JPH0545014B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material having a hydrophilic colloid layer with improved film properties. [Background of the Invention] Generally, hydrophilic colloid films used for producing photographic light-sensitive materials are required not only to have no adverse effect on photographic sensitivity characteristics but also to have specified strength in terms of film physical properties. Therefore, when coating a hydrophilic colloid layer such as a silver halide emulsion layer, intermediate layer, or protective layer on a support, a polymer latex in which various monomer compounds are polymerized is conventionally used in the hydrophilic colloid layer. Various attempts have been made to improve the physical properties of the hydrophilic colloid film, such as the dimensional stability, scratch strength, flexibility, pressure resistance, and drying properties, of the resulting hydrophilic colloid film. For example, the vinyl acetate polymer latex of U.S. Pat. No. 2,376,005, U.S. Pat. No. 3,325,286
Polymer latex of alkyl acrylate in Japanese Patent Publication No. 45-5331, polymer latex of n-butyl acrylate, ethyl acrylate, styrene, butadiene, vinyl acetate, acrylonitrile, etc. in Japanese Patent Publication No. 46-22506, alkyl acrylate, acrylic acid in Japanese Patent Publication No. 46-22506 , a polymer latex of sulfoalkyl acrylate, a polymer latex of 2-acrylamido-2-methylpropanesulfonic acid disclosed in JP-A-51-130217, and the like have been used for the above purpose. However, some of these polymer latexes tend to aggregate or precipitate when mixed with an aqueous solution of gelatin, which is a hydrophilic colloid, or in the presence of salts.
The transparency of the hydrophilic colloid film deteriorates and devitrification occurs, and some polymer latexes
It had drawbacks such as adverse effects on photographic properties such as sensitivity, fog, gradation, and development progress. Furthermore, since a large amount of emulsifier is used for dispersing these polymer latexes, this has been a cause of deterioration of the physical properties of the hydrophilic colloid film. On the other hand, JP-A-54-133324 and JP-A-56-19043 disclose polymer latexes that can be synthesized by reducing the amount of emulsifier in addition to being an antistatic agent, but these polymer latexes have good film properties. and good gelatin compatibility of polymer latex at the same time.
The polymer latex containing 20% by weight or more of an ethylene monomer compound having at least one free phosphoric acid group or its salt as described in No. Compatibility with certain gelatins was also not improved. [Object of the Invention] The present invention has been made in order to eliminate the above-mentioned drawbacks, and the first object of the present invention is to provide a structure that does not adversely affect photographic performance, does not cause devitrification phenomenon, and has dimensional stability. An object of the present invention is to provide a silver halide photographic material having a hydrophilic colloid layer with improved film properties such as hardness and scratch strength. A second object of the present invention is to provide a polymer latex which is sufficiently stable even when incorporated into a hydrophilic colloid layer of a silver halide photographic light-sensitive material. [Structure of the Invention] The above object of the present invention is to provide a silver halide photograph in which at least one hydrophilic colloid layer contains a latex of a polymer having a repeating unit derived from a monomer compound represented by the following general formula (1). This is accomplished using photosensitive materials. General formula (1) In the formula, R ₁ represents a hydrogen atom or a methyl group,
R ₂ and R ₃ each have a hydrogen atom and 1 carbon atom
~20 alkyl or aryl groups. However, the total number of carbon atoms of R ₂ and R ₃ is 3 or more. M represents a cation. [Specific structure of the invention] In the general formula (1) of the present invention, R ₂ and R ₃ 3
The alkyl group having 1 to 20 carbon atoms represented by may be branched or straight chain, such as methyl group,
Ethyl group, propyl group, butyl group, octyl group,
Examples include dodecyl group, pentadecyl group, and eicosyl group. The alkyl group represented by R ₂ and R ₃ is preferably an alkyl group having 1 to 10 carbon atoms. Examples of the aryl group represented by R ₂ and R ₃ include a phenyl group, and this aryl group may be substituted with an alkyl group, a hydroxy group, or a halogen atom. In the above general formula (1), examples of the cation represented by M include alkali metal ions, alkaline earth metal ions, ammonium ions, and quaternary ammonium salt ions. Typical specific examples of monomer compounds used in the present invention are shown below. Exemplary monomer compound M-1 M-2 M-3 M-4 M-5 M-6 M-7 M-8 M-9 M-10 M-11 M-12 M-13 M-14 M-15 M-16 M-17 M-18 M-19 The monomer compound represented by the general formula (1) used in the present invention (hereinafter referred to as the monomer compound of the present invention) is used in the present invention by copolymerizing with another ethylene monomer compound that can be copolymerized with the monomer compound. A latex-forming polymer (hereinafter referred to as the polymer of the present invention). In the polymer of the present invention, along with other copolymerizable ethylenic monomer compounds, the general formula
One or more of the monomer compounds (1) can be used. Other ethylenic monomer compounds copolymerizable with the monomer compound of the present invention that can form the polymer of the present invention include acrylic esters, methacrylic esters, vinyl esters, olefins, styrenes, and glycidyl esters. The polymer of the present invention preferably contains 30% by weight or more of at least one monomer compound selected from the following, as a constituent component, from the viewpoint of compatibility with the hydrophilic colloid layer. More specifically, these monomer compounds include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-propyl acrylate.
-Butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4- Chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2-hydroxy Ethyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso
-Propoxy acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)
Ethyl acrylate, ω-methoxypolyethylene glycol acrylate (number of added moles n = 9),
1-bromo-2-methoxyethyl acrylate,
Examples include 1,1-dichloro-2-ethoxyethyl acrylate. Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate,
tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate,
2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 4-hydroxybutyl 2-hydroxyethyl methacrylate methacrylate,
Triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-
Methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate,
2-iso-propoxyethyl methacrylate, 2
-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-
(2-ethoxyethoxy)ethyl methacrylate,
Examples include 2-(2-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (additional mole number n=6), allyl methacrylate, and dimethylaminoethyl methacrylate methyl chloride salt. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, etc. can be mentioned. Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene,
1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-
Dimethyl butadiene and the like can be mentioned. Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene,
Examples include chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromustyrene, trifluoromethylstyrene, and vinylbenzoic acid methyl ester. Glycidyl esters such as glycidyl acrylate and glycidyl methacrylate can be mentioned. The polymer of the present invention may be copolymerized with ethylenic monomer compounds other than those mentioned above within a range that does not impair the effects of the present invention. Examples of these monomer compounds include acrylamides, acrylic acid, methacrylic acid, crosslinkable Examples include monomer compounds. In the polymer of the present invention, the content of the monomer compound of the general formula (1) of the present invention is preferably 0.1 to 40% by weight, more preferably 0.5 to 30% by weight. When the content of the monomer compound of the present invention exceeds 40% by weight, the hydrophilicity of the polymer of the present invention increases, making it difficult to obtain stability as a latex;
If it is less than , the effects of the present invention cannot be fully obtained. The polymer latex of the present invention can be easily produced by known methods. For example, it can be easily produced by a method of redispersing the polymer of the present invention obtained by emulsion polymerization, solution polymerization, or bulk polymerization (hereinafter referred to as redispersion method). The preferred polymerization method is emulsion polymerization. In the emulsion polymerization method, the reaction temperature is 20 to 180℃,
More preferably at 40-100℃, with water and against water.
10 to 50% by weight of a monomer compound (containing a predetermined ratio of the monomer compound of the present invention and another ethylenic monomer compound copolymerizable with the monomer compound)
This is carried out using 0.05 to 5% by weight of a polymerization initiator and 0.1 to 20% by weight of an emulsifier based on the monomer compound. At this time, the polymerization initiator, concentration, reaction temperature, reaction time, etc. can be varied widely and arbitrarily depending on the purpose. Although the emulsifier can generally be synthesized without using it, it may be used in view of the stability of the resulting polymer latex over time, its compatibility with hydrophilic colloids, etc. Polymerization initiators used in the emulsion polymerization method for polymer latex of the present invention include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, sodium 4,4'-azobis-4-cyanovalerate, , 2'-azobis(2-amidinopropane) hydrochloride and other water-soluble azo compounds, and hydrogen peroxide can be used. The molecular weight of the latex of the polymer of the present invention is 2000.
〜1000000 is preferable, more preferably 5000〜
500000. The particle size is preferably 0.01 to 1 μm, more preferably 0.01 to 0.5 μm. In the present invention, the molecular weight is a value expressed as a number average molecular weight (hereinafter expressed as Mn) in terms of standard polyethylene using gel permeation chromatography HLC-802A [manufactured by Toyo Soda Co., Ltd.], and the particle size is a value measured using Coulter N4 (manufactured by Coulter). Specific representative examples of the polymer latex of the present invention are shown below, but the present invention is not limited thereto. Exemplary polymer latex Typical synthesis examples of the polymer latex of the present invention are shown below. Synthesis example 1 Distilled water degassed with _N2 gas in 1 Kolben 360
ml and raise the temperature to 80℃. To this, 0.27 g of ammonium persulfate dissolved in 5 ml of distilled water was quickly added, and a mixture of 89.1 g of ethyl acrylate and 0.9 g of the monomer compound (M-1) of the present invention was added dropwise thereto over about 1 hour. Stirring was continued for 4 hours to allow reaction. After the reaction was completed, unreacted monomer compounds were removed by steam distillation for 1 hour to obtain the desired polymer latex (L-1). Particle size = 0.05μm, Mn = 100000 Synthesis example 2 360 steamed water degassed with _N2 gas in the Kolben of 1
ml and emulsifier 6g and Add 1.2g and raise the temperature to 80℃. Distilled water 5
ml of ammonium persulfate was quickly added thereto, and a mixture of 80 g of ethyl acrylate and 10 g of the monomer compound (M-2) of the present invention was added dropwise thereto over about 1 hour, and after the dropwise addition was completed, stirring was continued for an additional 4 hours to react. I let it happen. After the reaction was completed, unreacted monomer compounds were removed by steam distillation for 1 hour to obtain the desired polymer latex (1-2). Particle size = 0.11μm, Mn = 150000 Synthesis example 3 Distilled water degassed with _N2 gas in the Kolben of 1 360
ml and raise the temperature to 80℃. Distilled water 5
ml of ammonium persulfate was quickly added thereto, and a mixture of 72 g of butyl acrylate and 13.5 g of the monomer compound of the present invention (M-11) was added dropwise thereto over about 1 hour, and after the dropwise addition was completed, the mixture was further stirred for 4 hours. react. After completion of the reaction, unreacted monomers are recovered by steam distillation for 1 hour, and the mixture is cooled to room temperature to obtain the desired polymer latex (L-14). Particle size: 0.20 μm, Mn=100000 The polymer latex of the present invention can be used in all photographic constituent layers using hydrophilic colloids in silver halide photographic materials, such as silver halide emulsion layers, interlayers, protective layers, antihalation layers, It can be used for back coat layers, etc. The content of the polymer latex of the present invention is preferably 80% by weight or less, more preferably 5% to 50% by weight, based on the hydrophilic colloid, and about 0.01% by weight per m ² .
g to 5.0 g is preferable, more preferably 0.1 g to 1.0 g
It is g. Hydrophilic colloids used in the present invention include:
It is advantageous to use gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, synthetic hydrophilic polymeric substances such as monopolymers or copolymers, etc. Hydrophilic colloids can also be used. In addition to coal-processed gelatin, acid-processed gelatin, Bull.Soc.Sci.Phot.Japan, No. 16,
Enzyme-treated gelatin as described on page 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Gelatin derivatives can be obtained by reacting gelatin with various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds. The one obtained by doing so is used. A specific example is U.S. Patent No.
No. 2614928, No. 3132945, No. 3186846, No. 3186846, No. 3132945, No. 3186846, No.
3312553, U.S. Patent No. 861414, U.S. Patent No. 1033189, U.S. Pat.
It is described in No. 1005784, Special Publication No. 42-26845, etc. Proteins include albumin, casein, etc.
Preferred examples of cellulose derivatives include hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters, and preferred sugar derivatives include sodium alginate and starch derivatives. Examples of graft polymers of gelatin and other polymers include gelatin with acrylic acid, methacrylic acid,
Derivatives such as esters and amides thereof, monomers (homo) or copolymers of vinyl monomers such as acrylonitrile and styrene may be used. Particularly preferred are graft polymers with polymers which are compatible with gelatin to some extent, such as acrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates, and the like. These examples are:
U.S. Patent No. 2763625, U.S. Patent No. 2831767, U.S. Patent No. 2956884
It is written in the number etc. Typical synthetic hydrophilic polymer substances include single or copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole. For example, West German Patent Application (OLS) No. 2312708, U.S. Patent No. 3620751
No. 3879205 and Special Publication No. 7561 of 1973. The silver halide emulsion used in the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver halide,
Any of those used in conventional silver halide emulsions can be used, such as silver chlorobromide and silver chloride. It is preferable to remove unnecessary soluble salts from the silver halide emulsion used in the present invention after the growth of silver halide grains is completed, but they may remain contained. If the salts are removed, research disclosure is required.
It can be carried out based on the method described in No. 17643. The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions. The silver halide emulsion of the present invention can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination. The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that does not have a spectral sensitizing effect by itself, or a strong dye sensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too. In addition to the above-mentioned additives, the silver halide photographic material of the present invention includes matting agents, stabilizers, development accelerators, hardeners, surfactants, anti-staining agents, lubricants,
Various additives useful for photographic materials such as ultraviolet absorbers, formalin scavengers, color couplers, antistatic agents, and others can be used. The support used in the silver halide photographic light-sensitive material of the present invention includes a flexible reflective support such as paper laminated with α-olefin polymer (for example, polyethylene, polypropylene, ethylene/butene copolymer), synthetic paper, etc. Films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, flexible supports with reflective layers on these films, glass, metals, Including pottery etc. Silver halide photographic materials to which the present invention can be used include black and white photosensitive materials such as black and white photosensitive materials for photography, black and white photosensitive materials for X-ray, and black and white photosensitive materials for printing, color reversal films, color negative films, color positive films, etc. Examples include multilayer color photosensitive materials. [Specific Effects of the Invention] As explained above, in the silver halide photographic material of the present invention, at least one group selected from carboxyl groups, sulfonic acid groups, and salts thereof
Since the hydrophilic colloid layer contains a latex of a polymer having a repeating unit derived from an ethylenic monomer compound having two groups and an ethylene oxide chain, there is no aggregation or precipitation in the hydrophilic colloid layer. It has good compatibility with polymer latex, does not cause devitrification, and improves the physical properties of the hydrophilic colloid film, such as dimensional stability, without adversely affecting photographic properties. [Examples] The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 Gelatin aqueous solution 1 containing 100g of gelatin
100 ml of the polymer latex L-1 of the present invention (solid content 20% by weight) was added to the solution, and the state of aggregation after storage at 40° C. for 1 hour and 5 hours was visually determined. The state of aggregation was evaluated in three stages: ◯: no aggregation, △: slight aggregation, and ×: aggregate precipitation. Each of the above polymer latexes L-1 and L-
2, L-3, L-4, L-5, L-10, L-11,
Samples were prepared in the same manner except that L-14, L-16, L-18, comparative polymer latex (A), and comparative polymer latex (B) were used, and the state of aggregation was determined. The results are shown in Table 1. Comparative polymer latexes are the following polymer latexes: Comparative polymer latex (A) (described in Japanese Patent Publication No. 45-5331) Comparative polymer latex (B) (described in JP-A-51-130217)

[Table] As is clear from the results in Table 1, the polymer latex of the present invention has good compatibility with hydrophilic colloids and does not form aggregates. Example 2 4-Hydroxy-6-methyl-1,3,3a,
After adding 7-tetrazaindene and mucochloric acid, the sample was coated on a subbed polyethylene terephthalate support to give a silver content of 50 mg/dm ² to serve as a control sample. Samples 13 to 21 were obtained in the same manner except that each of the polymer latexes shown in Table 2 was added to the control sample in an amount of 5% by weight based on the gelatin in the emulsion. After the above sample was wedge-exposed and subjected to the development treatment shown below, the effects on dimensional stability, scratch strength, devitrification, and photographic performance before and after the development treatment were examined. The results are shown in Table 2. [Processing process] Process Temperature (℃) Time (seconds) Development 30 45 Fixing 25 35 Washing with water 15 35 Drying 45 20 The composition of the developer used is shown below. [Developer composition] Phenidone 0.4g Metol 5g Hydroquinone 1g Anhydrous sodium sulfite 60g Sodium carbonate/H ₂ O 54g 5-nitroimidazole 100mg Potassium bromide 2.5g Add water to 1 and adjust the pH to 10.20. However, the dimensional stability, scratch strength,
The devitrification property and sensitivity are as follows. [Dimensional stability] Dimensional stability is expressed by the rate of change in dimension. The rate of dimensional change is determined by the following formula, where the dimension of an exposed sample with a length of 200 mm is X mm before processing and the dimension after processing is Y mm. Dimensional change rate (%) = ((Y-X)/200) x 100 According to the industry, a dimensional change rate of 0.01% or less is considered to be practically acceptable. [Scratch strength] After developing, fixing, and rinsing in the above processing steps, the film surface was scratched with a weighted metal needle while immersed in the rinsing water, and the minimum weight of the metal needle that caused scratches (scratching strength) was determined. Ta. [Devitrification] A: No decrease in transparency after development B: Slightly milky white C: Slightly milky white A, B, and C were visually judged. Devitrification describes the gelatin compatibility of the polymer latex. [Sensitivity] Measured with a sensitometer model KS-1 manufactured by Konishiroku Photo Industry Co., Ltd.
Sensitivity was expressed as the reciprocal of the exposure amount given at a density of fog + 0.7, and expressed as specific sensitivity with the same-day sensitivity of control sample 1 set as 100. The polymer latexes (A) and (B) are the same as those used in Example 1.

【table】

[Table] As is clear from Table 2, the halogen scratched silver photographic light-sensitive material samples of the present invention have good dimensional stability, no deterioration in photographic properties, and good devitrification properties.

Claims (1)

[Scope of Claims] 1. A silver halide photograph characterized in that at least one hydrophilic colloid layer contains a latex of a polymer having repeating units derived from a monomer compound represented by the following general formula (1). photosensitive material. General formula (1) In the formula, R ₁ represents a hydrogen atom or a methyl group,
R ₂ and R ₃ each have a hydrogen atom and 1 carbon atom
~20 alkyl or aryl groups. However, the total number of carbon atoms in R ₂ and R ₃ is 3 or more.
M represents a cation.