is a problem that it is difficult to view the photographic print. In particular, since the panoramic print is long horizontally, it is extremely difficult to appreciate when the rigidity is low. Since the rigidity of photographic prints depends on the support, a support with high rigidity has been desired, but RC base paper used for conventional photographic prints is extremely thick RC base paper in order to satisfy the rigidity required in the market. Therefore, it was inferior in the suitability for transporting the mini lab, and also became a problem in terms of cost.

[0007] As a support having high rigidity, European Patent Nos. 0880065, 0880066, and 08800
A paper support in which a biaxially stretched polypropylene sheet is provided on both sides of a base paper such as No. 67, No. 0880068, No. 0880069, and No. 0880071 is being studied.

However, when the photographic printing paper using the paper support is transported in a minilab, the rollers and belts in the transport section are not smoothly transported when the raw sample is transported. It has been found that a problem that the surface is easily damaged occurs.

In the minilab processing, after the development processing and drying, L
Prints of an appropriate size such as plate size are accumulated in units of about 100 sheets.However, when the number of prints accumulated after transporting a photographic paper using this paper support in a minilab is counted, several sheets are stuck together. It became very difficult to count.

Although the attached prints can be peeled off by applying an appropriate force, the work of counting the number of printed prints, that is, the inspection work, is an important work in a minilab shop. Inspection work was slower than photographic paper, which was a major problem for the profitability of minilab stores.

The silver halide photographic light-sensitive material using a paper support provided with a biaxially stretched polypropylene sheet described in the above-mentioned publication has been found to show a marked decrease in white background when stored for a long time after the development processing. .

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to have excellent rigidity, to prevent pressure fog and scratches from being transported in a minilab, and to easily count the number of prints accumulated after the minilab processing, The object of the present invention is to provide a silver halide photographic light-sensitive material comprising a paper support capable of improving the white background over time and further containing recycled pulp in the base paper.

[0013]

The present inventors have found that the above objects of the present invention can be achieved by the following silver halide photographic materials.

1. A silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on one side of a paper support having a resin coating layer coated on both sides of a base paper Wherein the resin coating layers on both sides of the paper support each comprise at least one layer of a stretched polymer sheet, having an adhesive layer between the stretched polymer sheet and a base paper; A silver halide photographic material having an antistatic layer on the coating resin layer on the side opposite to the emulsion layer coating side.

2. A silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on one side of a paper support having a resin coating layer coated on both sides of a base paper A resin coating layer on the side of the paper support on which the silver halide emulsion layer is coated, comprising at least one stretched polymer sheet, having an adhesive layer between the stretched polymer sheet and a base paper; A silver halide photographic material, wherein the non-photosensitive hydrophilic colloid layer furthest from the photosensitive layer contains at least one fluorine-containing surfactant.

3. A silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on one side of a paper support having a resin coating layer coated on both sides of a base paper A resin coating layer on the side of the paper support on which the silver halide emulsion layer is coated, comprising at least one stretched polymer sheet, having an adhesive layer between the stretched polymer sheet and a base paper; A silver halide photographic light-sensitive material, wherein the non-photosensitive hydrophilic colloid layer furthest from the photosensitive layer contains at least one organopolysiloxane.

4. A silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on one side of a paper support having a resin coating layer coated on both sides of a base paper The total pulp constituting the base paper of the paper support contains at least 10% by weight of recycled pulp made of waste paper, and the resin coating layer on the silver halide emulsion layer coating side of the paper support has at least A silver halide photographic material comprising a single layer of a stretched polymer sheet and having an adhesive layer between the stretched polymer sheet and a base paper.

5. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one non-light-sensitive layer on one side of a paper support having a resin coating layer coated on both sides of a base paper. The resin coating layer on the silver halide emulsion layer coating side of the support comprises at least one stretched polymer sheet, and has an adhesive layer between the stretched polymer sheet and the base paper. A silver halide photographic material comprising an antioxidant.

Hereinafter, the present invention will be described in detail.

The paper support of the present invention is based on paper, has a resin layer on both sides of a base paper, and has a resin layer on the side on which a silver halide emulsion layer is coated (hereinafter referred to as a surface resin layer). Is a paper support which is a resin layer containing a stretched polymer sheet, preferably 2
A paper support which is a surface resin layer containing an axially stretched polymer sheet, wherein the resin layer on the side opposite to the side on which the silver halide emulsion layer is coated (hereinafter referred to as a back resin layer) contains a stretched polymer resin sheet It may be a resin layer.

Recycled pulp can be used as the base paper of the paper support of the present invention. Recycled pulp is obtained from recovered waste paper through processes such as deinking, dust removal, washing, and bleaching.

In the present invention, recycled pulp may be used for 10% by weight or more of the pulp constituting the paper. It is preferable to use wood pulp as so-called virgin pulp used other than recycled pulp.

The base paper used in the paper support of the present invention can be selected from raw materials generally used for photographic printing paper. Examples include natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, and various raw materials for laminated paper. Generally, natural pulp mainly composed of softwood pulp, hardwood pulp, and mixed pulp of softwood pulp and hardwood pulp can be widely used. Neutral paper, acidic paper, and any other paper may be used, but photographic paper grade base paper is preferably used, and photographic grade neutral paper is particularly preferable. The thickness of the paper is preferably from 40 μm to 250 μm.

Further, additives such as a sizing agent, a fixing agent, a tension enhancer, a filler, an antistatic agent, a dye and an antifogging agent which are generally used in papermaking may be blended in the support. Further, a surface sizing agent, a surface tension agent, an antistatic agent or the like may be appropriately applied to the surface.

[0025] The stretched polymer sheet in the surface resin layer of the paper support may be a thermoplastic polymer suitable for stretching at 190 ° C to 35 ° C.
After forming a non-stretched film by a melt extrusion method under the condition of 0 ° C., it can be produced by performing a biaxial stretching process.

The thermoplastic polymers suitable for the stretching treatment include polyolefins, polyesters, polyamides, polycarbonates, cellulose esters, polystyrene, polyvinyl resins, polyethers, polysulfonamides, polyethers, polyimides, Examples include thermoplastic polymers such as polyurethanes, polyvinylidenes, and polyacetals. Polyolefins such as polypropylene, polyesters such as polyethylene terephthalate, and polystyrene are preferred.

The stretched polymer sheet in the surface resin layer of the paper support may have a laminated structure of two or more layers. The laminated structure of two or more layers may be a stretched polymer sheet of two or more layers having different polymer types, or a stretched polymer sheet of two or more layers having the same polymer and different filling ratios, for example, one layer has fine particle holes. Alternatively, a resin layer configuration in which another layer has a white pigment may be used.

It is preferable that at least one layer of the stretched polymer sheet in the surface resin layer of the paper support contains a white pigment or has fine pores.

The filling rate of the white pigment contained in at least one layer of the stretched polymer sheet in the surface resin layer is preferably 5% by weight or more, more preferably 7% by weight or more, from the viewpoint of print sharpness.

The white pigment contained in the stretched polymer sheet of the paper support of the present invention is, for example, rutile type titanium dioxide,
Anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used, but among them, titanium dioxide is preferable for various reasons.

The titanium dioxide may be either anatase type or rutile type, but anatase type titanium dioxide is preferred when whiteness is prioritized, and rutile type titanium dioxide is preferred when sharpness is emphasized. Taking both whiteness and sharpness into account, anatase-type titanium dioxide and rutile-type titanium dioxide may be blended and used.

The titanium dioxide used is generally one whose surface has been surface-treated with an inorganic substance such as hydrous aluminum oxide or hydrous silicon oxide, polyhydric alcohol, polyhydric alcohol in order to suppress the activity of titanium dioxide and prevent yellowing. Amines, metal soaps,
Those whose surface is treated with an organic substance such as alkyl titanate or polysiloxane, and those whose surface is treated with an inorganic or organic treating agent in combination can be used. The surface treatment amount is 0.2% by weight to 2.0% by weight of an inorganic substance with respect to titanium dioxide,
0.1% to 1.0% by weight of organic material is preferred. The particle size of titanium dioxide is preferably from 0.1 μm to 0.4 μm.

In order to disperse and mix the white pigment in the polymer resin, a three-roll mill (three-roll mill), a two-roll mill (two-roll mill), a Cowles dissolver, a homomixer, a sand grinder, and an ultrasonic disperser are used. can do.

The method of forming fine pores in the stretched polymer sheet of the paper support of the present invention is to add fine pore induction particles to a molten polymer, and then melt extrude and stretch the polymer. Formed inside.

The fine-particle porosity-inducing particles may be polymer fine particles having a different polymer type from the polymer forming the drawn polymer sheet or the drawn polymer film, or inorganic fine particles such as silica.
Fine particles such as polybutylene terephthalate and polypropylene, and the average particle diameter of the fine particles is 0.1 to
10 μm is preferred.

As the stretching method used for preparing the stretched polymer sheet of the paper support of the present invention, a biaxial stretching method is preferable, and the biaxial stretching method is a tubular method, a successive biaxial stretching flat film method, The biaxially stretched flat film method, the octobas method, and the like are known, and the stretched polymer sheet of the present invention can be produced using these methods. When the stretched polymer sheet of the present invention has a laminated structure, it may be stretched one layer at a time and then adhered with an adhesive or the like, but after a multilayer unstretched film is formed by a multilayer melt extrusion method, a stretching treatment is performed. Is preferably performed.

The thickness of the stretched polymer sheet in the surface resin layer of the paper support is preferably 5 to 70 μm, more preferably 10 to 70 μm.
５０50 μm.

The stretched polymer sheet used for the paper support of the present invention is adhered to a base paper via an adhesive layer. Examples of the adhesive method using the adhesive layer include polyolefins, polyesters, polyamides, polycarbonates, and cellulose. Biaxially stretched polymer sheet and base paper by melting thermoplastic polymers such as esters, polystyrene, polyvinyl resin, polyethers, polysulfonamides, polyethers, polyimides, polyurethanes, polyvinylidenes, polyacetals, etc. And a method in which the nip is applied and nip is applied. Preferred as the adhesive layer are polyolefins, more preferably polyethylene, and still more preferably low density polyethylene.

The adhesive layer of the paper support of the present invention preferably contains a white pigment. The filling ratio of the white pigment in the adhesive layer is from 1% by weight to 25% by weight, and preferably from 3% by weight to 20% by weight, from the viewpoint of print sharpness and production suitability.

The white pigment used in the adhesive layer is the same as the white pigment contained in the stretched polymer sheet of the paper support. Among them, titanium dioxide is preferable. As the titanium dioxide species, anatase type and rutile type are appropriately used. Can be done.

The surface treatment method and particle size of titanium dioxide used are the same as described above.

The method for dispersing and mixing the white pigment in the resin constituting the adhesive layer is the same as the method for dispersing and mixing in the polymer resin of the stretched polymer sheet of the paper support.

The thickness of the adhesive layer is preferably from 1 to 30 μm, more preferably from 5 to 20 μm.

The paper support of the present invention has a backside resin layer on the side opposite to the side on which the silver halide emulsion layer is coated. As the backside resin layer, there is a method of laminating a polyolefin resin or a polyethylene terephthalate resin, but it is preferable to use a stretched polymer sheet similar to the emulsion-side resin layer.

In the resin layer in which the back resin layer contains a stretched polymer sheet, the stretched polymer sheet is the same as the above-mentioned front resin layer.
After forming the sheet by the same method as the axially stretched polymer sheet, the base paper can be bonded by the same method as described above. Although the polymer resin of the stretched polymer sheet of the back resin layer may be different from the polymer resin of the stretched polymer sheet of the front resin layer, the same resin is preferable. The thickness of the stretched polymer sheet in the back resin layer is not particularly limited, but is preferably from 10 to 50 μm. The stretched polymer sheet in the back resin layer may be filled with a white pigment.

The olefin resin used for lamination as the back resin layer can be selected from ethylene, α-olefins and a mixture of at least two of them. Among them, low-density polyethylene, high-density polyethylene or a mixture thereof is used as a polyolefin resin widely used.

In general, a resin laminate can be formed by melt extrusion coating a resin composition on a support. In order to carry out the melt extrusion coating method, the resin composition is usually melt-extruded on a running support from a slit die of an extruder into a single-layer or plural-layer film. Usually, the melt extrusion temperature is preferably from 200 to 250 ° C. The thickness of the resin coating layer is not particularly limited, and is usually 10 to 60 μm.

The stretched polymer sheet used for the paper support of the present invention preferably contains an antioxidant. Antioxidants that can be used in the present invention are generally commercially available antioxidants for polyolefin resins,
As long as they have no obstacles when applied to photographic resin compositions, any can be used, but generally phenolic,
Antioxidants such as thioethers and phosphites are preferred. The amount of the antioxidant to be added to the stretched polymer sheet is preferably from 100 to 10,000 ppm.

Examples of the antistatic substance used in the antistatic layer of the present invention include an alkali metal salt of a copolymer disclosed in US Pat. No. 3,033,679 and US Pat. No. 3,437,484. Alkali metal salts such as sodium chloride or potassium chloride in a polyvinyl alcohol binder as disclosed, US Pat.
Combination of colloidal silica and an organic antistatic agent as disclosed in U.S. Pat.
No. 0,740, ionic film-forming polyelectrolytes as disclosed in U.S. Pat. No. 3,681,070, organic copolymers containing sulfonic acid groups as disclosed in U.S. Pat. Non-ionic surfactant polymers and alkali metal salts as disclosed in US Pat. No. 542,095, crosslinked styrene sulfonate-maleic acid copolymers as disclosed in US Pat. No. 4,916,011, US Pat. Vanadium pentoxide antistatic agent as disclosed in U.S. Pat. No. 4,203,769.
Polyaniline salt-containing antistatic layers as disclosed in US Pat. Nos. 4,070,189, 237,194, 4,308,332 and 4,526,706.
Quaternary ammonium polymer antistatic layers as disclosed in U.S. Pat. Nos. 4,394,441, 4,418,141 and 4,495,276. Any suitable antistatic material, such as a suitable conductive metal oxide, can be used in the antistatic layer of the present invention.

The antistatic layer of the present invention may be formed by adding the above antistatic substance directly to the polymer resin layer of the stretched polymer sheet of the present invention, but after adding it to a water-soluble binder such as gelatin or polyvinyl alcohol. A method of applying an antistatic substance to a solution of an organic solvent-soluble polymer such as cellulose triacetate in a low boiling point organic solvent after adding an antistatic substance; a method of applying heat to polyolefins such as polyethylene and polypropylene and polyesters such as polyethylene terephthalate. A method in which an antistatic substance is added to a plastic polymer, melt-extruded and laminated, and an antistatic layer is provided, or the like can be applied.

Next, the fluorine-containing surfactant of the present invention will be described.

The fluorine-containing anionic surfactant preferably used in the present invention includes those represented by the following general formula [FA].

Formula (FA) (Cf)-(Y) _{n wherein} Cf is an n-valent group containing at least three fluorine atoms and at least two carbon atoms, and Y is -COO
_{M, -SO 3 M, -OSO 3} M or -P (= O) (OM)
Represents ₂ wherein M represents a hydrogen atom or an alkali metal atom or an ammonium group, and n is 1 or 2.

More preferably used fluorine-containing anionic surfactants include those represented by the following general formula [FA '].

Formula [FA '] Rf- (D) _t -Y In the formula, Rf represents a fluorine-substituted alkyl group or an aryl group having 3 to 30 carbon atoms, and D represents -O-, -COO-,-.
Represents a divalent group having 1 to 12 carbon atoms containing at least one bond of CON (R ¹ ) — or —SO ₂ N (R ¹ ) —, wherein R ¹ is alkyl having 1 to 5 carbon atoms. Represents t, t is 1 or 2, and Y is -COOM, -S
O ₃ M, —OSO ₃ M or —P (＝ O) (OM) ₂ , wherein M represents a hydrogen atom or an alkali metal atom or an ammonium group.

Next, specific examples of the compounds will be given, but the present invention is not limited to these.

[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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It is particularly preferable to use a fluorine-containing anionic surfactant containing at least one bond of —SO ₂ N (R ¹ ) —.

The fluorine-containing cationic surfactant preferably used in the present invention is a compound represented by the following formula [FK].

[0065] Formula [FK] R'f-G-J ⁺ L ^- However, R'f is a 1-20C hydrocarbon group having a carbon, at least one hydrogen atom is substituted with a fluorine atom . G represents a chemical bond or a divalent group. J ⁺ is a cationic group, L ^- represents a counter anion.

As an example of R'f, -C _k F _{2k + 1} (k = 1
20, particularly preferably _{3~12), - HC q F 2q} , -
_{C q F 2q-1 (q} = 2~20, particularly preferably 3 to 12)
Etc., and examples of G include:

[0067]

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And the like.

As an example of J ⁺ ,

[0070]

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And the like.

R 'and R "represent a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms, A' represents an alkylene group or an arylene group, p is 0 to 6, and q 'is 2 to 6. 20
Represents

[0073] In addition, L ^- as an example of

[0074]

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The following can be mentioned.

Specific examples of the fluorine-containing cationic surfactant preferably used in the present invention are described below.

[0077]

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[0078]

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[0079]

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In the present invention, particularly, the hardly soluble -SO ₂ N
It is more preferable to use a fluorine-containing cationic surfactant having at least one bond of (R ′) —. Here, the term "poorly soluble" means that 2.0 g of the surfactant was added to 100 ml of pure water at 23 ° C., stirred for 1 hour, left at 23 ° C. for 24 hours, and then precipitates and suspended matters were visually observed. Sometimes poorly soluble. For example, FK-1, FK-8, FK-1
5, FK-16, etc., but are not limited to these, and can be separated by the above-described test.

Some of the fluorine-containing surfactants of the present invention are trade names of Megafac F from Dainippon Ink and Chemicals, and Fluorad FC from Minnesota Mining and Manufacturing Company. Under the trade name, Monflor (M)
onflor) under the trade name Zonils from EI Dupont Nemeras and Company or Licovet from Farbeberke Hoechst.
t) Each is commercially available under the trade name VPF.

In the present invention, it is particularly preferable to use a combination of a fluorinated cationic surfactant and a fluorinated anionic surfactant.

The total amount of the fluorinated cationic surfactant and the fluorinated anionic surfactant preferably used in the present invention is preferably 1.0 to 0.0001 g / m ² , more preferably 0.1 to 0.0001 g / m ² . 3 to 0.0005 g /
m ² , more preferably 0.15 to 0.001 g / m ² . When used in combination, two or more kinds of fluorine-containing cationic surfactants and two or more kinds of fluorine-containing anionic surfactants may be used in combination. In addition, a fluorine-containing nonionic surfactant, a fluorine-containing betaine surfactant, and a hydrocarbon surfactant may be used in combination. The addition ratio of the above-mentioned fluorinated anionic surfactant and fluorinated cationic surfactant is preferably 1:10 to 10: 1 in terms of molar ratio, and more preferably 3: 7 to 10: 1.
7: 3 is preferred.

In practicing the present invention, any of the methods of adding the above compound to the coating solution for the surface layer and coating, or overcoating or penetrating the surface layer is used. In the case of an organic solvent-based coating solution, it can be added as it is after dissolution in an organic solvent. The coating solution to which the compound has been added may be prepared, for example, by a dipping method described in US Pat. No. 3,335,026, for example, US Pat.
In the method such as the spray method described in No. 7,
It can be applied or penetrated.

When these compounds are used for the protective layer, it is preferable to use a hydrophilic colloid together, for example, cellulose derivatives such as gelatin, colloidal albumin, casein, carboxymethylcellulose, hydroxyethylcellulose, agar, sodium alginate, starch derivatives, Synthetic hydrophilic colloids, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives thereof, partial hydrolysates and the like can be mentioned. If desired, two or more compatible mixtures of these colloids may be used. Among them, gelatin is most preferably used.

Next, the organopolysiloxane of the present invention will be described.

The organopolysiloxane of the present invention is formed of an organopolysiloxane skeleton, and includes those having a structural unit represented by the following general formula [S1].

[0088]

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Here, R ₁ and R ₂ represent a hydrogen atom, an alkyl group,
Represents an aryl group, wherein the alkyl group and the aryl group may be substituted with a substituent, and R ₁ and R ₂ may be the same or different. Examples of the alkyl group represented by R ₁ and R ₂ include a methyl group, an ethyl group, and a propyl group, and examples of the aryl group include a phenyl group. Preferred groups for R ₁ and R ₂ are a methyl group and a phenyl group, and a particularly preferred group is a methyl group.

Further, the organopolysiloxane of the present invention comprises
Those having terminal groups represented by the following general formula [S2] at both ends are preferred.

[0091]

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[0092] wherein R _3, R ₄ and R ₅ are each a hydrogen atom, an alkyl group, an aryl group, an alkyl group, an aryl group may be substituted with a substituent, R _3, R ₄ and R ₅
May be the same or different. R ₃ ,
Examples of the alkyl group represented by R ₄ and R ₅ include a methyl group and an ethyl group, and examples of the aryl group include a phenyl group. Alkyl group represented by R _3, R ₄ and R ₅ also include those substituted with such a single or a plurality of aryl groups (e.g. phenyl group), and in R _3, R ₄ and R ₅ The aryl group represented includes those substituted with a single or plural alkyl groups (for example, a methyl group or the like). Preferred groups for R ₃ , R ₄ and R ₅ are an alkyl group and an aryl group, and a methyl group is particularly preferred.

Among the organopolysiloxanes of the present invention, the following modified organopolysiloxanes are preferably used.

That is, as the modified organopolysiloxane that is preferably used, the organic group bonded to the silicon atom forming the organopolysiloxane skeleton has an epoxy group, a fluorine-modified group, a vinyl group, and a cyano group. Or an epoxy group, a fluorine-modified group, a vinyl group, or a cyano group directly bonded to the silicon atom.

Among the modified organopolysiloxanes preferably used in the present invention, particularly useful ones have a structural unit represented by the following general formula [I].

[0096]

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In the formula, R ₇ represents a hydrogen atom, an alkyl group, an aryl group, or — (R ₆ ) _n —B, R ₆ represents a divalent linking group, B represents an epoxy group, a fluorine-modified group, Represents a vinyl group and a cyano group. n represents 0 or 1.

The alkyl group represented by R ₇ includes, for example, a methyl group and an ethyl group, and the aryl group includes, for example, a phenyl group. Preferred groups for R ₇ are a methyl group and a phenyl group, and a particularly preferred group is a methyl group.

The divalent linking group represented by R ₆ is preferably an alkylene group (eg, a monomethylene group, a dimethylene group, a trimethylene group, etc.) or an arylene group (eg, a phenylene group). Furthermore, carbon number 2-4
Are preferred, and a dimethylene group and a trimethylene group are particularly preferred.

The epoxy group represented by B is, for example, an ethylene oxide group (epoxyethyl group), a trimethylene oxide group (1,3-epoxypropyl group), a methylethylene oxide group (1,2-epoxypropyl group) or the like. And a particularly preferred epoxy group is an ethylene oxide group (epoxyethyl group).

Examples of the fluorine-modified group represented by B include a trifluoromethyl group, a difluoromethyl group and a monofluoromethyl group, and a particularly preferred fluorine-modified group is a trifluoromethyl group.

N represents 0 or 1. When B is an epoxy group, a fluorine-modified group or a cyano group, n is preferably 1. When B is a vinyl group, n is 0.
It is preferred that

The organopolysiloxane of the present invention preferably has an end group represented by the following general formula [II] at both ends.

[0104]

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In the formula, R ₈ , R ₉ and R ₁₀ are each a hydrogen atom, an alkyl group, an aryl group, or — (R ₆ ) _n —B
(R _6, B and n are respectively the same as R _6, B and n in the general formula [I].) Represents, R _8, R ₉ and R ₁₀ be different even each same Good. Examples of the alkyl group represented by R ₈ , R ₉ and R ₁₀ include a methyl group and an ethyl group, and examples of the aryl group include a phenyl group. R ₈ ,
The alkyl group represented by R ₉ and R ₁₀ includes those substituted with a single or plural aryl groups (for example, phenyl group and the like), and the aryl groups represented by R ₈ , R ₉ and R ₁₀ The group includes those substituted with a single or plural alkyl groups (for example, a methyl group or the like). Preferred groups for R ₈ , R ₉ and R ₁₀ are an alkyl group and an aryl group, and a methyl group is particularly preferred.

The organopolysiloxane of the present invention preferably has a structural unit represented by the following general formula [III].

[0107]

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In the formula, R ₁₁ and R ₁₂ each represent a hydrogen atom, an alkyl group, or an aryl group, and R ₁₁ and R ₁₂ may be the same or different.

The alkyl group represented by R ₁₁ and R ₁₂ is preferably an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group and a butyl group. And a phenyl group. The alkyl groups represented by R ₁₁ and R ₁₂ include those substituted with a single or plural aryl groups (for example, phenyl group and the like), and the aryl groups represented by R ₁₁ and R ₁₂ are Alternatively, those substituted with a plurality of alkyl groups (for example, a methyl group or the like) are also included. Preferred groups for R ₁₁ and R ₁₂ are a methyl group or a phenyl group.

The organopolysiloxane of the present invention has at least one structural unit selected from the structural units represented by the general formula [I] and / or the structural units represented by the general formula [III]. Those having a terminal group represented by the general formula [II] are more preferable. The terminal groups at both ends may be the same or different from each other, but preferably the same. However, when the main chain is formed only from the structural unit represented by the general formula [III], at least one of R ₈ , R ₉ and R _{10 in} the terminal group represented by the general formula [II] One is-(R ₆ ) _n -B.

Among the organopolysiloxanes represented by the general formula [I], an organopolysiloxane modified with an epoxy group is particularly preferably used.

Hereinafter, typical specific examples of the organopolysiloxane of the present invention will be shown, but the present invention is not limited to these.

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The production method of the organopolysiloxane of the present invention is described in, for example, EG Rocho.
u), Chemistry of the Silicone (Chapman and Hall, 1951), 66-70
Page, “Processing and Application of Silicone” (Kansai Plastics Technical Society 1954), page 26, FGA Stone and BB
"Inorganic Polymers" by W.A.G. Graham (Academic Press 19)
62), pp. 230-231, 288-295, etc., and JP-B-35-10771, 43-43.
No. 28694, No. 45-14898, etc., by a metal catalyst-addition reaction of olefins to siloxane containing SiH,
It can be synthesized by applying a method by co-hydrolysis of each component organofluorosilane as shown in No. 22361, and the like. In addition, a part of the organopolysiloxane of the present invention is obtained from Petrar Systems (US).
ch Systems. Ins), as well as domestic Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., and Toshiba Silicone Co., Ltd.
It can be easily obtained.

The viscosity of the organopolysiloxane of the present invention is preferably about 10 to 100,000 centistokes at 25 ° C. as measured by a rotational viscometer.

The organopolysiloxane of the present invention can be contained in a photographic constituent layer by a method of adding it to a coating solution in advance or a method of overcoating or penetrating the organopolysiloxane of the present invention. The former is preferred in that respect. As a method of adding to the coating solution, the organopolysiloxane of the present invention in the presence of a dispersant,
A method of dispersing in water or a hydrophilic colloid solution, for example, a gelatin solution, and further adding it to a desired photographic coating solution, or dispersing in a photographic gelatin solution in the presence of a dispersant, and coating as it is There are ways to do that.

As the dispersant, a surfactant generally used for photography can be used, and for example, it is appropriately selected from an anionic surfactant, a nonionic surfactant and a cationic surfactant. Can be used.

As a dispersion method, dispersion can be performed using an ultrasonic homogenizer or a valve homogenizer.

In the case of dispersion, low-boiling solvents such as ethyl acetate, methanol and acetone, and tricresyl phosphate are commonly used to facilitate dispersion and control the particle size of the dispersion. A high boiling solvent may be used.

The preferred particle size of the organopolysiloxane of the present invention in a dispersed state is 0.1 to 10 μm. If the particle size is too small, the effects of the present invention, in particular, the effect on the slip property and scratch resistance, cannot be seen.

Although the refractive index of the organopolysiloxane of the present invention is not particularly limited, the measured value at 25 ° C. is usually 1.
Those having a size of from 320 to 1.685 are suitable, and preferably 2
Those whose measured value at 5 ° C. is in the range of 1.350 to 1.540 are effective. Refractive index less than 1.320;
When the amount exceeds 685, the transparency of the applied light-sensitive material, particularly, the light-sensitive material dried after photographic processing may be affected.

The preferred use amount of the organopolysiloxane of the present invention is preferably 0.001 to 0.200 g per 1 m ^{2 of the} silver halide photographic light-sensitive material.
It is more preferable that the weight is 003 to 0.100 g.

The composition of the silver halide photographic emulsion used in the photosensitive layer of the photographic recording material of the present invention is silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, silver chloroiodide. And any other halogen composition.

For obtaining the silver halide emulsion according to the present invention, it is advantageous to include heavy metal ions. Heavy metal ions that can be used for such purposes include:
Eighth to tenth such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt
Examples include Group 12 metals, Group 12 transition metals such as cadmium, zinc, and mercury, and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex, the ligand or ion may be cyanide ion, thiocyanate ion, isothiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, or the like. Examples include nitrate ion, carbonyl, ammonia and the like. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order for the silver halide emulsion according to the present invention to contain heavy metal ions, the heavy metal compound must be physically added before, during, and after the formation of silver halide grains. What is necessary is just to add in arbitrary places of each process during ripening. In order to obtain a silver halide emulsion satisfying the above conditions, a heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-B-55-42
No. 737 and The Journal of Photographic Science (J. Photogr. Sci.) 2
1, 39 (1973), etc., particles having an octahedral, tetradecahedral, dodecahedral or the like shape can be prepared and used. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape are preferably used.

The grain size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm in consideration of other photographic properties such as rapid processing and sensitivity.
m, more preferably in the range of 0.2 to 1.0 μm.

The particle size can be measured by using the projected area of the particle or an approximate value of the diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains of the present invention is preferably a monodispersed silver halide grain having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably 0. .15 or less are added to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (where, S is the standard deviation of the particle size distribution, and R is the average particle size.) The particle size here is the diameter of a spherical silver halide particle. In the case of a particle having a shape other than a cube or a sphere, it represents a 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 according to the present invention may be obtained by any of an acidic method, a neutral method and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Also, JP-A-57-92523, JP-A-57-92523.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in a reaction mother liquor, and a water-soluble silver salt and a water-soluble solution described in German Patent Publication No. 292,164. Apparatus for continuously changing the concentration of an aqueous halide salt solution, JP-B-56-50
The reaction mother liquor was taken out of the reactor described in No. 1776, etc.
An apparatus that forms grains while keeping the distance between silver halide grains constant by concentrating by ultrafiltration may be used.

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 at the time of forming silver halide grains or after the completion of grain formation.

The silver halide emulsion according to the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As a chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, etc. can be used, but a sulfur sensitizer is preferable. Thiosulfates as sulfur sensitizers,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine, inorganic sulfur and the like can be mentioned.

As the gold sensitizer according to the present invention, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole.

The chemical sensitization of the silver halide emulsion according to the present invention may be a reduction sensitization.

The silver halide emulsion according to the present invention is intended to prevent fogging that occurs during the process of preparing a silver halide photographic material, reduce performance fluctuation during storage, and prevent fogging that occurs during development. A known antifoggant,
Stabilizers can be used. Examples of preferred compounds that can be used for such a purpose are described in JP-A No. 2-14 / 1990.
General formula (II) described in the lower column of page 7 of JP-A-6036
And more preferred specific compounds are (IIa-1) to (IIa-8), (IIb-1) to (IIb-) described on page 8 of the publication.
7) or 1- (3-methoxyphenyl) -5-
Compounds such as mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned. These compounds, depending on their purpose,
It is added in the steps of preparing the silver halide emulsion grains, the chemical sensitization step, the completion of the chemical sensitization step, and the coating liquid preparation step.

As the silver halide emulsion according to the present invention, a surface latent image type silver halide emulsion which forms a latent image on the surface by image exposure is used, and an emulsion which forms a negative image by developing is used. Is also good. Further, using an internal latent image type silver halide emulsion in which the surface of the grains is not fogged in advance, fog treatment (nucleation) after image exposure and then surface development, or fog treatment after image exposure. An emulsion capable of directly obtaining a positive image by performing surface development can be used. The internal latent image type silver halide emulsion refers to an emulsion containing silver halide grains having a photosensitive nucleus mainly inside silver halide crystal grains and forming a latent image inside the grains upon exposure. .

In the photographic material of the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, dyes having absorption in the visible region include those described in JP-A-3-2518.
The dyes of AI-1 to 11 described on page 308 of JP-A-40 and the dyes described in JP-A-6-3770 are preferably used.
The compounds represented by the general formulas (I), (II) and (III) described in the lower left column on page 2 of 280750 have preferable spectral characteristics and do not affect the photographic characteristics of a silver halide photographic emulsion. It is also preferable because there is no contamination due to residual color. Specific examples of preferred compounds are described in the same publication, page 3, lower left column to 5
Exemplary compounds (1) to (45) listed in the lower left column of the page
Can be mentioned.

For the purpose of improving sharpness, the amount of these dyes to be added is 680 nm for an unprocessed sample of a light-sensitive material.
Is preferable to make the spectral reflection density 0.7 or more, more preferably 0.8 or more.

When the photographic recording material of the present invention is used as a color photographic light-sensitive material, the photographic recording material may be used in combination with a yellow coupler, a magenta coupler and a cyan coupler in a range of 400 to 90.
It has a layer containing a silver halide emulsion spectrally sensitized to a specific region in a wavelength range of 0 nm. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, any known compounds can be used.
BS-1 to 8 described on page 28 of JP-A-251840 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red, green, and blue photosensitive sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-66515. Nos. S-1 to S-17 described on pages 15 to 17
Are preferably used in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

As a method of adding the sensitizing dye, the sensitizing dye may be dissolved in water or a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or the like, added as a solution, or added as a solid dispersion. It may be added.

As the coupler used in the silver halide photographic light-sensitive material according to the present invention, a coupling reaction with an oxidized form of a color developing agent is carried out to form a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm. Any compound that can be used can be used, and particularly typical examples include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 500.
Typical examples are magenta dye-forming couplers having a spectral absorption maximum wavelength in the range of -600 nm and cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

The cyan coupler preferably usable in the photographic recording material of the present invention is described in JP-A-4-114.
The general formula (C) described in the lower left column on page 5 of JP-A-154-154
-I) and couplers represented by (C-II). Specific compounds include those described as CC-1 to CC-9 in page 5, lower right column to page 6, lower left column in the same specification.

The magenta coupler which can be preferably used for the photographic recording material of the present invention is described in JP-A-4-11.
Couplers represented by general formulas (MI) and (M-II) described in the upper right column of page 4 of JP-A-4154 are described. Specific compounds include those described as MC-1 to MC-11 in the lower left column of page 4 to the upper right column of page 5 of the same specification. Among the above magenta couplers, a coupler represented by the general formula (MI) described in the upper right column on page 4 of the same publication is preferable, and among them, the RM of the general formula (MI) is tertiary. Couplers that are alkyl groups are particularly preferred because of their excellent light resistance.
MC-8 to MC- described in the upper column of page 5 of the gazette
No. 11 is preferable because it is excellent in reproducing colors from blue to purple and red, and is also excellent in detail description.

The yellow coupler which can be preferably used in the photographic recording material of the present invention is described in JP-A No. 4-11.
The general formula (Y-
The couplers represented by I) can be mentioned. Specific compounds are described in YC-1 to YC
What is described as C-9 can be mentioned. Of these, couplers in which RY1 of the general formula [Y-1] is an alkoxy group or couplers represented by the general formula [I] described in JP-A-6-67388 can reproduce yellow having a preferable color tone and are preferable. Of these, particularly preferred examples of the compounds include YC-8 and YC-9 described in the lower left column of page 4 of JP-A-4-114154 and N-type compounds described in JP-A-6-67388, pages 13-14.
o (1) to (47). The most preferred compound is described in JP-A-4-8184.
It is a compound represented by the general formula [Y-1] described in page 1 of JP-A No. 7 and pages 11 to 17 of the same patent publication.

When the oil-in-water type emulsification dispersion method is used to add the coupler or other organic compound used in the photographic recording material of the present invention, it is usually added to a water-insoluble high boiling organic solvent having a boiling point of 150 ° C. or more. If necessary, a low-boiling point and / or water-soluble organic solvent is used in combination to dissolve, 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. After or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high boiling organic solvents that can be used to dissolve and disperse the coupler include dioctyl phthalate, diisodecyl phthalate, phthalic acid esters such as dibutyl phthalate, tricresyl phosphate, and phosphoric acid esters such as trioctyl phosphate; Is preferably used. The high-boiling organic solvent has a dielectric constant of 3.5 to 7.0.
It is preferably 0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means.
Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

As a preferred compound used as a surfactant for dispersing a photographic additive or adjusting a surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. Containing. Specifically, A-1 to A described in JP-A-64-26854
-11. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution to the coating are preferably as short as 10 hours each. Preferably within 3 hours, more preferably within 20 minutes.

It is preferable to use an anti-fading agent in combination with each of the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541, phenolic compounds represented by general formula IIIB described in JP-A-3-174150, and Amine compounds represented by the general formula A described in JP-A-64-90445;
General formulas XII, XIII, XIV, XV described in -182741
Are particularly preferred for magenta dyes. Further, compounds represented by the general formula I 'described in JP-A-1-19649 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and compound (A) described in the lower left column of page 10 of the same publication are disclosed. Compounds such as' -1) can be used. In addition, U.S. Pat.
187 can also be used.

In the photographic recording material of the present invention, a compound which reacts with the oxidized developing agent is added to a layer between the photosensitive layers to prevent color turbidity, or added to a silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133056, and include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17 of the same publication. .

It is preferable to add an ultraviolet absorber to the photographic recording material of the present invention to prevent static fog or to improve the light fastness of the dye image. Preferable ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by the formula III-3 described in JP-A-1-250944, and JP-A-64-6664.
6, a compound represented by the general formula III,
UV-1L to UV-27 described in 3-187240
L, compounds represented by the general formula I described in JP-A-4-1633, and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

In the photosensitive layer of the photographic recording material of the present invention, gelatin is used as a binder. If necessary, other gelatin, a gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, and a sugar derivative may be used. ,
A hydrophilic colloid such as a cellulose derivative or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can be used in combination with gelatin.

The total amount of gelatin contained in the photosensitive layer of the photographic recording material of the present invention is preferably 7 g / m ² or less, more preferably 6.5 g / m ² , because of the speed of the processing step and the speed of the drying step.
The following is more preferred. The lower limit is not particularly limited, but generally from the viewpoint of physical properties or photographic performance.
It is preferably 0 g / m ² or more. The amount of gelatin was 11.0% according to the method of measuring water described in the Pagui's method.
Of gelatin containing water.

The gelatin used in the photosensitive layer of the photographic recording material of the present invention may be a lime-processed gelatin or an acid-processed gelatin. Manufactured gelatin may be used, but lime-processed gelatin obtained from cow bone and pig skin is preferred.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener, a chlorotriazine hardener, a polymer hardener, or a carboxyl group-active hardener alone or in combination. JP-A-61-249054
And the compounds described in JP-A-61-245153 are preferably used. Further, in order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image storability, a method disclosed in
It is preferable to add a preservative and an antifungal agent as described in JP-A-157646. Further, in order to improve the physical properties of the surface of the light-sensitive material or the sample after processing, a protective layer is disclosed in
It is preferable to add a slip agent described in JP-A-118543 or JP-A-2-73250.

In order to form a photographic image using the photographic recording material of the present invention, an image recorded on a negative is optically formed on a silver halide photographic material to be printed and printed. Alternatively, after the image is once converted into digital information, the image is formed on a CRT (cathode ray tube), and this image is formed on a silver halide photographic material to be printed and printed. Alternatively, printing may be performed by scanning while changing the intensity of the laser beam based on digital information.

The present invention is preferably applied to a photographic material in which the developing agent is not incorporated in the photographic material, and particularly preferably to a photographic material which directly forms an image for viewing. For example, color paper, color reversal paper,
Examples of the light-sensitive material include a light-sensitive material for forming a positive image, a light-sensitive material for display, and a light-sensitive material for color proof. It is particularly preferable to apply the invention to a photosensitive material having a reflective support.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can 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- (N-ethyl-N- (β-hydroxyethyl) amino) 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) 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-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-
N- (γ-hydroxypropyl) aniline In the present invention, the above color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
And more preferably pH 9.8-1.
It is used in the range of 2.0.

The processing temperature for color development according to the present invention is 35
The temperature is preferably from 70 ° C to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds.

To the color developing solution, known developing component compounds can be added in addition to the above color developing agents. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used.

The photographic recording material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a water washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed. The developing apparatus used for developing the silver halide photographic light-sensitive material of the present invention may be a roller transport type in which the light-sensitive material is conveyed between rollers arranged in a processing tank, and the photosensitive material may be transferred to a belt. An endless belt system that transports fixedly may be used, but a processing tank is formed in a slit shape, and a processing liquid is supplied to this processing tank and a photosensitive material is transported. A method, a web method by contact with a carrier impregnated with a treatment liquid, a method using a viscous treatment liquid, and the like can also be used. When processing in large quantities, it is usual to perform a running process using an automatic developing machine. At this time, the replenishment amount of the replenisher is preferably as small as possible. Is to add a treating agent in the form of
The method described in 4-16935 is most preferred.

[0180]

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 <White base paper> A basis weight of 170 g / m ² composed of 50% by weight of sulfated bleached hardwood pulp (LBKP) and 50% by weight of sulfated bleached softwood pulp (NBSP) for photographic grade photographic paper.
Was prepared.

<Paper Support A> Polyethylene was melt-extruded and laminated at 300 ° C. as a back resin layer of the white base paper to cover a 25 g / m ² back laminate layer.

Next, as a surface resin layer, 90% by weight of polyethylene and 10% by weight of anatase type titanium oxide were kneaded, and then melt-extruded at 300 ° C. to be 30 g / m ^2.
To form a paper support A having a resin coating layer on both sides.

<Paper support B> As a backing resin layer of the white base paper, a polypropylene resin was melt-extruded at 300 ° C., and then biaxially oriented polypropylene having a thickness of 20 μm was produced using a sequential biaxial stretching apparatus using a flat film method. After preparing the resin sheet, a low-density polyethylene melt-extruded with a thickness of 10 μm as an adhesive layer was laminated between the white base paper and the sheet, and then nipped to prepare a back resin layer.

Next, polypropylene 80 was used as the surface resin layer.
% By weight, average particle size 0.3 μm as fine particle porosity-inducing particles
After kneading 20% by weight of the polybutylene terephthalate particles, the mixture was melt-extruded at 300 ° C., and then flat-film-sequential biaxial stretching apparatus was used.
After preparing an axially stretched laminated polypropylene resin sheet, a low-density polyethylene melt-extruded with a thickness of 10 μm as an adhesive layer was laminated between the white base paper and the sheet, and then nipped to produce a surface resin layer.

<Paper support C> As a backing resin layer of the white base paper, a polypropylene resin was melt-extruded at 300 ° C., and then a biaxially oriented polypropylene having a thickness of 20 μm produced using a flat film sequential biaxial stretching apparatus. After preparing the resin sheet, a low-density polyethylene melt-extruded with a thickness of 10 μm as an adhesive layer was laminated between the white base paper and the sheet, and then nipped to prepare a back resin layer.

Next, polypropylene 80 was used as the surface resin layer.
% By weight, average particle size 0.3 μm as fine particle porosity-inducing particles
15 μm after stretching, a polypropylene resin layer kneaded with 20% by weight of polybutylene terephthalate particles of the above, 90% by weight of polypropylene on both sides thereof, and anatase type titanium oxide 1
After laminating and extruding at 300 ° C. so that the polypropylene resin layer kneaded with 0% by weight becomes 5 μm each after stretching,
Using a flat film method sequential biaxial stretching device,
After preparing a 5 μm biaxially stretched laminated polypropylene resin sheet, a low-density polyethylene containing 5% by weight of rutile titanium oxide melt-extruded with a thickness of 10 μm as an adhesive layer was laminated between the white base paper and the sheet. After the nip, a surface resin layer was prepared.

<Paper support D> As a back resin layer of the white base paper, a polypropylene resin was melt-extruded at 300 ° C., and then a biaxially oriented polypropylene having a thickness of 20 μm was produced using a sequential biaxial stretching apparatus using a flat film method. After preparing the resin sheet, a low-density polyethylene melt-extruded with a thickness of 10 μm as an adhesive layer was laminated between the white base paper and the sheet, and then nipped to prepare a back resin layer.

Next, polypropylene 90 was used as the surface resin layer.
After kneading 10 wt% of anatase-type titanium oxide and melt-extruding at 300 ° C., a biaxially stretched polypropylene resin sheet having a thickness of 25 μm was prepared using a flat film sequential biaxial stretching apparatus, and then bonded. 1 as a layer
A low-density polyethylene melt-extruded with a thickness of 0 μm and containing 5% by weight of anatase titanium oxide was laminated between the white base paper and the sheet, and then nipped to produce a surface resin layer.

After subjecting the surface resin layer side of each of the supports A to D to a corona discharge treatment (output current value: 2 amps), a gelatin undercoat layer is provided by coating and drying to a gelatin coverage of 40 mg / m ^2. Was.

Next, supports A to D provided with a gelatin undercoat layer
Were coated with the photographic constituent layers shown in Tables 1 and 2 below to prepare multilayer color photographic paper samples 101 to 104. The coating solution was prepared as follows.

In the layer order, the layer closest to the support is the first layer, and the layer farthest from the support is the seventh layer.

First layer coating solution 23.4 g of yellow coupler (Y-1), 3.34 g of dye image stabilizer (ST-1), dye image stabilizer (ST-
2) 3.34 g, dye image stabilizer (ST-5) 3.34
g, 0.34 g of stain inhibitor (HQ-1), 5.0 g of image stabilizer A, 5.0 g of high-boiling organic solvent (DBP) and 1.67 g of high-boiling organic solvent (DNP), and ethyl acetate 6
Add 0 ml and dissolve, 10% surfactant (SU-1)
Emulsified and dispersed in 320 ml of a 7% aqueous gelatin solution containing 5 ml using an ultrasonic homogenizer to prepare 500 ml of a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive emulsion prepared under the following conditions to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer so that the coating amounts were as shown in Tables 4 and 5.

Further, (H-1), (H-2)
Was added. Surfactants (SU-
2) and (SU-3) were added to adjust the surface tension. Further, F-1 was added to each layer so that the total amount became 0.04 g / m ² .

[0196]

[Table 1]

[0197]

[Table 2]

SU-1: sodium tri-i-propylnaphthalene sulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate SU-3: di (2,2,3,3,4, sulfosuccinate) 4,
5,5-octafluoropentyl) sodium DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-Dichloro-6-hydroxy-s-triazine sodium 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-hexyloxycarbonyl) butyl] Hydroquinone Image stabilizer A: pt-octylfe Nord

[0199]

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[0200]

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[0201]

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[0202]

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(Preparation of Blue-Sensitive Silver Halide Emulsion) 40 ° C.
The following (solution A) and (solution B) were added in 1 liter of a 2% aqueous gelatin solution kept at a temperature of pAg = 7.3 and pH = 3.0.
And simultaneously added over 30 minutes.
Solution) and (Solution D) were added simultaneously 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 the pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B) 10 g of silver nitrate 200 ml with addition of water (Solution C) 102.7 g of sodium chloride 102.7 g of K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the mixture was again mixed with an aqueous gelatin solution to give an average particle diameter of 0.71.
μm, variation coefficient of particle size distribution 0.07, silver chloride content 9
A 9.5 mol% monodispersed cubic emulsion EMP-1 was obtained.

Next, EMP was performed except that the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) were changed.
In the same manner as -1, a monodispersed cubic emulsion EMP-1B having an average particle size of 0.64 μm, a coefficient of variation of 0.07, and a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver amount of 1: 1 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 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX (green-sensitive silver halide emulsion Preparation) (Solution A) and (Solution B)
The average particle size was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%.

Next, similarly to EMP-2, the average particle size is 0.50 μm, the coefficient of variation is 0.08, and the silver chloride content is 99.
A 5% monodisperse cubic emulsion EMP-2B was obtained.

The above EMP-2 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also, EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 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 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 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)
The average particle size was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation of 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5% were obtained. A monodispersed cubic emulsion EMP-3B having an average particle size of 0.38 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained in the same manner as in EMP-3.

The above-mentioned EMP-3 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed at a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion Em-R.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 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 2.0 × 10 ^-3 mol of SS-1 was added per mol of silver halide.

[0213]

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[0214]

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Next, on the back surfaces of the paper supports B to D (the side opposite to the emulsion layer coating side), as shown in Table 3, a coating solution having the following composition was applied to provide an antistatic layer. , All samples 1
Samples 105 to 116 were produced in the same manner as 01 to 104.

[Antistatic Layer a] Copolymer of dialkylaminoalkyl (meth) acrylate and styrenesulfonic acid 50 g Carrageenan gum 10 g Hardener Denacol EX-521 5 g Water was added to the mixture. 1000 ml The above 1 liter coating solution was 20 ml / m2. ^Then , an antistatic layer a was provided.

[Antistatic layer b] The following cationic polymer 6.8 g Ethylene glycol 20.6 g Methanol 400 ml Acetone 200 ml Water was added 1000 ml The above 1 liter coating solution was applied to 20 ml / m ² to prevent antistatic. Layer b was provided.

[0218]

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[0219] Antistatic layer c] 5 vanadium oxide 5g acetone 400ml ethanol 400ml cellulose nitrate 10g water was added coating solution 1000ml above 1l in a was coated so that 10 ml / m ^2, provided with an antistatic layer c .

[Antistatic layer d] Gelatin 5.0 g Tin oxide colloid 20.0 g Hardener [H-1] 0.1 g Water was added to 1000 ml. The above 1 liter coating solution was applied to 10 ml / m ^2. Thus, an antistatic layer d was provided.

Samples 101 to 116 produced in this manner
Was evaluated as follows.

<Measurement of Rigidity> The unexposed sample was subjected to the following developing step A, and the obtained white sample was 69.2 mm long and 3 width wide so that the paper-making direction of the paper support was long.
It was cut out into a rectangle having a size of 8.1 mm, and measured by a predetermined measurement method when a 15-degree bending force was applied using a Taber stiffness tester MODEL150-D manufactured by Taber. The higher the number, the higher the stiffness, and practically 20 g · cm or more is preferable.

<Evaluation of Number of Defective Prints> After printing 100 samples of each sample using Konica Minilab NPS-878J under the conditions of 23 ° C. and 50% relative humidity, are there any scratches or pressure fog on the print surface? I saw

Table 3 shows the number of defective prints with abrasion and pressure fog.

<Evaluation of Print Inspection Property> Under the conditions of 23 ° C. and a relative humidity of 10%, 1000 samples of each sample were printed using Konica Minilab NPS-878J.
00 sheets were stacked at a time.

The easiness of the manual work of counting the prints accumulated on the 100 sheets was evaluated by a sensory evaluation by 10 panelists.

◎: Smooth counting is possible one by one. ：: In some cases, printing is stuck and it is difficult to count.
No problem level Δ: The number of times the prints are stuck increases and it is difficult to count. The workability is reduced, and the level of improvement is required. X: The number of times the print is stuck is large, and it is difficult to count. Unacceptable level in the market.

[Development Processing Step A] Processing Step Processing Temperature Time Replenishment Color Development 38.0 ± 0.3 ° C. 45 seconds 80 ml Bleaching and Fixing 35.0 ± 0.5 ° C. 45 seconds 120 ml Stabilization 30-34 ° C. 60 Second 150ml Drying 60-80 ° C 30 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g 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 diethylenetriaminepentaacetic acid Penta sodium salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make a total volume of 1 liter. 1
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fix solution and replenisher Ferric ammonium diethylenetriaminepentaacetate dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2 0.0g ammonium sulfite (40% aqueous solution) 27.5ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenisher 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 (Tinopal 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 Polyvinylpyrrolidone 1.0 g Ammonia water (25% aqueous ammonium hydroxide solution) 2.5 g Nitrilotriacetic acid disodium salt 1.5 g Water is added to make up to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

Table 3 shows the obtained results.

[0233]

[Table 3]

From Table 3, it can be seen that the sample of the present invention has high rigidity, has no abrasion or pressure fog during transportation in the minilab, and has excellent inspection properties.

Example 2 <Paper support E> Polyethylene was melt-extruded and laminated at 300 ° C. as a back resin layer of the white base paper used in Example 1 to cover a 25 g / m ² back laminate layer. .

Next, polypropylene 90 was used as the surface resin layer.
After kneading 10 wt% of anatase-type titanium oxide and melt-extruding at 300 ° C., a 27 μm-thick biaxially-stretched polypropylene resin sheet is produced by using a flat film sequential biaxial stretching device, and then bonded. 8 as layers
A low-density polyethylene melt-extruded with a thickness of μm was laminated between the white base paper and the sheet, and then nipped to form a surface resin layer.

<Paper support F> As a back resin layer of the white base paper used in Example 1, a polypropylene resin was melt-extruded at 300 ° C., and was then formed using a flat film method sequential biaxial stretching apparatus to a thickness of 20 μm. After preparing a biaxially stretched polypropylene resin sheet, a low-density polyethylene melt-extruded with a thickness of 8 μm as an adhesive layer was laminated between the white base paper and the sheet, and then nipped to produce a back resin layer. .

Next, polypropylene 80 was used as the surface resin layer.
% By weight, average particle size 0.3 μm as fine particle porosity-inducing particles
Of a polybutylene terephthalate particle kneaded at 20% by weight is stretched to 10 μm after stretching, 90% by weight of polypropylene on both sides thereof, and anatase type titanium oxide 1
Laminated melt extrusion at 300 ° C. so that the polypropylene resin layer kneaded with 0% by weight becomes 7 μm each after stretching.
Using a flat film method sequential biaxial stretching device,
After preparing a 4 μm biaxially stretched laminated polypropylene resin sheet, a low density polyethylene melt-extruded to a thickness of 8 μm as an adhesive layer was laminated between the white base paper and the sheet, and then nipped to form a surface resin layer. Produced.

After subjecting the surface resin layers of the supports E and F to a corona discharge treatment (output current value: 2 amps), a gelatin undercoat layer was formed by coating and drying to a gelatin coverage of 40 mg / m ^2. Was.

Next, supports E and F provided with a gelatin undercoat layer
Then, the same photographic constituent layer as in Example 1 was applied thereto to prepare multilayer color photographic paper samples 201 and 202.

Table 4 further shows the photographic constituent layers used in Example 1.
Samples 203 to 216 shown in Table 4 were prepared in the same manner as in Samples 201 and 202, except that the fluorine-containing activator was added to the seventh layer and / or the organopolysiloxane was added to the seventh layer. Produced.

The water-insoluble organopolysiloxane in the organopolysiloxane was dispersed as described below and added to the seventh layer.

(Solution A) Organopolysiloxane 100 g Ethyl acetate 200 ml (Solution B) Gelatin 50 g Di (2-ethylhexyl) sulfosuccinate sodium salt (1% aqueous solution) 300 ml Water 300 ml (Solution A) and (Solution B) After dissolving each at a temperature of 40 ° C., (Liquid A) was added to (Liquid A), mixed and stirred, and then emulsified and dispersed with an ultrasonic homogenizer, and the particle size of the emulsified and dispersed particles was 0.2 μm. It was adjusted to be. The method of measuring the emulsified and dispersed particles here can be easily measured by a method well known in the art. After completion of the emulsification and dispersion, water was added to the emulsified dispersion to make up to 1000 ml. At this time, before finishing by adding water, a means for completely evaporating the ethyl acetate in the emulsified dispersion may be used, or it may be used separately.

Samples 201 to 216 thus prepared
Was evaluated in the same manner as in Example 1.

[0245]

[Table 4]

From Table 4, it can be seen that the sample of the present invention has high rigidity, has no abrasion or pressure fog during transportation in the minilab, and has excellent inspection properties.

Example 3 <Paper support G> 40% by weight of sulfated bleached hardwood pulp (LBKP) for photographic grade photographic paper, 40% by weight of sulfated bleached softwood pulp (NBSP), and reproduction of the following production method A white base paper having a basis weight of 170 g / m ² and containing 20% by weight of pulp was prepared.

As the backing resin layer of the white base paper, 25 g of polyethylene was melt-extruded and laminated at 300 ° C.
/ M ² of the back laminate layer.

Next, as a surface resin layer, 90% by weight of polyethylene and 10% by weight of anatase-type titanium oxide were kneaded, and then melted at 300 ° C. by melt extrusion lamination to obtain 30 g / m ^2.
To form a paper support G having a resin coating layer on both sides.

<Paper Support H> A white base paper having a basis weight of 170 g / m ² and comprising 100% by weight of recycled pulp prepared by the following method was prepared.

As the backing resin layer of the white base paper, 25 g of polyethylene was melt-extruded and laminated at 300 ° C.
/ M ² of the back laminate layer.

Next, as a surface resin layer, 90% by weight of polyethylene and 10% by weight of anatase type titanium oxide were kneaded, and then melted at 300 ° C. by extrusion lamination to obtain 30 g / m ^2.
To form a paper support H having a resin coating layer on both sides.

<Paper support I> 40% by weight of sulfated bleached hardwood pulp (LBKP), 40% by weight of sulfated bleached softwood pulp (NBSP) for photographic grade photographic paper, and 20% by weight of recycled pulp produced by the following production method % Basis weight 170g /
It was prepared white base paper m ^2.

As the backing resin layer of the white base paper, a polypropylene resin was melt-extruded at 300 ° C., and then a biaxially oriented polypropylene resin sheet having a thickness of 20 μm was produced using a flat film sequential biaxial stretching apparatus. A low-density polyethylene melt-extruded with a thickness of 10 μm as an adhesive layer was laminated between the white base paper and the sheet, and then nipped to form a back resin layer.

Next, polypropylene 80 was used as the surface resin layer.
% By weight, average particle size 0.3 μm as fine particle porosity-inducing particles
15 μm after stretching, a polypropylene resin layer kneaded with 20% by weight of polybutylene terephthalate particles of the above, 90% by weight of polypropylene on both sides thereof, and anatase type titanium oxide 1
After laminating and extruding at 300 ° C. so that the polypropylene resin layer kneaded with 0% by weight becomes 5 μm each after stretching,
Using a flat film method sequential biaxial stretching device,
After preparing a 5 μm biaxially stretched laminated polypropylene resin sheet, a low-density polyethylene containing 5% by weight of rutile titanium oxide melt-extruded with a thickness of 10 μm as an adhesive layer was laminated between the white base paper and the sheet. After the nip, a surface resin layer was prepared.

<Paper Support J> A white base paper having a basis weight of 170 g / m ² and comprising 100% by weight of recycled pulp prepared by the following method was prepared.

As a back resin layer of the white base paper, a polypropylene resin was melt-extruded at 300 ° C., and then a biaxially oriented polypropylene resin sheet having a thickness of 20 μm was produced by using a flat film sequential biaxial stretching apparatus. A low-density polyethylene melt-extruded with a thickness of 10 μm as an adhesive layer was laminated between the white base paper and the sheet, and then nipped to form a back resin layer.

Next, polypropylene 80 was used as the surface resin layer.
% By weight, average particle size 0.3 μm as fine particle porosity-inducing particles
15 μm after stretching, a polypropylene resin layer kneaded with 20% by weight of polybutylene terephthalate particles of the above, 90% by weight of polypropylene on both sides thereof, and anatase type titanium oxide 1
After laminating and extruding at 300 ° C. so that the polypropylene resin layer kneaded with 0% by weight becomes 5 μm each after stretching,
Using a flat film method sequential biaxial stretching device,
After preparing a 5 μm biaxially stretched laminated polypropylene resin sheet, a low-density polyethylene containing 5% by weight of rutile titanium oxide melt-extruded with a thickness of 10 μm as an adhesive layer was laminated between the white base paper and the sheet. After the nip, a surface resin layer was prepared.

<Preparation of Recycled Pulp> The raw paper is disintegrated, the separated ink is washed, concentrated to a concentration of 10%, and the pulp is retained in a reaction tower for 2 hours to perform an aging reaction. Thereafter, the ink is further dehydrated and concentrated to a concentration of about 30%, a deinking agent is added, kneading is performed, and the unstripped ink is stripped.
After completion of the kneading, the ink is diluted to about 1%, flotation is performed, and the ink separated by aging and kneading is separated. The foreign matter is separated from the pulp after the flotation with a screen, a cleaner or the like. Further, the release ink that could not be separated by flotation is removed by rewashing. The pulp after the re-washing was concentrated and dehydrated to 10%, a bleaching chemical was added, and the mixture was stirred.
The bleaching reaction is carried out after staying for about an hour. The entire process is completed by a final wash of the bleached pulp.

Next, a corona discharge treatment (output current value: 2 amps) was applied to the surface resin layer side of the paper supports A and C of Example 1 and the paper supports G to J described above, followed by gelatin undercoating. The layer was coated and dried to give a gelatin loading of 40 mg / m ² .

Next, a support A provided with a gelatin undercoat layer,
Photographic constituent layers similar to those in Example 1 were applied to C and G to J to prepare multilayer color photographic paper samples 301 to 306 shown in Table 5.

Samples 301 to 306 prepared in this manner
Was evaluated as follows.

<Measurement of Stiffness> An unexposed sample was prepared in Example 1.
Is carried out in the developing step A, and the obtained white background sample has a length of 69.2 so that the paper making direction becomes longer in the case of a paper support.
mm, width 38.1 mm, cut out into a rectangle, using Taber's Taber rigidity tester MODEL150-D
The measurement was performed by a predetermined measuring method when a 15-degree bending force was applied. The higher the number, the higher the stiffness.
g · cm or more is preferable.

<Evaluation of fogging for storage of raw sample> Each sample was prepared in two rolls, one was stored at 50 ° C. and a relative humidity of 40% for 4 weeks, and the other was stored in a refrigerator. The development processing step A of Example 1 was performed without exposing the sample thus stored over time, and the yellow density D1 at which fogging was most likely to occur was measured.

The samples stored in the refrigerator were treated in the same manner as above to determine the yellow density D0.

The degree of fog was indicated by (D1-D0). A value closer to 0 indicates a smaller increase in fog during storage of the raw sample.

Table 5 shows the obtained results.

[0268]

[Table 5]

From Table 5, it can be seen that the sample of the present invention has high rigidity even when recycled pulp is used as the base paper, and is excellent in raw sample preservability.

Example 4 <White base paper> A basis weight of 160 g / m ² consisting of 50% by weight of sulfated bleached hardwood pulp (LBKP) and 50% by weight of sulfated bleached softwood pulp (NBSP) for photographic paper for photographic grade.
Was prepared.

<Paper support K> As a back resin layer of the white base paper, a polypropylene resin was melt-extruded at 300 ° C., and then a biaxially oriented polypropylene having a thickness of 20 μm was produced using a sequential biaxial stretching apparatus using a flat film method. After preparing the resin sheet, a low-density polyethylene melt-extruded with a thickness of 5 μm as an adhesive layer was laminated between the white base paper and the sheet, and then nipped to prepare a back resin layer.

Next, polypropylene 80 was used as the surface resin layer.
% By weight, average particle size 0.3 μm as fine particle porosity-inducing particles
Of a polybutylene terephthalate particle kneaded at 20% by weight is stretched to 10 μm after stretching, 90% by weight of polypropylene on both sides thereof, and anatase type titanium oxide 1
After laminating and extruding at 300 ° C. so that the polypropylene resin layer kneaded with 0% by weight becomes 5 μm each after stretching,
Using a flat film method sequential biaxial stretching device,
After preparing a 0 μm biaxially stretched laminated polypropylene resin sheet, a low-density polyethylene containing 5 wt% of rutile titanium oxide melt-extruded with a thickness of 5 μm as an adhesive layer was laminated between the white base paper and the sheet. Nip after
A surface resin layer was produced.

<Paper support L> A pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4) as an antioxidant was added to a polypropylene resin used for the front and back stretched polypropylene sheets of the paper support K. -Hydroxyphenyl) propionate] was added in the same manner as in paper support K except that 500 ppm of paper support L was prepared.

<Paper support M> The polypropylene resin used for the front and back stretched polypropylene sheets of the paper support K was added with octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) as an antioxidant. A paper support M was prepared in the same manner as the paper support K except that propionate was added at 200 ppm.

Next, after a corona discharge treatment (output current value: 2 amps) was applied to the surface resin layer side of the paper supports K to M, a gelatin subbing layer was applied so that the gelatin coverage was 40 mg / m ^2. It was provided dry.

Next, supports K to M provided with a gelatin undercoat layer
The same photographic constituent layers as in Example 1 were applied to the samples to prepare multilayer color photographic paper samples 401 to 403 shown in Table 6.

The samples 401 to 403 thus prepared
Was evaluated as follows.

<Evaluation of Variation of Printed White Background with Time> The development processing step A was performed with each sample left unexposed to prepare a white background sample.

Next, the obtained color analyzer (607)
The reflection density was measured with a mold (manufactured by Hitachi, Ltd.) to evaluate the white background, and b * (0) was determined based on the CIE1976 color system.

Next, each white background sample was subjected to a temperature of 85 ° C. and a relative humidity of 40%.
After 3 weeks storage, the white background was evaluated in the same manner and b *
(1) was determined.

From this, the degree of white background fluctuation is calculated as [b * (1)
−b * (0)] in Table 6. The smaller the numerical value, the smaller the white background fluctuation.

[0282]

[Table 6]

From Table 6, it can be seen that the sample of the present invention is excellent in the variation of the white background of the printed white background with time.

[0284]

According to the present invention, it is possible to obtain a silver halide photographic light-sensitive material which is excellent in rigidity, hardly suffers from pressure fog and scratches in the transportation of a minilab, and can easily count the number of prints accumulated after the minilab processing. Is completed,
Further, it is possible to provide a silver halide photographic light-sensitive material comprising a paper support in which the white background over time after print formation is improved and the base paper can contain recycled pulp.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 7/00 520 G03C 7/00 520 F term (Reference) 2H016 BC03 BD00 2H023 CD09 FA02 FA03 FA04 FA05 FA09 FC00 GA03 GA04 4L055 AC09 AJ02 EA04 GA32

Claims (5)

[Claims] 1. A halogenated paper comprising at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on one side of a paper support having a resin coating layer coated on both sides of a base paper. In a silver photographic light-sensitive material, the resin coating layers on both sides of the paper support each comprise at least one stretched polymer sheet, and have an adhesive layer between the stretched polymer sheet and a base paper. A silver halide photographic light-sensitive material having an antistatic layer on the coating resin layer on the side opposite to the side coated with the silver halide emulsion layer. 2. A halogenated paper comprising at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on one side of a paper support having a resin coating layer coated on both sides of a base paper. In a silver photographic light-sensitive material, the resin coating layer on the side of the paper support on which the silver halide emulsion layer is coated is composed of at least one stretched polymer sheet, and has an adhesive layer between the stretched polymer sheet and the base paper. A silver halide photographic material, characterized in that the non-photosensitive hydrophilic colloid layer furthest from the support contains at least one fluorine-containing surfactant. 3. A halogenated paper having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on one side of a paper support having a resin coating layer coated on both sides of a base paper. In the silver photographic light-sensitive material, the resin coating layer on the side of the paper support on which the silver halide emulsion layer is coated is composed of at least one stretched polymer sheet, and has an adhesive layer between the stretched polymer sheet and the base paper. A silver halide photographic material, characterized in that the non-photosensitive hydrophilic colloid layer furthest from the support contains at least one organopolysiloxane. 4. A halogenated paper having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on one side of a paper support having a resin coating layer coated on both sides of a base paper. In a silver photographic light-sensitive material, the total pulp constituting the base paper of the paper support contains at least 10% by weight of recycled pulp made of waste paper, and the resin on the side of the paper support coated with the silver halide emulsion layer is used. A silver halide photographic material, wherein the coating layer comprises at least one layer of a stretched polymer sheet, and has an adhesive layer between the stretched polymer sheet and a base paper. 5. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one non-photosensitive layer on one side of a paper support having a resin coating layer coated on both sides of a base paper. In the material, the resin coating layer on the silver halide emulsion layer coating side of the paper support comprises at least one stretched polymer sheet, and has an adhesive layer between the stretched polymer sheet and a base paper; A silver halide photographic light-sensitive material, characterized in that the stretched polymer sheet contains an antioxidant.