JP2003252851A - Method for producing bisvinylsulfone compound and method for preventing deterioration - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a bisvinylsulfone compound by which the self-polymerization at its purification step is suppressed, and to provide an inexpensive and easy method for preventing the deterioration of the bisvinylsulfone compound. <P>SOLUTION: The method for producing the bisvinylsulfone compound represented by general formula (I) (wherein, R is a divalent linking group; R<SB>1</SB>and R<SB>2</SB>are each independently a hydrogen atom or a 1-5C alkyl group) involves a purification step wherein a mixture of a crude product containing the bisvinylsulfone compound with an organic solvent is heated in the presence of at least one kind of a phenothiazine derivative. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a bisvinylsulfone compound, a method for preventing deterioration, and a composition.

[0002]

2. Description of the Related Art A bisvinyl sulfone compound is useful as a curing agent for curing a hydrophilic colloid film when a hydrophilic colloid is used as a binder. Examples of the hydrophilic colloid include proteins such as gelatin, albumin and casein, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, sugar derivatives such as agar, sodium alginate and starch derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol and poly. -N-Vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or its derivatives are known. Further, photographic elements, particularly silver halide photographic light-sensitive materials are known as those using a hydrophilic colloid as a binder.

The bisvinylsulfone compound has an active vinyl group at the end of the molecule in order to react with a hydrophilic colloid, particularly gelatin, to exhibit a hardening effect. The vinyl group is affected by alkali or heat. However, there is a problem that it is easy to self-polymerize. In particular, as the hardening activity of vinyl-based gelatin on gelatin increases, self-polymerization tends to occur. If this self-polymerization occurs before reacting with the hydrophilic colloid,
It is disadvantageous in that it causes a factor that makes the hardener unable to act on the desired crosslinking reaction with the hydrophilic colloid. When such self-polymerization occurs, the desired concentration of the hardener in the hardener cannot be maintained. It also has the drawback that the polymer produced can clog piping and other equipment, which requires uptime for cleaning and maintenance. Further, in the production of a silver halide photographic light-sensitive material, this self-polymerized product is insoluble in water and an organic solvent. If such a self-polymerized product is added to a silver halide emulsion coating solution containing such an insoluble product, it will be There is a problem in that a photographic image is defective, such as impairing the coating properties such as spots and lines.

On the other hand, self-polymerization similarly occurs during the production process of the bisvinylsulfone compound and during storage and storage of the compound. These water- and organic solvent-insoluble self-polymerized products are also produced in the process of purifying the crude product in the production process. In particular, in recrystallization with an organic solvent such as alcohols and ketones, self-polymerization occurs because it is heated and dissolved during recrystallization. Further, the obtained bisvinyl sulfone compound, as a hardener, causes self-polymerization during storage and storage before actually used.

Means for suppressing and preventing such self-polymerization of bisvinyl sulfone compounds include, for example, dinitrobenzoic acid in US Pat. No. 4,171,976 and US Pat. No. 3,84.
No. 1,872 proposes the use of hydroquinone.
Further, Japanese Patent Laid-Open No. 2000-275777 proposes to use tartaric acid, oxalic acid and salts thereof as a method for suppressing self-polymerization with respect to ferric ion. However, these methods are not always sufficient, and in silver halide photographic light-sensitive materials, they sometimes affect the photographic characteristics. In particular, the self-polymerization in the production process of the bisvinyl sulfone compound, especially the self-polymerization by the dissolution heating by recrystallization, becomes a dilemma between the purification of the compound and the self-polymerization. Therefore, there has been a strong demand for development of means for suppressing and preventing self-polymerization during the manufacturing process and during storage and storage. In addition, in the refining step of the obtained bisvinylsulfone compound in the manufacturing step, the recrystallized slurry has poor flowability, which makes separation difficult.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a production method in which self-polymerization is suppressed in the production step of a bisvinylsulfone compound, particularly in the purification step. In addition, it is another object of the present invention to provide a manufacturing method in which the operability in the recrystallization step using a hot organic solvent is improved (suppression of the formation of slurry, which has poor fluidity and is difficult to separate). Another object of the present invention is to provide an inexpensive and simple method for preventing deterioration of a bisvinylsulfone compound and a bisvinylsulfone compound-containing composition in which the means is constructed. Another object of the present invention is to provide a bisvinyl sulfone compound in which defects in a photographic image (particularly, not impairing coating properties such as spots and stripes) in a silver halide photographic light-sensitive material are reduced.

[0007]

As a result of earnest studies, the present inventors have found that the above-mentioned problems can be solved by the following means. (1) When producing a bisvinylsulfone compound represented by the following general formula (I), in the purification step, in the presence of at least one phenothiazine derivative represented by the following general formula (II), the bisvinylsulfone compound A method for producing a bisvinylsulfone compound, which comprises heating a mixture of a crude product containing the organic solvent and an organic solvent.

[0008]

Embedded image General formula (I)

In the general formula (I), R represents a divalent linking group,
R ₁ and R ₂ are each independently a hydrogen atom or a carbon atom number of 1 to 5.
Represents an alkyl group.

[0010]

Embedded image General formula (II)

In the general formula (II), R ₁₁ and R ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom. (2) A method for preventing deterioration of a bisvinylsulfone compound represented by the following general formula (I), characterized in that at least one phenothiazine derivative represented by the following general formula (II) is allowed to coexist.

[0012]

Embedded image General formula (I)

In the general formula (I), R represents a divalent linking group,
R ₁ and R ₂ are each independently a hydrogen atom or a carbon atom number of 1 to 5.
Represents an alkyl group.

[0014]

Embedded image General formula (II)

In the general formula (II), R ₁₁ and R ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. (3) A bisvinylsulfone compound-containing composition represented by the following general formula (I), which contains a phenothiazine derivative represented by the following general formula (II).

[0016]

Embedded image General formula (I)

In the general formula (I), R represents a divalent linking group,
R ₁ and R ₂ are each independently a hydrogen atom or a carbon atom number of 1 to 5.
Represents an alkyl group.

[0018]

Embedded image General formula (II)

In the general formula (II), R ₁₁ and R ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION First, the bisvinylsulfone compound represented by the general formula (I) of the present invention will be described. The bisvinyl sulfone compound of the present invention is represented by the following general formula (I).

[0021]

Embedded image General formula (I)

In the general formula (I), R represents a divalent linking group,
R ₁ and R ₂ are each independently a hydrogen atom or a carbon atom number of 1 to 5.
Represents an alkyl group. The divalent linking group represented by R may be any group as long as it is a divalent group, but is preferably an alkylene group. These alkylene groups may have a substituent, and an ether bond in the alkylene chain,
It may be linked via a functional group such as a thioether bond, an amide bond or a sulfonyl bond. Examples of the unsubstituted alkylene group include ethylene, propylene, butylene and pentylene. Examples of the branched alkylene group include 1-methylethylene and 2-methylpropylene. Examples of the substituent of the substituted alkylene group include a hydroxy group, an alkoxy group, and an aryloxy group. Of these substituted alkylene groups, a hydroxy group or an alkylene group substituted with an alkoxy group having 1 to 5 carbon atoms is preferable, and a hydroxy group is particularly preferable. Specific examples of the alkylene group substituted with a hydroxy group or an alkoxy group include 2-hydroxypropylene, 3-hydroxypentylene, 2-methoxypropylene, 2-ethoxypropylene, 3-methoxypentylene, and 3-ethoxypentylene. Ren is mentioned. Examples of the alkylene group having an ether bond in the alkylene chain include, for example, 3-oxa-1,5-pentylene, 3-oxa-2,4-dimethyl-pentylene, 3,6-dioxaoctylene, and carboxylic acid amide bond. as alkylene radicals containing from, for _{example, -CH 2 CONHCH 2 CH 2 NHCOCH} 2 -, - CH 2 CONHCH 2 CH 2
CH ₂ NHCOCH ₂ -is mentioned.

R is more preferably ethylene, 3-hydroxypentylene, 3-oxapentylene, -CH ₂ CONHCH ₂ C.
_{H 2 NHCOCH 2 -, - CH} 2 CONHCH 2 CH 2 CH 2 NHCOCH 2 - a. R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom and a methyl group, and more preferably a hydrogen atom. R ₁ , R ₂ and R
The combination of may be any of the above, but preferably,
R is ethylene, propylene, pentylene, 2-methylpentylene, 2-hydroxypropylene, 3-hydroxypentylene, 2-methoxypropylene, 3-methoxypentylene,
3-oxa-1,5-pentylene, 3,6-dioxaoctylene,-
_{CH 2 CONHCH 2 CH 2 NHCOCH 2} -, - CH 2 CONHCH 2 CH 2 CH 2 NHCOCH 2 - a a, a R ₁ is a hydrogen atom or a methyl group, a combination wherein R ₂ is a hydrogen atom or a methyl group good. More preferably, R is ethylene, 3-hydroxypentylene, 3-
Methoxy pentylene, 3-oxypentylene, 3,6-dioxy _{octylene, -CH 2 CONHCH 2 CH 2 NHCOCH} 2 -, - CH 2 CONHCH 2 C
A combination of H ₂ CH ₂ NHCOCH ₂ — in which R ₁ is a hydrogen atom or a methyl group and R ₂ is a hydrogen atom or a methyl group is preferable.

The compound represented by the general formula (I) of the present invention is specifically 1,2-bis (vinylsulfonyl) ethane, bis {2- (vinylsulfonyl) ethyl} ether,
1,5-bis (vinylsulfonyl) -3-hydroxypentane, 1,2-bis (vinylsulfonylacetamido) ethane, 1,3-bis (vinylsulfonylacetamido) propane, 1,5-bis (vinylsulfonyl) -3 -Methoxypentane, 1,8-bis (vinylsulfonyl) -3,6-oxaoctane, bis {2- (1'-methylvinylsulfonyl) ethyl} ether, 1,2-bis {(1'-methylvinylsulfonyl) ) Acetamide} ethane, 1,3-bis {(1′-vinylsulfonyl) acetamide} propane, but the invention is not limited to these specific compounds. Next, the phenothiazine derivative represented by the general formula (II) of the present invention will be described in detail.

General formula (II)

[Chemical 14]

In the formula (II), R ₁₁ and R ₁₂ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, i-propyl, n-butyl, t). -
Butyl, n-pentyl), an alkoxy group having 1 to 5 carbon atoms (eg, methoxy, ethoxy, pentyloxy)
And a halogen atom (eg, fluorine, chlorine, bromine). Preferably R ₁₁ and / or R ₁₂ is a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a chlorine atom or a bromine atom. More preferably, one of R ₁₁ and R ₁₂ is a hydrogen atom, and the other is a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a chlorine atom and a bromine atom.

Specific examples of the compound represented by the general formula (II) of the present invention include phenothiazine, 1-methylphenothiazine, 2-methylphenothiazine, 3-methylphenothiazine, 4-methylphenothiazine, 1-ethylphenothiazine, 2-ethylphenothiazine, 3-ethylphenothiazine, 4-ethylphenothiazine, 1-methoxyphenothiazine, 2-methoxyphenothiazine, 3-methoxyphenothiazine, 4-methoxyphenothiazine, 1-ethoxyphenothiazine, 2-ethoxyphenothiazine, 3-ethoxyphenothiazine, 1-chlorophenothiazine, 2-chlorophenothiazine, 3-chlorophenothiazine, 4-chlorophenothiazine, 1-bromophenothiazine, 2-bromophenothiazine, 3-bromophenothiazine, 4-bromophenothiazine, 1,2-dimethylbromophenothiazine, 1, 3- Methyl phenothiazine, 1,4-dimethyl-phenothiazine, 1,6-dimethyl-phenothiazine, 1,7-dimethyl-phenothiazine,
1,8-Dimethylphenothiazine, 1,9-Dimethylphenothiazine, 2,3-Dimethylphenothiazine, 2,4-Dimethylphenothiazine, 2,6-Dimethylphenothiazine, 2,7-Dimethylphenothiazine, 2,8-Dimethylphenothiazine, 3 , 6-
Dimethylphenothiazine, 3,7-dimethylphenothiazine, 1,2-dimethoxyphenothiazine, 1,4-dimethoxyphenothiazine, 2,3-dimethoxyphenothiazine, 2,7-dimethoxyphenothiazine, 2,8-dimethoxyphenothiazine, 3,7-dimethoxy Phenothiazine, 1,2-dichlorophenothiazine, 1,3-dichlorophenothiazine, 1,4-dichlorophenothiazine, 1,7-dichlorophenothiazine, 1,8-
Dichlorophenothiazine, 2,3-dichlorophenothiazine, 2,4-dichlorophenothiazine, 2,6-dichlorophenothiazine, 2,7-dichlorophenothiazine, 2,8-dichlorophenothiazine, 3,7-dichlorophenothiazine, 1,3-dibromo Phenothiazine, 2,4-dibromophenothiazine,
Examples include 2,7-dibromophenothiazine and 3,7-dibromophenothiazine. The compound represented by the general formula (II) of the present invention is not limited to these. In the present invention, the phenothiazine derivative represented by the general formula (II) may be used alone, or a plurality of derivatives may be mixed and used.

The bisvinyl sulfone compound represented by the general formula (I) (crude product) can be synthesized by deprotecting the protecting group X of the compound represented by the following general formula (III) with a base. .

[0029]

Embedded image General formula (III)

In the general formula (III), R represents a divalent linking group, R ₁ and R ₂ are each independently a hydrogen atom or the number of carbon atoms.
1 to 5 alkyl groups, X represents a protecting group such as a mesyl group and a tosyl group. In the above, R, R ₁ and R ₂ have the same meanings as in formula (I), and the preferred ranges are also the same. The obtained crude crystals of the bisvinylsulfone compound represented by the general formula (I) are subsequently purified. In this purification, recrystallization is carried out by dissolving in a hot organic solvent, filtering the insoluble matter by heat, and then cooling, but self-polymerization due to heat proceeds even after filtration of the self-polymerized matter, and an insoluble matter is produced. However, this phenomenon can be prevented by allowing the phenothiazine derivative represented by the general formula (II) of the present invention to coexist during the heating recrystallization.

The purification of the bisvinyl sulfone compound represented by the general formula (I) will be described in detail below. In the present invention, in the purification step, purification is performed in the presence of at least one phenothiazine derivative represented by the general formula (II) of the present invention. The phenothiazine derivative may be added before the purification step (that is, a crude product of the bisvinylsulfone compound represented by the general formula (I) containing the phenothiazine derivative is used) or added at the purification stage. Although it is good, it is preferably added at the stage of the purification process. In the purification step, even if the phenothiazine derivative is added at once (for example, only before heating the bisvinylsulfone compound and the recrystallization solvent),
It may be added in three times (for example, in addition to the above-mentioned addition, further addition after filtration of the insoluble matter). Preferably,
In the case of adding in two steps, the crude product of the bisvinylsulfone compound and the recrystallization solvent are added before heating, and further the insoluble matter after heating under reflux [adsorbent (when used for purification ( Preferably, activated carbon) or an insoluble matter in a crude product of a bisvinylsulfone compound or an insoluble matter generated by heating] is added at a stage after filtering and before cooling. Specifically, the recrystallization of the bisvinyl sulfone compound represented by the general formula (I) is preferably performed as follows.

Crude crystals of the bisvinyl sulfone compound represented by the general formula (I) are suspended in a recrystallization solvent to give the general formula (II).
The phenothiazine derivative represented by is added. The suspension is heated under reflux for a certain period of time to form a uniform solution, which is then hot-filtered through activated carbon and a phenothiazine derivative is added. The recrystallization solution is cooled to separate the precipitated crystal of the bisvinylsulfone compound represented by the general formula (I). As the recrystallization solvent, a ketone solvent having 3 to 6 carbon atoms (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone), and / or an alcohol solvent having 1 to 4 carbon atoms (for example, methanol, ethanol, isopropanol,
Butanol) can be used, but an alcohol-based agent alone or a mixed solvent with an equivalent volume to 6 times the volume of a ketone-based solvent with respect to the alcohol-based solvent is preferable. The amount of the recrystallization solvent can be 3 to 10 times by mass based on the crude crystal of the bisvinylsulfone compound represented by the general formula (I),
It is preferably 4 to 7 times the mass. The melting temperature during recrystallization is 55
℃ to the boiling point of the recrystallization solvent, the heating time is preferably 30
~ 120 minutes. Separation temperature during recrystallization is from -10 ℃ to -20
The crystals can be separated at 0 ° C, but the separation at 0 to -20 ° C is preferable for securing the yield.

The amount of the phenothiazine derivative represented by the general formula (II) added to the suspension of the bisvinyl sulfone compound represented by the general formula (I) before dissolution is 10 to 100 ppm.
However, when an adsorbent is used, it is adsorbed by the adsorbent, so that it is preferably 20 to 300 ppm, more preferably 50 to 100 ppm. In the present invention, it is preferable to use an adsorbent for purification, and activated carbon is preferable as the adsorbent. The amount of the phenothiazine derivative represented by the general formula (II) added to the recrystallized solution after hot filtration is 0.1 to 500 ppm, which is effective, but the amount of the bisvinylsulfone compound represented by the general formula (I) after purification is effective. 0.5 to 3 in consideration of residual amount and influence on photographic properties
00 ppm is preferable, and 1 to 100 ppm is more preferable. Further, at the time of recrystallization of the bisvinylsulfone compound represented by the general formula (I), if cooling is started immediately after dissolution by heating in a recrystallization solvent, fluidity of the bisvinylsulfone compound can be improved regardless of crystallization conditions such as cooling rate and stirring rate. It becomes a bad slurry and becomes difficult to separate.
This phenomenon is caused by heating and dissolving the bisvinylsulfone compound represented by the general formula (I) in a recrystallization solvent to which the phenothiazine derivative represented by the general formula (II) of the present invention is added, and then applying a heat load for a certain period of time. Can be solved with. By applying a heat load for a certain time after dissolution, the agglomeration state of the crystals changes, the separability is improved, the separation time is shortened, and the cleaning effect of the crystals is also improved. By adding the phenothiazine derivative represented by the general formula (II) of the present invention, even if heating is continued near the boiling point of the recrystallization solvent, formation of a self-polymerized bisvinylsulfone compound is not observed, but The heating time is preferably 30 to 120 minutes, because larger agglomerates may be generated and the workability may be rather deteriorated by continuing the heating for a time.

When recrystallization is carried out under such conditions, the phenothiazine compound of the present invention remains in the bisvinylsulfone compound represented by the general formula (I) after separation and drying. It also helps prevent deterioration due to heat load during storage. The phenothiazine derivative represented by the general formula (II) remaining in the bisvinylsulfone compound represented by the general formula (I) is effective at 0.1 to 500 ppm, preferably 0.5 to 300 ppm, Preferably, 1 to 100 ppm is effective, especially 2 to 100 p
pm is preferred.

The bisvinyl sulfone compound produced as described above is useful as a curing agent (crosslinking agent) for curing the hydrophilic colloid film of a product using a hydrophilic colloid as a binder, and particularly as a hydrophilic colloid, gelatin is mainly used. Is useful as a curing agent for a silver halide photographic light-sensitive material. Specifically, color negative photosensitive materials described in JP-A-2000-105445 and JP-A-11-305396, and color printing described in JP-A-2001-42481 and JP-A-11-7109. Paper photosensitive material, color reversal film described in JP-A No. 11-84601, etc.
It can be used as a curing agent for the hydrophilic colloid used in the film photosensitive material for photographic printing described in 01-296628, 2001-296640, 2001-337429 and the like. Hereinafter, the present invention will be described in more detail and specifically with reference to Examples.

Example 1 30 g of crude crystals of 1,3-bis (vinylsulfonylacetamido) propane and 210 m of methanol
50 ppm of phenothiazine was added to the suspension of 1, relative to 1,3-bis (vinylsulfonylacetamido) propane, and dissolved by heating at an external temperature of 70 to 75 ° C. Heating was continued for 30 minutes after the methanol started to reflux while maintaining the external temperature at 70 to 75 ° C. After that, while maintaining the liquid temperature at 40 to 50 ℃, activated carbon 3g
Was pre-coated and the solution was filtered and washed with 30 ml of methanol. To the filtrate, phenothiazine (50 ppm) was added to 1,3-bis (vinylsulfonylacetamide) propane, and after cooling to 0 ° C, the precipitated crystals were separated and dried to give 25.5 g of a purified product with a recovery rate of 85%. Obtained. The obtained purified product of 1,3-bis (vinylsulfonylacetamide) propane contained 5 ppm of phenothiazine. A 15 mass% methanol solution of 1,3-bis (vinylsulfonylacetamido) propane obtained by this method was stored at 70 ° C.
No insoluble matter was observed even after 0 hour.

(Comparative Example 1) Recrystallization was carried out in the same manner as in Example 1 except that phenothiazine was not added. What was obtained after the treatment was a slurry which was muddy and difficult to stir and take out. A white insoluble matter was observed in a 15% by mass methanol solution of 1,3-bis (vinylsulfonylacetamido) propane obtained by this method.

(Example 2) 1,3-bis (vinylsulfonylacetamide) propane containing 3 ppm of phenothiazine added to 1,3-bis (vinylsulfonylacetamide) propane
A 15 mass% methanol solution of propane was stored at 70 ° C.
The turbidity of the solution was 1.0 ppm or less even after 50 hours, and formation of a polymer was not observed when the solution was stored.

(Comparative Example 2) When stored in the same manner as in Example 2 except that phenothiazine was not added, a white insoluble matter was observed after 24 hours.

(Comparative Example 3) In Example 2, instead of phenothiazine, 3 ppm of 3,5-dinitrobenzoic acid was used with respect to 1,3-bis (vinylsulfonylacetamido) propane. A white insoluble material was observed after a period of time.

(Comparative Example 4) In Example 2, instead of phenothiazine, 3 ppm of 2,4-dinitrobenzoic acid was used with respect to 1,3-bis (vinylsulfonylacetamido) propane. A white insoluble material was observed after a period of time.

(Comparative Example 5) In Example 2, instead of phenothiazine, 3 ppm of 2,4-dinitrobenzenesulfonic acid sodium salt with respect to 1,3-bis (vinylsulfonylacetamido) propane was used and similarly stored. However, the turbidity of the solution exceeded 1 ppm after 8 hours, and a white insoluble matter was observed after 48 hours.

(Comparative Example 6) Further, when 3 ppm of hydroquinone was used for 1,3-bis (vinylsulfonylacetamido) propane instead of phenothiazine in Example 2, the same preservation was carried out. The turbidity exceeded 1 ppm, and white insoluble matter was observed after 48 hours.

Example 3 1,3-Bis (vinylsulfonylacetamido) propane containing 3 ppm of phenothiazine was stored at 70 ° C. for 48 hours and then used as a 15 mass% methanol solution. The turbidity of this solution was 1.0 ppm or less, and formation of a polymer was not observed even when stored in the solid state.

(Comparative Example 7) 1,3 containing no phenothiazine
-Bis (vinylsulfonylacetamide) propane 70
After storing at 48 ° C. for 48 hours, a 15 mass% methanol solution was prepared.
The turbidity of this solution was 10 ppm, and the formation of a polymer was observed even when stored in the solid state in the absence of phenothiazine.

Example 4 Instead of 1,3-bis (vinylsulfonylacetamido) propane in Examples 1 to 3,
1,2-bis (vinylsulfonylacetamide) ethane, 1,
2-bis (vinylsulfonyl) ethane, 3-hydroxy-1,5
Example 1 using -bis (vinylsulfonyl) pentane and bis (2-vinylsulfonylethyl) ether
Results were similar to ~ 3.

(Comparative Example 8) Instead of 1,3-bis (vinylsulfonylacetamido) propane in Comparative Examples 1 to 7
1,2-bis (vinylsulfonylacetamide) ethane, 1,
2-bis (vinylsulfonyl) ethane, 3-hydroxy-1,5
-When using bis (vinylsulfonyl) pentane and bis (2-vinylsulfonylethyl) ether, respectively,
The results were similar to those of Control Examples 1 to 7.

Example 5 When 2-methylphenothiazine, 2-chlorophenothiazine, 2-methoxyphenothiazine, 2-ethylphenothiazine, or 2-ethoxyphenothiazine was used in place of phenothiazine in Examples 1 to 4, The results were similar to 1 to 4.

(Comparative Example 9) Under the condition that the phenothiazine derivative was not present in Example 5, the results were similar to those of Comparative Examples 1 and 2.

(Example 6) Japanese Patent Laid-Open No. 2000-105445
In producing the sample 110 of Example 1 of No.
The hardener H-1 used in the protective layer) was prepared according to Example 1 of the present invention.
1,3-bis (vinylsulfonylacetamide) obtained in
A sample changed to propane (containing 5 ppm of phenothiazine) was prepared. Similarly, further 10,20,50,1 respectively
Each sample was made using 1,3-bis (vinylsulfonylacetamido) propane containing 00,300 ppm phenothiazine. Next, these samples were subjected to wedge exposure with white light and subjected to color photographic development processing in the same manner as in JP-A 2000-1054465. As a result, the photographic sensitivity and fog of any of the samples were not different from those of the sample to which the phenothiazine derivative was not added. That is, it can be seen that the phenothiazine derivative does not affect the photographic properties at the above addition amount.

[0051]

According to the present invention, when a phenothiazine derivative represented by the general formula (II) is added at the time of recrystallization of the bisvinylsulfonyl compound represented by the general formula (I), a polymer produced by heat load is added. Can be prevented from being generated. In addition, by adding the phenothiazine derivative at the time of recrystallization and then applying a heat load for a certain period of time, it is possible to control the aggregation state of the crystals and obtain crystals with good separation operability. The bisvinylsulfone compound represented by the general formula (I) obtained by the method of the present invention is difficult to polymerize in a solid state or a solution state because it contains a phenothiazine derivative.
Furthermore, it was found that the bisvinylsulfone compound represented by the general formula (I) thus obtained did not impair the photographic properties when used as a photographic material.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Junichi Tomizuka             2700 Suga, Hiratsuka City, Kanagawa Prefecture Daito Chemical Co., Ltd.             Inside the company (72) Inventor Yuji Tagami             2700 Suga, Hiratsuka City, Kanagawa Prefecture Daito Chemical Co., Ltd.             Inside the company (72) Inventor Taki Kumagai             2700 Suga, Hiratsuka City, Kanagawa Prefecture Daito Chemical Co., Ltd.             Inside the company (72) Inventor Akihiko Ikegawa             2-12-1, Ogimachi, Odawara City, Kanagawa Prefecture             Shishi Film Co., Ltd. F-term (reference) 4H006 AA02 AD41 BB14 TA02 TB22

Claims (3)

[Claims] 1. When producing a bisvinyl sulfone compound represented by the following general formula (I), in the purification step,
Production of a bisvinylsulfone compound, which comprises heating a mixture of a crude product containing the bisvinylsulfone compound and an organic solvent in the presence of at least one phenothiazine derivative represented by the following general formula (II). Method. ## STR00001 ## General formula (I) In the general formula (I), R represents a divalent linking group, and R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. [Formula 2] General formula (II) In formula (II), R ₁₁ and R ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. 2. A method for preventing deterioration of a bisvinylsulfone compound represented by the following general formula (I), which comprises coexisting at least one phenothiazine derivative represented by the following general formula (II). Embedded image General formula (I) In the general formula (I), R represents a divalent linking group, and R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Embedded image General formula (II) In formula (II), R ₁₁ and R ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. 3. A bisvinylsulfone compound-containing composition represented by the following general formula (I), which contains a phenothiazine derivative represented by the following general formula (II). Embedded image General formula (I) In the general formula (I), R represents a divalent linking group, and R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Embedded image General formula (II) In formula (II), R ₁₁ and R ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.