JPH03263034A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To make improvement in matt characteristics, lubricity and vacuum adhesive property by drying the water up to 1000 to 200% contents at <=20 deg.C coated surface temp. in accordance with the dry weight of the binder incorporate into the hydrophilic colloidal layers of the silver halide photographic sensitive material. CONSTITUTION:The moisture up to 1000 to 200% contents is dried at <=20 deg.C coated surface temp. in accordance with the dry weight of the binder incorporate into the hydrophilic colloidal layers of the silver halide photographic sensitive material constituted by having two layers of the non-photosensitive hydrophilic colloidal layers on a silver halide emulsion layer and incorporating a matting agent into the non-photosensitive hydrophilic colloidal layer in the outermost layer. The silver halide material which is excellent in the vacuum adhesive property and matt-pinhole evaluation is obtd. in this way without deteriorating productivity.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a silver halide photographic material.

[Background of the invention]

Generally, a hydrophilic colloid such as gelatin is used as a binder in the outermost layer of a silver halide photographic light-sensitive material. For this reason, the surface of the silver halide photographic light-sensitive material exhibits increased adhesion or tackiness in an atmosphere of high temperature and high humidity, and when it comes into contact with another object, it easily adheres to it. This adhesion phenomenon occurs between the photosensitive materials or between the photosensitive materials and other objects that come into contact with them during the production, storage, photographing, processing, projection, or storage after processing. , a serious malfunction had occurred. To solve this problem, the outermost layer is made of inorganic substances such as silicon dioxide, magnesium oxide, titanium dioxide, and calcium carbonate, and organic substances such as polymethyl methacrylate, cellulose acetate propionate, and methyl methacrylate/methacrylic acid copolymer. By incorporating fine particles and increasing the roughness of the surface of the photosensitive material, creating a so-called cloak,
It has been proposed to reduce the adhesion, improve the antistatic effect and the vacuum adhesion to the printer, especially during the return process, and shorten the vacuum time. For this purpose, for boat fishing, the amount of manting agent used and the grain size are increased, but the matting agent sinks into the silver halide emulsion layer and becomes matte pins. This will cause serious drawbacks. Therefore, in order to avoid this, it is known to increase the thickness of the matting agent layer and dry it slowly over time to prevent the matting agent from sinking, but this reduces productivity. Go backwards.

[Disclosure of the invention]

A first object of the present invention is to provide a silver halide photographic material with improved matte properties, slip properties, and vacuum adhesion. A second object of the present invention is to provide a silver halide photographic material with improved matte pins. A third object of the present invention is to provide a /S silver halide photographic material that achieves the above objects without reducing productivity. The object of the present invention is to have at least two non-photosensitive hydrophilic colloid layers on a silver halide emulsion layer, and
A silver halide photographic light-sensitive material containing a matting agent in the non-photosensitive hydrophilic colloid layer in the outermost layer, and based on the dry amount of binder contained in the hydrophilic colloid layer of this silver halide photographic light-sensitive material This is achieved by a silver halide photographic light-sensitive material which has a moisture content of 1000 to 200% and is dried at a coating surface temperature of 20 DEG C. or less. In addition, based on the dry amount of binder contained in the hydrophilic colloid layer, the moisture content is 1000 to 200% at a coating surface temperature of 10°C.
It is preferable that the coating be dried at a temperature of C or higher, and even more preferably, that the coating surface be dried at a temperature of 10 to 16°C. Further, the relative humidity of the drying air that dries the moisture content from 1000% to 200% is preferably 60% or less,
More preferably it is 50% or less. Further, the time for this drying treatment is preferably about 35 to 70 seconds. 1000 to 200 based on the dry weight of the binder contained in the hydrophilic colloid layer of such a silver halide photographic light-sensitive material.
% moisture content at coating surface temperature below 20°C,
This is done as follows. For example, from 1000% to 700%, the dry bulb temperature is 23.5
Using a wind with a relative temperature of 30% °C1, the coating surface temperature is 13.
Dry at 5°C for 17 seconds, then 700% to 500%
The coated surface was dried for 20 seconds at a dry bulb temperature of 21°C and a relative humidity of 43% using air at a coating surface temperature of 14°C. Furthermore, 5
00% to 200% was dried for 26 seconds at a coating surface temperature of 16° C. using air at a dry bulb temperature of 2V C1 and a relative humidity of 56%. Furthermore, as disclosed in Japanese Patent Application Laid-Open No. 1-230035, 5 minutes after the average temperature of the coated surface rises to a temperature 1°C lower than the contacting air (effectively the point at which drying ends).
The dimensional stability may be improved by contacting with air at a temperature of 35° C. or more and 80° C. or less for a minute to 1 minute. Furthermore, as in JP-A-1-229244, after drying,
Also, by performing heat treatment at 30°C or higher in an atmosphere with an absolute humidity of 1% or less and storing it in an atmosphere with an absolute humidity of 1% or less, the film surface can be Even if the film is wound up at a temperature of 40°C to 50°C, there is no change in the effects of the present invention. Further, in this silver halide photographic light-sensitive material, the gelatin concentration of the non-photosensitive coating liquid of the outermost layer is lower than the gelatin concentration of the non-photosensitive coating liquid of the other layers, and at least one of the other layers is non-photosensitive. The gelatin concentration of the coating solution is 3.8%.
(w/v) or more, more preferably 4.5% (w/v)
The above is preferable. Also, the particle size of the matting agent is 0.1 to 10I! m, more preferably 1.0 to 8.0 μm, and the amount added is 0.1 to 300 mg/m2,
More preferably, it is 10 to 200 mg/m''. Also, the thickness of the outermost layer containing this matting agent immediately after coating is preferably 3 to 30 μ. The present invention will be described in more detail below. Examples of matting agents contained in the outermost non-photosensitive layer above the silver halide emulsion layer include natural vehicles,
Mention may be made of finely divided inorganic powders such as silica, barium sulfate, calcium sulfate, zinc oxide, titanium oxide, diatomaceous earth, desensitized silver halide, zinc carbonate in various forms dispersed in a synthetic vehicle. , these are U.S. Patent Nos. 2,192,241, 1,201,905, and 3.
No. 257206, No. 3437484, No. 3322
No. 555, No. 3411907, No. 3353958
British Patent No. 3370951, British Patent No. 3G15554, British Patent No. 3523022, British Patent No. 3062649, British Patent No. 1260772, British Patent No. 3635714, British Patent No. 37
No. 69020, No. 4029504, No. 40212
No. 45, No. 760,775, and West German Publication No. 2,529,321. Finely divided powders and organic beads can also be used, such as calcium organic salts, starches containing starch esters, wheat flour, arrowroot powder, Indian rubber, talc, hardened deionized or demineralized gelatin, casein. , other polymeric substances such as various forms of cellulose, α3β-ethylenically unsaturated mono(di)carboxylic acids, esters, half esters and their sulfonic acid congeners (especially acrylic acid, methacrylic acid and their methyl esters) ), styrene, 1-crylonitrile, fluorinated ethylene polymers, and also materials such as polycarbonate and polyvinyl alcohol can also be used as matting agents. Regarding these, US Patent No. 1939213, US Patent No. 2221873, US Pat.
No. 268662, No. 2322037, No. 3591
No. 379, No. 2376005, No. 2992101
No. 2391181, No. 2701245, No. 3516832, No. 3079257, No. 34
No. 43946, No. 326'2782, No. 3754
No. 924, No. 3767448, British Patent No. 1055
No. 713 explains this. The silver halide photographic material of the present invention preferably contains at least one type of polyalkylene oxide compound. The polyalkylene oxide compound can be contained in any photographic constituent layer of the light-sensitive material of the present invention. In particular, it is preferable to include it in the silver halide emulsion layer. The polyalkylene oxide compound used in the present invention consists of at least 10 units of alkylene oxide having 2 to 4 carbon atoms, such as ethylene oxide, propylene-1,2-oxide, butylene-1,2-oxide, and preferably ethylene oxide. A condensate of polyalkylene oxide and a compound having at least one active hydrogen atom such as water, aliphatic alcohol, aromatic alcohol, fatty acid, organic amine, hexitol derivative, or a block copolymer of two or more polyalkylene oxides. contains. Examples of polyalkylene oxide compounds include polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers, polyalkylene glycol alkylaryl ethers, polyalkylene glycol esters, polyalkylene glycol fatty acid amides, and polyalkylene glycols. Examples include amines, polyalkylene glycol block copolymers, and polyalkylene glycol graft polymers. It is important that the molecular weight is 600 or more. The number of polyalkylene oxide chains is not limited to one in the molecule, and two or more may be included. In that case, the individual polyalkylene oxide chains may consist of less than 10 alkylene oxide units, but the total number of alkylene oxide units in the molecule must be at least 10.
If there is more than one polyalkylene oxide chain in the molecule, each of them may consist of different alkylene oxide units, such as ethylene oxide and brobylene oxide. The polyalkylene oxide compound used in the present invention preferably contains 14 to 100 alkylene oxide units. Specific examples of the polyalkylene oxide compounds used in the present invention are as follows. Polyalkylene oxide compound example 1 1 1'l0(CHzCHzO)*oH1-2C4
[(90(CBICI!0)Is)]1 3 C+t
HzsO(CToCHzO)tsHl 4 C+5
H3tO(CHzClhO)tsHl 5 C+5
H3tO(CHzCHzO)aoHl 6 C,1
(ttCH=CHCsH+10(CHzCHtO)ts
Hl 10 C++HziCOO(C)Igcl
(go)s. ■1 11 C++1hsCOO(C
HtCHlO>z<0CCrtHtsI 13
C++HzxCONH(CHzCHzO)+5l(11
5C+aHzJ(CFlz)(CHiCFlzO)za
HCH2-0-CH-C1hOC++Hゎ1-16
H(OCR1CF12)+4O-C)1-C)1-CH
-((JI2CH20)14HO-(CHzCHzO)
1aH 1-17H (CEIICH!0), (CHCHxO
)b (CH2CH!0)cHlh a+b+c=50 b:a+c=10:9 When these polyalkylene oxide compounds are added to a silver halide emulsion, they can be added as an aqueous solution with an appropriate concentration or as a low boiling point miscible with water. It can be dissolved in an organic solvent and added to the emulsion at an appropriate time before coating, preferably after chemical ripening. Instead of being added to the emulsion, it may be added to a non-photosensitive wood-philic colloid layer, such as an intermediate layer, protective layer, filter layer, etc. The polyalkylene oxide compound used in the present invention is 1 x 10-5 mol-lXl per mol of silver halide.
A range of 0-g mole is desirable. Further, in the silver halide photographic material of the present invention, at least one layer of the hydrophilic colloid layer contains a hydrazine compound and/or a hydrophilic colloid layer.
Or it can contain a tetrazolium compound. The hydrazine compounds used include compounds represented by the following formula []]. General formula (I[) represents a monolsulfonyl group, M\IA or an unsubstituted acyl group. Typical hydrazine compounds represented by the above-mentioned formula (n) are shown below. I[-1 1-2 is a formyl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, an alkoxy or aryloxycarbonyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, represents a sulfanyl group or a heterocyclic group, and X and Y are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted ali 1
-3 The hydrazine compound is added to the silver halide emulsion layer and/or the non-photosensitive layer (!!aqueous colloid N) on the silver halide emulsion layer side of the support. The amount added is preferably 10-S to 10-1 mol/silver 1 mol, more preferably 10-4 to 10-t mol/silver.
1 mole of silver. Also, a tetrazolium compound will be explained. As the tetrazolium compound used, there is a compound represented by the following formula (I[[). In the above formula (III), preferred examples of the substituents represented by R1-R1 include alkyl groups (e.g. methyl, ethyl, cyclopropyl, propyl, isopropyl, cyclobutyl, butyl, isobutyl, pentyl, cyclohexyl, etc.), amino groups, acylamino groups (e.g. acetylamino), hydroxy groups, alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentoxy, etc.),
Acifreoxy group (e.g. acetyloxy), norogen atom (e.g. fluorine, chlorine, bromine, etc.), carbamoyl group, acylthio group (e.g. acetylthio), a! Examples include a lekoxycarbonyl group (eg, ethoxycarbonyl), a carboxyl group, an acyl group (eg, acetyl), a cyano group, a nitro group, a mercapto group, a lehooxy group, an aminosulfoxy group, and the like. Examples of the anion represented by X include halogen ions such as chloride ion, bromide ion, and iodide ion, acid groups of inorganic acids such as nitric acid, sulfuric acid, and perchloric acid, and acid groups of organic acids such as sulfonic acid and carboxylic acid. , anionic activator,
Specifically, lower alkylbenzenesulfonate anions such as p-)7 leenesulfonate anions, higher alkylbenzenesulfonate anions such as p-dodecylbenzenesulfonate anions, higher alkyl sulfate ester anions such as lauryl sulfate anions, and tetraphenyl. Boric acid anions such as boron, dialkyl sulfosuccinate anions such as di-2-ethylhexyl sulfosuccinate anions, polyether alcohol sulfate ester anions such as cetyl polyethenoxy sulfate anions, higher aliphatic anions such as stearate anions,
There are polymers such as polyacrylate anions with acid groups attached. Even if the tetrazolium compound is added to the silver halide emulsion layer, it is not added to the non-photosensitive hydrophilic colloid layer directly adjacent to the silver halide emulsion layer, or to the non-photosensitive hydrophilic colloid layer adjacent to the silver halide emulsion layer via an intermediate layer. It's okay. Alternatively, the tetrazolium compound is dissolved in a suitable organic solvent, such as alcohols such as methanol and ethanol, ethers, esters, etc., and applied to the outermost layer on the silver halide emulsion layer side of the light-sensitive material by an overcoating method or the like. It may also be incorporated into a photosensitive material by direct coating. The tetrazolium compound is preferably used in an amount of 1X10-' mol to 10 mol, particularly 2X10-' mol to 2X10-' mol, per mol of silver halide contained in the light-sensitive material of the present invention. Particularly favorable results can be obtained when an anion that binds to the above-mentioned tetrazolium compound and lowers the hydrophilicity of the tetrazolium compound is used in combination. Examples of such anions include acid groups of inorganic acids such as perchloric acid, acid groups of organic acids such as sulfonic acids and carboxylic acids, anionic activators, and specifically lower groups such as P-)luenesulfonic acid anions. Dialkyl sulfosuccinate anions such as alkylbenzenesulfonic acid anions, p-dotecylbenzenesulfonic acid anions, alkylnaphthalenesulfonic acid anions, lauryl sulfate anions, tetraphenylpolones, di-2-ethylhexylsulfosuccinate anions, etc. , polyether alcohol sulfate ester anions such as cetyl polyethenoxysulfate anions, stearate anions, and polyacrylate anions. Such anions may be added to the hydrophilic colloid layer after being mixed with the tetrazolium compound in advance, or may be added alone to the silver halide emulsion layer or hydrophilic colloid layer containing or not containing tetrazolium. good. In the silver halide emulsion used in the present invention, any silver halide used in ordinary silver halide emulsions, such as silver chloride and silver chlorobromide, can be used. The average grain size and grain size distribution of the silver halide emulsion are arbitrary, but preferably the average grain size is 0.05 μm to 0.777 m,
More preferably, it is 0.05 μm to 0.4 μm. Further, at least 75% or more, particularly preferably 80% or more of the total number of particles have an average particle size of 0.7 to 1.
It is preferred to use emulsions that are three times the grain size. Silver halide grains used in silver halide emulsions contain cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salts containing), rhodium salt ( These metal elements can be added inside the particles and/or on the particle surface by adding metal ions using at least one selected from iron salts (complex salts containing) and iron salts (complex salts containing iron salts), in particular water-soluble rhodium salts. It is suitable to contain. Further, by placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces. When adding a water-soluble rhodium salt, the amount added is lXl0-' to lxl0-4 mol/AgX
Preferably it is 1 mol. Silver halide emulsions can be sensitized using, for example, chemical sensitizers or sensitization methods. Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographs may be taken during chemical ripening, at the end of chemical ripening, and/or after chemical ripening and before coating a silver halide emulsion. Compounds known in the art as antifoggants or stabilizers can be added. Furthermore, all the hydrophilic colloid layers of the photosensitive material contain various photographic additives as necessary, such as gelatin plasticizers, hardening agents, surfactants, image stabilizers, ultraviolet absorbers, antistain agents, and PN adjusters. , antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed adjusting agents, etc. can be used within the range that does not impair the effects of the present invention. As mentioned above, gelatin is used as the binder for the silver halide photographic light-sensitive material used in the present invention, but gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives,
Hydrophilic colloids such as cellulose derivatives and synthetic hydrophilic polymer substances (latex polymers) such as single or copolymers can also be used in combination. However, the content of these substances other than gelatin is preferably 60% or less.

[Preparation of emulsion] A silver chlorobromide emulsion having a silver bromide content of 2 mol % was prepared as follows. An aqueous solution containing 23.9 mg of potassium pentabromorodium salt, sodium chloride, and potassium bromide per 60 g of silver nitrate and an aqueous silver nitrate solution were stirred into an aqueous gelatin solution, and the average particle size was 0. A 3μ silver chlorobromide emulsion was prepared. After adding 200 mg of 6-methyl-4-hydroxy-1,3,3a,7-chitrazaindene as a stabilizer to this emulsion, the emulsion was washed with water and desalted. After adding 20 mg of 6-methyl-4-hydroxy-1,3,,3a,7-chitrazaindene to this, sulfur sensitization was performed. After sulfur sensitization, 6-methyl-4-hydroxy-1,3,3a7-titrazaindene was added as a stabilizer, and the emulsion was then finished to 2607 with water to prepare an emulsion. [Preparation of emulsion coating solution]

Add 9 mg of the following compound (A) as a bactericide to the milk cutting fluid.
After addition, adjust the pH using 0.5N sodium hydroxide solution.
was adjusted to 6.5, 360 mg of the following compound (T) was added, and 5 d of a 20% aqueous solution of saponin, 180 mg of sodium dodecylhenzenesulfonate, and 80 mg of 5-methylbenztriazole were added per mole of silver halide.
mg, 43m of latex liquid (L) synthesized by the method described in JP-A-1-230035, 60mg of the following compound (M), and 280mg of styrene-maleic acid copolymer aqueous polymer as a thickening side. In addition, the emulsion coating liquid E-1 was prepared by finishing the emulsion to 475 d with water. In the same manner, only finishing was performed to 370 cc to prepare emulsion coating liquid E-2. Compound (T) Tetrazolium compound CH3CH3 Compound (Z) Compound (N) So, Na Compound (B) 0■0zCJs Then, an emulsion protective film coating solution was prepared as follows. [Preparation of emulsion protective film coating solution P-1] Add 101 g of pure water to 1 kg of gelatin and heat at 40°C after swelling.
T: Dissolution, then 1 of the above compound (Z) as a coating aid
% aqueous solution at 2.92%, 80 g of the above compound (N) as a filter dye, 20 g of amorphous silica with an average particle size of 8 μm as a matting agent, and 1 g of amorphous silica with an average particle size of 3 μm as a matting agent.
0g and 62g of the above compound (B) were added in sequence, and the pH was adjusted to 5.4 with citric acid solution, and the pH was adjusted to 22ffi with water to protect the emulsion. ! A coating liquid P-1 was prepared. [Preparation of emulsion protective film coating solutions P-2, P-3, P-4゜P-5] Similarly to P-1, add 52 g of pure water to 500 g of gelatin,
After swelling, the compound (Z) was dissolved at 40°C as a coating aid.
), 40g of compound (N) as a filter dye, 20g of amorphous silica with an average particle size of 8 μm as a matting agent, Log of amorphous silica with an average particle size of 3 μm, and compound (B). Add 31g one by one, adjust the pH to 5.4 with citric acid, and adjust to 14.0g with water. 'l! An emulsion protective film coating solution P-2 was prepared. In the same manner, emulsion protective film coating solution P-3 was prepared by finishing to 12.5 f with water. Similarly, 111 with water! An emulsion protective film coating solution P-4 was prepared. In the same manner, emulsion protective film coating solution P-5 was prepared by finishing the emulsion to 8.31 with water. Next, an emulsion protective film intermediate layer coating solution was prepared as follows. [Emulsion protective film intermediate layer coating solution CP-1, CP-2CP-3
, Preparation of CP-4] 51 g of pure water was added to 500 g of gelatin, and after swelling, it was dissolved at 40° C., and then 1.5 g of a 1% aqueous solution of compound (Z) was added as a coating aid. Ojl! , 40g of Compound (N) as a filter dye and a1gM of Compound (B) were added, the pH was adjusted to 5.4 with citric acid, and 14.7j! was added with water. An emulsion protective film intermediate layer coating solution CP-1 was prepared. In the same manner, the emulsion protective film intermediate layer coating solution CP-2 was prepared by finishing the coating solution to 13.21 with water. In the same manner, the emulsion protective film intermediate layer coating solution CP-3 was prepared by finishing to 1lffi with water. In the same manner, the emulsion protective film intermediate layer coating solution CP-4 was prepared by finishing to 8°31 with water. [Preparation of evaluation sample] Next, using the backing lower layer coating solution and the backing layer protective film coating solution prepared by the method described in Example 1 of JP-A-1-230035,
It was coated on one side of a polyethylene terephthalate film (thickness: 100 μm) provided with an undercoat layer according to Example 1 of Publication No. 1. Next, the other surface was coated under the conditions of the combination of coating liquids shown in Table 1 to obtain evaluation samples S-1 to S-9. At that time, a backing underlayer coating solution was used on one side of the support coated with the undercoat layer so that the gelatin dry weight was 2 g/m2.
At the same time, apply a backing protective film layer on top using a protective film solution, and add gelatin with a dry weight of 1g7m.
Next, an emulsion layer was coated on the other side of the support with an emulsion layer of E-1 so that the gelatin dry weight was 1.8 g/m and the coated silver amount was 3.4 g/m. Or E-2
It is coated using an emulsion coating solution, and the upper part is coated with an emulsion protective film intermediate layer coating solution CP-1, CP-2, cp-3, or CP-.
4 was coated so that the dry weight of gelatin was 0.4 g/ml, and on top of that, emulsion protective film coating solution P-2, P-3, P-4, or P5 was applied so that the dry weight of gelatin was 0.4 g/ml.
The emulsion layer and the intermediate layer were coated and dried at the same time while adding formalin as a hardening agent to give a hardening agent of 4 g/m'' (Evaluation samples S-2 to 5-9). The dry weight of gelatin was 1.8 g/m'' and the amount of coated silver was 3.4.
g/m", and on top of that, apply an emulsion protective layer 111 using protective film solution P-1 so that the gelatin dry weight is 0.
It was coated and dried at the same time as the emulsion layer while adding formalin as a hardening agent to give a hardening agent of 8 g/m.
Cool and solidify, then dry bulb temperature 26℃, relative humidity 13%
The gelatin moisture content of the coated layer was dried to 1600% using dry air at a coating surface temperature of 11°5°C, and then dried at a dry bulb temperature of 3°C.
Applying surface temperature 19 using dry air at 7℃ and relative temperature 15%
The gelatin was dried at 10°C until the gelatin moisture content of the coated layer reached 1000%. Next, under the conditions shown in Table 1, the coated layer was dried until the gelatin moisture content was 200%, and from 200% to the end of drying, it was dried with air at a dry bulb temperature of 28.5°C and a relative humidity of 44%. . Furthermore, after 10 seconds after drying, the dry bulb temperature was 48℃,
It was treated for 40 seconds using dry air at a relative temperature of 16%. After drying, the evaluation samples S-1 to S-9 were moistened once at a temperature of 25° C. and a relative humidity of 50% (dew point 14° C.) and wound up. Table-1 The gelatin concentration in the coating solution is 4.5 for P-1.
5%, P-2 3.4%, P3 4.0%
, P-4 is 4.55%, P-5 is 6.0%
, 3.4% for CP-1 and 3.8% for CP-2.
%, 4.55% for CP-3, 6 for CP-4
．． 0%, E-1 3.5%, E-2 4.
It is 5%. *1; Emulsion coating surface drying conditions are based on the total binder dry amount.
Dry from ooo% to 200% in 45 seconds at a coating surface temperature of 14°C to 18°C (relative temperature 13 to 42%) *2; Emulsion coating surface drying conditions are based on the total binder dry weight.
000% to 200% was dried in 45 seconds at a coating surface temperature of 21° C. The matte properties of the samples S-1 to S-9 were evaluated. [Matt test] After each sample was conditioned for 3 hours at an environmental temperature of 23°C and a relative humidity of 148%, the matte appearance of the emulsion surface was measured using a Smooster meter (manufactured by Toei Denshi Kogyo Co., Ltd., model digital Smooster meter). Measured using The results are shown in Table-2. As shown in Table 2, in the samples S-2 to S-8 of the present invention, the matte ratio was high, indicating good results. In particular, S
-3, S-4, S-5, and S-6 are good. [Matte pin evaluation] After each sample was exposed to light for 40 counts using a bright room printer (type P-627FM) manufactured by Dainippon Screen Co., Ltd., it was exposed using an automatic processor under the following development processing conditions using the following developer and fixer. Processed. [Development processing conditions] (Process) (Temperature) (Time) (Tank capacity)
Development 28°C 30 seconds 20 1 fixing
28°C 20 seconds 20 ffi water washing 18
℃ 20 seconds 15 f drying 40℃
25 seconds 2Of dryer heat transfer coefficient: 95kc
al/hr, ffi"・"C automatic developing machine installation environment temperature and humidity: (temperature) = 23°C (relative humidity) = 40% Each process time also includes the so-called wading conveyance time to the next process. Dry to Dry Time: 85 seconds Line speed: 1500 ml/sin [Developer composition] (Composition A) Pure water (ion exchange water) 150 m Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% H/V aqueous solution) ) 100I11 potassium carbonate
so g hydroquinone
15 g 5-Methylbenzotriazole 200 mg l-Phenyl-5-mercaptotetrazole 0 mg Potassium hydroxide Amount to adjust the pH of the working solution to 10.4 Potassium bromide 4.5 g (consisting of I) Pure water (ion-exchanged water) 3I11 Diethylene glycol 50 g ethylenediaminetetraacetic acid disodium salt 25 mg vinegar #(9
0% aqueous solution') 0.3 jd!
1105 g of 5-nitroindazole 50011 g of 1-phenyl-3-pyrazolidone When using a developer, the above composition A was dissolved in the order of composition A and composition 11 in water 5001d and used. [Fixer formulation] (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 24
0 Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid
6g sodium citrate dihydrate 2g acetic acid (90%-/V aqueous solution)
13.6a+ff1 (composition) Pure water (ion exchange water) 3d sulfuric acid (
55%-/V aqueous solution) 6g aluminum sulfate (AhOi equivalent content is 8.1% w/v aqueous solution) 26.5
When using the G fixer, it was dissolved in 500 ml of water in the order of the above composition A and the composition, and finished to 1i and used. The pH of this fixer was about 4.3. Thereafter, the matte pins were observed on a high-intensity Scherkasten using 10x and 100x loupes. The evaluation was performed on a 10-point scale as a visual evaluation. Good〉5~1〉
Consider it inferior. Furthermore, Dm was measured using a PDA-65 concentration needle (high concentration type) (manufactured by Konica). These results are shown in Table-2. As shown in Table 2, it can be seen that in the samples S-2 to S-8 of the present invention, there were fewer matte pinholes (matte pins) due to sinking of the matting agent, and the Dm concentration was also high. In particular, S-3, S-4, S5, and S-6 are good. [Vacuum adhesion test] Each sample was tested using a bright room printer manufactured by Dainippon Screen Co., Ltd. ■ Samples S-1 to S-9, ■ 10. Five sheets of θμ polyethylene terephthalate base were stacked, (1) a 90% halftone original was stacked, vacuum contact treatment was performed for 8 seconds, and then exposure was performed for 40 counts. Next, the film was processed using an automatic processor, developer, fixer, and processing conditions similar to those for the matte pin evaluation. At the boundary where five 100 μm polyethylene terephthalate bases are stacked, the samples S-1 to S-9 begin to float, causing darkening due to the wraparound of light. Therefore, the vacuum adhesion was evaluated by measuring the length α of this blackened portion. The results are shown in Table-2. As shown in Table 2, S-2 to S-8 of the present invention exhibit better vacuum adhesion than the comparative example. In other words, if the air escapes in a short time and the adhesion is good, the line width α in this part will be small. In particular, S-3, S-4, S-5, and S-6 have shown good results. (The following is a blank space) Table 2 Example 2 Emulsion coating liquid E-1, emulsion protective film coating liquid P-2, and emulsion protective interlayer liquid CP3 were prepared in the same manner as in Example 1. Similar to Example 1, this was applied using a backing lower layer coating solution and a backing layer protective film coating solution prepared by the method described in Example 1 of JP-A No. 1-230035. Polyethylene terephthalate film (thickness: 100μ
) was applied to one side of the top. Next, the other side was coated and dried according to the coating liquid combination conditions and drying conditions shown in Table 3.
-10 to 5-15 were obtained. At that time, a backing underlayer coating solution was used on one side of the support coated with the undercoat layer so that the gelatin dry weight was 2 g/m2.
At the same time, apply a backing protective film layer on top using a protective film solution, and add gelatin with a dry weight of 1g7m.
The emulsion layer was then coated on the other side of the support so that the gelatin dry weight was 1.8 g/m, and dried.
Emulsion protection intermediate layer coating solution C was applied on top of the E-1 emulsion coating solution so that the coating silver amount was 3.4 g/m''.
Apply P-3 so that the dry weight of gelatin is 0.4 g/m2, and then apply emulsion protective film coating liquid P-2 on top.
was coated and dried at the same time as the emulsion layer and the intermediate layer while adding formalin as a hardening agent so that the dry weight of gelatin was 0.4 g/m''. It was the same as the s-i sample except that only the drying conditions were changed as shown in Table 3.
The drying conditions were the same as in Example-1 except that the gelatin water content of the coating layer was 1000% to 200%. After drying, evaluation samples 5-16 and 5-10 to 5-15 were conditioned at a temperature of 25° C. and a relative humidity of 50% (dew point 14° C.) and wound up. The obtained sample was treated in the same manner as in Example-1, with matte degree,
Mat pin and vacuum adhesion tests were conducted. The results are shown in Table 4. As shown in Table-4, 100% based on the total binder dry weight.
A great effect can be seen by drying the water content of ~200% at a coating surface temperature of 20°C or less. In particular, No. 5-10, in which the coating surface temperature was 16° C., was extremely good. Note that there is no particular difference between 5-14, where the drying time (moisture content 1000% to 200%) was 70 seconds, and 5-15, where the drying time was 90 seconds. 1
4 is preferable, however, drying time (moisture content 1000%
~200%) becomes too short, unfavorable trends begin to appear. Moisture content is 1000% to 200% based on total binder dry weight
The drying conditions for the emulsion coated surface are *1: 16°C, 135 seconds, *2: 2V, 135 seconds, *3: 19°C, 35 seconds, *4
is 16°C for 125 seconds, *5 is 19°C for 570 seconds, and *6 is 19°C for 190 seconds. (Hereafter, margin) Table

【effect】

According to the present invention, a silver halide material excellent in vacuum adhesion and matte pin can be obtained without deteriorating productivity.

Claims (2)

[Claims] (1) Silver halide having at least two non-photosensitive hydrophilic colloid layers on the silver halide emulsion layer, and the outermost non-photosensitive hydrophilic colloid layer containing a matting agent. A photographic light-sensitive material, wherein the water content is 1000 to 200% based on the dry amount of the binder contained in the hydrophilic colloid layer of the silver halide photographic light-sensitive material, and is dried at a coating surface temperature of 20°C or less. A silver halide photographic material characterized by: (2) In the silver halide photographic light-sensitive material according to claim 1, the gelatin concentration of the non-photosensitive coating liquid of the outermost layer is lower than the gelatin concentration of the non-photosensitive coating liquid of the other layers; At least one of the non-photosensitive coating liquids has a gelatin concentration of 3.8% (w/v) or more.