JP3598131B2 - Novel substituted alkylsulfinic acid ammonium salts - Google Patents
Novel substituted alkylsulfinic acid ammonium salts Download PDFInfo
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- JP3598131B2 JP3598131B2 JP16126994A JP16126994A JP3598131B2 JP 3598131 B2 JP3598131 B2 JP 3598131B2 JP 16126994 A JP16126994 A JP 16126994A JP 16126994 A JP16126994 A JP 16126994A JP 3598131 B2 JP3598131 B2 JP 3598131B2
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- Prior art keywords
- acid
- alkylsulfinic
- ammonium
- alkylsulfinic acid
- ammonium salts
- Prior art date
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- 239000002253 acid Substances 0.000 title claims description 18
- 150000003863 ammonium salts Chemical class 0.000 title claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- -1 silver halide Chemical class 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical compound O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DILXLMRYFWFBGR-UHFFFAOYSA-N 2-formylbenzene-1,4-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(S(O)(=O)=O)C(C=O)=C1 DILXLMRYFWFBGR-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- AYTHAXUMFKBTSN-UHFFFAOYSA-N [NH4+].CS([O-])=O Chemical compound [NH4+].CS([O-])=O AYTHAXUMFKBTSN-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CLVWTYRTWKEEEL-UHFFFAOYSA-N azanium;ethanesulfinate Chemical compound [NH4+].CCS([O-])=O CLVWTYRTWKEEEL-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FRYHCSODNHYDPU-UHFFFAOYSA-N ethanesulfonyl chloride Chemical compound CCS(Cl)(=O)=O FRYHCSODNHYDPU-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- UWIVVFQECQYHOB-UHFFFAOYSA-M sodium;ethanesulfinate Chemical compound [Na+].CCS([O-])=O UWIVVFQECQYHOB-UHFFFAOYSA-M 0.000 description 1
- LYPGDCWPTHTUDO-UHFFFAOYSA-M sodium;methanesulfinate Chemical compound [Na+].CS([O-])=O LYPGDCWPTHTUDO-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は新規なアルキルスルフィン酸無置換アンモニウム塩に関するものであり、さらに詳しくは、医療用途、写真用途、特にハロゲン化銀写真感光材料分野で使用される安定化剤、例えばハロゲン化銀カラー写真感光材料の漂白定着処理及び定着処理に使われるチオ硫酸アンモニウム等の安定化剤として有用な新規なスルフィン酸無置換アンモニウム塩に関するものである。
【０００２】
【従来の技術】
従来、スルフィン酸は医療用、写真用等に幅広く用いられているが、特にハロゲン化銀写真感光材料分野で使用される安定化剤、例えばハロゲン化銀カラー写真感光材料の漂白定着処理及び定着処理に使われている安定化剤として用いられている。安定化剤として従来はアリールスルフィン酸（例えばフェニルスルフィン酸、ｐ−トルエンスルフィン酸）等を用いていたが、より水溶性、安定化能を高めるためにアルキルスルフィン酸の開発が望まれていた。しかしアルキルスルフィン酸は非常に不安定であり、その塩もナトリウム塩等は結晶として単離されているが、より水溶性の高いアミン塩（例えば無置換アンモニウム塩）は結晶として得られておらず、使用用途に制限があった。
【０００３】
【発明が解決しようとする課題】
本発明は上記の事情を解決するためなされたものであり、結晶として単離困難であったアルキルスルフィン酸アミン塩を提供するものである。
【０００４】
【課題を解決するための手段】
上記の目的は、下記一般式（１）で表されるスルフィン酸無置換アンモニウム塩によって達成された。
一般式（１） Ｒ−ＳＯ2 −・ＮＨ4 +
（式中、Ｒは炭素数１〜３の、無置換アルキル基を表す。）
【０００５】
以下に本発明のスルフィン酸アミン塩について詳細に説明する。一般式（１）においてＲで表される炭素数１〜３の、無置換アルキル基としてはメチル、エチル、１−プロピル、２−プロピルが挙げられ、より好ましいアルキル基はメチルである。
【０００７】
以下に一般式（１）で表されるスルフィン酸アミン塩の具体例を挙げるが、本発明はこれらに限定されるものではない。
【０００８】
化合物１ ＣＨ3ＳＯ2 −・ＮＨ4 +
化合物２ ＣＨ3ＣＨ2ＳＯ2 −・ＮＨ4 +
化合物３ ＣＨ3ＣＨ2ＣＨ2ＳＯ2 −・ＮＨ4 +
【００１０】
本発明の合成法の詳細を以下に説明する。
本発明のアルキルスルフィン酸無置換アンモニウム塩は、既に文献＊）で合成法が知られているアルキルスルフィン酸のアルカリ金属塩及び／またはアルカリ土類金属塩のカチオン交換法によって合成することができる。
＊）(1) ジャーナル・オブ・オルガニック・ケミストリー（ J.Org.Chem.) 第７巻、２３−３０、１９４２年
(2) ザ・ケミストリー・オブ・スルフィニック・アシッド、エステルズ・アンド・ゼアー・デリバティブス(The Chemistry of sulphinic acid, esters and their derivatives) パタイ・シリーズ・エディター（PATAISeries Editor), CHAPTER7, １９９０年
その反応はアルキルスルフィン酸のアルカリ金属塩及び／またはアルカリ土類金属塩をアルコール溶媒に溶解した後、無機酸（例えば硫酸、塩酸、硝酸）のアミン塩（アンモニウム塩）を添加するものである。
その添加量はアルキルスルフィン酸のアルカリ金属塩及び／またはアルカリ土類金属塩の５〜３０当量が好ましい。
この不均一な反応液を３０℃〜５０℃で攪拌すると、酸塩基平衡によりアルキルスルフィン酸より強酸な無機酸（例えば硫酸等）は、アミンよりも強塩基なアルカリ金属及び／またはアルカリ土類金属とイオン結合を形成し、同時にアルキルスルフィン酸はアミンとイオン結合を形成する。
使用するアルコール溶媒に生成するアルキルスルフィン酸のアミン塩は易溶であり、無機酸のアルカリ金属塩及び／またはアルカリ土類金属塩は難溶であり析出するため、カチオン交換終了後濾過を行なうことにより簡便にアルキルスルフィン酸アミン塩のアルコール溶液が得られる。濾過温度は２５℃から４０℃が好ましい。
【００１１】
アルキルスルフィン酸無置換アンモニウム塩の溶液からアルキルスルフィン酸無置換アンモニウム塩を結晶として単離する方法は、貧溶媒（例えば酢酸エチル、塩化メチレン）の添加により結晶を析出させた後濾別する方法が好ましい。貧溶媒の添加により結晶を析出させる方法ではその温度は１０℃から２５℃が好ましい。
【００１２】
【実施例】
実施例１
化合物１の合成
メタンスルホニルクロライドと亜硫酸ナトリウム及び水酸化ナトリウム水溶液から容易に合成できるメタンスルフィン酸ナトリウム（１０２ｇ、１ｍｏｌ）をメタノール（１リットル）に溶解し、１０当量の硫酸アンモニウム（６６０ｇ、５ｍｏｌ）を添加したのち４０℃で５時間攪拌した。次いで反応液を２５℃まで冷却した後メタノールに難溶な硫酸ナトリウムと過剰に添加した硫酸アンモニウムを濾過して除去した。濾液に１０℃まで冷却した後酢酸エチル（３リットル）を添加し析出した結晶を濾過することによりメタンスルフィン酸アンモニウム目的化合物１（８５． ４ｇ、０． ８８ｍｏｌ）を得た。収率８８％。また、化合物１のカチオンの純度はイオンクロマトグラフィーにより９９％。
【００１３】
実施例２
化合物２の合成
エタンスルホニルクロライドと亜硫酸ナトリウム及び水酸化ナトリウム水溶液から容易に合成できるエタンスルフィン酸ナトリウム（１１６ｇ、１ｍｏｌ）をメタノール（１リットル）に溶解し、１０当量の硫酸アンモニウム（６６０ｇ、５ｍｏｌ）を添加したのち４０℃で５時間攪拌した。次いで反応液を２５℃まで冷却した後メタノールに難溶な硫酸ナトリウムと過剰に添加した硫酸アンモニウムを濾過して除去した。濾液に１０℃まで冷却した後酢酸エチル（３リットル）を添加し析出した結晶を濾過することによりエタンスルフィン酸アンモニウム目的化合物２（９４. ５ｇ、０. ８５ｍｏｌ）を得た。収率８５％。また、化合物２のカチオンの純度はイオンクロマトグラフィーにより９９％。
【００１５】
参考例１
特開平５−７２６９６号の実施例１に記載されているハロゲン化銀写真感光材料の処理方法において、定着液中の定着剤としてはチオ硫酸アンモニウム液（７０ｗｔ％）を使用し、安定化剤としてアリールスルフィン酸アンモニウム、アルキルスルフィン酸ナトリウム、及び本発明で結晶として単離したアルキルスルフィン酸のアンモニウム塩の化合物１を添加した際の脱銀時間を第１表に示した。
（定着液組成） 母液（ｇ） 補充液（ｇ）
エチレンジアミン四酢酸二ナトリウム塩 ０．５ １．０
亜硫酸ナトリウム ７．０ １２．０
重亜硫酸ナトリウム ５．０ ９．５
チオ硫酸アンモニウム水溶液（７０ｗｔ％） １７０ｍｌ ２４０ｍｌ
安定化剤；表１に記載の安定化剤 ０．１モル ０．１５モル
水を加えて １．０リットル １．０リットル
ｐＨ ６．７ ６．７
【００１６】
【表１】
第１表より本発明の化合物を安定化剤として用いた場合、ランニング処理時にも沈澱が起こらず、アリールスルフィン酸アンモニウムや、アルキルスルフィン酸ナトリウムのように定着を遅らせることがないという効果があり、この効果は低補充化した場合特に顕著である。[0001]
[Industrial applications]
The present invention relates to a novel alkylsulfinic acid unsubstituted ammonium salt, and more particularly, to a stabilizer used in medical applications, photographic applications, particularly in the field of silver halide photographic materials, for example, silver halide color photographic materials. The present invention relates to a novel sulfinic acid -unsubstituted ammonium salt useful as a stabilizer such as ammonium thiosulfate used for bleach-fixing and fixing of materials.
[0002]
[Prior art]
Conventionally, sulfinic acid has been widely used for medical use, photographic use, etc., and in particular, a stabilizer used in the field of silver halide photographic light-sensitive materials, for example, bleach-fixing processing and fixing processing of silver halide color photographic light-sensitive materials. It is used as a stabilizer used in Conventionally, arylsulfinic acid (for example, phenylsulfinic acid, p-toluenesulfinic acid) or the like has been used as a stabilizer, but development of an alkylsulfinic acid has been desired in order to further increase water solubility and stabilization ability. However, alkylsulfinic acid is very unstable, and its salts such as sodium salts are isolated as crystals, but more water-soluble amine salts (eg, unsubstituted ammonium salts) are not obtained as crystals. , There were restrictions on the intended use.
[0003]
[Problems to be solved by the invention]
The present invention has been made to solve the above circumstances, and provides an alkylsulfinic acid amine salt which has been difficult to isolate as crystals.
[0004]
[Means for Solving the Problems]
The above object has been achieved by an unsubstituted sulfinic acid ammonium salt represented by the following general formula (1).
General formula (1) R—SO 2 — · NH 4 +
(In the formula, R represents an unsubstituted alkyl group having 1 to 3 carbon atoms.)
[0005]
Hereinafter, the amine salt of sulfinic acid of the present invention will be described in detail. Examples of the unsubstituted alkyl group having 1 to 3 carbon atoms represented by R in the general formula (1) include methyl, ethyl, 1-propyl and 2-propyl, and a more preferred alkyl group is methyl.
[0007]
Specific examples of sulfinic acid amine salt represented in following formula (1), but the present invention is not limited thereto.
[0008]
Compound 1 CH 3 SO 2 − · NH 4 +
Compound 2 CH 3 CH 2 SO 2 − · NH 4 +
Compound 3 CH 3 CH 2 CH 2 SO 2 - · NH 4 +
[0010]
The details of the synthesis method of the present invention are described below.
The alkylsulfinic acid unsubstituted ammonium salt of the present invention can be synthesized by a cation exchange method of an alkali metal salt and / or an alkaline earth metal salt of alkylsulfinic acid, which is already known in the literature *).
*) (1) Journal of Organic Chemistry (J.Org. Chem.), Vol. 7, 23-30, 1942
(2) The reaction of The Chemistry of sulphinic acid, esters and their derivatives (PATAISeries Editor), CHAPTER7, 1990 after the alkali metal salt and / or alkaline earth metal salts of alkyl sulfinic acid was dissolved in an alcohol solvent, but the addition of inorganic acids (e.g. sulfuric, hydrochloric, nitric) an amine salt of (a ammonium salt).
The addition amount is preferably 5 to 30 equivalents of the alkali metal salt and / or the alkaline earth metal salt of the alkylsulfinic acid.
When the heterogeneous reaction solution is stirred at 30 ° C. to 50 ° C., an inorganic acid (eg, sulfuric acid) stronger than alkylsulfinic acid due to acid-base equilibrium becomes an alkali metal and / or alkaline earth metal stronger than amine. Forms an ionic bond with the alkylsulfinic acid, and at the same time forms an ionic bond with the amine.
The amine salt of alkylsulfinic acid formed in the alcohol solvent used is easily soluble, and the alkali metal salt and / or alkaline earth metal salt of the inorganic acid is hardly soluble and precipitates. Thus, an alcohol solution of an alkylsulfinic acid amine salt can be easily obtained. The filtration temperature is preferably from 25 ° C to 40 ° C.
[0011]
The method of isolating the unsubstituted alkylsulfinic acid ammonium salt as a crystal from the solution of the unsubstituted alkylsulfinic acid ammonium as a crystal includes a method of adding a poor solvent (eg, ethyl acetate, methylene chloride) to precipitate the crystal, and then separating the crystal by filtration. preferable. In the method of depositing crystals by adding a poor solvent, the temperature is preferably from 10 ° C to 25 ° C.
[0012]
【Example】
Example 1
Synthesis of Compound 1 Dissolve methanesulfonyl chloride, sodium sulfite and sodium methanesulfinate (102 g, 1 mol) which can be easily synthesized from an aqueous sodium hydroxide solution in methanol (1 liter), and add 10 equivalents of ammonium sulfate (660 g, 5 mol). Thereafter, the mixture was stirred at 40 ° C. for 5 hours. Then, the reaction solution was cooled to 25 ° C., and sodium sulfate which was hardly soluble in methanol and ammonium sulfate which was excessively added were removed by filtration. After cooling the filtrate to 10 ° C., ethyl acetate (3 liters) was added, and the precipitated crystals were filtered to obtain ammonium methanesulfinate target compound 1 (85.4 g, 0.88 mol). Yield 88%. The cation purity of Compound 1 was 99% by ion chromatography.
[0013]
Example 2
Synthesis of Compound 2 Ethane sulfonyl chloride, sodium sulfite and sodium ethane sulfinate (116 g, 1 mol) which can be easily synthesized from an aqueous sodium hydroxide solution are dissolved in methanol (1 liter), and 10 equivalents of ammonium sulfate (660 g, 5 mol) are added. Thereafter, the mixture was stirred at 40 ° C. for 5 hours. Then, the reaction solution was cooled to 25 ° C., and sodium sulfate which was hardly soluble in methanol and ammonium sulfate which was excessively added were removed by filtration. After cooling the filtrate to 10 ° C., ethyl acetate (3 liters) was added, and the precipitated crystals were filtered to obtain ammonium ethanesulfinate target compound 2 (94.5 g, 0.85 mol). Yield 85%. The cation purity of compound 2 was 99% by ion chromatography.
[0015]
Reference Example 1
In the processing method of a silver halide photographic light-sensitive material described in Example 1 of JP-A-5-72696, an ammonium thiosulfate solution (70 wt%) is used as a fixing agent in a fixing solution, and an aryl is used as a stabilizer. Table 1 shows the desilvering time when ammonium sulfinate, sodium alkyl sulfinate, and Compound 1 of the ammonium salt of alkyl sulfinate isolated as crystals in the present invention were added.
(Composition of fixer) Mother liquor (g) Replenisher (g)
Ethylenediaminetetraacetic acid disodium salt 0.5 1.0
Sodium sulfite 7.0 12.0
Sodium bisulfite 5.0 9.5
Ammonium thiosulfate aqueous solution (70wt%) 170ml 240ml
Stabilizer: Stabilizer described in Table 1 0.1 mol 0.15 mol Water was added to add 1.0 liter 1.0 liter pH 6.7 6.7
[0016]
[Table 1]
According to Table 1, when the compound of the present invention is used as a stabilizer, precipitation does not occur even during running treatment, and there is an effect that fixation is not delayed unlike ammonium arylsulfinate and sodium alkylsulfinate, This effect is particularly remarkable when the replenishment is reduced.
Claims (2)
一般式（１） Ｒ−ＳＯ2 −・ＮＨ4 +
（式中、Ｒは炭素数１〜３の、無置換アルキル基を表す。）An alkylsulfinic acid unsubstituted ammonium salt represented by the following general formula (1).
General formula (1) R—SO 2 — · NH 4 +
(In the formula, R represents an unsubstituted alkyl group having 1 to 3 carbon atoms.)
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| Application Number | Priority Date | Filing Date | Title |
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| JP16126994A JP3598131B2 (en) | 1994-07-13 | 1994-07-13 | Novel substituted alkylsulfinic acid ammonium salts |
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| JP16126994A JP3598131B2 (en) | 1994-07-13 | 1994-07-13 | Novel substituted alkylsulfinic acid ammonium salts |
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| JP3598131B2 true JP3598131B2 (en) | 2004-12-08 |
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