JPS6353543A - Silver halide photographic sensitive material preventing sweating phenomenon and formation of static mark - Google Patents

Abstract

PURPOSE:To prevent the formation of static marks without causing a sweating phenomenon by using a polymer derived from repeating units of a monomer having at least one of specified UV absorbing groups. CONSTITUTION:A polymer derived from repeating units of a monomer having at least one of UV absorbing groups represented by formulae I, II, III, etc., is used. In the formula I, R<1> is an aliphatic group or aryl, each or R<2>-R<5> is H, aliphatic group or aryl, Y<1> is O, S or the like, and each of V<1> and W<1> is H, -CN or the like. In the formulae II, III, R<13> is an aliphatic group or aryl, each of R<14>, R<14>', R<15> and R<15>' is H or an aliphatic group, R<14> and R<15> may bond with each other to form a benzene or naphthalene ring, Y<2> is O, S or the like, and each of V<2> and W<2> is -CN, -COR<17> or the like.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to silver halide photographic material F4 (hereinafter referred to as "photosensitive material"), and in particular, the surface quality can be improved by containing a polymer ultraviolet absorber. This invention relates to a photographic material with improved static marks and without the adverse effects of.

[Background of the Invention] Photographic materials are made by coating a light-sensitive photographic emulsion on a support with relatively high electrical insulation, such as polyethylene terephthalate film or laminated paper coated with polyethylene. During the manufacturing process, during use, etc., the accumulation of electrostatic charge causes sparks to be generated due to air discharge, and after the development process, various image defects such as dendritic marks, so-called static marks, are produced, which reduces the product value. may cause significant damage.

Conventionally, ultraviolet absorbers have been used, especially in the range of 300 to 400nff.
Attempts have been made to prevent the generation of static marks by blocking ultraviolet light.

As ultraviolet absorbers, we use
No., JP-A-53-97425, JP-A No. 53-133033
No. 53-131837, No. 53i34431, No. 59-10944, R10, 18032, JP 54-18727, British Patent No. 2, 083.239
No. 2.083,240, JP-A-53-1296
33, British Patent No. 2.083.241, British Patent No. 1,1
No. 98,337, West German patent issue M (OLS) 2
, No. 118,798 was added, but
It has been found that the static prevention effect is insufficient and that a sweating phenomenon occurs in which oil-like substances or powdery crystal-like substances appear on the surface of photographic light-sensitive materials.

[Object of the Invention] An object of the present invention is to provide a photographic material that does not cause the sweating phenomenon and prevents the generation of static marks.

[Structure 1 of the Invention] As a result of intensive research to achieve the above object, the present inventors have developed a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, which has the following general formula [ I], [IIa, [nb], [II[], [IV
It has been found that the above objects can be achieved by a silver halide photographic light-sensitive material containing a polymer derived from a single repeating unit having at least one UV-absorbing group selected from Ta.

General formula [I] [wherein R1 represents an aliphatic group or an aryl group, R2
, R3, R4 and R5 each represent a hydrogen atom, an aliphatic group or an aryl group.

Yl represents an oxygen atom, a sulfur atom, an ethylene group or a methylene group.

■1 and Wl are hydrogen atoms, -CN, -COR6, respectively
, -COOR7, -8○2R8, where R6, R7 and Ra each represent an aliphatic group or an aryl group,
R9, RIO, RI+ and R12 each represent a hydrogen atom, an aliphatic group or an aryl group, and R9 and RTo and R11 and R12 may be bonded to each other to form a ring. However, at least one of R1, R2, R3, R4, R5, Vl and WI (7) is bonded to the polymerizable group.

General formula [IIa] General formula [111)]c In the formula, R13 represents an aliphatic group or an aryl group. R special,
R147, R45 and R15' each represent a hydrogen atom, an aliphatic group or an aryl group. R1 and R15 may be bonded to each other to form a benzene ring or a naphthalene ring.

vinegar.

V2 and W2 are -CN, -COR17, -G, respectively
OOR18, -8○2Rno, where R''+7, R18 and R19 each represent an aliphatic group or an aryl group, and R, R, R and R2J each represent a hydrogen atom, an aliphatic group or an aryl group. where R2Q and R2/ and R22- and R23 represent nonmetallic atomic groups necessary to form them. However, R13, R14
, R15, V2 and W2 are bonded to a polymerizable group.

General formula [ll11 2 condolence 25″ 9 2ri :2
? [In the formula, R, R, R, R and R are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an alkylami LL arylamim L hydroxy group, Cyam L represents an acylamino group, carbacyl group, acyl group, sulfonyl group, sulfamoyl group, sulfonamide group, acyloxy group or oxycarbo21+ λ9 2Δ, 2cnyl group, R and R, R (R and R29 and 1 are each bonded to each other) A 5- to 6-membered ring may be formed.

Z2 represents a group of nonmetallic atoms necessary to form a 5- or 6-membered acidic keto ring.

R2″, R2s″, R:L6, R2″′, R” and U
l 2(f) Small: i At least one is bonded to a polymerizable group.

General formula [IV] First 30 31 31 33 3g [In the formula,
R, R, R, R, R, R, 3 and 39 R, R, R and R9 are each hydrogen atom, halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group , amino group,
alkylamino group, arylamino group, hydroxy group,
Represents a cyano group, acylamino group, carbamoyl group, acyl group, sulfonyl group, sulfamoyl group, sulfonamido group, acyloxy group or oxycarbonyl group, R
: L9 and R30, R3' and R22, R3L and R33, R
36 and R3'7, R" and R" and R' and "4.t sot
L may be bonded to each other to form a 5- to 6-membered ring.

R3' and R35'' each represent a hydrogen atom, an alkyl group or an aryl group.

However, R29, R30, R3j, R32, R33, R3
'h, R35'', R3ζ, R3Q, R', R3? and R
At least one of O bonds with a polymerizable group.

General formula [V] [wherein ψ' is a hydrogen atom, an acyl group, a carbamoyl group,
Represents an aliphatic group or an aryl group. R9, R43 and R
44 is a hydrogen atom, a halogen atom, an alkyl group,
Aryl group, acyl group, sulfonyl group, alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
It represents an amino group, an alkylaminocarbamoyl group, an arylamino group, a hydroxyl group, a cyanoacylamino group, a sulfamoyl group, a sulfonamide group, an acyloxy group, or an oxycarbonyl group.

At least one of R4+, R+2, R43 and R44 is bonded to a polymerizable group.

[Specific structure of the invention] General formula [E], [IIa], [IIb], [1]
The ultraviolet absorbing groups represented by No. 111, [IV] and [V] will be explained.

The general formula [I], CIIa ], [IIb ], [1
The aliphatic groups represented by R1 and R13 in [[], [rV] and [V] may be saturated or unsaturated, preferably have 1 to 10 carbon atoms, and may have a substituent. , specifically unsubstituted alkyl groups such as methyl, ethyl, n-pentyl, isohexyl, 2-hydroxypropyl, benzyl, phenethyl, ethoxycarbonylethyl, methoxyethoxyethyl, 2.3.3-tetrafluoropropyl, allyl. The following groups are mentioned. Examples of the aryl group represented by R1 and RI3 include phenyl, p
-Tolyl and other groups can be mentioned.

The aliphatic group represented by R41 may be saturated or unsaturated,
Preferably, it is a straight chain, branched or cyclic type having 1 to 10 carbon atoms, and may have a substituent. Specific examples include unsubstituted alkyl groups such as methyl, ethyl, 2-ethylhexyl, and cyclohexyl; Examples include groups such as 2-hydroxypropyl, benzyl, ethoxycarbonylethyl, and furyl.

Examples of the aryl group represented by R41 include phenyl, tolyl, etc.; examples of the acyl group include acetyl, benzoyl, etc.; examples of the carbamoyl group include methylcarbamoyl, dimethylcarbamoyl, etc. .

R2, R3, R4, R5, Re, R7, R'', Re
, RIO, R11, RI2, RI4, R16, R47
, R18, R+9, R20, R21, R22 and R23
The aliphatic group represented by is an alkyl group having 1 to 20 carbon atoms, and may have a substituent. Specifically) methyl, ethyl, °C-butyl, 2-ethylhexyl, 5e
unsubstituted alkyl groups such as c-dodecyl, and hydroxyethyl, benzyl, carbamoylmethyl. Furthermore, examples of aryl groups include phenyl, D-tolyl, ■-aminophenyl, p-methoxyphenyl, p-
Examples include groups such as -dodecyloxyphenyl and m-ethoxycarbonylphenyl.

R9 and R10, R11 and R+2. , R'' and R2' and R
Examples of the ring formed by combining 22 and R23 include rings such as morpholine, piperidine, and pyrrolidine.

The benzene ring or naphthalene ring formed by combining R+4 and R15' may have a substituent, and examples of substituents include fluorine, chlorine, etc. atoms, methyl, methoxy, phenyl, carbamoyl, methanesulfonyl. , carboxy, human Ooxy, phenyloxy, and the like.

Examples of the alkyl group represented by R46, R34- and R35'' include methyl, ethyl, benzyl and the like.

Examples of the aryl group represented by R34 and R35'' include groups such as phenyl and p-tolyl.

Examples of the halogen atom represented by R~Rη, Rλ9~R33, R3≦~R, Rku~R" include fluorine, chlorine, bromine, etc. Examples of the alkyl group include methyl, Examples of aryl groups include groups such as ethyl, n-propyl, methoxyethyl, droxyethyl, chloropropyl, benzyl, cyanoethyl, and carboxyethyl. Examples of aryl groups include phenyl, tolyl, mesityl, and chlorophenyl groups, and alkoxy groups. Examples are methoxy,
Groups such as ethoxy, octyloxy, 2-ethylhexyloxy, and methoxyethoxy; examples of aryloxy groups include phenoxy and 4-methylphenoxy; examples of alkylthio groups include methylthio and propylthio; Examples of arylthio groups include phenylthio group,
Examples of alkylamino groups include methylamine, dimethylamino, ethylamino, benzylamino, diallylamino, and cyanoethylamino; examples of arylamino groups include anilino, anisidine, toluidino, diphenylamino, and acylamino groups. Examples of groups include acetylamino, benzoylamino, etc., carbamoyldimethylcarbamoyl, etc., acyl groups include acetyl, benzoyl, etc., and sulfonyl groups include methylsulfonyl, phenylsulfonyl, etc. Each group,
Examples of sulfamoyl groups include ethylsulfamoyl,
Examples of groups such as dimethylsulfamoyl, examples of sulfonamide groups include methanesulfonamide and benzenesulfonamide, examples of acyloxy groups include acetoxy and benzoyloxy, and examples of oxycarbonyl groups. Examples include groups such as methoxycarbonyl, ethoxycarbonyl, and phenoxycarbonyl.

R24 and R5, R2g R29, R2'7 R3, R
29 To R30, R31 and R32, R31 and R33, R3
Groups formed by bonding 6 and R39, R3Q and R2H, and R' and R2O include methylenedioxy, tetramethylene, trimethylene, and the like.

The 5- or 6-membered acidic keto ring formed by zl and z2 includes a 1,3-indanedione nucleus, a barbylic acid nucleus (
For example, barbylic acid, 1-phenylbarbylic acid,
1-methyl-3-octylbarbic acid, etc.), 2-
Thiobarbylic acid nuclei (e.g. 2-thiobarbylic acid, 1-ethyl-3-decyl-2-thiobarbylic acid, etc.), cyclohexane-1,3-dione nuclei (e.g. dimedone-5,5-diethylcyclohexane-1,3-dione, etc.) ), 2,4-diaza-1-alkoxy-3,5-
Dioxocyclohexene cough (e.g. 2,4-diaza-1
-ethoxy-4-[3-(2°4-di-tert-amylphenoxy)propyl]-3,5-dioxocyclohexene, etc.), 2,4-thiazolidinedione nuclei (e.g., 3
-phenyl-2゜4-thiazolidinedione, 3-(2-
hydroxyethyl)-2,4-thiazolidinedione, 3
-amino-2,4-thiazolidinedione, etc.), 2-iminothiazolidin-4-one nucleus (e.g. 2-phenyliminothiazolidin-4-one, 3-), 12-2-decyliminothiazolidin-4-one, 3 -ethyl-2-[
2° 4-oxazolidinedione nucleus (e.g. 3-ethyl-2,4-oxazolidinedione, 3-phenyl-2
, 4-oxazolidinedione, etc.), 2-iminooxazolidin-4-one nuclei (e.g. 3-ethyl-2-iminooxazolidin-4-one, 3-phenyl-2-ethyliminooxazolidin-4-one, 3-ethyl- 2-Phenyliminooxazolidin-4-one, 3-ethyl-
2-[3-di-tert-amylphenoxy)propylimino-1oxazolidin-4-one, etc.),
2-iminoimidazolidin-4-one nucleus (e.g. 2-imino-1,3-diethylimidazolidin-4-one, 2
-Decylimino-1-ethyl-3-)-dilimidazolidin-4-one, 2-phenylimino-1-phenyl-
3-cyclohexylimidazolidin-4-one, 1.3
-diethyl-2-[3-(2,4-di-tert-amylphenoxy)propylimino 1thiazolidin-4-one, etc.), isoxacilone nucleus (e.g. 3-phenyl-
5-isoxacilone, 3-methyl-5-isoxacilone, etc.).

The silver halide photographic light-sensitive material of the present invention has the general formula [
I], [lIa], [IIb], [■1, [rV]
It contains a polymer (hereinafter referred to as the polymer of the present invention) derived from a monocyclic repeating unit having at least one ultraviolet absorbing group selected from the ultraviolet absorbing groups represented by [V] and [V], but preferably the following: - A polymer derived from a single repeating unit represented by the general formula [VI].

General formula [VI] CH2-C-X-<A)-(U)-Q7L
In the formula, R is a hydrogen atom or carbon? 111-4 represents an alkyl group or a halogen atom, × is 10 〇 N H--C
OO- or phenylene group, A has 1 to 20 carbon atoms
represents an alkylene group or an arylene group having 6 to 20 carbon atoms, and U represents -COO-1-OCO-1-CONH-1-
NHCO-1-802NH-1-NHSO2-1-3
It represents O2- or -0-, Q represents the above-mentioned ultraviolet absorbing group, and m and n each represent O or 1.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R include methyl, ethyl, n-propyl, and isopropyl, and examples of the halogen atom include fluorine and chlorine atoms.

Examples of the alkylene group having 1 to 20 carbon atoms represented by A include groups such as methylene, ethylene, trimethylene, 2-hydroxytrimethylene, hexamethylene, and 3-oxapentamethylene; An example of an arylene group is a phenylene group.

The polymer of the present invention may be a homopolymer of a monomer having an ultraviolet absorbing group, a copolymer of two or more of the monomers, or a combination of the monomer and a monomer having no ultraviolet absorbing group. It may also be a copolymer of

In the case of a copolymer, examples of the comonomer having no ultraviolet absorbing group include acrylic acid, α-chloroacrylic acid, α-alacrylic acid (for example, esters derived from acrylic acids such as methacrylic acid, preferably Lower alkyl esters and amides such as acrylamide, methacrylamide, t-butylacrylamide, methyl acrylate, methyl methacrylate, n-butylacrylate, 2-ethylhexyl acrylate and lauryl methacrylate, methylenebisacrylamide, etc.), vinyl esters (e.g. (vinyl acetate and laurate, etc.), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (such as styrene and its derivatives, such as vinyltoluene, divinylbenzene, vinyl acetophenone, sulfostyrene and styrene sulfinic acid, etc.), itaconic acid, citraconic acid , crotonic acid, vinylidene chloride, vinyl alkyl ether (for example, vinyl ethyl ether chopsticks), maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and 4-vinyl and lysine, etc. .

Among these, acrylic esters, methacrylic esters, and aromatic vinyl compounds are particularly preferred.

Two or more of the above comonomer compounds can also be used together.

Representative examples of the compound represented by the general formula [VI] of the present invention are shown below.

Example: 1 Yu 1 blindness satel, s H3 C,H.

18)F one) vinegar H6 1v two) $ Book CH, CH20CH+ vinegar Specific examples of the polymer of the present invention are shown below.

Exemplified polymers P-1 to P-35: Homopolymer copolymer of exemplary monomers 1) to 35) Monomer molar ratio P-36
Exemplary monomer 1): MMA 6:4P-37 Exemplary monomer 3): BA 5:5P-38 Exemplary monomer 5)=
BA 6:4P-39 Exemplary Single Unit 8): BA
5:5P-40 Exemplary Monomer 14):ST:MMA6
:1 :3 P-41 Exemplary Monomer 16) :MMA :AA5:3
．． 9: o, 1 P-42 exemplified monomer 18):ST:APS6:3:1 P-43 exemplified l1ffi form 22):MMA 6:4P
-44 exemplified monomer 26):VA:BA6:1:3 P-45 exemplified ratio Mt body 27):BA 5:5P-4
6 Exemplary Monomer 34): MA 6:4 MMA-methyl methacrylate, BA-n-butyl acrylate, ST-styrene, AA-acrylic acid, APS-2-acrylamido-1-propanesulfonic acid Na1vA-vinyl acetate, MA- Methyl acrylate Next, typical synthetic examples of the monomers and polymers of the present invention will be shown.

Synthesis Example 1 Exemplary monomer 5) is dissolved in a synthesis tank 600d and refluxed. 55 g of ethylene iodide was dropped into this over 2 hours. After the dropwise addition, the reaction was continued for 6 hours and then cooled to air temperature. After this addition, reflux again. After 5 hours of reaction, acetonitrile was distilled off, cooled to 60°C, methanol 600g, isopropanol 30t
Add h12 and dissolve. Cool with water, cause crystallization, and collect the precipitate by filtration.

23g of this compound and CH2-CHCOOCH2CH20
COCH2CN40Q, acetonitrile 6501 in which 2 g of hydroquinone and 131 g of triethylamine were dissolved.
In addition to β, acetic anhydride 1339 is added to this mixture at 50°C.

After dropping, the mixture was allowed to flow rapidly for 2 hours and cooled to room temperature to form a precipitate. This precipitate was recrystallized from acetonitrile, and the target product 25
I got g.

The structure was confirmed by IR and NMR.

Synthesis Example-2 Synthesis of Exemplified Monomer 8) Synthesis Example 1 CH2=CHCOOCH2CH2O to =C
25 g of the target product was obtained in the same manner as in Synthesis Example 1 using H20COCH2CN. It was confirmed by IR and NMR that it was the desired product.

megnol λ,, 393rv.

Synthesis Example-3 Synthesis of Exemplified Monomer 16) CλH! : Add 280 to 400 tJ2 of acetonitrile in which 0.5 g of hydroquinone monomethyl ether has been dissolved, add triethylamine 13 (l) dropwise, and react with stirring for 2 hours. Add ether to precipitate, and recrystallize the resulting crystals from ethanol to obtain the desired product. 10g of compound was obtained.Structure is IR,N
Confirmed with MR.

2-methoxyethanol TQO in which 0.5 (] of hydroquinone monomethyl ether is dissolved in deprivation-CH○ 20Q
Flow in tN and add methylamine.

After refluxing for 1 hour, the mixture was cooled to room temperature and the resulting precipitate was recrystallized from ether to obtain 5 g of the desired product.

The structure was confirmed by IR and NMR.

AcH3cN374na.

Blade 4X Synthesis Example 5 Exemplary monomer 27) was dissolved in Dorofuran 3001β and kept at 0 to 5°C. Slowly drop 20 (l) of triethylamine there.

After completion of the dropwise addition, the mixture was reacted for 2 hours, and the resulting salt was filtered. Tetrahydrofuran was distilled off from the filtrate under reduced pressure, and the resulting crystals were recrystallized from ethanol to obtain 629 of the desired product.

Synthesis Example-6 Synthesis of Polymer P-5 tcH2CH2CH2SO3Na 10! It Iri
50011 aqueous solution was deoxidized through a nitrogen stream.
Heat to 0°C. Add 350 g of potassium persulfate to this aqueous solution.
A 201 g aqueous solution of 1.0 mg was added. Next, exemplified monomer 5)
509 was dissolved in ethanol 200xR and added.

After addition, stirring was continued for 1 hour, and 15% of potassium persulfate was added.
Add 0 mg of 1011 aqueous solution and react for 1 hour.

After the reaction was completed, ethanol was distilled off as an azeotrope of water, and the I)H was adjusted to 6.0 with 0.1N sodium hydroxide, followed by filtration. The polymer concentration of the latex was 7.2%.

Synthesis Example-7 Synthesis of Polymer P-39 Sodium dodecylbenzenesulfonate 10 (500d of I)
The aqueous solution is heated to 80° C. while being deoxidized through a nitrogen stream. Add 350 mg of potassium persulfate to this aqueous solution.
g aqueous solution was added. Next, 601:l of exemplified monomer 8) and 20 g of n-butyl acrylate were heated and dissolved in 150 d of ethanol and added. After the addition, stirring was continued for 1 hour, and 250 mg of potassium persulfate was added.
After reacting for 1 hour, ethanol and unreacted monomers were distilled off as an azeotrope of water to give 0. 6.1) H with IN sodium hydroxide. Of: Filtered after adjustment.

The polymer concentration of the latex was 10.2%, and the exemplified monomer 8
) unit's spending was 50 mol%.

Synthesis Example 8 Synthesis of Polymer P-41 Exemplary monomers 8) 60 and 11 in Synthesis Example 7 were replaced with exemplified monomers 16) 40a, and 20 g of n-butyl acrylate were replaced with 8 g of methyl methacrylate and acrylic acid 19. Polymer P-41 was obtained using the same base as synthetic PA7. The polymer concentration of the latex was 6.6%, and the content of exemplified single m units was 60 mol%.

Synthesis Example-9 Synthesis of Polymer P-43 Exemplary Monomer 22) 70g and methyl methacrylate 10f
Dissolve 1 liter in 1501 g of dioxane, and dissolve under nitrogen stream for 70 minutes.
270 mg of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in dioxane 5112 was added to the mixture while heating and stirring at <RTI ID=0.0>C,</RTI> followed by reaction for 4 hours. After the reaction was completed, the reaction solution was cooled to room temperature, poured into ice water 21, and the precipitated solid was collected by filtration.

This solid was a polymer containing 60 mol % of units of the exemplified monomer 22).

A latex was produced using this polymer as follows.

5 g of polymer was dissolved in 20112 ethyl acetate at 38°C and 70 g of sodium dodecylbenzenesulfonate was added.
Add wt% methanol solution. Next, this was mixed with a 10% by weight aqueous gelatin solution 700 and dispersed using a double cylindrical disperser, and then ethyl acetate and methanol were distilled off under reduced pressure to prepare a latex.

Synthesis Example-10 Synthesis of Polymer P-45 70g of Exemplified Monomer 22) of Synthesis Example-9 was added to Exemplified Monomer 27
) 60 (l), a polymer was synthesized in the same manner as in Synthesis Example 1, except that 10 g of methyl methacrylate was replaced with 20 g of n-butyl acrylate, and a latex was also made. It contained 50 mol%.

Synthesis Example-11 Synthesis of Polymer P-39 (core-shell latex) 15 g of sodium salt of oleyl methyl tauride 12
The aqueous solution was heated to 80° C. while being deoxidized through a nitrogen stream. Potassium persulfate 250+11(+
20112 aqueous solution was added, and then 10 g of lobethyl acrylate was added and reacted for 1 hour. To this latex was added 2001 fl of ethanol in which 120 g of exemplified monomer 8) and 30 g of n-butyl acrylate were dissolved.
Next, 201 g aqueous solution of 300 mg of potassium persulfate was added, and after further reaction for 1 hour, potassium persulfate 20 (la
g of 20i12 aqueous solution was added.

After a subsequent 1 hour reaction, ethanol and unreacted monomers were distilled off as an azeotrope of water, and the pH was adjusted to 6.0 with OIN sodium hydroxide. ol: After adjustment, it was filtered.

The polymer concentration of the latex was 7.4%, and the content of ultraviolet absorbing monomer units was 51 mol%.

The polymer of the present invention may be added as a latex to a silver halide photographic light-sensitive material by polymerizing the above polymer by an emulsion polymerization method, or by adding a lipophilic polymer obtained by another polymerization method to an R solvent. It may also be prepared by dispersing a latex in an aqueous gelatin solution.

Examples of initiation methods and their effects are given by F.A. Bobey (F.
Emulsion Polymerization (Emulsion Polymerization) by A. Bovey)
n)” Intersctence Pub! 1she
s Inc. New"y'ark, 1955, pages 59-93.

As the emulsifier used in emulsion polymerization, a compound having surface activity is used, and preferred examples include soaps, sulfonates, sulfates, cationic compounds, amphoteric compounds, and polymeric protective colloids. Examples of these groups and their effects can be found in B clotsche Chem
ischer industry vol. 28 no. 16~
20 (1963).

When the polymer of the present invention is dispersed in the form of a latex in an aqueous gelatin solution, the organic solvent used to dissolve the polymer of the present invention may be used before or (less preferably) after coating the dispersion. It is removed during evaporation during drying.

The proportion of the monomer having an ultraviolet absorber moiety in the polymer of the present invention is usually 5 to 100% by weight, but from the viewpoint of film thickness and stability, the polymer of the present invention is particularly suitable for 35 to 100% by weight. It is used by being added to hydrophilic colloid layers such as surface protective layers, intermediate layers, and silver halide emulsion layers of silver halide photographic light-sensitive materials, but it is especially used in surface protective layers or hydrophilic colloid layers adjacent to surface protective layers. is preferable.

The amount of the polymer of the present invention used is not particularly limited, but it is 10 to 3,000 a+g per square meter, especially 5
It is preferable that it is 0-2.000 mg.

Examples of the silver halide photographic material of the present invention include color negative film, color reversal film, X-ray film paper, and color diffusion transfer method sensitive material.

In the silver halide emulsion used in the light-sensitive material of the present invention, any silver halide used in ordinary silver halide emulsions, such as silver iodobromide and silver chlorobromide, can be used. The silver oxide particles may be obtained by any of the acid method, neutral method, and ammonia method.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is mainly formed inside the particle. Further, it may have a regular crystal shape, or it may have an irregular crystal shape such as a spherical shape or a plate shape.

Also, emulsions with any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions)
Alternatively, an emulsion with a narrow particle size distribution (referred to as a monodisperse emulsion) may be used alone or in combination of several types. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye. The sensitizing dyes may be used alone or in combination of two or more.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a retachable agent and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of a light-sensitive material for color photography. The couplers are typically selected such that a dye is formed for each emulsion layer that absorbs light in the emulsion layer's sensitive spectrum, with a yellow coupler for the blue-sensitive emulsion layer and a yellow coupler for the green-sensitive emulsion layer. A magenta coupler is used in the red-sensitive emulsion layer, and a cyan coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These couplers may be either 4-equivalent or 2-equivalent. Coupling with a colored coupler that has a color correction effect and an oxidized form of a developing agent produces development inhibitors, development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, and hardeners. film agent, fogging agent, antifogging agent,
Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers, and desensitizers are included.

Although a coupling reaction is carried out with an oxidized product of an aromatic primary amine developer, a colorless coupler that does not form a dye (referred to as a competitive coupler) can also be used in combination.

As the yellow coupler, known 7-syl acetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta coupler, known 5-virazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used.

As the cyan coupler, phenol or naphthol couplers are generally used.

Among couplers, DIR compounds, image stabilizers, fluorescent brighteners, etc. that do not need to be adsorbed on the silver halide crystal surface, hydrophobic compounds can be dispersed using the solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc. Various methods can be used, and can be appropriately selected depending on the chemical structure of the hydrophobic compound.

Moreover, when it has an acid group, it can also be introduced into a hydrophilic colloid as an alkaline aqueous solution.

A color antifoggant is used to prevent the oxidized product of the developing agent or the electron transfer agent from migrating between the WAs, causing color turbidity, deterioration of sharpness, and noticeable graininess.

The color antifoggant may be contained in the emulsion layer itself, or
An intermediate layer may be provided between adjacent emulsion layers and used as the intermediate layer.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer.

These layers and/or the emulsion layer may contain dyes that flow out of the light-sensitive material or are bleached during development.

A formalin scavenger-1 optical brightener, a matting agent, a lubricant, an image stabilizer, a surfactant, a phenomenon accelerator, a phenomenon retarder, and a bleach accelerator can be added to the photosensitive material.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

In order to obtain a black and white image using the photosensitive material of the present invention, a developing step, a fixing step and/or a stabilizing step may be performed.
To obtain a pigmented image, take a color photo after exposure! Il! do the right thing. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleaching solution and the process using a fixing solution. It is also possible to perform a bleach-fixing process using a one-bath bleach-fixing solution, or a monobath process using a one-bath developing, bleach-fixing solution, which allows color development, bleaching, and fixing to be carried out in one bath. You can also do it.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these processes, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution, or an activator process may be performed in the monobath process. Beta processing can be applied.

[Example 1] Next, examples of the present invention will be shown, but the present invention is not limited thereto.

Implementation FA-1 A sample was prepared by simultaneously coating a green-sensitive emulsion layer and a protective layer having the following composition on a cellulose triacetate transparent base and drying them.

-th layer: Green-sensitive emulsion layer Green-sensitive iodobromide containing 7 mol% of silver iodide and having an average grain size of 1.2 μm! ! An fL agent was prepared.

Then, per mole of silver halide, 1-(2,4,6-drichlorophenyl)-3 was added as a magenta coupler.
-[3-(2,4-di(-amylphenoxyacetamide)benzamide 1-5-pyrazolone as 8001 colored magenta coupler, 1-(2,4,64 lecrophenyl)-4-(1-naphthylazo)-3 -(2-
Chloro-5-octadecenyl succinimide anilino)
- Weighed 245g of 5-pyrazolone, then 120g of tricresyl phosphate and 2401i of ethyl acetate.
were mixed and dissolved by heating, and then a coupler solution emulsified and dispersed in a solution of 5 g of sodium triisoprogolnaphthalene sulfonate and 550 μg of a 75% aqueous gelatin solution was added to the above emulsion.

Further, a gelatin hardener was added to prepare a green-sensitive silver halide coating solution XI, which was coated to a dry film thickness of 55 μm.

Second layer: Comparison of protective layer Tricresyl phosphate is used as an ultraviolet absorber and a high boiling point solvent. Tricresyl phosphate is heated and dissolved in ethyl acetate (twice the weight of the combined weight of the ultraviolet absorber and tricresyl phosphate). It was added to a gelatin solution containing sodium naphthalene sulfonate, emulsified and dispersed in a colloid mill, ethyl acetate was removed by evaporation, and the mixture was coated and dried to prepare a comparative sample.

On the other hand, samples according to the present invention (see Table 1) were prepared by applying and drying the polymer of the present invention in place of the comparative ultraviolet absorber and tricresyl phosphate.

The amount of gelatin in the protective layer was 10 mg/100 cf for both the comparative sample and the sample according to the present invention.

Table 1 After storing a portion of each sample unexposed in an atmosphere of 55°C and 80% RH for 7 days, visually inspect the surface condition (state of appearance of oil, crystals, etc.) as shown in A to C below. Observed based on standards.

A Appearing or not B Appearing C Appearing Also, after conditioning the unexposed sample at 25°C and 20% RH for 6 hours, rub the emulsion side of the sample with a neoprene rubber roller in the dark under the same air conditioning conditions. After that, development, bleaching, fixing, washing, and stabilization were performed using the processing solution shown below, and the degree of static mark occurrence was examined.

Processing process Temperature Processing time (1 liter developer...38℃ 3 minutes 15 seconds (2) Bleaching...38℃ 4 minutes 30 seconds (3) Fixing...
...38℃ 4 minutes 20 seconds (4) Washing with water...38
℃ 3 minutes 15 seconds (5) Stabilization...38℃
1 minute - 05 seconds The compositions of the developing solution, bleaching solution, fixing bath and stabilizing bath are as follows.

Developer (1) H-10,05> Hydroxyamine sulfate 2.5g 4-Amino-3-methyl-N- (β-hydroxyethyl) Aniline VliI acid salt 4.56
gDiethylenetriaminohexaacetic acid a, 7 partsgK2
CO330.3g Sodium chloride 4g Add water to make 11.

Bleach bath (1) H-5,70) Ammonium bromide 173g80%
Acetic acid 20t42EDTA
Fe NH4103 (IEDTA 27g
Add water to make 12.

Fixing bath (+) H-6,50) Ammonium thiosulfate 800vj2 Sodium sulfite 4.69 Sodium bisulfite 5.0g Add water and 12
shall be.

Stable bath (DH-7,30) 40% formalin 6.6%
% polyoxyethylated lauryl alcohol 0.6. Add J2 water to make 1i.

The degree of occurrence of static marks was evaluated on the following four levels A to D.

A: No static marks are observed B: Some static marks are observed C: A considerable amount of static marks are observed D: Static marks are observed almost on the entire surface Shown in the table.

As shown in Table 2 below, the samples of the present invention are excellent in surface condition and static mark occurrence rate.

In addition, the samples of the present invention can be further thinned (for example, sample 13.
For 19 and 25, 6m of gelatin.

/ 100Cf, samples 4.15, 20.21 and 26
(reduced to 8I11g/100Cv),
It was found that the sharpness of images could be improved because the surface condition and static marks did not deteriorate in performance.

Example 2 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a multicolor silver halide photographic material.

1st layer: blue-sensitive silver halide emulsion layer α-pivaloyl-α-(2,4
-dioxo-1-benzylimidazolidin-3-yl)
-2-chloro-5-[γ-(2゜4-di-t-amylphenoxy)butyramide 1 acetanilide at 6.81
g/toOcv', blue-sensitive silver chlorobromide emulsion (silver bromide 8
5 mol%) converted to silver is 3.2 mQ/100c
l, dibutyl phthalate 3.5mg/100C
f and gelatin were coated to give a maximum coating weight of 13.511 g/100 Ct'.

2nd layer; middle layer 2.5-G℃-octylhydroquinone at 0.51 (
J/toocv, dibutyl phthalate 0.5 t/100Ct” and gelatin 9.0mg/10Q
It was painted so that it became Ct'.

3rd layer; green-sensitive silver halide emulsion layer 4.2 mg of 1-(2,4,6-dolichlorophenyl)-3-<2-chloro-5-tetradecanamidoanilino)-5-pyrazolone as a magenta coupler / 10
0cf, green-sensitive chlorobromide limited emulsion (containing 80 mol% silver bromide)
2.5H/100C in terms of silver, dibutyl phthalate 3.0ma/100cf and gelatin 12. It was applied to the rocky shore with On/100Cr.

4th layer: Intermediate layer ultraviolet absorber (Table 3), dibutyl phthalate, 2,
5-di-octylhydroquinone (0.5mg/1
00ct') and'Cj 5 ち：/ (12,0m
(Amounts of other materials are shown in Table 3.) 5th layer: Red-sensitive silver halide emulsion layer containing 2-[α-(2,4-G(- Pentylphenoxy)butanamide]-4゜6-dichloro-5-ethylphenol at 4.2mv/100Cv'
, red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver: 3.011+2/100Ct', l'licresyl phosphate 3.5u/100Cf and gelatin 11.5mM 100Cf It was painted so that

6th layer; interlayer layer containing gelatin (10+ag/100Cv'), UV absorber (Table 3) and dioctyl phthalate.

(Other amounts are shown in Table 3.) 7th layer: Protective layer gelatin in 8. It was coated to give OJI/100Cf.

An appropriate amount of gelatin hardener was added to the protective layer.

The test piece of the sample was left unexposed at 55°C and 80% R.
After being stored in an H atmosphere for 3 days, the surface condition was visually observed. The evaluation criteria are the same as in Example-1.

Also, after conditioning the unexposed sample at 25°C and 20% RH for 6 hours, the emulsion side of the sample was rubbed with a neoprene rubber roller in a dark room under the same air conditioning conditions, and then developed with the following processing solution. Bleaching, fixing, washing, and stabilization were performed to examine the degree of static mark occurrence. The evaluation criteria are the same as in Example-1.

[Processing process]

Processing temperature Processing time Color development 33℃ 3 minutes 30 seconds bleaching
Wash with water at 33℃ for 1 minute and 30 seconds
Dry for 3 minutes at 33℃ 50-80
℃ 2 minutes The components of each treatment solution are as follows.

[Color developer]

Benzyl alcohol 121g Diethylene glycol 1 (h12 Potassium carbonate 25g Sodium bromide
0.6 (1 Anhydrous sodium TiA acid 2.OfJ hydroxylamine sulfate 2.5 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate 4.5 g Water was added to 11 and at Na 01-1 1)) -110,
2km adjustment.

Bleach-fix solution] 120 g of ammonium ferric acid and 120 g of sodium metabisulfite 15 g of anhydrous sodium sulfite 3Q EDTA ferric ammonium 'J: Add 65 g of water and 1j! Bind, pH 6
, adjusted to 7-6.8.

The results are shown in Table 3.

From Table 3, it can be seen that the sample of the present invention is superior to the comparative sample in terms of surface condition and occurrence of static marks. Moreover, among the samples of the present invention, samples such as Samples 53 and 56, in which the sixth skin M was increased, were particularly good. Furthermore, for the samples of the present invention, it was also possible to make the ultraviolet absorber layer thinner.

[Effect of the present invention 1] As explained in detail above, by using the polymer of the present invention, it is possible to improve static marks and prevent deterioration of surface condition due to storage under harsh conditions, and also to improve thin film formation. It becomes possible to

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, comprising the following general formulas [I], [IIa], [IIb], [III], A silver halide photographic material comprising a polymer derived from a repeating unit of a monomer having at least one ultraviolet absorbing group selected from [IV] and [V]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 represents an aliphatic group or an aryl group, and R
^2, R^3, R^4 and R^5 are each a hydrogen atom,
Represents an aliphatic group or an aryl group. Y^1 represents an oxygen atom, a sulfur atom, an ethylene group or a methylene group. V^1 and W^1 are hydrogen atoms, -CN, -CO, respectively
R^6, -COOR^7, -SO_2R^8, ▲ Formula,
Represents a chemical formula, table, etc. ▼ or ▲ a mathematical formula, chemical formula, table, etc. exists ▼. Here, R^6, R^7 and R^8 each represent an aliphatic group or an aryl group, and R^9, R^1^0, R^
1^1 and R^1^2 each represent a hydrogen atom, an aliphatic group, or an aryl group, and R^9, R^1^0, and R^
1^1 and R^1^2 may each be bonded to each other to form a ring. However, R^1, R^2, R^3, R^4,
At least one of R^5, V^1 and W^1 is bonded to a polymerizable group. ] General formula [IIa] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [IIb] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula,
R^1^3 represents an aliphatic group or an aryl group. R^1
^4, R^1^4', R^1^5 and R^1^5' each represent a hydrogen atom, an aliphatic group or an aryl group. R
^1^4 and R^1^5 may be bonded to each other to form a benzene ring or a naphthalene ring. Y^2 represents an oxygen atom, a sulfur atom, or ▲a numerical formula, a chemical formula, a table, etc. are available▼, where R^1^6 represents a hydrogen atom or an alkyl group. V^2 and W^2 are -CN and -COR^1^7 respectively
, -COOR^1^8, -SO_2R^1^9, Represents ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. Here, R^1^7, R^1^8 and R^1^9 each represent an aliphatic group or an aryl group, and R^2^0,
R^2^1, R^2^2 and R^2^3 each represent a hydrogen atom, an aliphatic group or an aryl group, and R^2^0
and R^2^1, R^2^2 and R^2^3 may be bonded to each other to form a ring. Furthermore, V^2 and W^2
may be combined with each other to form a ring, where Z^1 represents a group of nonmetallic atoms necessary to form a 5- or 6-membered acidic keto ring. . However, R^1^3, R^1^4, R^1^5, V^2 and W
At least one of ^2 is bonded to a polymerizable group. ] General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^2^4, R^2^5, R^2^6, R^2
^7 and R^2^8 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, an amino group,
alkylamino group, arylamino group, hydroxy group,
Represents a cyano group, acylamino group, carbamoyl group, acyl group, sulfonyl group, sulfamoyl group, sulfonamido group, acyloxy group or oxycarbonyl group, R
^2^4 and R^2^5, R^2^6 and R^2^7 and R
^2^7 and ^2^8 may be bonded to each other to form a 5- to 6-membered ring. Z^2 represents a group of nonmetallic atoms necessary to form a 5- or 6-membered acidic keto ring. R^2^4, R^2^5, R^2^6, R^2^7, R
At least one of ^2^8 and Z^2 is bonded to a polymerizable group. ] General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^2^9, R^3^0, R^3^1, R^3
^2, R^3^3, R^3^6, R^3^7, R^3^
8, R^3^9 and R^4^0 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
Represents an amino group, alkylamino group, arylamino group, hydroxy group, cyano group, acylamino group, carbamoyl group, acyl group, sulfonyl group, sulfamoyl group, sulfonamido group, acyloxy group or oxycarbonyl group, R^2^9 and R^3^0, R^3^1 and R^3
^2, R^3^2 and R^3^3, R^3^6 and R^3^
7. R^3^7 and R^3^8 and R^3^9 and R^4^
0 may be bonded to each other to form a 5- to 6-membered ring. R^3^4 and R^3^5 each represent a hydrogen atom, an alkyl group, or an aryl group. However, R^2^9, R^3^0, R^3^1, R^3^
2, R^3^3, R^3^4, R^3^5, R^3^6
, R^3^7, R^3^8, R^3^9 and R^4^0
At least one of them is bonded to a polymerizable group. ] General formula [V] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R^4^1 represents a hydrogen atom, an acyl group, a carbamoyl group, an aliphatic group, or an aryl group. R^4^2,
R^4^3 and R^4^4 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an alkylamino group , carbamoyl group, arylamino group, hydroxy group, cyano group, acylamino group, sulfamoyl group, sulfonamide group, acyloxy group or oxycarbonyl group. At least one of R^4^1, R^4^2, R^4^3 and R^4^4 is bonded to the polymerizable group. ]