JPS61236541A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having an improved film characteristics of a hydrophilic colloidal layer by incorporating a latex composed of a (co)polymer coming from an ethylenic monomer having a group selected from COOH or SO3H group or a salt thereof, and having an ethylene oxide chain to a hydrophilic colloidal layer. CONSTITUTION:The titled material is prepared by incorporating a polymer latex composed of a homopolymer or a copolymer of a monomer shown by formula I wherein R1 is H or CH3 group, X is -COO- or -CONH- group or a group shown by formula II or III, Z is -SO3- or -COO- group, M is H or a cation, (l) is 1-30, (m) is 0 or 1, (m) is 2, when X is a group shown by formula III, otherwise, (m) is 1, Y is 1-4C alkylene group to the hydrophilic colloidal layer such as a silver halide emulsion layer, an intermediate layer and a protec tive layer etc. By constituting the titled material as mentioned above, the titled material having a less tendency for reducing a transparency after developing the titled material, and having excellent film characteristics such as a dimension al stability, a scratch strength, a pressure proof and a drying of the hydrophilic colloidal layer, is obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material.
The present invention relates to a silver halide photographic material having a hydrophilic colloid layer with improved film properties.

[Background of the Invention] In general, hydrophilic colloids 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 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 made by polymerizing various monomer compounds is conventionally contained in the hydrophilic colloid layer. Various attempts have been made to improve the physical properties of the hydrophilic colloid films formed, such as dimensional stability, scratch strength, flexibility, pressure resistance, and drying properties.

For example, the vinyl acetate polymer latex of U.S. Pat. No. 2,376.005, U.S. Pat. No. 3,325.
Polymer latex of alkyl acrylate of No. 286, n-butyl acrylate of Japanese Patent Publication No. 45-5331,
Polymer latex of ethyl acrylate, styrene, butadiene, vinyl acetate, acrylonitrile, etc., polymer latex of alkyl acrylate, acrylic acid, sulfoalkyl acrylate of Japanese Patent Publication No. 46-22500, 2-acrylamide of Japanese Patent Publication No. 51-130217
Polymer latexes of 2-methylpropanesulfonic acid and the like have been used for the above purpose.

However, when these polymer latexes are mixed with an aqueous solution of gelatin, which is a hydrophilic colloid, or in the presence of salts, some of these polymer latexes tend to aggregate or precipitate, resulting in deterioration of the transparency of the hydrophilic colloid film. Some types of polymer latexes also have drawbacks such as the occurrence of devitrification phenomenon and adverse effects on photographic properties such as sensitivity, fog, gradation, and progress of development. Furthermore, since a large amount of emulsifier is used for dispersing these polymer latexes, this also causes deterioration of the physical properties of the hydrophilic colloid film.

On the other hand, JP-A-54-133324, JP-A-56-1904
No. 3 discloses a polymer latex that can be synthesized by reducing the amount of an emulsifier in addition to being an antistatic agent, but these polymer latexes must simultaneously satisfy good film properties and good gelatin compatibility of the polymer latex. In particular, a polymer latex containing 20% by weight or more of an ethylenic monomer compound having at least one free phosphoric acid group or its salt as described in JP-A No. 54-133324 has poor physical properties of the hydrophilic colloid film. was significantly impaired, and compatibility with gelatin, a hydrophilic colloid, was 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 that 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 polymer having a repeating unit derived from an ethylenic monomer compound having at least one group selected from a carboxyl group, a sulfonic acid group and a salt thereof and an ethylene oxide chain. This was achieved using a silver halide photographic material containing latex in at least one hydrophilic colloid layer.

[Specific Structure of the Invention] The ethylenic monomer compound having at least one group selected from a carboxyl group, a sulfonic acid group, and a salt thereof and an ethylene oxide group used in the present invention is represented by the following general formula (1). Preferred are monomer compounds that can be used in combination.

General formula (1) In the formula, R1 represents a hydrogen atom or a methyl group, and x bar coo-1-CONH-1Y has 1 to 4 carbon atoms.
represents an alkylene group, 2 is -8o3- or -CO
It represents O-, and M represents a hydrogen atom or a cation.

A represents an integer from 1 to 30, I represents O or 1, and n represents each.

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.

In the above general formula (1), Y is preferably a fullkylene group having 3 or 4 carbon atoms, and l is preferably a fullkylene group having 3 to 4 carbon atoms.
It is an integer of 15.

Specific examples of the ethylenic monomer compounds used in the present invention are shown below in the margins.

Exemplary Monomer Compound CHs=CH COO+CHs CHz O+S Os N&C City=C
H COO+CHsCHzO+, 5OsN&CHs=CH C00+CHs CHt OstosOsNaCH1=
CH C00+CHs CHsO”+,, S Os NaC
H2=CH C00Cfi2C) hO+CH2, 5OsNaC mountain=
CH COO+CH2CH20-)+CH2+3SO3NaC
H,=CH COO+CHz CHt 0+-+CHs +4S 0
3NaO CH, -C)i C00+CHzCHsO+1. CH2C)izsOsN
aLVI -9 C city■ CH2= C COO+CHs CHt 0+S Oa NaHs C city=C COO+CH2CHzO+3SOsNaHs C city=C C00+CHz CHt 0+, DS O3N&CH3 C mountain=C COC)+CHt CHt 0+, 5S Os NaC
H3 C1(2=C ” C00+CI(2C) Lt Osu+CHz+s SO
x NaC city 0 Karasu 20C00 (-C) 120H20 force ±CHz +s S O
s Na(-15 Hs ■ CH2=C Coo(-CLC)ho-)dcL, S Os N
ILCH3 Cxin=C COO+CI(2CHt 0+-+CPh9S Os
N&C mountain=011 C0N) (CHzCH20SOaNa CMz=C) (CONH+CH2C)i20+3S Os NaC'k
b = Ckl CONH + CHh CHt 0”r-+ Chie,
S Os N&M-20 M-21 C) Ls CH2=C C0NHCHsCHzO8OsN& C mountain CH2=C CONH+C)h Ckb O+3S 03NaCH3 C) i2=C C0N)1+CHzC)i20S→CHz+3SO3N
aCHz C) Ls ■ CH2=CH CooCH2CH20+CHz+3COONaCle=C
H COO+C)I2CH20+i+CH2+3COONa
CH2=CH ■ C00(-(JI2CH20+-+CHz+4COON
aCHz"'CH COO+CH2CHz O+15CH2CH2COON
aC mountain C&=C COO+CH2C)120++CH2+3COONaC
City CH2=C COO+C11z CH20+-e Ci(z + C
OON&CH3 CHs = C ■ Coo+CHsCHsO+-+CHs+4COONaG CH3 cnz=c COO+CHi CH20+-+CH2+2C00Na
CH2=CH C0NR+CHzCH20+-eCH2+ COONa
CH3 CH2=C C0NH+CH2CFbO+-+CH2+3COONa
M-40 CHs CH2=CM COO+CH2C)i20-+-+C 4COORC
H3 C) 12=C C00 (-C City CF120+i-+C Luna 2COOHC
Hz=CH C00+CH2CH2O force CH ke. 503H-N City C
Hs CHz = C CONH + CH2C) (2USs S Os K An ethylenic monomer compound having an ethylene oxide chain and at least one group selected from a carboxyl group, a sulfonic acid group and a salt thereof used in the present invention (preferably a compound having the general formula The monomer compound represented by (1) (hereinafter referred to as the monomer compound of the present invention) is copolymerized with another ethylenic monomer compound copolymerizable with the monomer compound to form a latex used in the present invention (hereinafter referred to as the monomer compound of the present invention). polymer).

In the polymer of the present invention, one or more monomer compounds of the general formula (1) can be used together with other copolymerizable ethylenic monomer compounds.

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 at least 30% by weight 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 are as follows:
Examples of acrylic esters include methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 5ea-butyl acrylate, t
ert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanethyl acrylate, 2- Acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 5-hydroxypentyl Acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-
Methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-+SOS Bupoxy acrylate, 2-
Butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate-1 to (number of moles added n-9), 1-bromo-2 -methoxyethyl acrylate, 1.1-dichloro-2-ethoxyethyl acrylate, and the like.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 5ec-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, talesyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-
7cetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxy ethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (number of moles added n-
6), allyl methacrylate, methacrylic acid dimethylaminoethyl methyl chloride salt, and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate, etc. Can be mentioned.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-7tene, 1-pentene,
Examples include vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromstyrene, trifluoromethylstyrene, vinyl Examples include benzoic 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, it is 0.5 to 30% by weight.

The content of the monomer compound of the present invention is 40f! If the amount exceeds %, the hydrophilicity of the polymer of the present invention will increase, making it difficult to obtain stability as a latex, and if the amount is less than 0.3%, the effects of the present invention may not be sufficiently obtained.

The polymer latex of the present invention can be easily produced by a known method. 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°C, more preferably 40 to 100°C, and water and
~501111% monomer compound (containing the monomer compound of the present invention and other ethylenic monomer compounds copolymerizable with the monomer compound in a predetermined ratio) and 0.05 to 5% by weight based on the heptamer compound. Polymerization initiator and 0.1
-20% by weight of emulsifier. 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;
Water-soluble azo compounds such as sodium azobis-4-cyanovalerate and 2,2'-azobis(2-amidinopropane) hydrochloride, and hydrogen peroxide can be used.

The molecular weight of the latex of the polymer of the present invention is from 2.000 to
1,000,000 is preferred, more preferably s, o
oo~soo, ooo. Particle size is 0.01~1μ
a+ is preferred, and more preferably 0.01 to 0.5μ.

In the present invention, the molecular weight is determined by gel permeation chromatography HLC-802A [Toyo Soda Co., Ltd.
The value is expressed as the number average molecular weight (hereinafter referred to as Mn) in terms of standard polyethylene using Coulter N4.
(manufactured by Coulter).

Specific representative examples of the polymer latex of the present invention are shown below in the margins, but the present invention is not limited thereto.

Exemplary polymer latex COOCdb C00CHsC&O5OsNa
x:y=99:I Mn=100,000 COOCzHs COO+CHzCkbO+
, 5OsNax:y=89:11 Mn=110,000 x:y=90:10 Mn=80.00O X:y=95:5 84n=72.00O CHs x : y = 95 : 5 Mn = 80,000 C) (3 ■ x : y = 90 : 10 Mn = 70,000 x : y = 95 : 5 Mn = 91,000 X:) F = 99: I Mn = 77,000 x: '! : Z ;== 40 :
40: 20Mn-=70.00O x: y = 70: 30 Mn=110.000 C city 0+CH2CHsO square C city ÷ 1sOaNjx:y=
90:10 Mn=87,000 X:y=99:I Mn=99,000 COOCzHs C00+CB(2CH20+3
+CHx+, C00Nax:y=90:10 Mn=60,000 X:y=95:5 Mn=91,000 X:y=90:10 Mn=76.000 C) La x:y=90:10 Mn= 76,000 L-18 x:y:z=40:40:20 Mfl=63. OOO CHsO(-CHsC%0-ic& 9C■Nax:y
e=90:10 Mn=100.000 x:y=90:10 Mn=77.000 C) (!0+CH,CH+V+”IIs +s C
00Hx:y=95:5 Mn=120.00O *-COOH x:y:z=80:15:5 Mn=94,000 COOCzHs COO+C 5 Mn = 113,000 x : y = 90 : 10 Mn = 78,000 Typical synthesis examples of the polymer latex of the present invention are shown below.

Synthesis Example 1 Distilled water degassed with N2 gas in 11 Kolben asos
1 and raise the temperature to 80°C. Distilled water 51% to this]
Immediately add 0.2713 g of ammonium persulfate dissolved in , to which 89.1 g of ethyl acrylate and 0.271 g of the monomer compound of the present invention (M-1) are added. About 1 h of the mixture
The mixture was added dropwise over a period of time, and after the completion of the addition, the mixture was stirred for an additional 4 hours to allow the reaction to continue. 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 -0,07μrp, Mn -100,00
0 Synthesis Example 2 Distilled water degassed with N2 gas in a 1f Kolben
Island 3eosR and emulsifier (a-3) 6g and (n-
4) Add 1.2g and raise the temperature to 80°C. To this was quickly added 0.27 g of ammonium persulfate dissolved in 5 kg of distilled water, and about 1 g of a mixture of 809 ethyl acrylate and 10 g of the monomer compound (M-2) of the present invention was added thereto.
The mixture was added dropwise over a period of time, and after the completion of the addition, the mixture was stirred for an additional 4 hours to allow the reaction to continue. After the reaction was completed, unreacted monomer compounds were removed by steam distillation for 1 hour to obtain the desired polymer latex (L-2).

Particle size -0.10, czw, Mn -110.0
00 Synthesis Example 3 Distilled water degassed with N2 gas in 1β Kolben 360
11 and raise the temperature to 80°C. Add 5j of distilled water to this
! Add 0.27Q of ammonium persulfate dissolved in
A mixture of 4.5 g of the monomer compound (M-5) of the present invention was added dropwise over about 1 hour, and after the addition was completed, the mixture was further stirred for 4 hours to 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-5).

Particle size 0.10 μm, Mn -140,000
The polymer latex of the present invention can be used in all photographic constituent layers using hydrophilic colloids of silver halide photographic light-sensitive materials, such as silver halide emulsion layers, intermediate layers, protective layers, antihalation layers, back coat layers, etc. .

The polymer latex of the present invention is preferably 80% by weight or less, more preferably 5% by weight or less based on the hydrophilic colloid.
50% by weight, about o, oig to 5. O
g is preferable, more preferably 0.1 g to 1. It is OQ.

As the hydrophilic colloid used in the present invention, it is advantageous to use gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, other proteins,
Hydrophilic colloids such as sugar derivatives, cellulose derivatives, synthetic hydrophilic polymeric substances such as monopolymers or copolymers can also be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, Phot,
.

Enzyme-treated gelatin as described in Japan, No., p. 16.30 (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. Specific examples are U.S. Patent Nos. 2,614,928, 3,132,945, 3,186,846, and
, No. 312,553, British Patent No. 881,414, No. 1
, No. 033, 189, No. 1, 005, 784, and Japanese Patent Publication No. 42-26845.

Proteins include albumin, casein, etc. Cellulose derivatives include hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, etc.
As the sugar derivative, sodium alginate and Den 6 derivatives are preferred.

The graft polymer of gelatin and other polymers may be a single (homo) or copolymer of vinyl monomers such as gelatin, acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. A grafted material can be used. In particular, polymers which are compatible to some extent with gelatin, such as acrylic acid, acrylamide, methacrylamide,
Graft polymers with polymers such as hydroxyalkyl methacrylates are preferred. Examples of these are U.S. Pat.
．． No. 956,884, etc.

Typical synthetic hydrophilic polymer substances include polyvinyl alcohol, polyvinyl alcohol partial acetal, and poly-N-
Single or copolymers of vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc.
For example, West German patent application (OLS) 2,312,7
No. 08, U.S. Patent No. 3,620.751, U.S. Patent No. 3,87
No. 9,205 and Japanese Patent Publication No. 43-7561.

The silver halide emulsion used in the present invention includes any silver halide used in conventional silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. You can use the following.

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. When removing the salts, please refer to Research Disclosure t--(Res.
This method can be carried out based on the method described in 17643 (Each D 1 Closure) 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. Sensitizing dyes may be used alone, but
You may use two or more types in combination. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, 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 also contains matting agents, stabilizers, development accelerators, hardeners, surfactants, anti-staining agents, lubricants, ultraviolet absorbers, and formalin scavengers. -, color couplers, antistatic agents, and various other additives useful for photographic materials can be used.

The support used in the silver halide photographic material of the present invention includes α-olefin polymers (e.g. polyethylene,
Flexible reflective supports such as paper laminated with polypropylene (polypropylene, ethylene/butene copolymer), synthetic paper, etc., semi-synthesis or synthesis of cellulose acetate, cellulose nitrate, Boristyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. Examples include films made of polymers, flexible supports provided with reflective layers on these films, glass, metals, ceramics, and the like.

Silver halide photographic materials to which the present invention can be used include black-and-white photographic materials, black-and-white photographic materials for X-ray, black-and-white photographic materials such as black-and-white photographic materials for printing, color reversal films, color negative films, color positive films, etc. Examples include multilayer color photosensitive materials.

[Specific effects of light] As explained above, in the silver halide photographic light-sensitive material of the present invention, an ethylenic material having at least one group selected from a carboxyl group, a sulfonic acid group and a salt thereof and an ethylene oxide chain is used. Since the hydrophilic colloid layer contains a latex of a polymer having a repeating unit derived from a heptamer compound, there is no aggregation or precipitation in a counterfeit hydrophilic colloid, and the compatibility between the hydrophilic colloid and polymer latex is good and there is no loss. It was possible to improve the physical properties of the hydrophilic colloid film, such as its soot stability, without causing any seepage phenomenon and without adversely affecting the photographic properties.

[Example] The present invention will be described in detail below using a practical example, but the embodiment of the present invention is not limited to these examples.

Example 1 Gelatin aqueous solution 10 containing 100 g of gelatin was
Polymer latex L-1 of the present invention (solid content 2 ori
a%>1oomt After all processing and storage at 40° C. for 1 hour and 5 hours, the agglomeration state was visually determined. The aggregation state is O
Evaluation was performed in three stages: : no aggregation, Δ: slight aggregation, and ×: aggregate precipitation.

The above polymer latex L-1 is used as L-2 and L-, respectively.
3, L-4, L-6, L-8, L-10°L-12, L
Samples were prepared in the same manner except that -30, L-35, Comparative Polymer Latex (A), and Comparative Polymer Latex (8) were used, and the state of aggregation was determined. The results are shown in Table 1.

Comparative polymer latexes are the following polymer latexes:

The following margins are comparative polymer latex (A) (described in Japanese Patent Publication No. 45-5331) +CH, -CH-) C00CzHa Mn=110.000 Comparative polymer latex (B) (described in Japanese Patent Publication No. 45-18415) x:y=90: 10 Mn=91,000 Table 1 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 in a silver iodobromide gelatin emulsion containing 3 mole percent silver iodide.

After adding 7-titrazaindene and mucochloric acid, the sample was coated onto a subbed polyethylene terephthalate support to give a silver content of 50 no/da' to serve as a control sample.

The polymer latex shown in Table 2 was added to the above control sample for each gelatin in the emulsion at 5I! Samples 13 to 22 were obtained in the same manner except that 1% by amount was added.

After the above sample was exposed to wedge light 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 ('C) Time (seconds) Development 3o 45 constant 11
25 35 Wash with water
1 5 - 3 5 drying
The composition of the developer used in 452° is shown below.

[Developer composition] Phenidone 0.4g Metol 5g Hydroquinone
1g anhydrous sodium sulfite
60 Q Sodium carbonate/H2O540 5-nitroimidazole 100mg Potassium bromide 2.5g Add water to make 1g and adjust to pl-110,20.

However, the dimensional stability, scratch strength, devitrification properties shown in Table 2,
The sensitivity is 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 cm before treatment is Xll+, and the dimension after treatment is YllIll.

According to the industry, a dimensional change rate of 0.01% or less is considered to pose no practical problem.

[Scratch strength] After developing, fixing, and rinsing in the above processing steps, the film surface is scratched with a weighted metal needle while immersed in the rinsing water, and the minimum weight of the metal needle that causes scratches (scratching strength) is 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 refers to the gelatin compatibility of the polymer latex.

[Sensitivity] Measured with Konishiroku Photo Industry Co., Ltd. 1 sensitometer KS-1 model. The reciprocal of the exposure amount given at a density of fog+0.7 was defined as the sensitivity, and the same-day sensitivity of control sample 1 was taken as 100, and the sensitivity was expressed as a specific sensitivity.

Note that polymer latex (A) and (8) are the same as those used in Example 1, and polymer latex (C
) has the following structure as described in Example 1 of JP-A-51-130217.

Table 2 Holimer 5 Te, 77, ζ() Mr+'95,000 As is clear from Table 2, the silver halide photographic light-sensitive material samples of the present invention have good dimensional stability and no deterioration in photographic properties. It can be seen that it has good devitrification.

Patent applicant Konishiroku Photo Industry Co., Ltd. Representative Patent Attorney Miyao Ichinose 1. ....

Procedural Minister 1 Official Paper (spontaneous) July 11, 1985

Claims (1)

[Claims] A latex of a polymer having a repeating unit derived from an ethylenic monomer compound having at least one group selected from a carboxyl group, a sulfonic acid group, and a salt thereof and an ethylene oxide chain.
1. A silver halide photographic light-sensitive material containing a hydrophilic colloid in two hydrophilic colloid layers.