JPS6370849A - Method for preserving fixer by which preservable property is improved - Google Patents
Method for preserving fixer by which preservable property is improvedInfo
- Publication number
- JPS6370849A JPS6370849A JP21630086A JP21630086A JPS6370849A JP S6370849 A JPS6370849 A JP S6370849A JP 21630086 A JP21630086 A JP 21630086A JP 21630086 A JP21630086 A JP 21630086A JP S6370849 A JPS6370849 A JP S6370849A
- Authority
- JP
- Japan
- Prior art keywords
- fixer
- general formula
- salt
- org
- packaging material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000005022 packaging material Substances 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920000620 organic polymer Polymers 0.000 claims description 16
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 239000003755 preservative agent Substances 0.000 abstract description 4
- 230000002335 preservative effect Effects 0.000 abstract description 4
- 230000007423 decrease Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract 5
- 239000010410 layer Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229960004106 citric acid Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- -1 silver halide Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- KYKNRZGSIGMXFH-ZVGUSBNCSA-M potassium bitartrate Chemical compound [K+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O KYKNRZGSIGMXFH-ZVGUSBNCSA-M 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- 241000272814 Anser sp. Species 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-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
- 101100265966 Sinorhizobium fredii (strain NBRC 101917 / NGR234) NGR_a00950 gene Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000016337 monopotassium tartrate Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 229940086065 potassium hydrogentartrate Drugs 0.000 description 1
- 239000001472 potassium tartrate Substances 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 235000011005 potassium tartrates Nutrition 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- NKAAEMMYHLFEFN-ZVGUSBNCSA-M sodium;(2r,3r)-2,3,4-trihydroxy-4-oxobutanoate Chemical compound [Na+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O NKAAEMMYHLFEFN-ZVGUSBNCSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
- G03C5/267—Packaging; Storage
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はハロゲン化銀写真感光材料用定着液の保存方法
に関し、特に写真製版用の分野で有用な高コントラスト
画像を得る現像処理に用いる定着液の保存方法に関する
ものである。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for preserving a fixing solution for silver halide photographic light-sensitive materials, and in particular to a fixing solution used for development processing to obtain a high contrast image useful in the field of photolithography. This relates to a method of preserving liquid.
写真製版分野では、近年ラピッドアクセス用定着液（白
黒用硬調定着？１１）が多く用いられるようになってき
ている。In the field of photolithography, rapid access fixers (black and white high contrast fixers? 11) have come into widespread use in recent years.
ラピッドアクセス用定着液は、迅速に定着できるように
、定着剤としてチオ硫酸塩、および保恒斉畷として亜硫
酸塩を含有しており、また、高ｐｌ＋の現像液を中和し
、かつ現像反応を停止させることが必要であり、そのた
めｐＨを酸性にする有機塩や無機塩を含有させている。The fixer for rapid access contains thiosulfate as a fixer and sulfite as a preservative for rapid fixing, and also neutralizes high pl+ developer and speeds up the development reaction. Therefore, organic salts and inorganic salts are included to make the pH acidic.
該定着液は、含有亜硫酸塩濃度が比較的高いにも拘わら
ず、長期の保存では酸化されてしまうことが知られてい
る。Although the fixer contains a relatively high concentration of sulfite, it is known that it is oxidized during long-term storage.
定着液の保管方法は、通常ハロゲン化銀写真感光材料に
比して悪条件の倉庫内あるいは戸外に放置されるため、
このような悪条件下でも安定であることが望まれている
。Fixer solutions are usually stored in warehouses or outdoors, which are in poor conditions compared to silver halide photographic materials.
It is desired that it be stable even under such adverse conditions.
ラピッドアクセス用定着液は、使用し馬いように、その
まま使用でさるタイプの外に、輸送の便宜やコスト関係
からできるだけ濃縮して用いる濃縮タイプのものがある
。この場合、千オ硫酸アムモニウム塩や亜硫酸塩量の多
いほど濃縮度が低下してしまうので、できるだけ少ない
亜硫酸塩濃度で７ｊ４′Ｒする必要がある。このような
方法では保存性が不十分となり、別の良い方法が求めら
れている。Rapid access fixing solutions include not only the type that can be used as is, but also the concentrated type, which is concentrated as much as possible for convenience of transportation and cost considerations. In this case, the concentration level decreases as the amount of ammonium periosulfate or sulfite increases, so it is necessary to carry out 7j4'R with as low a sulfite concentration as possible. Such a method results in insufficient preservation, and a better method is required.
包装材料の酸素透過性に着目して、酸素透過性あるいは
空気透過性の少い処理液貯蔵包装材料で封入すればよい
ことが考えられる。It may be possible to pay attention to the oxygen permeability of the packaging material and encapsulate it with a processing liquid storage packaging material that has low oxygen permeability or air permeability.
しかしながら、酸素透過性の面からの追求では写真定着
液の保存方法として好ましいとすることができないこと
を我々は見出した。即ち、これらの合成有機高分子材料
を貯蔵用包装材料に使用して高温高湿度下で定着液を保
存してみると、保存性が決して良くならないのである。However, we have found that this method cannot be preferred as a preservation method for photographic fixers in terms of oxygen permeability. That is, when these synthetic organic polymeric materials are used as storage packaging materials and fixers are stored under high temperature and high humidity conditions, the storage stability never improves.
それは高湿度下では酸素を容易に透過させてしまったり
、定着剤その他の化合物等による要因で保存性を劣化さ
せてしまうからではないかと考えられる。定着液に合っ
た包装材料が望まれる所以である。This is thought to be because oxygen easily permeates under high humidity conditions, and storage stability deteriorates due to factors such as fixing agents and other compounds. This is why a packaging material that is compatible with the fixer is desired.
本発明の目的は、定着剤と保恒剤とｐｌ＋を６以下にす
る有機塩および／または無機塩を含有する定着液を安定
に保存する方法を提供することにある。An object of the present invention is to provide a method for stably preserving a fixing solution containing a fixing agent, a preservative, and an organic salt and/or inorganic salt that makes pl+ 6 or less.
本発明の目的は、（イ）定着剤、（ロ）亜硫酸塩０．６
モル／ｌ以下、ならびに（ハ）定着液のｐＨを６以下に
する有機塩お上り／または無機塩を少なくとも含有する
定着液を有機高分子包装材料で作られた容器に貯蔵する
定着液の保存方法において、該包装材料が少なくとも３
ＷＩからなり、定着液に接する層の有機高分子が下記一
般式［１］で表され、内部の層の有機高分子が下記一般
式［ｂｌまたは［ｅｌで表されることを特徴とする定着
液の保存方法によって達成される。更に、上記少なくと
も３Ｎのうちの最外層の有機高分子が下記一般式［ａｌ
で表されるらのであるとさ、本発明の目一般式［１１
％式％）
式中、Ｘお上りＹは各々水素原子、ハロゲン原子または
アルキル基を表し、ｎは１００以上の整数を表す。The objects of the present invention are (a) fixing agent, (b) sulfite 0.6
mol/l or less, and (c) storage of a fixer containing at least an organic salt and/or an inorganic salt to bring the pH of the fixer to 6 or less in a container made of an organic polymer packaging material. In the method, the packaging material has at least 3
A fixing device consisting of WI, characterized in that the organic polymer in the layer in contact with the fixer is represented by the following general formula [1], and the organic polymer in the inner layer is represented by the following general formula [bl or [el]. This is achieved by a method of preserving liquids. Furthermore, the organic polymer in the outermost layer of at least 3N has the following general formula [al
The object of the present invention is the general formula [11% formula%], where X and Y each represent a hydrogen atom, a halogen atom, or an alkyl group, and n represents an integer of 100 or more. .
一般式［ｂｌ
＋ＯＣ（ＣＨ２）ｐｃＯＮ■（Ｃ１，）ｑＮＨ←式中、
ｐお上りｑは各々１〜１２の整数を表し、膿は１００以
上の整数を表す。General formula [bl +OC(CH2)pcON■(C1,)qNH←In the formula,
p and q each represent an integer of 1 to 12, and pus represents an integer of 100 or more.
一般式［６Ｆ
＋Ｎｌｌ （ＣＨｔ）ｒｃｏ ＋ｆ
式中、ｒは１〜１２の整数を表し、ｌは１００以上の整
数を表す。General formula [6F +Nll (CHt)rco +f In the formula, r represents an integer of 1 to 12, and l represents an integer of 100 or more.
一般式［ａｌにおいて、ＸおよびＹが表すアルキル基は
直鎖でも分岐でもよ（、好ましくは炭素数１〜５であり
、ハロゲン原子、ヒドロキシル基またはカルボキシル基
で置換されていてもよい、ｎは好ましくは１００００以
下である。In the general formula [al, the alkyl group represented by Preferably it is 10,000 or less.
一般式［ｂｌにおいて、−は好ましくは１００００以下
であり、一般式［０１において、ｌは好ましくは１００
００以下である。In the general formula [bl, - is preferably 10,000 or less, and in the general formula [01, l is preferably 100
00 or less.
一般式［ａ］で示される化合物の具体例として下記を挙
げることができる。Specific examples of the compound represented by the general formula [a] include the following.
（ａ−１） Ｈ＋ｃＨ２−ＣＩ２＋ｒｒｒｏＨ（ａ−２
） Ｈ＋ ＣＨｚ −ＣＨｔ ｈｗ、Ｉ＋（ａ−３）
Ｈ−ＣＬ −ＣＬ ＋ｒｒｒ、ＨＩ
（ａ−４） Ｈ＋ＣＨ＊−Ｃ＋ｒｒｒｏＨｔ
（ａ−５） ｌｌ＋ｃＨｚ−ＣＨ七ＴＴｏＨ鵞
（ａ−６） Ｈ＋ＣＦＩニーＣＨ＋ｒ−！ＴｏＨ０Ｏ
Ｈ
一般式［ｂｌで示される化合物の具体例として下記を挙
げることができる。(a-1) H+cH2-CI2+rrroH(a-2
) H+ CHz -CHt hw, I+(a-3)
H-CL -CL +rrr, HI (a-4) H+CH*-C+rrroHt (a-5) ll+cHz-CH7TToH Goose (a-6) H+CFI knee CH+r-! ToH0O
H Specific examples of the compound represented by the general formula [bl] include the following.
（ｂ−１） ８０士Ｃｏ（Ｃ）Ｉ２）＜Ｃ０ＮＨ（Ｃｌ
ｌｚ ）ａＮＨ＋ｒｒｒｏＨ（ｂ−２） Ｈ（ｌｆｃｏ
（ＣＨｚ）ｓｃＯＮＨ（Ｃｕｔ）ｓＮＨ＋ｒ５−ＴｏＨ
（ｂ−３） ８０士Ｃ０（ＣＨｔ）、Ｃ０Ｎ）Ｉ（ＣＨ
ｚ）ｓＮＨ＋ＴＴＴｏＨ（ｂ−４） １０÷Ｃ０（ＧＨ
ｚ）２ｃＯＮＨ（ＣＨｚ）ｓＮＨ＋ｒＴＴ−Ｈ一般式［
ｃｌで示される化合物の具体例として下記を挙げること
ができる。(b-1) 80 Co(C)I2)<C0NH(Cl
lz )aNH+rrroH(b-2) H(lfco
(CHz)scONH(Cut)sNH+r5-ToH
(b-3) 80shi C0 (CHt), C0N) I (CH
z)sNH+TTToH(b-4) 10÷C0(GH
z)2cONH(CHz)sNH+rTT-H general formula [
Specific examples of the compound represented by cl include the following.
（ｃ−１） ＩＩ＋８１１（Ｃ１１ｘ）ｓｃＯ±１ｏＯ
１１（ｃ−２） Ｈ＋ＮＨ（ＣＨｚ）ｓｃｏ±ＴＴｏＯ
）ｌ（ｃ−３） Ｉｆ ＋ ＮＨ（ＣＨｉ）ｉｃｏ
＋ｒｆＴｏＯＨ（ｃ−４）ト十ＮＨ（Ｃ１，） 、 、
ＣＯ＋ｒｒｒ、ＯＨ本発明における前記一般式［８１、
Ｔｏｌまたは［６１で表される有機高分子はモノマーか
ら単一重合、共重合あるいは縮重合により容易に合成す
ることができる１重合度は任意でよいが、好ましくは１
００以上１０万以下である。なお、これらの一般式にお
いて、末端基は示してないが、このような重合反応で通
常生ずるものが含まれる。(c-1) II+811(C11x)scO±1oO
11(c-2) H+NH(CHz)sco±TToO
)l(c-3) If + NH(CHi)ico
+rfToOH(c-4)toNH(C1,) , ,
CO+rrr, OH The general formula [81,
The organic polymer represented by Tol or [61 can be easily synthesized from monomers by homopolymerization, copolymerization, or condensation polymerization.The degree of polymerization may be arbitrary, but preferably 1.
00 or more and 100,000 or less. Note that although terminal groups are not shown in these general formulas, those that normally occur in such polymerization reactions are included.
本発明の有機高分子包装材料を構成する上記各単一層の
厚さはそれぞれ１０〜２００μ論の範囲が好ましく、積
層された全膜厚としては３０〜６００μ−の範囲がより
好ましい、更に好ましくは各単一層の厚さがそれぞれＺ
Ｏ〜１００μ−で、ギ貞層された全膜厚が６０〜３００
μ−の範囲にあることである。The thickness of each of the above-mentioned single layers constituting the organic polymer packaging material of the present invention is preferably in the range of 10 to 200 μm, and the total thickness of the laminated layers is more preferably in the range of 30 to 600 μm, even more preferably The thickness of each single layer is Z
O~100μ-, the total thickness of the layered layer is 60~300μ
It is in the range of μ-.
本発明の有機高分子包装材料を構成する上記各単一膜の
厚さは、１０μ−以下では定着液を１０〜２０１封入す
る容器として定着液の保存性が悪（、強度も小さいので
、１ＯＨ論以上であることが好ましく、また、Ｚｏｏμ
−以上の１ｇさでは包装材料の柔軟性が悪（、内部の定
着液の量に応じて変形しないため、歪の下の死空間に空
気が′ＦＩ！まり易く、このため定着液の保存性が悪く
なる。If the thickness of each of the above-mentioned single films constituting the organic polymer packaging material of the present invention is 10μ or less, the fixer will have poor storage stability as a container for enclosing 10 to 20 μm of fixer (and its strength will be low, so 1OH It is preferable that it is above the theoretical level, and also
- If the weight is 1 g or more, the flexibility of the packaging material is poor (because it does not deform according to the amount of fixer inside, air tends to get trapped in the dead space under the distortion, and this makes it difficult to store the fixer). becomes worse.
本発明における積層した有機高分子包装材料は、一般式
［ａｌで示される化合物の好ましくは１ｏ〜２００μｍ
の７１膜フイルム上に好ましくは１０〜２００ ｉｔ健
の一般式［ｂｌまたは［ｅｌで示される化合物の薄膜を
そのまま重ねたり過熱接触または接着剤で張り合わせ（
いわゆるラミネーシ鱈ン）るか、更にその上に一般式［
ａ］で示される化合物のＷｉ膜を上記のように重ねるか
張り合わせて得ることができる。The laminated organic polymer packaging material of the present invention preferably has a compound represented by the general formula [al] with a thickness of preferably 10 to 200 μm
A thin film of a compound represented by the general formula [bl or [el] with a thickness of 10 to 200 times is preferably overlaid on a 71-layer film of
The so-called laminated cod) or the general formula [
It can be obtained by stacking or bonding Wi films of the compound represented by a] as described above.
本発明の包装材料で作られる容器は該包装材料の１重で
作ればよいが、更にその上を１重または２ｍに該包装材
料で覆い、即ち該包装材料の２重または３重で作っても
よく、２重ないし３重の態様によれば本発明の効果を一
層高めることができる。A container made of the packaging material of the present invention may be made of one layer of the packaging material, but it may be further covered with one layer or 2 meters of the packaging material, that is, it may be made of two or three layers of the packaging material. The effect of the present invention can be further enhanced by a double or triple embodiment.
本発明の包装材料において、最外側の層を構成する材料
は任意に選択できるが、好ましくは、前記のように該層
の有機高分子が前記一般式［１１で表される化合物から
選ばれることである。In the packaging material of the present invention, the material constituting the outermost layer can be arbitrarily selected, but preferably, as described above, the organic polymer of this layer is selected from the compounds represented by the general formula [11]. It is.
本発明の好ましい態様として、包装材料の層構成を３層
または４Ｎとし、これらの層のうち、最内側の層お上り
最外側の層の有機高分子を一般式［ａ］で表されるもの
とし、この２層以外の層の少なくともＩＭの有機高分子
を一般式［ｂｌ または［ｅｌで表されるものとする態
様が挙げられる。In a preferred embodiment of the present invention, the packaging material has a layer structure of 3 layers or 4N, and among these layers, the innermost layer and the outermost layer have an organic polymer represented by the general formula [a]. An embodiment may be mentioned in which at least the IM organic polymer in the layers other than these two layers is represented by the general formula [bl or [el].
本発明の方法が適用される定着液が含有する定着剤は、
チオ硫酸アンモニウム、チオ硫酸ナトリウム、チオ硫酸
カリウム等の通常定着剤として用いられる千オ硫酸塩で
ある。定着剤の濃度に制限はなく、一般に用いられてい
る０、１〜５モル／ｌの範囲で少なくとも本発明は有効
である。The fixing agent contained in the fixing solution to which the method of the present invention is applied is:
These are periosulfates commonly used as fixing agents, such as ammonium thiosulfate, sodium thiosulfate, and potassium thiosulfate. There is no limit to the concentration of the fixing agent, and the present invention is effective at least within the commonly used range of 0.1 to 5 mol/l.
本発明の方法が適用される定着液が含有する亜硫酸塩と
しては、例えば亜硫酸ナトリウム、亜硫酸カリウム、亜
硫酸アンモニウム等通常定着液に用いられるものが挙げ
られる。定着液中の亜硫酸塩の濃度は、市販品において
通常パーツＡ液と称される濃縮された保存処方で０．６
モル／ｌ以下において本発明の効果が顕著である。該濃
度は該液の保存性の点から０．３モル／ｌ以上であるこ
とが好ましい。Examples of the sulfite contained in the fixer to which the method of the present invention is applied include those commonly used in fixers, such as sodium sulfite, potassium sulfite, and ammonium sulfite. The concentration of sulfite in the fixer is 0.6 in concentrated preservative formulations, commonly referred to as part A solution in commercial products.
The effect of the present invention is significant below mol/l. The concentration is preferably 0.3 mol/l or more from the viewpoint of storage stability of the liquid.
本発明の方法が適用される定着液のｐＨを６以下にする
のに用いられる有機塩および無機塩は、公知の定着液に
ｐＨ緩衝剤（例えば、酢酸、はう酸、二塩基酸およびこ
れらの塩等）やｐＨｉｉｌ！ｉ剤（例えば、硫酸）とし
て用いられるものが含まれる。ｐＨｔｌ、ｌＩｉ剤は、
酢酸、はう酸およびクエン酸塩の総量で１０〜５０ｇ／
ｌの範囲、特に１５〜３０ｇ／ｉの範囲が好ましい、該
定着液のｐＨは、あまり下げすぎても液の保存性が悪く
なるので、好ましくは３以上、より好ましくは４以上で
ある。Organic salts and inorganic salts used to adjust the pH of the fixing solution to 6 or less to which the method of the present invention is applied may be added to known fixing solutions with pH buffers (for example, acetic acid, oxalic acid, dibasic acids, and salt, etc.) and pHiil! Includes those used as i-agents (eg, sulfuric acid). pHtl, IIi agents are
The total amount of acetic acid, halonic acid and citrate is 10-50g/
The pH of the fixing solution is preferably in the range of 15 to 30 g/i, particularly 15 to 30 g/i.If the pH of the fixer is lowered too much, the storage stability of the solution will deteriorate, so it is preferably 3 or more, more preferably 4 or more.
上記二塩基酸として、酒石酸あるいはその誘導体、クエ
ン酸あるいはその塩が単独で、あるいは二種以上を併用
することができる。これらの化合物を定着Ｐ１１１１に
つき０．００５モル以上、特に０．０１モル／ｌ〜０．
０３モル／ｌ含有する定着液に対し少なくとも本発明は
有効である。As the dibasic acid, tartaric acid or a derivative thereof, citric acid or a salt thereof can be used alone or in combination of two or more kinds. These compounds should be added in an amount of 0.005 mol or more per fixing P1111, especially 0.01 mol/l to 0.01 mol/l.
The present invention is effective at least for a fixer containing 0.03 mol/l.
具体的には、酒石酸、酒石酸カリウム、酒石酸ナトリウ
ム、酒石酸水素カリウム、酒石酸水素ナトリウム、酒石
酸アンモニウム、などがある。Specifically, there are tartaric acid, potassium tartrate, sodium tartrate, potassium hydrogen tartrate, sodium hydrogen tartrate, ammonium tartrate, and the like.
クエン酸あるいはその塩の例としてクエン酸、クエン酸
ナトリウム、クエン酸カリウム、クエン酸リチウム、ク
エン酸アンモニウムなどがある。Examples of citric acid or its salts include citric acid, sodium citrate, potassium citrate, lithium citrate, and ammonium citrate.
本発明が適用される定着液は、その他に硬膜剤、例えば
水溶性アルミニウム塩（例えば塩化アルミニウム、硫酸
アルミニウム、カリ明ばん等）を含有することができる
。この水溶性アルミニウム塩の安定化のためには、本発
明における前記有機塩および無機塩として酢酸または上
記二塩基酸を用いるのが好ましい。The fixing solution to which the present invention is applied can also contain a hardening agent, such as a water-soluble aluminum salt (eg, aluminum chloride, aluminum sulfate, potassium alum, etc.). In order to stabilize this water-soluble aluminum salt, it is preferable to use acetic acid or the above-mentioned dibasic acid as the above-mentioned organic salt and inorganic salt in the present invention.
テストフィルムの作成
特公昭５９−５０９７６号公報の比較例３によってハロ
ゲン化銀写ｇ感光材料を作成した。Preparation of test film A silver halide photosensitive material was prepared according to Comparative Example 3 of Japanese Patent Publication No. 59-50976.
現像液の調製 下記処方に従い、組成Ａおよ１組成りより調合した。Preparation of developer Compositions A and 1 were prepared according to the following recipe.
現像液処方
（組成Ａ）
純水（イオン交換水） １５０ｗｊ
！エチレンノアミン四酢酸二ナトリウム塩 ２ｇジエチ
レングリコール ５０ｇ亜硫酸カリウ
ム（５５％阿／Ｖ水溶液） １００ｍｊ！炭酸
カリウム ５０ｇハイドロキ
ノン １５ｇ５−メチルベンゾ
トリアゾール ２００ｍｇ１−フェニル−５−
メルカプトテトラゾール０−ｇ
水酸化カリウム 使用液のｐｌｌを１０．４にする量
臭化カリウム ４．５ｇ（ｊ［
を成り）
純水（イオン交換水）３ｍｌ
ジエチレングリコール ５０ｇエチレ
ンジアミン四酢酸二ナトリウム塩２５ｍｊ！酢酸（９０
％水溶ｅ、Ｉ Ｏ，３ｍｊ！５−
ニトロイングゾール １１０ｍｇ１−フ
ェニル−３−ピラゾリドン ５００ｍｇ現像液
の使用時に水５００＋ａｌ中に上記組成Ａ１組成りの順
に溶かし、１１に仕上げて用いた。Developer prescription (composition A) Pure water (ion exchange water) 150wj
! Ethylenenoaminetetraacetic acid disodium salt 2g Diethylene glycol 50g Potassium sulfite (55% A/V aqueous solution) 100mj! Potassium carbonate 50g Hydroquinone 15g 5-methylbenzotriazole 200mg 1-phenyl-5-
Mercaptotetrazole 0-g Potassium hydroxide Amount to make pll of working solution 10.4 Potassium bromide 4.5 g (j[
) Pure water (ion exchange water) 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium salt 25 mj! Acetic acid (90
% water soluble e, I O, 3mj! 5-
Nitroingsol 110mg 1-phenyl-3-pyrazolidone 500mg When using a developer, the above compositions were dissolved in 500+al of water in the order of composition A1 and finished to 11 for use.
定着液の調製 下記処方に従い、濃縮定着液ＡおよびＢを調製した。Preparation of fixer Concentrated fixers A and B were prepared according to the following formulations.
定着液処方
（濃縮定着ＩＡ）
千オ硫酸アンモニウム（７２，５％−ハ水溶液）２５０
論ｌ
亜硫酸すＦリウム １７ｇ酢酸ナ
トリウム・３水塩 ７．０ｇ硼酸
７ｇクエン酸ナトリウム・
２水塩 ２ｇ酢酸（９０％阿／ＩＩＩ水溶液
）１４論！ｐＨ５，０
（濃縮定着液Ｂ）
純水（イオン交換水） １７ｍ１
硫！ （５０％Ｗ／Ｗ（１’） 水’１１７１ＦＮ ）
５．０ｇ定着液の使用時に水５００
ｍ／中に上記濃縮定着液Ａ１濃縮定着液Ｂの穎に溶かし
、１１に仕上げて用いた。この定着液のｐＨは約４．３
であった。Fixer prescription (concentrated fixing IA) Ammonium 1000 sulfate (72.5%-HA aqueous solution) 250
Theory l Sodium sulfite F 17g Sodium acetate trihydrate 7.0g Boric acid
7g sodium citrate
Dihydrate 2g Acetic acid (90% A/III aqueous solution) 14 theories! pH5.0 (Concentrated fixer B) Pure water (ion exchange water) 17ml
Sulfur! (50%W/W(1')Wed'1171FN)
500 g of water when using 5.0 g of fixer
The above-mentioned concentrated fixer A1 was dissolved in the concentrated fixer B in a solution of 11, and used. The pH of this fixer is approximately 4.3.
Met.
定着液貯′ｉ＆容器の作成
下記表−１に示されるようなＭ構成および、膜厚の容１
１０１の有機高分子包装材料を作製した。Fixer storage & container creation M configuration and film thickness capacity 1 as shown in Table 1 below
101 organic polymer packaging materials were produced.
上記の濃縮定ｙ４ｗＪ、Ａ （パーツ定着液）の１０１
を上記容器に密封して高温高温で保存（サーモ試験器内
に７０℃、相対湿度９０％で１２時間放置した後、１２
時間常温常温（２５℃、相対湿度６０％）に戻し、この
温度および湿度の履歴を２週間繰り返して保存した）
した後、該液を用いて使用液を調製した。101 of the above concentration constant y4wJ, A (parts fixer)
Seal it in the above container and store it at a high temperature (after leaving it in a thermometer at 70℃ and 90% relative humidity for 12 hours,
The temperature was returned to room temperature (25°C, relative humidity 60%), and this temperature and humidity history was repeated for 2 weeks and stored.)
After that, a working solution was prepared using the solution.
定Ｎ能の測定は、感光材料に前記テストフィルム（５ｅ
ｍＸ ５ ｃｍ）を、現像液に前記現像液を、定Ｍｎに
上記使用液をそれぞれ用い、自動現像！蔑で下記処理条
件で処理し、定着された度合（定着ぬけ性）を目視判定
して評価した。最も定着ぬけの良い場合を「５」とし、
順次「４」、「３」、「２」、「１」のランク付けをし
た。The constant N capacity was measured by applying the test film (5e
mX 5 cm), the above-mentioned developer is used as the developer, and the above-mentioned solution is used as the constant Mn, and automatic development! The samples were treated under the following processing conditions, and the degree of fixation (fixability) was visually judged and evaluated. The case with the best fixation is set as "5".
They were ranked sequentially as "4", "3", "2", and "1".
処理条件は
現像 ３３℃ ２０秒
定着 ３０℃ ２０秒水洗
２５℃ ２０秒
乾燥 ５０℃ ２０秒
のように設定した。Processing conditions are development, fixing at 33°C for 20 seconds, and washing with water at 30°C for 20 seconds.
The settings were as follows: drying at 25°C for 20 seconds and drying at 50°C for 20 seconds.
結果を表−２に示す。The results are shown in Table-2.
表−２
表−２から明らかなように、定着液の包装材料に本発明
によるものを用いることにより、高温高湿下に保存され
たときの定着ぬけ性の劣化が改良される。Table 2 As is clear from Table 2, by using the fixer packaging material according to the present invention, the deterioration of fixing removability when stored under high temperature and high humidity is improved.
また、保存容器内の液状をａ察した結果、Ｎｏ。Also, as a result of checking the liquid condition in the storage container, No.
１〜Ｎｏ、 ５は分解物が全く析出していないのに対し
て、Ｎｏ、 ６〜Ｎｏ、 ８は黄色状の分解物が析出し
ているのがｗＬ寮された。In Nos. 1 to 5, no decomposed products were precipitated, whereas in Nos. 6 to 8, yellowish decomposed products were precipitated.
本発明により、有機高分子包装材料で構成される容器に
入れて定着液を保存する方法における、定着剤、亜硫酸
塩０．６モル／ｌ、ならびに定着液のｐＨを６以下にす
る有機塩および／＊たは無機塩を少なくとも含有する定
着液の保存性が改良される。According to the present invention, a fixing agent, a sulfite salt of 0.6 mol/l, and an organic salt which lowers the pH of the fixing solution to 6 or less and /*The storage stability of the fixing solution containing at least an inorganic salt is improved.
Claims (2)
定着液のｐＨを６以下にする有機塩および／または無機
塩を少なくとも含有する定着液を有機高分子包装材料で
作られた容器に貯蔵する現像液の保存方法において、該
包装材料が少なくとも３層からなり、定着液に接する層
の有機高分子が下記一般式［ａ］で表され、内部の層の
有機高分子が下記一般式［ｂ］または［ｃ］で表される
ことを特徴とする定着液の保存方法。 一般式［ａ］ ▲数式、化学式、表等があります▼ ［式中、ＸおよびＹは各々水素原子、ハロゲン原子また
はアルキル基を表し、ｎは１００以上の整数を表す。］ 一般式［ｂ］ −（ＯＣ（ＣＨ＿２）ｐＣＯＮＨ（ＣＨ＿２）ｑＮＨ）
−＿ｍ［式中、ｐおよびｑは各々１〜１２の整数を表し
、ｍは１００以上の整数を表す。］ 一般式［ｃ］ −（ＮＨ（ＣＨ＿２）ｒＣＯ）−＿ｌ ［式中、ｒは１〜１２の整数を表し、ｌは１００以上の
整数を表す。］(1) A container made of organic polymer packaging material for storing a fixing solution containing at least a fixing agent, 0.6 mol/l or less of sulfite, and an organic salt and/or inorganic salt that makes the pH of the fixing solution 6 or less. In a method for storing a developer, the packaging material is composed of at least three layers, the organic polymer in the layer in contact with the fixer is represented by the following general formula [a], and the organic polymer in the inner layer is represented by the following general formula [a]. A method for preserving a fixer, characterized by being represented by formula [b] or [c]. General formula [a] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, X and Y each represent a hydrogen atom, a halogen atom, or an alkyl group, and n represents an integer of 100 or more. ] General formula [b] -(OC(CH_2)pCONH(CH_2)qNH)
-_m [where p and q each represent an integer of 1 to 12, and m represents an integer of 100 or more. ] General formula [c] -(NH(CH_2)rCO)-_l [In the formula, r represents an integer of 1 to 12, and l represents an integer of 100 or more. ]
一般式［ａ］で表されることを特徴とする特許請求の範
囲第１項記載の定着液の保存方法。(2) The method for preserving a fixer according to claim 1, wherein the organic polymer in the outermost layer of the at least three layers is represented by the general formula [a].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61216300A JPH061357B2 (en) | 1986-09-12 | 1986-09-12 | Fixer storage method with improved storage stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61216300A JPH061357B2 (en) | 1986-09-12 | 1986-09-12 | Fixer storage method with improved storage stability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6370849A true JPS6370849A (en) | 1988-03-31 |
| JPH061357B2 JPH061357B2 (en) | 1994-01-05 |
Family
ID=16686366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61216300A Expired - Fee Related JPH061357B2 (en) | 1986-09-12 | 1986-09-12 | Fixer storage method with improved storage stability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH061357B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006339435A (en) * | 2005-06-02 | 2006-12-14 | Disco Abrasive Syst Ltd | Processing machine provided with cleaner |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58198041A (en) * | 1982-05-14 | 1983-11-17 | Fuji Photo Film Co Ltd | Composition for processing silver halide photograph |
| JPS6173147A (en) * | 1984-09-19 | 1986-04-15 | Fuji Photo Film Co Ltd | Conservative method of high ph developing solution |
-
1986
- 1986-09-12 JP JP61216300A patent/JPH061357B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58198041A (en) * | 1982-05-14 | 1983-11-17 | Fuji Photo Film Co Ltd | Composition for processing silver halide photograph |
| JPS6173147A (en) * | 1984-09-19 | 1986-04-15 | Fuji Photo Film Co Ltd | Conservative method of high ph developing solution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006339435A (en) * | 2005-06-02 | 2006-12-14 | Disco Abrasive Syst Ltd | Processing machine provided with cleaner |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH061357B2 (en) | 1994-01-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |