C41 代用配方

25 September, 2008


這一網頁是重新整理過的,舊的請見:原文備份檔

2008年4月
將 C41 的原理和正規做法抽出整理成另一篇。

寫在前面


在旅日友人 - 箔樵 的建議下,我開始嘗試自己沖底片。他還提供了簡要配方及處理摘要 (感謝 箔樵 花時間整理並答應公開上網)。這些配方和我後來上網找到的有很大的不同。我把 C41 的坊間配方分成兩大類,一是日系傳出來的,一是西方傳出來的。下方列出的不同配方中,以Formula 01 和 04 就是日系的配方,其他的都是美系的配方。日系和美系最大的不同是有沒有使用碘化鉀,日系一般都沒有加這一成份,美系很多都會把這一成份列入,而且其濃度非常的低。再來的是漂白(Bleach)時, Ferric Ammonium EDTA 都是會用上。國外的 Blix 的配方也一定會有用到這一試劑。就是說大家都離不開 Ferric ammonium EDTA。這是最有效的存在形式就是了,一旦有 Na+ 離子的存在,EDTA 就會形成較不活躍的形式,作用也會不完全。但日本的配方就只是單純的 Ferric EDTA disodium,也就是被認為是很難去除銀離子的 EDTA 形式。
同時,在顯影及漂白之間最好要有 停影劑,否則容易有污染的問題,停影劑多加入 Sodium Sulfite。我一開始是使用 BLIX 的配方在嘗試,也一直覺得這沒甚麼問題。一直到後來在 APUG 論壇看了很多討論串,尤其是 PE 的發言,指出 BLIX 很難處理,也很難把銀給取代清除。這也是我後來努力去找出 Bleach 和 Fix 分開的配方的原因。

總之,從一開始的日系的簡要配方到目前找到的眾多的配方,可以了解到自己配試劑真不是簡單的事。

CD4 的化學名稱


C41 的重要發色劑是 CD4,color development 4. CD4 是商業名稱,化學名稱我從 Kodak 的patent 文件中查到是 4-(N-ethyl-N-2-hydroxyethyl)-2-methylphenylenediamine sulfate 。在第一次沖洗測試後,因發生了色偏問題,所以就到處找可能的原因。
從日本的自調 C41 教學網查到的名稱是:
「4アミノ3メチルNエチルNβヒドロキシエチルアニリン硫酸塩」
經翻成英文是:4-amino-3methyl-N-ethyl-N-p-hydroxyethylaniline sulfate

另外在 photonet討論區查到的則是
(3-Methy1-4-Amino-N-Ethyl-N-(2-Hydroxyethyl) Aniline Sulfate(Monohydrate)。

這就讓我很困惑到底那一個是正確的名稱。後來問到化學友人,他的解釋是這三個名稱都是同一個化合物,只是命名不同。後來在 APUG 論壇上就有很多人提到 CD4 的化學式,大家都曉得一樣。


不同的 C41 代用配方


{Formula 01} C-41彩色負片代用配方


引用自「カラー写真現像/引伸しの実技(フィルム現像編)」、1975年5月15日發行、寫真工業出版社

發色顯影
H2O @ 40℃ ......................................... 800ml
無水亞硫酸鈉 (Sodium Sulfite, anhydrous) ............. 1.20g
無水碳酸鈉 (Sodium Carbonate, anhydrous) ............. 12.80g
溴化鉀 (Potassium Bromide) ........................... 0.60g [minimize silver fog and dye stain formation.]
氫氧化鈉 (Sodium hydroxide) .......................... 1.60g
碳酸氫鈉 (Sodium Bicarbonate) ........................ 1.35g
硼砂 (Sodium Tetraborate Decahydrate) ................ 6g
6-NitroBenzimidazole 0.2% solution .................. 12ml
Kodak CD-4 ........................................... 3.2g
加水至總量 1000ml

* CD-4 是 ( 4-(N-ethyl-N-2-hydroxyethyl)-2-methylphenylenediamine sulfate )

漂白定影液配方
H2O @ 40℃ ......................................... 800ml
Sequestrene NaFe(NaFe-EDTA) or Fe-EDTA ................. 100g
氨20%溶液 (Ammonium Hydroxide 20% solution) ............. 10ml
硫氰酸鉀 (Potassium Thiocyanate) ......................... 10g
硫代硫酸銨 (Ammonium Thiosulfate) ........................ 120g
加水至總量 1000ml


{Formula 02} C-41 Developer (Official ??)

source: http://www.apug.org/forums/forum40/26717-processing-c-41-home.html#post288486


Water (50° C) ........................... 800 ml
Potassium carbonate (anhy) ........ 37.5 g [accelerator.]
Sodium sulfite (anhy) ................. 4.3 g
Potassium iodide ....................... 0.002 g [minimize silver fog and dye stain formation.]
Sodium bromide ......................... 1.3 g
Hydroxylamine sulfate ................. 2.0 g
Kodak Anti-Cal #3 ...................... 2.5 g (註:2,4-Dihydroxybenzophenone, 可忽略)
CD-4 ....................................... 4.8 g
Water to make .......................... 1.0 l

pH 10.00 +/- 0.03


{Formula 03} Bonavolta - C-41 Developer

source:http://www.bonavolta.ch/hobby/en/photo/c41_ra4_chemicals.htm


Water (Room Temp)..............800.0ml
Potassium Carbonate.............32.0g [accelerator.]
Sodium Sulfite...................3.5g
Potassium Bromide................1.5g [minimize silver fog and dye stain formation.]
Hydroxylamine Sulfate............2.0g
CD-4.............................5.0g
Water to make....................1.0L



{Formula 04} Vasolza Home-brew Final Formula

source:カラーネガフィルム現像液の自家調合


H2O @ 40℃ ......................................... 800ml
無水亞硫酸鈉 (Sodium Sulfite, anhydrous) ............. 1.20g
碳酸氫鈉 (Sodium Bicarbonate) ........................ 1.5g
溴化鉀 (Potassium Bromide) ........................... 0.60g [minimize silver fog and dye stain formation.]
無水碳酸鈉 (Sodium Carbonate, anhydrous) ............. 13.0g [accelerator.]
氫氧化鈉 (Sodium hydroxide) .......................... 0.80g
Kodak CD-4 ........................................... 4.0g
加水至總量 1000ml



{Formula 05} Formula provided by oldbikerpete

http://lokienhock.googlepages.com/Blogspot_OldBikerPete-MyC41Formulae.pdf



{Formula 06} Here's a formula for C-41 published in 'Photo Techniques'

source:http://groups.google.com/group/rec.photo.film+labs/browse_thread/thread/5315093a633b0be2/27909efe01d60fd6?lnk=gst&q=iodide#27909efe01d60fd6


DEVELOPER
Water 800 ml
Potassium carbonate 38 g
Sodium sulfite 4.7 g
Potassium bromide 1.5 g
Kodak anti-cal (optional) 1 g
Hydroxylamine sulfate 3.9 g
CD4 5.9 g
Potassium iodide 1 mg (或 1ml 的 0.1% 溶液)
Acetic Acid to pH 10.00
Water to make 1 liter

*Potassium iodide可取1g溶於1 Liter 水,配製成 0.1% 溶液儲藏於4℃下備用(需避光)。

BLEACH
Water 700 ml
Ferric ammonium EDTA
(-50% solution) 170 ml
Ammonium bromide 172 g
Potassium nitrate 54 g
Acetic acid (99%) 15 ml
Water to make 1 liter
pH 5.80

FIXER
Water 700 ml
Ammonium thiosulfate 189 ml
any sodium salt of EDTA 1.5 g
Sodium bisulfate 15 g
Water to make 1 liter
pH 6.50

STABILIZER
Water 800 ml
Formaldehyde (37%) 5 ml
Photo-Flo 600 1.6 ml
Water to make 1 liter

PROCESS TIMES (100F)
Developer 3.25'
Bleach 6.50'
Rinse 3.25'
Fix 6.50'
Rinse 3.25'
Stabilizer 1.50'


{Formula 07} an alternative ferricyanide bleach is approved for use with C-41

Source:Provided by nworth


Kodak SR-34 bleach
Alternate bleach for Process ECN-2 for motion picture negative films (Potassium “UL House” bleach)
Water (21 – 38C) 700 ml
Proxel GXL 0.07 ml (mold inhibitor)
Kodak Chelating Agent No. 1 30.6 g
Potassium hydroxide (45%) 42.7 ml
Potassium bromide (anh) 51.5 g
Acetic acid (Glacial) 7.65 ml
Ferric nitrate (nonahydrate) 35.7 g
Water to make 1 l
pH at 25C = 5.30; density = 1.070; total iron (ferric only) 5.1 g/l
Bleach motion picture film 3 minutes at 27C



{Formula 08} alternative Bleach and Fixer formula by PE{more about PE, click here}

source:PE


Stop
Acetic acid glacial 20ml/L
Sodium Sulfite 10 g/L
Water to 1000ml
Use between developer and bleach for 30 seconds 100F. This can prolong the life time of the bleach solution.

Bleach
Ammonium Ferric EDTA 60% 200 ml
Ammonium Bromide 50 g
Ammonium Sulfite 10 g
Disodium EDTA 10 g
pH to 6.7 with either Ammonium Hydroxide or 28% acetic acid
Water to 1 liter. Use for 7 minutes at 100F.

Another substitute Ferric Ammonium EDTA Bleach formula by PE
source:APUG discussion

1 mole of Ferric Chloride + 1.1 moles of Ammonium EDTA should do the job. Adjust pH to 6.5 with Acetic Acit 28% and Ammonium Hydroxide solution as needed.
Ammonium Bromide 50 g
Ammonium Sulfite 10 g
Diammonium EDTA 359g
Ferric chloride 162g
Disodium EDTA 10 g

Water to 1 liter. Use for 7 minutes at 100F.

Fixer formular
Ammonium Thiosulfate 60% 200 ml
Ammonium Sulfite 10 g
Disodium EDTA 10 g
pH to 6.7 with either Ammonium Hydroxide or 28% acetic acid.
Water to 1 liter. Use for 7 minutes at 100 F.
pH range 6.5 - 6.8 for either solution at 20 degrees C (68F)
Wash after the bleach for 5 mins and after the fix for 8 mins.

Stabilizer | source
The old type is 10 ml of 37% formalin (about) added to 1 liter of standard Photo Flo 200 working solution.或是以 3ml 的 Formaldehyde (35-37%)及 3ml 的 L-clear (Chugai photo 生產,光影代理)調配成 500ml 溶液亦可。photo Flo 200 或是 L-clear 的作用是界面活性劑,只要是界面活性劑即可取代。

較早期的底片,在沖片後面必須要再加一道的穩定液處理來加強底片染料的穩定性。現代的底片多已不需要穩定劑的作用來加強染料的穩定性了。除此之外,因為彩負底片在沖洗過程中是把銀離子給去除,只留下彩色染料。這些會殺菌的銀離子不存在下,彩負底片則是不比黑白底片有強烈的抑菌性。所以,現在的穩定液只是剩下去除水滴斑和抑菌作用而已。


9859
在配製 Formula 08 的 Bleach 時,加入 Diammonium EDTA 和 Ferric chloride 後,如果溶液太酸的話就會產生沈澱。pH調整到 6.5可以解決這問題。
DSC_9896
以 Ammonium Hydroxide 和冰醋酸調整 pH值到 6.5。當 pH 達 5 時,結晶和沈澱就不會有了,但溶液還是像泥漿那樣。當 pH 超過 6 時,溶液就澄清了。



{Formula 09} C-27

Source:Provided by Stefan

800ml tab water
1 ml A905(wetting agent, can be omitted)
2g Calgon
34g potassium carbonate
1.9g Sodium Bikarbonate
3.5g Sodium Sulphite
1.4 g Potassium bromide
1.4 mg (!) Potassium iodide
2g HAS
5.3g CD4

Up to 1 Litre,

pH adjusted with KOH or sulphuric acid to 10.11 at 25°C. pH has to be above 10.11 (measured with my unit 10.13), there is absolutely no chance to get a proper developed film with lower pH! Red will suffer badly!



BUT whatever you do, pH has to be above 10.11 (measured with my unit 10.13), there is absolutely no chance to get a proper developed film with lower pH! Red will suffer badly!






{Formula 10} C-41

Source:Provided by RPC

Water, distilled (50° C)................. 800 ml
Potassium carbonate (anhy) ........ 37.5 g
Sodium sulfite (anhy) ................. 4.3 g
Potassium iodide ....................... 0.002 g
Sodium bromide ......................... 1.3 g
Hydroxylamine sulfate ................. 2.0 g
CD-4 ....................................... 4.8 g
Water to make .......................... 1.0 l
pH 10.00 +/- 0.03




Bleach 非常貴,而且實際上它可以使用很久。據論壇上的討論指出, Bleach 如果定時的打氣就可以活化使用過的活性。同時,再配合不定時的補充新鮮的 bleach(50~100ml) 及 置換掉等體積的老化 bleach 就可以使用非常的久。另外,Ammonium Sulfite 和 Disodium EDTA 也是有必要不定時補充{參考資料}。

試劑活性檢測(from PE)

Developer
First, check out a piece of film or paper by fogging it in the light and then developing for a specified time and temperature. This is a fresh developer test. You may want to develop more than one piece for more data.

With that time recorded, any time later on that you want to test the developer just run the same test and if the paper or film fails to get the same densities at the same times then the developer is bad. Up until that point, the developer is still good.

Bleach solution Stick a piece of processed B&W negative into the bleach and let it go for about 10 minutes. The image should almost completely vanish. Then, fix the film and the image should be gone. There may be a faint ghost image remaining due to some insoluable salts that form or due to distortion of the gelatin, but the film should be clear with no brown dmin.

Fix solution When using a fix with unknown properties, it is best to run 3 tests:

1. Fixation test. Sodium Sulfide solution turns brown if the fix was exhausted or weak or the time was too short.
2. Wash test. Silver Nitrate in Acetic Acid, with a color chart will tell you how good your wash cycle was.
3. Exhaustion test. Potassium Iodide in fix forms yellow cloudy precipitate if fixer is bad.

#1 is Sodium Sulfide solution and #2 is Silver Nitrate in Acetic Acid mixed. A drop of each on different spots of your paper or film and if the drops become yellow spots, then fixing and washing were not correct.


一些藥物的作用資料



•the developing agent, CD-2, CD-3, or CD-4, which are derivatives of paraphenylenediamine;
•a preservative, usually sodium or potassium sulfite, but in low concentration to ensure an adequate supply of oxidized developing agent for the coupling reaction;
•an alkali, usually potassium hydroxide, because high solution pH values are needed for efficient silver development and dye formation;
•a restrainer, usually potassium bromide, but also potassium iodide, to minimize silver fog and dye stain formation.
•a weak developing agent, such as hydroxylamine or ascorbic acid, may be included to suppress stain formation by oxidized color developer.
source: Imaging Processes and Materials By John Sturge, Vivian Walworth, Allan Shepp

Critical items are: The pH, iodide, bromide, color developing agent and sulfite. These are in order of importance high to low. The first 3 are critical.



降溫作業的討論:
As temperature goes down, the bottom layer becomes less developed when the top layer is properly developed. If you properly develop the bottom layer, then the top layer is overdeveloped. The final result can be fog and crossover. Don't do it.

PE
source:http://www.apug.org/forums/forum40/48734-c-41-effect-changing-temperature.html



調配方法要領跟顯影液一樣。漂白定影液沒有劣化問題。
藥品保存期限
處理溶液
保存期限
發色顯影液(有加CD-4)
1週
發色顯影液(沒加CD-4)
6個月
CD-4 20%儲存液
2個月
漂白定影液
2~3個月
備註:

  • 此保存期限指調配好的新溶液。

  • 保存條件為密封、瓶內空氣量降到最少。

  • 保存環境為陰暗涼爽處。

  • 此二液可使用透光瓶保存。
藥品處理能力
處理溶液
1公升藥水可處理底片數量
面積(dm2
135-36
120
發色顯影液
5
6
30
漂白定影液
20
24
100~120
備註:
漂白定影液的處理能力為參考用,請再詳細測試。
1L 顯影劑成本約 nt 176; 1L 定影劑成本約 nt 1296,平均每卷的費用約為100元。
沖片順序、溫度跟時間
處理工程
溫度(℃)
處理時間
發色顯影
38 ± 0.2 ℃
3分15秒
水洗
約30度以上即可
約30秒
漂白定影
38 ± 3 ℃
4分20秒
最終水洗(流水)
常溫水即可
約5分
自然風乾

依環境條件,至少兩小時以上。


注意事項:

*溶液開始倒入時開始計時。完全倒入後,蓋上蓋子,在桌上輕敲5~6次,將底片上附著的氣泡排除。此動作稱為昇泡。然後第1分鐘持續攪拌。這1分鐘的攪拌方法是:上下顛倒攪拌,1分鐘內約6~7次。也就是說,轉180度之後,要停2秒左右,再轉回來。第1分鐘是這樣,再來剩下的時間是30秒轉來回1次就好。

*漂白定影步驟和顯影一樣。

*處理時間到之前前十秒,停止攪拌將溶液倒出。處理時間已包括倒液體的時間。

*最終水洗事實上以流水洗約3分鐘即可,為保險起見定5分鐘。

*風乾前必須用底片用海綿,吸滿水滴斑溶液擠乾後,將底片兩面輕輕擦乾。以避免水漬。海綿及水滴斑溶液可從一般相機器材店買到。

*配好溶液後,在最後倒進儲存桶的時候,要拿個濾網過濾。重點是要避免沒有溶化的藥劑進入
。然後調好後最後放過一天 讓他完全溶化再開始用。

* pH: developer是10.1~10.2; fixer 是 pH ~6.5。

測試結果


12月初已開始試用,但有色偏問題,不曉得那裡有狀況。有在 flickr 提問:
http://www.flickr.com/groups/diy_color/discuss/72157610912385776

毫無頭緒,但找到一些有幫助的資料,如下:

4-Amino-3-methyl-N-ethyl-N-(.beta.-hydroxyethyl)-aniline sulfate;

2-Amino-5-diethylaminotoluene Monohydrochloride; and

4-Amino-3-methyl-N-ethyl-N-(.beta.-methanesulfonamidoethyl)-m-toluidine sesquisulfate monohydrate.

The first developing agent listed above is commonly used in the C-41 process for developing conventional color negative film. In fact, a C-41 developer solution may be used in the present invention. The developer solution may be aqueous, andmay be maintained at an alkaline pH. In addition to the developing agent, the developer solution can include various other additives well-known to those skilled in the art. Suitable additives include, for example, various preservatives (e.g., sodiumsulfite, sodium bisulfite, sodium metabisulfate or potassium metabisulfate), accelerators (e.g., potassium or sodium carbonate, potassium or sodium hydroxide, borax, or sodium metaborate), restrainers (such as potassium bromide), and antifoggants (suchas benzotriazole or 6-nitrobenzimidazole nitrate).


注意事項



調配注意事項:

* 首先準備約800ml,40度以上但不要超過50度的熱水。
* 由上往下將藥品邊攪拌邊加入水裡。務必完全溶解一個藥品後再加入下一個藥品。
* 6-NitroBenzimidazole 難溶於水,可以用酒精配製 0.2% 溶液。

其他注意事項:
由於Kodak CD-4為顯影主藥,且容易劣化,可在顯影前6小時再加入。但此方法麻煩。
代用方法為,先將CD-4 20g與K2S2O5 3g加水100ml溶解成為CD-4 20%的儲存液。在顯影前以一公升的顯影液加13ml的CD-4儲存液的比例加入,則能馬上進行顯影。

註:每一公升溶液使用 100g,每次成本約 858元


延伸閱讀

6 comments:

Mr.K said...

感覺很讚!!期待

PBFinchocoland said...

您好
想向您請教
何處可以購買Kodac CD4呢
感謝您了
謝謝

PBFinchocoland said...
This comment has been removed by the author.
Ahock said...

你好!
可以從日本購買或是從美國網購入手。

Ahock said...

可以試試看: stores.photoformulary.com

PBFinchocoland said...

感謝您了

徑蕪

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