Method of hardening gelatin and photographic light-sensitive material

A photographic silver halide light-sensitive material having at least one hydrophilic colloid layer containing gelatin and/or a gelatin derivative hardened with a compound represented by the following general formula (I): ##STR1## wherein a and d each represents 1 or 2; b and c each represents 0, 1 or 2 with the proviso that both b and c are not simultaneously 0; R represents a divalent group; and n is 0 or 1, which compound provides a preferred hardening rate and does not adversely affect the photographic properties of photographic light-sensitive materials, and a method of hardening gelatin and/or a gelatin derivative comprising treating the gelatin and/or the gelatin derivative with a compound represented by the general formula (I) above.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to a method of hardening gelatin and/or a 
gelatin derivative with an improved hardening agent, more particularly, it 
relates to a method of hardening a hydrophilic colloid layer containing 
gelatin and/or a gelatin derivative of a silver halide photographic 
light-sensitive material and to the silver halide photographic 
light-sensitive material. 
2. Description of the Prior Art 
Gelatin is used as a binder for many photographic light-sensitive 
materials. For example, gelatin is used as the main component of a silver 
halide light-sensitive emulsion layer, an emulsion protective layer, a 
filter layer, an intermediate layer, an antihalation layer, a backing 
layer, a film support subbing layer and a baryta layer. 
These photographic materials containing gelatin are treated with various 
aqueous solutions having different pH's and temperatures. Since a layer 
containing gelatin which has not been treated with a hardening agent has 
properties mainly dependent on the gelatin, it has poor water resistance 
and swells excessively in an aqueous solution, so that the mechanical 
strength is greatly reduced, and, in an extreme case, the gelatin layer is 
sometimes dissolved, particularly in an aqueous solution having a high 
temperature of above 30.degree. C. or a highly alkaline aqueous solution. 
These properties are fatal defects for the physical properties of layers 
which make up photographic light-sensitive materials. 
Many compounds are known to be effective for increasing the water 
resistance, heat resistance and abrasion resistance of a gelatin layer by 
hardening. 
These compounds are well known as hardeners which are used in the 
production of photographic light-sensitive materials. Examples of known 
hardeners are formaldehyde, glutaraldehyde and like aldehyde type 
compounds; compounds having a reactive halogen as described in U.S. Pat. 
No. 3,288,775 and so on; compounds containing a reactive ethylenically 
unsaturated bond as described in U.S. Pat. No. 3,635,718 and so on; 
aziridine type compounds as described in U.S. Pat. No. 3,017,280, etc.; 
epoxy compounds as described in U.S. Pat. No. 3,091,537, etc.; and 
halocarboxyaldehydes such as mucochloric acid, dioxanes such as 
dihydroxydioxane and dichlorodioxane, or inorganic hardeners such as 
chromium alum and zirconium sulfate and the like. 
However, these known gelatin hardeners have one or more deffects, when they 
are used in photographic light-sensitive materials, in that the hardening 
effect is insufficient, in that the gelatin hardening rate is not 
sufficiently fast, so that the hardening proceeds slowly with the passage 
of time after the production of the photographic materials (i.e., 
after-hardening), in that harmful effects to the properties of the 
photographic light-sensitive materials occur (particularly, increase of 
fog, decrease of sensitivity, etc.), in that the hardening effect is 
destroyed by other photographic additives which are present, in that they 
adversely affect other photographic additives (for example, color forming 
couplers for color photographic light-sensitive materials), in that the 
preparation thereof is difficult and large scale production is not 
appropriate, in that the hardeners per se are unstable and storage thereof 
is difficult, in that they have a very strong odor which causes a decrease 
in work efficiency during production thereof, in that they are harmful to 
the human body, and the like. 
It is also known that hardeners having active vinyl sulfone groups are 
relatively advantageous for hardening purposes. For example, 
divinylsulfone, which is an example of a hardener, is not practically used 
due to its quite harmful affects on the human body. Compounds having 
vinylsulfonyl groups in which such a defect is decreased are described in 
German Pat. No. 1,100,942, U.S. Pat. No. 3,490,911, etc. 
Those vinylsulfone type hardeners have advantages as hardeners because they 
have generally a high hardening rate and a small after-hardening effect 
which is a variation of hardening effect with the passage of time, because 
they have less harmful effects on photographic properties such as fog 
formation, desensitization, etc., and because they have relatively less 
adverse affects on color photographic emulsions such as decoloration, etc. 
However, these vinylsulfone compounds are expensive or a special method is 
required for their production in which a large amount of organic solvents 
is used in order to utilize these compounds and thus it cannot always be 
said that they are sufficient for practical use. 
For example, since the compounds described in German Pat. No. 1,622,260 
have poor water solubility, when they are used for the production of 
photographic light-sensitive materials, they tend to deposit in a gelatin 
solution nd cause difficulties during coating and an uneven hardening of 
the photographic layer. Further, it is essential to use a large amount of 
an organic solvent which involves risks of fire and explosion and is 
undesirable in view of the harmful effects on the human body. 
The compounds described in U.S. Pat. No. 3,642,486 are improved in this 
point. That is, these compounds have a good solubility due to ether bonds 
present in the compounds and are advantageous in the production of 
photographic light-sensitive materials. However, a compound which is known 
to induce cancer is used as a starting material in the production of the 
compounds described in U.S. Pat. No. 3,642,486 and, thus, the production 
of these compounds involves a large risk.Further, mass production is also 
disadvantgeous, since these compounds are relatively hard to crystallize 
because of the presence of ether bonds. Furthermore, gelatin layers or 
photographic light-sensitive materials hardened with these compounds have 
poor resistance to dissolution in an aqueous alkaline solution and this is 
quite a defect when it is considered that developer solutions for 
photographic light-sensitive materials are most generally highly alkaline 
aqueous solutions. 
The compounds described in Japanese patent application (OPI) No. 44164/1976 
have improved solubility in an alkaline solution. However, these compounds 
have very poor water solubility and require the use of a large amount of 
organic solvent in the production of photographic light-sensitive 
materials which is extremely disadvantageous in view of minimizing the 
hazards of explosion, providing safe working conditions and preventing 
environmental pollution. 
The compounds described in Japanese patent application (OPI) Nos. 
74832/1973 and 24435/1974 have improved water solubility and reduced 
toxicity due to the function of a polar group introduced into their 
molecules, that is, an acylamide bond. However, the compounds described in 
Japanese patent application (OPI) No. 74832/1973 require use of acylamide 
which is highly poisonous to produce. Also, the compounds described in 
Japanese patent application (OPI) No. 24435/1974 require the use of 
1,3,5-triacyloylhexahydro-s-triazine which has a relatively high cost of 
production and, further, they are only soluble in water substantially up 
to about 2 weight % at room temperature (about 25.degree. C.). In 
addition, the melting points and solubilities of the compounds described 
in Japanese patent application (OPI) No. 24435/1974 are interrelated and 
compounds having a higher purity have higher melting points and lower 
solubilities than those described in Japanese patent application (OPI) No. 
24435/1974. 
SUMMARY OF THE INVENTION 
It has now been discovered that almost all of the disadvantages of known 
hardeners are improved and the advantages described hereinbelow are 
obtained in the method of this invention comprising treating a hydrophilic 
colloid layer containing gelatin and/or a gelatin derivative with a 
compound represented by the following general formula (I): 
##STR2## 
wherein a and d each represents 1 or 2; b and c each represents 0, 1 or 2 
with the proviso that both b and c are not simultaneously O; R represents 
a divalent group; and n represents 0 or 1. 
The hardeners which are used in the present invention are completely free 
from these defects and are quite ideal compounds as hardeners which can be 
used in the production of photographic light-sensitive materials. 
In greater detail, the hardeners used in the present invention have a very 
good solubility in water, i.e., they are soluble to an extent of more than 
about 8 weight % at room temperature and more than about 20 weight % with 
slight heating at about 40.degree. C. This has a very important meaning. 
That is, the larger the amount of water which is required in order to use 
a hardener in the production of photographic light-sensitive materials, 
the larger is the drying load for removing the water and this leads to 
higher energy costs, a larger space and larger equipment needs for drying 
and decreases in productivity. Further, photographic light-sensitive 
materials are nowadays produced at a higher speed and, for instance, when 
extrusion coating using a slide hopper is employed for coating, the 
gelatin solution or the emulsion solution to be coated must have a certain 
high viscosity. However, the use of a large amount of water in order to 
add a hardener to a solution has the apparent tendency to reduce the 
viscosity of the solution and may occasionally result in fatal defects. 
Therefore, a very important advantage in the photographic art is for the 
solubility of the hardener in water to be more than about 7 weight %. In 
addition, since the present hardeners have a strong hardening effect per 
unit weight, a small amount of the compounds can be used in comparison 
with other hardeners and, thus, the amount of water used can be further 
reduced. 
Also, a gelatin or gelatin derivative (hereinafter for simplicity the term 
"gelatin" will be used to describe both gelatin and gelatin derivatives) 
or light-sensitive layer hardened with the hardener according to the 
present invention has extremely high resistance to dissolution in an 
alkaline solution. 
The hardener used in the present invention has a very high activity and 
exhibits a rapid hardening effect so that the variation of hardening 
effect with the passage of time, i.e., the so-called after-hardening, is 
not observed. In spite of its high activity, the compound is stable and an 
aqueous solution thereof possesses a very good storage stability. 
Not only does the hardening reaction take place rapidly and after hardening 
does not occur with the present hardener, but also it is relatively 
unaffected by temperature and/or humidity during the drying process and/or 
during storage after drying. 
Further, the hardener used in the present invention can be prepared in a 
high yield from a very common compound such as an epoxy compound or a 
chlorohydrin type compound as described hereinafter and, thus, can be 
obtained at a low production cost. Also, the compound is easily 
crystallized due to the presence of a hydroxy group in the molecule 
thereof and is easy to produce. Furthermore, the vapor pressure thereof is 
low and it is odorless which is advantageous in handling. 
Moreover, the hardener used in the present invention does not interact with 
other photographic additives which are present such as color forming 
couplers for color photographic materials and, thus, the present hardener 
does not reduce the effects of such photographic additives, nor is the 
hardening effect of the present hardener destroyed. In addition, the 
hardener does not adversely affect the properties of photographic 
light-sensitive materials (for example, cause fog, reduce sensitivity, 
etc.). 
DETAILED DESCRIPTION OF THE INVENTION 
In the above general formula (I), the divalent group represented by R 
includes any divalent group, but preferably a cyclic hydrocarbon group 
such as an arylene group having 6 to 12 carbon atoms, e.g., an m-phenylene 
group, etc., an acyclic hydrocarbon group such as an alkylene group having 
1 to 8 carbon atoms, e.g., a methylene group, an ethylene group, a 
trimethylene group, a tetramethylene group, etc. The divalent group 
represented by R can also be an aralkylene group having a total of 8 to 10 
carbon atoms. One to three of the carbon atoms of the group defined above 
for R can be replaced by a hetero atom such as a nitrogen atom, a sulfur 
atom, an oxygen atom, etc. Suitable examples of groups containing hetero 
atom(s) include a group containing a --CH.sub.2 OCH.sub.2 -- group, a 
--(CH.sub.2 Ch.sub.2 O).sub.2 -CH.sub.2 CH.sub.2 -- group, a --CH.sub.2 
CH.sub.2 OCH.sub.2 CH.sub.2 -- group, a 
##STR3## 
group, etc. More preferably R is a divalent branched or straight chain 
alkylene group having 1 to 4 carbon atoms. Also, the chain can be 
substituted, for example, with one or more of an alkoxy group having 1 to 
4 carbon atoms such as a methoxy group, an ethoxy group, etc., a halogen 
atom such as a chlorine atom, a bromine atom, etc., a hydroxy group, an 
acetoxy group and the like. 
Further, preferred compounds of the general formula (I) are those in which 
a, b, c, d and R are so selected that the relationship represented by the 
following equation is fulfilled. 
##EQU1## 
That is, it is preferred for the numerical value obtained by dividing the 
molecular weight by the total number of hydroxy groups per molecule is 
about 260 or less. When the numerical value is greater than about 260, the 
water solubility which is one of the advantages according to the present 
invention is reduced. 
The hardeners used in the present invention are all novel compounds and can 
be prepared in good yield using known general reactions. Tht is, the 
vinylsulfonyl compounds of the general formula (I) can be prepared 
according to general methods for forming a vinyl group, for example, by 
dehydrochlorinating a haloethylsulfonyl compound such as a 
chloroethylsulfonyl compound, etc., using a base such as triethylamine, 
trimethylamine, triethylenediamine, 1,8-diazobicyclo[5,4,0]-7-undecene, 
etc., in a solvent such as acetone, acetonitrile, chloroform, benzene, 
etc., at -60.degree. to 80.degree. C. at atmospheric pressure for about 10 
minutes to several days, or by dehydrating a hydroxyethylsulfonyl 
compound. Further, the chloroethylsulfonyl compound, i.e., the starting 
material, can be prepared, for example, by oxidizing a hydroxyethylsulfide 
using an oxidizing agent such as hydrogen peroxide, peracetic acid, etc., 
in a solvent such as water, acetic acid, ethyl acetate, acetone, methanol, 
etc., in the presence of a catalyst such as tungstic acid, phosphoric 
acid, acetic acid, etc., at 0.degree. to 120.degree. C. and at atmospheric 
pressure for about 10 minutes to several days to form a 
hydroxyethylsulfone and chlorinating this hydroxyethylsulfone using a 
chlorinating agent such as thionyl chloride, phosphorus pentachloride, 
phosphorus trichloride, etc., in the absence of a solvent or in the 
presence of a solvent such as chloroform, toluene, etc., in the presence 
of a catalyst such as pyridine, dimethylformamide, etc., at about 
-20.degree. to about 200.degree. C. and at atmospheric pressure for about 
10 minutes to several days, or by chlorinating a hydroxyethylsulfide and 
then oxidzing the product obtained. Furthermore, the hydroxyethylsulfide, 
i.e., the starting material, can be easily prepared by reacting a compound 
having an epoxy group or a precursor thereof, i.e., a halo compound having 
a hydroxy group with mercaptoethanol in a solvent such as water, methanol, 
ethanol, dimethylformamide, etc., in the presence of a catalyst such as 
potassium hydroxide, sodium hydroxide, triethylamine, etc., at about 
-40.degree. to about 120.degree. C. and at atmospheric pressure for about 
10 minutes to several days. 
Examples of compounds of the general formula (I) which can be used in the 
present invention are given below, but the present invention is not to be 
construed as being limited to these examples. 
##STR4## 
The amount of the hardener of the present invention used can be selected 
freely depending on the desired objective. The amount used generally 
ranges from about 0.01 to about 20 wt%, preferably ranges from 0.1 to 10 
wt%, based on the weight of dry gelatin. When the hardener of the present 
invention is used in an amount of more than about 20 wt% based on the 
weight of the dry gelatin, the gelatin solution is occasionally gelled and 
hardened, so that it is impossible to use the gelatin aqueous solution 
containing the hardener, e.g., it is impossible to form a film by coating 
or spray coating. On the other hand, with the amount of the hardener of 
the present invention used is less than about 0.01 wt%, sufficient 
hardening cannot be obtained even after drying, and insufficient film 
strength is obtained, although it is possible to form a film using the 
gelatin aqueous solution. Use of an amount in the above range provides the 
ability to rapidly harden gelatin, which is an advantage of the hardener 
of the present invention, and such can be achieved satisfactorily. 
The hardeners of the present invention can be used individually or as 
mixtures of two or more hardeners of the present invention. Further, the 
hardeners of the present invention can be used in combination with other 
known hardeners. Suitable known hardeners which can be used therewith are, 
for example, formaldehyde, glutaraldehyde and like aldehyde type 
compounds, diacetyl, cyclopentadione and like ketone compounds, 
bis(2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine; and other 
compounds containing a reactive halogen as described in U.S. Pat. Nos. 
3,288,775 and 2,732,303 and British Pat. Nos. 974,723 and 1,167,207; 
divinylsulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine and other 
compounds containing a reactive olefin bond as described in U.S. Pat. Nos. 
3,635,718 and 3,232,763 and British Pat. No. 994,869; 
N-hydroxymethylphthalimide, and other N-methylol compounds as described in 
U.S. Pat. Nos. 2,732,316 and 2,586,168; isocyanates as described in U.S. 
Pat. No. 3,103,437; aziridine compounds as described in U.S. Pat. Nos. 
3,017,280 and 2,983,611; acid derivatives as described in U.S. Pat. Nos. 
2,725,294 and 2,725,295; carbodiimide type compounds as described in U.S. 
Pat. No. 3,100,704; epoxy compounds as described in U.S. Pat. No. 
3,091,537; isoxazole type compounds as described in U.S. Pat. Nos. 
3,321,313 and 3,543,292; halocarboxyaldehydes such as mucochloric acid; 
dioxane derivatives such as dihydroxydioxane and dichlorodioxane; and 
inorganic hardeners such as chromium alum and zirconium sulfate. In 
addition to the above hardening compounds, the hardeners of the present 
invention can be used in combination with precursors of the 
above-described compounds, such as alkali metal bisulfite aldehyde 
adducts, methylol derivatives of hydantoin and primary fatty 
nitroalcohols, etc. When using the hardener of the present invention in 
combination with other hardeners, the amount of the hardener(s) of the 
present invention used can be selected as desired depending on the object 
and the effect. 
In using the hardener of the present invention for photographic 
light-sensitive materials, a silver halide emulsion can be prepared by 
mixing a water-soluble silver salt (e.g., silver nitrate) solution and a 
water-soluble halide (e.g., potassium bromide) solution in the presence of 
a water-soluble polymer (e.g., gelatin) solution. Useful silver halides 
include silver chloride, silver bromide and mixed silver halides such as 
silver chlorobromide, silver iodobromide and silver chloroiodobromide, 
etc. 
The form of the silver halide grains may be any of a cubic, octahedral and 
mixed system. The grain size and average grain size distribution are not 
particularly limited, and any grain size and grain size distribution can 
be used. 
These silver halide grains can be prepared using known conventional 
procedures, e.g., a single or double jet method, a controlled double jet 
method and the like. Further, two or more kinds of silver halide emulsions 
which have been separately prepared may be mixed. 
The crystal structure of the silver halide grains may be uniform throughout 
the grains, the grains may be heterogeneous where the outer layer and an 
inner layer are different or the grains may be of the conversion type as 
described in British Pat. No. 635,841 and U.S. Pat. No. 3,622,318. 
Further, the grains may be of the type which form a latent image 
principally on the surface of the grains or may be of the inner latent 
image type which form a latent image in the interior of the grains. These 
photographic emulsions are described in C. E. K. Mees & T. H. James, The 
Theory of the Photographic Process, 3rd Ed., Macmillan, New York (1967); 
P. Grafkides, Chimie Photographique, Paul Montel, Paris (1957) and the 
like, and can be prepared using known methods such as the ammonia method, 
the neutral method, the acid method and the like. 
After the formation of such silver halide grains, water-soluble salt 
by-products (e.g., potassium nitrate when producing silver bromide from 
silver nitrate and potassium bromide) can be removed from the system by 
water-washing, and then heating is conducted in the presence of a chemical 
sensitizer such as sodium thiosulfate, N,N,N'-trimethylthiourea, a 
thiocyanate complex salt of monovalent gold, a thiosulfate complex salt of 
monovalent gold, stannous chloride or hexamethylenetetramine without 
coarsening the grains to thereby increase the sensitivity. Such a 
procedure is described in the abpve-cited references. 
The above silver halide emulsions can be chemically sensitized using 
conventional techniques, if desired. Chemical sensitizers which can be 
used include, for example, chloroaurate, auric chloride and like gold 
compounds as described in U.S. Pat. Nos. 2,399,083, 2,540,085, 2,597,856 
and 2,597,915; salts of noble metals such as platinum, palladium, iridium, 
rhodium and ruthenium as described in U.S. Pat. Nos. 2,448,060, 2,540,086, 
2,566,245, 2,566,263 and 2,598,079; sulfur compounds forming silver 
sulfide upon reaction with a silver salt, as described in U.S. Pat. Nos. 
1,574,944, 2,410,689, 3,189,458 and 3,501,313; stannous salts, amines and 
other reducing materials, as described in U.S. Pat. Nos. 2,487,850, 
2,518,698, 2,521,925, 2,521,926, 2,694,637, 2,983,610 and 3,201,254. 
The photographic emulsion in which the hardener of the present invention is 
employed can, if desired, be spectrally sensitized or supersensitized by 
the use of cyanine, merocyanine, carbocyanine and like cyanine dyes, 
individually or in combination, or in combination with styryl dyes. 
Such dye sensitizing techniques are well known and are described in U.S. 
Pat. Nos. 2,493,748, 2,519,001, 2,977,229, 3,480,434, 3,672,897, 
3,703,377, 2,688,545, 2,912,329, 3,397,060, 3,615,635, 3,628,964, British 
Pat. Nos. 1,195,302, 1,242,588 and 1,293,862, German patent application 
(OLS) Nos. 2,030,326 and 2,121,780, Japanese Pat. Nos. 4936/1968, 
14030/1969 and 10773/1968, U.S. Pat. Nos. 3,511,664, 3,522,052, 3,527,641, 
3,615,613, 3,615,632, 3,617,295, 3,635,721, 3,694,217, British Pat. Nos. 
1,137,580 and 1,216,203 and the like. The material(s) can freely be 
selected depending on the wavelength range to which the emulsion is to be 
sensitized, the sensitivity desired, the end-use objective and the like. 
Various compounds can be added to the above photographic emulsion in order 
to prevent a reduction in sensitivity and a generation of fog during the 
manufacture, storage or processing of the photographic materials. Many 
such compounds are known, for example, 
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 3-methylbenzothiazole, 
1-phenyl-5-mercaptotetrazole and like heterocyclic compounds, mercury 
containing compounds, mercapto compounds and metal salts. Examples of 
usable compounds are described in C. E. K. Mees & T. H. James, The Theory 
of the Photographic Process, 3rd Ed., pp. 344-349, Macmillan, New York 
(1966) and the original literature references cited therein; and in the 
following patents: U.S. Pat. Nos. 1,758,576, 2,110,178, 2,131,038, 
2,173,628, 2,697,040, 2,304,962, 2,324,123, 2,394,198, 2,444,605-8, 
2,566,245, 2,694,716, 2,697,099, 2,708,162, 2,728,663-5, 2,576,536, 
2,824,001, 2,843,491, 2,886,437, 3,052,544, 3,137,577, 3,220,839, 
3,226,231, 3,236,652, 3,251,691, 3,252,799, 3,287,135, 3,326,681, 
3,420,668, 3,622,339, British Pat. Nos. 893,428, 403,789, 1,173,609 and 
1,200,188. 
The gelatin to which the hardener of the present invention can be applied 
can be any type of gelatin such as alkali treated gelatin obtained by 
immersion in an alkali bath (lime-treatment) before gelatin extraction, 
acid treated gelatin obtained by immersion in an acid bath and enzyme 
treated gelatin as described in Bull. Soc. Sci. Photo. Japan, No. 16, page 
30 (1966). Further, the present hardener can be applied to the low 
molecular weight gelatin which is obtained by partial hydrolysis of 
gelatin by heating in a water bath or interaction with protenase. 
The gelatin to which the hardener of the present invention is applied may, 
if desired, be partially replaced by colloidal albumin, casein, cellulose 
derivatives such as carboxymethylcellulose and hydroxyethylcellulose, 
agar, sodium alginate, starch derivatives and like saccharide derivatives, 
and synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinyl 
pyrrolidone, polyacrylic acid copolymers, polyacrylamide and the 
derivatives or partially hydrolyzed products thereof. In addition, the 
gelatin may be replaced by a gelatin derivative which is obtained by 
treating or modifying the amino, imino, hydroxy or carboxyl groups present 
as functional groups in the gelatin molecule with an agent having a group 
capable of reacting with such functional groups, or may be replaced by a 
graft gelatin in which a molecular chain of another polymeric material is 
grafted onto the gelatin molecule. 
Agents for producing the above gelatin derivatives include, for example, 
isocyanates, acid chlorides or acid anhydrides as described in U.S. Pat. 
No. 2,614,928; acid anhydrides as described in U.S. Pat. No. 3,118,766; 
bromoacetic acids as described in Japanese Pat. No. 5514/1964; 
phenylglycidyl ethers as described in Japanese Pat. No. 26845/1967; 
vinylsulfone compounds as described in U.S. Pat. No. 3,132,945; 
N-allylvinylsulfonamides as described in British Pat. No. 861,414; 
maleinimide compounds as described in U.S. Pat. No. 3,186,846; 
acrylonitriles as described in U.S. Pat. No. 2,594,293; polyalkylene 
oxides as described in U.S. Pat. No. 3,312,553; epoxy compounds as 
described in Japanese Pat. No. 26845/1967; acid esters as described in 
U.S. Pat. No. 2,763,739; and alkanesultones as described in British Pat. 
No. 1,033,189. 
Suitable polymers which can be grafted onto the gelatin molecule are 
described in many literature publications such as U.S. Pat. Nos. 
2,763,625, 2,831,767 and 2,956,884, Polymer Letters, 5, 595 (1967), Photo 
Sci. Eng., 9, 148 (1965), J. Polymer Sci., A-1, 9, 3199 (1971) and the 
like, and polymers or copolymers of vinyl monomers such as acrylic acid, 
methacrylic acid, or the esters, amides, nitriles and like derivatives 
thereof, or styrene, may be used. Hydrophilic vinyl polymers compatible to 
some extent with gelatin, such as polymers or copolymers of acrylic acid, 
acrylamide, methacrylamide, hydroxyalkyl acrylates and hydroxyalkyl 
methacrylates are particularly preferred. 
In using the hardener of the present invention in photographic 
light-sensitive materials, the photographic emulsion layer or other layers 
may contain therein synthetic polymer compounds, e.g., latex-like water 
dispersable polymers of vinyl compounds, particularly compounds which 
increase the dimensional stability of the photographic materials, 
individually or as a mixture thereof (a mixture of different kinds of 
polymers), or in combination with hydrophilic water-permeable colloids. 
Many such polymers are described, for example, in U.S. Pat. Nos. 
2,376,005, 2,739,137, 2,853,457, 3,062,674, 3,411,911, 3,488,708, 
3,525,620, 3,635,715, 3,607,290, 3,645,740 and in British Pat. Nos. 
1,186,699 and 1,307,373. Of these compounds, copolymers and homopolymers 
of monomers selected from alkyl acrylates, alkyl methacrylates, acrylic 
acid, methacrylic acid, sulfoalkyl acrylates, sulfoalkyl methacrylates, 
glycidyl acrylates, glycidyl methacrylates, hydroxyalkyl acrylates, 
hydroxyalkyl methacrylates, alkoxyalkyl acrylates, alkoxyalkyl 
methacrylates, styrene, butadiene, vinyl chloride, vinylidene chloride, 
maleic anhydride and itaconic anhydride are generally used. If desired, a 
graft type emulsion polymerization latex obtained by emulsion polymerizing 
the above-described vinyl compounds in the presence of a hydrophilic 
protective colloidal polymer compound may be used. 
The gelatin hardener of the present invention may be used in the 
photographic light-sensitive materials in combination with a matting 
agent. Examples of matting agents which may be used include particles of 
water-insoluble organic or inorganic compounds, with an average particle 
size of about 0.2.mu. to about 10.mu., preferably 0.3 to 5.mu.. Examples 
of suitable organic compounds which can be used are water-dispersable 
vinyl polymers such as polymethyl acrylate, polymethyl methacrylate, 
polyacrylonitrile, acrylonitrile-.alpha.-methylstyrene copolymers, 
polystyrene, styrene-divinylbenzene copolymers, polyvinyl acetate, 
polyethylene carbonate, polytetrafluoroethylene; cellulose derivatives 
such as methyl cellulose, ethyl cellulose, cellulose acetate, cellulose 
acetate propionate; starch derivatives such as carboxy starch, 
carboxynitrophenyl starch, urea-formaldehyde-starch reaction products; and 
gelatin hardened with known hardeners and hollow microcapsules of hardened 
gelatin, which is obtained by hardening of a coacervate. Examples of 
inorganic compounds which can be used are silicon dioxide; titanium 
dioxide; magnesium oxide; aluminum oxide; barium sulfate; calcium 
carbonate; silver chloride and silver bromide desensitized using known 
methods; glass and the like. The above matting agents may, if desired, be 
used individually or as a mixture of two or more thereof. 
The gelatin hardener of the present invention may be used in the 
photographic light-sensitive materials in combination with one or more 
couplers. In this case, diffusion resistant couplers can be incorporated 
in a silver halide emulsion layer. 
Examples of suitable couplers which can be used are 4-equivalent 
diketomethylene yellow couplers and 2-equivalent diketomethylene yellow 
couplers, for example, compounds as described in U.S. Pat. Nos. 3,415,652, 
3,447,928, 3,311,476 and 3,408,194; compounds as described in U.S. Pat. 
Nos. 2,875,057, 3,265,506, 3,409,439, 3,551,155 and 3,551,156; compounds 
as described in Japanese patent application (OPI) Nos. 26133/1972 and 
66836/1973; 4-equivalent or 2-equivalent pyrazolone magenta couplers and 
indazolone magenta couplers, for example, compounds as described in U.S. 
Pat. Nos. 2,600,788, 2,983,608, 3,062,653, 3,214,437, 3,253,924, 
3,419,391, 3,419,808, 3,476,560 and 3,582,322, Japanese Pat. No. 
20636/1970, Japanese patent application (OPI) No. 26133/1972; 
.alpha.-naphthol type cyan couplers and phenol type cyan couplers, for 
example, compounds as described in U.S. Pat. Nos. 2,474,293, 2,698,794, 
3,034,892, 3,214,437, 3,253,924, 3,311,476, 3,458,315, 3,591,383, Japanese 
Pat. Nos. 11304/1967 and 32461/1969. In addition, the compounds as 
described in U.S. Pat. Nos. 3,227,554, 3,297,445, 3,253,924, 3,311,476, 
3,379,529, 3,516,831, 3,617,291, 3,705,801, German patent application 
(OLS) No. 2,163,811, etc., can be used. 
Surface active agents individually or in admixture may be added to the 
photographic emulsion of the photographic light-sensitive materials, to 
which the hardener of the present invention is applied. Although such 
surface active agents are generally used as coating aids, they may also be 
used for other purposes, for example, for the purposes of emulsification 
and dispersion, sensitization, improvement of photographic properties, 
prevention of the generation of static charges and prevention of adhesion. 
These surface active agents can be classified as naturally occurring 
surface active agents such as saponin; nonionic surface active agents such 
as those of the alkylene oxide type, the glycerin type and the glycidol 
type; cationic surface active agents such as higher alkylamines, 
quaternary ammonium salts, pyridine and like heterocyclic compounds, 
phosphoniums and sulfoniums; anionic surface active agents containing 
acidic groups such as carboxylic acid, sulfonic acid, phosphoric acid, 
sulfuric acid ester and phosphoric acid esters; and amphoteric surface 
active agents such as amino acids, amino sulfonic acids, and sulfates or 
phosphates of amino alcohols. 
Specific examples of useful surface active agents are described not only in 
U.S. Pat. Nos. 2,271,623, 2,240,472, 2,288,226, 2,739,891, 3,068,101, 
3,158,484, 3,201,253, 3,210,191, 3,294,540, 3,415,649, 3,441,413, 
3,442,654, 3,475,174, 3,545,974, German patent application (OLS) No. 
1,942,665, British Pat. Nos. 1,077,317, 1,198,450, but also in references 
such as Ryohei Oda, Synthesis and Application of Surface Active Agents, 
Maki Publisher, Tokyo (1964), A. W. Schwartz et al., Surface Active 
Agents, Interscience Publications Incorporated, (1958), J. P. Sisley, 
Encyclopedia of Surface Active Agents, Vol. 2, Chemical Publishing Company 
(1964) and the like. 
The photographic emulsions described above can be coated on a planar 
support which does not undergo any substantial dimensional change during 
processing, for example, rigid supports such as glass, metal and ceramics, 
and flexible supports, depending on the objective. 
Representative examples of flexible supports include those generally used 
for photographic light-sensitive materials such as cellulose nitrate 
films, cellulose acetate films, cellulose acetate butyrate films, 
cellulose acetate propionate films, polystyrene films, polyethylene 
terephthalate films, polycarbonate films and laminates thereof; thin glass 
films; paper coated with baryta; papers coated or laminated with an 
.alpha.-olefin polymer, particularly a polymer of an .alpha.-olefin 
containing 2 to 10 carbon atoms, such as polyethylene, polypropylene and 
ethylene-butene copolymers; and synthetic resin films whose surface is 
roughened to thereby improve adhesion to other polymeric materials and to 
improve the printability thereof as described in Japanese Pat. No. 
19068/1972. 
Depending on the end-use of the photographic materials, transparent or 
opaque supports can be used. Suitable transparent supports can be not only 
colorless but also colored by the addition of dyes and/or pigments. 
Colored transparent supports have long been used in the production of 
X-ray films, and such is described in J. SMPTE 67, 296 (1958). 
Suitable opaque supports include not only intrinsically opaque supports 
such as paper, but also opaque supports obtained by adding to a 
transparent film a dye and/or pigment such as titanium oxide, a surface 
treated synthetic resin film as described in Japanese Pat. No. 19068/1972, 
and papers and synthetic resin films which have been rendered completely 
light-shielding by the addition of carbon black or dyes. 
When the adhesion strength between the support and the photographic 
emulsion layer is insufficient, a subbing layer which has a good adhesion 
for both is provided. In order to further improve the adhesion, the 
surface of the support can be subjected to a pre-treatment such as 
treatment with a corona discharge, an ultraviolet light irradiation or a 
flame treatment, etc. 
In using the hardener of the present invention, each layer of the 
photographic light-sensitive materials can be coated using various coating 
methods including dip coating, air knife coating, curtain coating, spray 
coating, extrusion coating using a hopper as described in U.S. Pat. No. 
2,681,294, etc. If desired, two or more layers can be simultaneously 
coated using the methods as described in U.S. Pat. Nos. 2,761,791, 
3,508,947, 2,941,898 and 3,526,528. 
The hardener according to the present invention can be used not only by 
incorporation in the photographic materials but also by addition to a 
processing solution. A suitable amount of the hardener of this invention 
used in a processing solution ranges from about 0.1 to about 10% by 
weight, preferably 0.2 to 5% by weight.

Examples of the synthesis of the compounds used in the present invention 
and Examples of the present invention are given below to illustrate the 
present invention in greater detail. Unless otherwise indicated, all 
parts, percents, ratios and the like are by weight. 
SYNTHESIS EXAMPLE 1 
Preparation of 1,3-bis(Hydroxyethylsulfonyl)-2-propanol 
2.7 g of sodium hydroxide was dissolved in a solution of 60 ml of ethanol 
and 10 g of mercaptoethanol. To the solution, 5.9 g of epichlorohydrin was 
added dropwise at 60.degree. C. with stirring. After stirring for 3 hours 
at 75.degree. C., the mixture was cooled and filtered to remove crystals. 
The filtrate was concentrated and to which 50 ml of water and 0.2 g of 
sodium tungstate were added and the pH was adjusted to 6.0 with acetic 
acid. 24.5 g of a 34% by weight hydrogen peroxide aqueous solution was 
added dropwise at 70.degree. C. with stirring to the mixture and the 
mixture was stirred for 3 hours at 75.degree. C. The resulting solution 
was concentrated and the crystals obtained were recrystallized from 
methanol to obtain 16.2 g of white crystals. 
______________________________________ 
Elemental Analysis 
C H S 
______________________________________ 
Calculated (%): 30.43 5.84 23.21 
Found (%): 30.35 5.81 23.29 
______________________________________ 
SYNTHESIS EXAMPLE 2 
Preparation of 1,3-bis(Chloroethylsulfonyl)-2-propanol 
To 10 g of 1,3-bis(hydroxyethylsulfonyl)-2-propanol obtained as described 
in Synthesis Example 1, a catalytic amount of pyridine was added, then 15 
ml of thionyl chloride was added thereto, and the mixture was stirred for 
2 hours at 50.degree. C. The mixture was concentrated under reduced 
pressure, and the crystals obtained were recrystallized from water to 
obtain 9.2 g of white crystals. 
______________________________________ 
Elemental Analysis 
C H Cl S 
______________________________________ 
Calculated (%): 
26.84 4.51 22.64 20.47 
Found (%): 26.82 4.50 22.61 20.40 
______________________________________ 
SYNTHESIS EXAMPLE 3 
Preparation of Compound 1: 1,3-bis(Vinylsulfonyl)-2-propanol 
5.0 g of 1,3-bis(chloroethylsulfonyl)-2-propanol obtained as described in 
Synthesis Example 2 was dissolved in 50 ml of acetone. To the solution was 
added dropwise 3.3 g of triethylamine with stirring at room temperature. 
After removing the crystals by filtration, the filtrate was concentrated 
under reduced pressure to obtain crystals. The crystals were 
recrystallized from ethanol to obtain 3.1 g of white crystals. 
______________________________________ 
Elemental Analysis 
C H S 
______________________________________ 
Calculated (%): 34.99 5.03 26.69 
Found (%): 34.99 5.11 26.57 
______________________________________ 
SYNTHESIS EXAMPLE 4 
Preparation of 1,4-bis(Hydroxyethylsulfonyl)-2,3-butanediol 
8.3 g of sodium hydroxide, 100 ml of ethanol, 15.6 g of mercaptoethanol and 
15.9 g of 1,4-dichloro-2,3-butanediol were reacted in the same manner as 
described in Synthesis Example 1 to obtain 29 g of white crystals. 
______________________________________ 
Elemental Analysis 
C H S 
______________________________________ 
Calculated (%): 31.36 5.92 20.93 
Found (%): 31.34 5.95 20.87 
______________________________________ 
SYNTHESIS EXAMPLE 5 
Preparation of 1,4-bis(Chloroethylsulfonyl)-2,3-butanediol 
To 15.3 g of 1,4-(hydroxyethylsulfonyl)-2,3-butanediol obtained as 
described in Synthesis Example 4, a catalytic amount of dimethylformamide 
was added. 30 ml of thionyl chloride was reacted in the same manner as 
described in Synthesis Example 2 to obtain 13.7 g of white crystals. 
______________________________________ 
Elemental Analysis 
C H Cl S 
______________________________________ 
Calculated (%): 
27.99 4.70 20.66 18.68 
Found (%): 28.03 4.71 20.61 18.69 
______________________________________ 
SYNTHESIS EXAMPLE 6 
Preparation of Compound 2: 1,4-bis(Vinylsulfonyl)-2,3-butanediol 
11.4 g of 1,4-bis(chloroethylsulfonyl)-2,3-butanediol was dissolved in 300 
ml of acetone and the same procedures as described in Synthesis Example 3 
were followed using 6.8 g of triethylamine to obtain 7.6 g of white 
crystals. 
______________________________________ 
Elemental Analysis 
C H S 
______________________________________ 
Calculated (%): 35.54 5.22 23.72 
Found (%): 35.55 5.28 23.66 
______________________________________ 
EXAMPLE 1 
A silver iodobromide emulsion containing 6.0 mol % of silver iodide was 
optimally ripened using a sulfur-containing sensitizer and a gold 
sensitizer to prepare a high speed negative emulsion. To the emulsion were 
added 
anhydro-5,5'-tetrachloro-1,1'-diethyl-3,3'-di-(3-sulfopropyl)-benzimidazol 
ocarbocyanine hydroxide as a spectral sensitizer, 
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as a stabilizer, and 
1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-tert-amylphenoxyacetamide)benzamido 
]-5-pyrazolone (which was dissolved in tricresyl phosphate and ethyl 
acetate and dispersed in gelatin with sodium dodecylbenzenesulfonate) as a 
magenta color forming coupler to prepare an emulsion for a green-sensitive 
layer of a color negative light-sensitive material. The emulsion 
thus-obtained was divided into four portions and a first portion was used 
as control. To the other three portions were added an aqueous solution of 
Compound 1 of the present invention, dimethylol urea (Compound A) and 
mucochloric acid (Compound B), respectively, in an amount of 1.5 g per 100 
g of dry gelatin. Each emulsion was coated on a subbed cellulose 
triacetate support in a coated coupler amount of 1.5.times.10.sup.-3 
mol/m.sup.2 and dried. 
These samples were exposed to green light using an NSG II type sensitometer 
and processed according to the color processing procedure as described in 
Example 1 of Japanese patent application (OPI) No. 51940/1976 as follows. 
______________________________________ 
Processing Step (I) 
Color Development 38.degree. C. 
31/4 min 
Bleaching " 61/2 min 
Water Washing " 31/4 min 
Fixing " 61/2 min 
Water Washing " 31/2 min 
Stabilizing " 11/2 min 
Drying " 
Color Developer 
Water Softener x g 
Sodium Sulfite 2.0 g 
Sodium Carbonate (monohydrate) 
30 g 
Potassium Bromide 2.0 g 
Hydroxylamine Sulfate 3.0 g 
3-Methyl-4-amino-N-ethyl-N-.beta.- 
5.0 g 
hydroxyethyl Aniline Sulfate 
Diethylenetriaminepentaacetic Acid 
3.5 g/l 
Water to make 1 l 
Bleaching Solution 
Ammonium Bromide 150 g 
Aqueous Ammonia Solution (28%) 
5 ml 
Sodium Iron (III) Ethylenediamine- 
100 g 
tetraacetate 
Water to make 1 l 
Fixing Solution 
Sodium Tetrapolyphosphate 2.0 g 
Sodium Sulfite 15 g 
Ammonium Thiosulfate (70% aq. soln.) 
150 ml 
Water to make 1 l 
Stabilizing Solution 
Formaldehyde 5 ml 
Water to make 2 l 
______________________________________ 
The density of the magenta dye image thus-obtained was measured and fog, 
relative sensitivity and maximum density were determined. The results 
obtained are shown in Table 1 below. 
TABLE 1 
______________________________________ 
Sample Relative Maximum 
No. Hardener Fog Sensitivity 
Density 
______________________________________ 
1 None 0.12 100 2.95 
(control) 
2 Compound 1 0.10 92 2.80 
(present 
invention) 
3 Compound A 0.18 90 1.98 
(comparison) 
4 Compound B 0.14 85 2.70 
(comparison) 
______________________________________ 
As is apparent from the results in Table 1, in Sample 2, containing the 
compound according to the present invention, the color formation of the 
magenta dye is not prevented and the photographic properties are not 
adversely affected. 
EXAMPLE 2 
An emulsion for a green-sensitive layer of a color negative light-sensitive 
material obtained in the same manner as described in Example 1 was divided 
into four portions, a first portion was used as a control. To the other 
three portions were added an aqueous solution of Compound 1, 
1,3,5-tris(.beta.-vinylsulfonylpropyl)hexahydro-s-triazine (Compound C), 
bis(vinylsulfonylmethyl) ether (Compound D) in an amount of 1.5 g per 100 
g of dry gelatin, respectively. Each emulsion was coated on a subbed 
polyethylene terephthalate support at a thickness of 5.mu. and dried. 
The strength of the layer was determined using the two methods described 
below with samples stored at 25.degree. C., 65% RH for 2 days or for 20 
days and a sample heat treated at 50.degree. C., 80% RH for 2 days. 
(1) Strength of Layer Surface 
A sample was immersed in water at 25.degree. C. for 5 minutes. A pin 
equipped with a steel ball having a radius of 0.2 mm on the point thereof 
was pressed on the surface of the sample and the pin was moved at a rate 
of 5 mm per second on the surface of the sample while the load applied to 
the pin was continuously varied in the range of 0 to 100 g. The load (g) 
at which a scratch occurred on the surface was measured. 
(2) Melting Time 
A sample strip was immersed in a 0.2 N aqueous solution of sodium hydroxide 
at 60.degree. C. and the time (min) when the emulsion layer began to melt 
was measured. 
The results obtained are shown in Table 2. 
TABLE 2 
______________________________________ 
Strength of 
Layer Surface (g) 
Melting Time (min) 
Sample 2 20 2 Days 
2 20 2 Days 
No. Hardener Days Days Heated 
Days Days Heated 
______________________________________ 
5 None 2 3 8 0.2 0.3 0.5 
(control) 
6 Compound 1 68 76 81 13.5 27 30 
(present 
invention) 
7 Compound C 13 20 26 1 2.5 3 
(comparison) 
8 Compound D 28 33 35 7.5 13.5 15 
(comparison) 
______________________________________ 
It is apparent from the results in Table 2 that the compound according to 
the present invention has a superior hardening effect and provides 
improved strength for the layer surface and resistance to melting in 
comparison with other comparison vinylsulfone type hardeners. 
EXAMPLE 3 
A solution obtained by heating and dissolving a mixture of 52.3 g of 
.alpha.-pivaloyl-.alpha.-2,4-dioxo-5,5-dimethyl-3-hydantoinyl-2-chloro-5-[ 
.gamma.-(2,4-di-tert-amylphenoxy)butyramido]-acetanilide, 55 ml of 
tri-n-hexyl phthalate and 100 ml of ethyl acetate was added to 1,000 ml of 
an aqueous solution containing 50 g of gelatin and 3.0 g of sodium 
cetylsulfate, and the mixture was dispersed to prepare a yellow coupler 
dispersion. 
The dispersion was added to 1 kg of a photographic emulsion containing 0.3 
mol of silver chlorobromide (silver chloride: 50 mol %) and 100 g of 
gelatin to prepare an emulsion for a blue-sensitive layer of a color print 
paper. The emulsion was divided into four portions. A first portion was 
used as control, and to the other three portions were added Compound 1 of 
the present invention, Compound D and 1,2-bis(vinylsulfonyl)ethane 
(Compound E), respectively, in an amount of 5.times.10.sup.-5 mol per g of 
dry gelatin as solutions as shown in Table 3. 
TABLE 3 
______________________________________ 
Sample No. Hardener Solvent Concentration 
______________________________________ 
9 None -- -- 
(control) 
10 Compound 1 Water 10 wt % 
(present 
invention) 
11 Compound D Water 0.5 wt % 
(comparison) 
12 Compound E Methanol 2 wt % 
(comparison) 
______________________________________ 
In the case of Sample 10, since the compound of the present invention had a 
high solubility in water, the amount of the hardening solution added to 
the emulsion was small and the physical properties of the emulsion were 
not changed. On the contrary, in the case of Samples 11 and 12, the 
viscosities of the emulsions were reduced markedly because of the addition 
of a large amount of the hardening solution and the viscosities must be 
increased by adding poly-(styrenesulfonic acid) in order to achieve the 
required viscosity for coating. 
These four emulsions were coated on a paper, both surfaces of which were 
laminated with polyethylene, as a support, in a dry thickness of 3.5.mu. 
and dried. With respect to Sample 11, in order to achieve the required 
thickness, it was necessary to increase the amount of the coating solution 
applied from the coater to the support or to decrease the travelling speed 
of the support and the time required for drying markedly increased, and 
many difficulties were encountered in the coating step. Further, in the 
case of Sample 12, the concentration of the organic solvent in the exhaust 
drying air increased and it was necessary to remove it to insure worker 
safety. On the contrary, such disadvantages were not encountered in Sample 
10 using the compound according to the present invention. 
EXAMPLE 4 
A 5% solution of gelatin was divided into four portions, a first portion 
was used as a control and to the other three portions were added Compound 
1 of the present invention, Compound B and Compound E in an amount of 
5.times.10.sup.-5 mol per g of dry gelatin, respectively. Each gelatin 
solution was coated on a subbed polyester film support and dried. 
After storing the samples obtained under conditions of 25.degree. C., 65% 
RH, the strength of the gelatin layer surface thereof was determined. The 
results obtained are shown in Table 4 below. 
TABLE 4 
______________________________________ 
Sample Strength of Layer Surface (g) 
No. Hardener 2 Days 7 Days 
14 Days 
21 Days 
______________________________________ 
13 None 2 3 5 6 
(control) 
14 Compound 1 48 56 58 60 
(present 
invention) 
15 Compound B 21 36 45 52 
(comparison) 
16 Compound E 18 25 32 36 
(comparison) 
______________________________________ 
It is apparent from the results in Table 4 that the hardener of the present 
invention exhibited less after-hardening, had a high rate of hardening, 
and provided a gelatin layer having a strong layer surface strength and a 
mechanical strength resistant to severe processing procedures of high 
temperature and high speed. 
While the invention has been described in detail and with reference to 
specific embodiments thereof, it will be apparent to one skilled in the 
art that various changes and modifications can be made therein without 
departing from the spirit and scope thereof.