JPS5831334A - Cyan dye forming coupler - Google Patents
Cyan dye forming couplerInfo
- Publication number
- JPS5831334A JPS5831334A JP13045981A JP13045981A JPS5831334A JP S5831334 A JPS5831334 A JP S5831334A JP 13045981 A JP13045981 A JP 13045981A JP 13045981 A JP13045981 A JP 13045981A JP S5831334 A JPS5831334 A JP S5831334A
- Authority
- JP
- Japan
- Prior art keywords
- group
- cyan dye
- coupler
- forming coupler
- color
- 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
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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/32—Colour coupling substances
- G03C7/34—Couplers containing phenols
- G03C7/346—Phenolic couplers
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- 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】 本発明は新規なシアン色素画倫形成カプラー。[Detailed description of the invention] The present invention is a novel cyan dye color-forming coupler.
およびこれを含有するハpゲン化銀カラー算真感光材料
に関するものである。通常カラー画像は芳香族票1級ア
建ン系発色現像主薬が、露光されたハ費ゲン化銀粒子を
還元することkより、生成する発色現像主薬の酸化生成
物と、黄色、マゼンタ、シアンの各色素を形成するカプ
ラーとがハーゲ/化銀乳剤中、酸化カップリングするこ
とkより形成される。and a silver halide color satin photosensitive material containing the same. Normally, color images are produced by the reduction of exposed silver halide grains by an aromatic class 1 adenyl color developing agent. The dye is formed by oxidative coupling with the coupler forming each dye in a silver/silver emulsion.
シアン色素を形成する為KAII的に使用されるカプラ
ーはフェノール類及びナフトール類である。Couplers commonly used in KAII to form cyan dyes are phenols and naphthols.
@に7エノール類に於いて従来カプラーの写真性能より
考えて要求される基本的性質としては色素の分光吸収特
性が真好なこと、即ちスペクシルの縁領域に歇駅がなく
、シャープなこと、形成される色素が光、熱、湿気II
aK対して十分な竪牢性を有すること、発色性が良好な
こと、即ち十分な発色感度と発色濃度を有すること、更
KBD’rA第2鉄塙を主成分とする標白浴あるいは漂
白定着浴がうymmダグ疲労しても色素損失がないこと
等が要求される・
また脱金書の見麺から発色現像液に添加されるベンジル
アル;−ルの除去が大館な問題として取り上げられてき
ている。ところが一般にベンジルアル;−ルを添加しな
いと十分な発色性が得られないというのが現状である。Considering the photographic performance of conventional couplers, the basic properties required for 7-enols are that the spectral absorption characteristics of the dye are excellent, that is, the edge region of the speckle should be sharp and without any gaps. The pigment formed is light, heat, moisture II
It should have sufficient toughness for aK, good color development, that is, sufficient color development sensitivity and color density, and a whitening bath or bleach-fixing mainly composed of KBD'rA No. 2 iron wall. Removal of benzyl alcohol added to color developing solution has been taken up as a major issue in the ``Meimen of Dekin'' book. ing. However, the current situation is that sufficient color development cannot generally be obtained unless benzyl alcohol is added.
べ/ジルアルコール除去での発色性の低下はフェノール
シアンカプラーに於いてqlK顕著であり、この面から
もベンジk 7 k :l−ルがなくと411色性の高
いフェノールシアンカプラーが要望されている。The decrease in color development due to removal of benzyl alcohol is remarkable in phenolic cyan couplers, and from this point of view, there is a demand for phenolic cyan couplers with high 411 color properties without benzyl alcohol. There is.
これまで上記の諸要件を満足すべく、研冑が行われてぎ
ているが本li明の知る限りKfkいては、上記の要求
される性質をすべて満足したシアンカプラーは未だ見い
出されていない。Efforts have been made to satisfy the above-mentioned requirements, but as far as we know, a cyan coupler that satisfies all of the above-mentioned required properties has not yet been found.
例えば、米Il轡許第九801,171漫に記載されて
いる6−〔α−(2,4−ジーt−、−’7電ルフェノ
キシ)ブタンアfド]−2.4−シーりtyロー3−メ
チルフェノールは耐光性は良好であるが耐熱性に欠点を
有し、加えて疲労した漂白定着液での色素損失も大きい
、またベンジルアルコールへの発色依存性が大であり、
発色現像液よりのベンジルアルコールの除去は困難であ
る。米国特許2,895,826号記載の2−ヘペタフ
ルオロプタンア?)”−5−(α−(2,4−ジーt−
ア建ルア翼ノキシ)ヘキサンアンド〕フェノールは耐熱
性、疲労した漂白定着浴での色素損失という点で秀れて
いるが、耐光性、発色性という点で番±劣る。また特開
昭53−109630号公報に記載されているカプラー
もベンジルアルコールの除去、更には耐光性という点で
問題を残しているJ更に米国特′許第3,839,04
4号、特開昭47−37421$1公報%轡金昭48−
36894号公報、特gil昭50−10135号、同
50−1174124、同5G −1114411)、
IIl 5G−1051841号、ftfl 50−1
203344公報等に記載されるフェノール歴シアンカ
プラーも耐熱性、ベンジルアルコールの除去という点テ
不満足である。!位にウレイド基を有するフェノールカ
プラーは英国特許厘1.O11,940号及び米国特許
鮪3,446,622−1.同3,998,253号、
同3,758,308号尋に記載されているが、これら
のカプラーより形成されるシアン色素は分光吸収がプ費
−ドな事・更kll駅極大が赤領域の比較的短波部にあ
ることよりスペクトルの縁領域kかなりの吸収を有し色
再現上好ましくない、4$−@ 56−65134に記
載の2位にウレイド基を有するフェノールカプラーはス
ペクシル領域の級数IIKついてはかなり改善されてい
るが、その他の善性は今一つ不十分である。For example, 6-[α-(2,4-di-t-,-'7-electrophenoxy)butanead]-2,4-cyte is described in U.S. Pat. No. 9,801,171. Although rho-3-methylphenol has good light resistance, it has shortcomings in heat resistance, and in addition, there is a large loss of dye in a tired bleach-fix solution, and color development is highly dependent on benzyl alcohol.
Removal of benzyl alcohol from color developing solutions is difficult. 2-Hepetafluoroptana described in U.S. Pat. No. 2,895,826? )”-5-(α-(2,4-G-t-
Phenol is superior in terms of heat resistance and dye loss in a fatigued bleach-fixing bath, but is inferior in terms of light resistance and color development. Furthermore, the coupler described in JP-A-53-109630 still has problems in terms of removal of benzyl alcohol and light resistance.
No. 4, Japanese Patent Publication No. 47-37421 $1 Publication% 轡金显48-
No. 36894, Special Gil No. 50-10135, No. 50-1174124, No. 5G-1114411),
IIl 5G-1051841, ftfl 50-1
The phenolic cyan couplers described in Publication No. 203344 and the like are also unsatisfactory in terms of heat resistance and removal of benzyl alcohol. ! A phenol coupler having a ureido group in the British patent 1. No. 011,940 and U.S. Patent Tuna 3,446,622-1. No. 3,998,253,
As described in No. 3,758,308, the cyan dye formed by these couplers has a low spectral absorption, and furthermore, the kll station maximum is in the relatively short wavelength region of the red region. Although the phenol coupler having a ureido group at the 2-position described in 4$-@56-65134, which has considerable absorption in the edge region of the spectrum and is unfavorable for color reproduction, has considerably improved series IIK in the spectroscopic region. , other goodness is not enough.
こういった従来技留に対して、本発明者らは鋭意研究を
重ねた結果、下記一般式゛(■)および(If)で表わ
されるカプラーにより前記の如きフェノールシアンカプ
ラーとして要求される緒特性を十分に―足することを見
い出すに到った。As a result of extensive research into these conventional techniques, the present inventors have found that the couplers represented by the following general formulas (■) and (If) have the characteristics required for the above-mentioned phenolic cyan couplers. I have found that I can add enough.
一般式(II)
ケエル基、アリール基、複素環基、シフシアルキル基、
アシル基(例えばアルキルカルゼニル基、了り−ルカル
ボエル基)を表わす、を換基として例えば、アルキル基
、アリール基、ハ薗ゲンM子(フッ素、塩素又は臭素)
、トリフルオ四メチル基、工)胃基、シアノ基、水酸基
、アルプキシ基、アシルオキシ基、アジルアZノ基、ス
ルホンアミド基、スルホニル基、スルホンア()”lス
ルファ峰イル基、スルホ基、カルボン酸基郷を有しても
よ、い、またアルキル基は直鎖でも分岐でもよい。General formula (II) Kel group, aryl group, heterocyclic group, shifsia alkyl group,
Representing an acyl group (e.g. alkylcarzenyl group, carboel group), for example, an alkyl group, an aryl group, a substituent (fluorine, chlorine or bromine)
, trifluorotetramethyl group, cyano group, hydroxyl group, alpoxy group, acyloxy group, azila group, sulfonamido group, sulfonyl group, sulfonyl group, sulfo group, carboxylic acid group The alkyl group may have a straight chain or a branched chain.
また、ν、νは亙いに結合t、?5またはIJjlmを
形成してもよい*Rを構成する原子は脚素原子。Also, ν, ν are connected across t, ? 5 or IJjlm may be formed.*The atoms constituting R are base atoms.
酸素原子、會l!原子、イオウ原子から選ぶことができ
る R1はバラスト基を表わす。ここでバラスト基とは
カプラーが設置された層から拡散することを防止するた
めにカプラー分子に与えられるかさ高い有機基な示し1
例えば全炭素原子数が8〜諺のアルキル基、アリール基
がある。置換基としてはアルキル基、アルクキシ基、ア
リール基、アリールオキシ基、アルキルチオ基、アリー
ルチオ基、アルキルスルホニル基、アリールスルホニル
基、アルコキシカルボニル基、アリールオキシカルlニ
ル基、アシル基、アシルオキシ基、スルホンア々ド基、
スルファモイル基、ハロゲン原子、水酸基、カルボキシ
基等を有してもよくこれらの置換基のアルキルおよびア
リール部分はさらに上記の置換基で置換されていてもよ
い。Oxygen atoms, meet! R1 represents a ballast group, which can be selected from atom and sulfur atom. Here, the ballast group refers to a bulky organic group given to the coupler molecule to prevent it from diffusing from the layer in which the coupler is installed.
For example, there are alkyl groups and aryl groups having a total number of carbon atoms of 8 to 8. Substituents include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylthio groups, arylthio groups, alkylsulfonyl groups, arylsulfonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyl groups, acyloxy groups, sulfonyl groups, etc. do group,
It may have a sulfamoyl group, a halogen atom, a hydroxyl group, a carboxy group, etc., and the alkyl and aryl moieties of these substituents may be further substituted with the above-mentioned substituents.
Xは水素または発色現侭主嬉の酸化生成物とのカップリ
ング反応時に脱離可能な基を表わし、例えばハロゲン原
子(例えば塩素、臭素、弗素等の各原子)、酸素原子ま
たは窒素原子が直接カップリング位に結合しているアリ
ールオキシ基、カルバ毫イルオキシ基、カルバモイルメ
トキシ基、アシルオキシ基、スルホンアミド基、コ/1
り酸イ建ド基部が挙げられ、更に具体的な例としては、
米国特許3,471,563号、特開昭47−3742
5号、特公昭48−36894号、49開昭50−10
135号、同50−117422号、同5G −130
441号、同51−1088414!I。X represents a group that can be eliminated during a coupling reaction with hydrogen or a color-forming oxidation product; Aryloxy group, carbamyloxy group, carbamoylmethoxy group, acyloxy group, sulfonamide group, co/1 bonded to the coupling position
A more specific example is a phosphoric acid group.
U.S. Patent No. 3,471,563, JP 47-3742
No. 5, Special Publication No. 48-36894, 49 1973-10
No. 135, No. 50-117422, No. 5G-130
No. 441, 51-1088414! I.
同So −120384号、同52− tssts号、
同53−52428号、同53−105226号醇の各
公報に記載されているもの轡が有用である。So-120384, So-52-tssts,
The methods described in Publications No. 53-52428 and No. 53-105226 are useful.
本発明の特許請求の範囲で表わされるシアンカプラーを
以下に例示するが、これらに限定されるものではない。Examples of cyan couplers defined in the claims of the present invention are shown below, but the invention is not limited thereto.
以下に本発明のカプラーの代表的合成ルートおよび合成
例を示す。Typical synthetic routes and synthetic examples of the couplers of the present invention are shown below.
合成例!(例示カプラーlの合成)
2−(α−(2,4−ジーtert−ペンチルフェノキ
シ)テトラデカンアミド)−4−り6四−5−(3−(
3−工Fキシカルボニル7エエル)ウレイド)フェノー
ルの合成。Synthesis example! (Synthesis of Exemplary Coupler I) 2-(α-(2,4-di-tert-pentylphenoxy)tetradecanamide)-4-ri64-5-(3-(
Synthesis of 3-enoxycarbonyl7ethyl)ureido)phenol.
1&、りの2−アミへ′−りa a −5−x= )
* フェノールを1OO−のアセトニトリルに溶かし、
i、opのピリジンを加えた。1m温攪拌下4811の
α−(2,4−ジーt@rt−ペンチルフェノキシ)テ
トラデカン酸りレライドをtoo slのアセトニトリ
ルに溶かした溶禦を約1時間かかって滴下した。さらに
攪拌を続けた後、反応*1を氷水中に注ぎ、酢酸エチル
で抽出した。抽出液を水洗後、無水硫酸ナト亨つムで乾
燥後、減圧濃縮して55Iの油状物を得た。1&, 2-ami'-ri a a -5-x= )
* Dissolve phenol in 1OO- acetonitrile,
i, op pyridine was added. While stirring at 1 m temperature, a melt of 4811 α-(2,4-di-t@rt-pentylphenoxy)tetradecane acid relide dissolved in too sl of acetonitrile was added dropwise over about 1 hour. After further stirring, the reaction *1 was poured into ice water and extracted with ethyl acetate. The extract was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 55I as an oil.
上記のようkして得られた油状物をアル;−ルtooo
−中に@解し、パラジウム炭素触媒を用いて接触還元を
行った。ll論量の水素を吸収させた後。The oily substance obtained as described above is mixed with alcohol.
catalytic reduction was carried out using a palladium-carbon catalyst. After absorbing 1 stoichiometric amount of hydrogen.
黴引纏過にようて触媒を除去した。濾液を減圧濃縮し、
ヘキナyで洗い粗結晶53IIを得た。The catalyst was removed by filtration. Concentrate the filtrate under reduced pressure,
Crude crystal 53II was obtained by washing with Hekina y.
上記粗結晶131iをtso lIjのトルエンに@郷
し。The above crude crystal 131i was dissolved in toluene.
3.8JII 8−エトキシカルボニル7Xニルイン
シアネーFの100−のFルエン溶液を添加した0反応
混合物を2時間加熱還流後、減圧下にてトルエンな除去
した0反応組成物をシリカゲルカラムクーマドグラツイ
ーにてヘキサン、トルエンの混合溶媒で溶出後、ヘキサ
ンと酢酸エチルの混合111媒にて再結晶し、1j!i
e)@約物を得た。目的物の構造確認は電解脱離質量分
析およびプ四トン協Bスペクトルにて行なった。3.8JII 8-Ethoxycarbonyl 7 After elution with a mixed solvent of hexane and toluene, recrystallization was performed with a mixed solvent of hexane and ethyl acetate. i
e) @ got a promise. The structure of the target product was confirmed by electrolytic desorption mass spectrometry and Psitonkyo B spectrum.
合成例2(例示カプラー6の合成)
2−(4−(3−ドデシルオキシフェノキシ)ブタンア
建ド)−4−フレロー5− (N、N−べyタメチレy
)ウレイドフェノール
tHpの2−ア考ノー4−り胃ロー5−!ドロフェノー
ルを100−のアセトニトリル#cfIIかし、1、O
jのピリジンを加えた。室温攪拌下器の4−(3−ドデ
シルオキシフェノキシ)ブタン讃り撃ライドを&)aJ
のアセトニトリルに溶かした溶液を滴下した。さらに攪
拌を続けた後、反応S*を氷水中に注ぎ酢酸エチルで抽
出した。抽出液を水洗後無水硫酸す)9ウムで乾燥し、
減圧濃縮してアセ)息トリルにて再結晶した。45Iの
白色固体を得た。上記の白色固体を300117のアル
コールKWかしパラジウム−炭素触媒を用いて接触還元
を行なりた。ll論量の水素を吸収させた後、甑引瀘過
にようて触媒を除去した。濾液を減圧濃縮し、へ命サン
で洗い粗結晶431を得た。Synthesis Example 2 (Synthesis of Exemplary Coupler 6) 2-(4-(3-dodecyloxyphenoxy)butanyl)-4-Flerot 5-(N,N-betamethyl)
) Ureidophenol tHp 2-A consideration no 4-ri stomach low 5-! Drophenol was dissolved in 100-acetonitrile #cfII, 1,0
Pyridine of j was added. Add 4-(3-dodecyloxyphenoxy)butane in a stirred vessel at room temperature.
A solution of 100% in acetonitrile was added dropwise. After further stirring, the reaction S* was poured into ice water and extracted with ethyl acetate. After washing the extract with water, drying with 9 um of anhydrous sulfuric acid,
It was concentrated under reduced pressure and recrystallized in acetotrile. A white solid of 45I was obtained. The above white solid was subjected to catalytic reduction using 300117 alcohol KW and palladium-carbon catalyst. After absorbing 1 stoichiometric amount of hydrogen, the catalyst was removed by filtration. The filtrate was concentrated under reduced pressure and washed with hemisan to obtain crude crystals 431.
上記粗結晶129を100−のトルエyK@解し、10
1の1−ピペリジンカルが7層クロライドの(資)dト
ルエン*Wを加えた。室温攪拌1時間後析出した1体を
濾別し、濾液をS縮した。濃縮液をシリカゲルカラムク
ーマドグラ74にてヘキサン、トルエンの混合溶媒で溶
出後、ア−k)ニトリルから再結晶り、、 8.s#f
)!約物を得た。目的物の構造確認は電解脱離質量分析
、およびプ四トン蘭スペクトルにて行なった。The above crude crystal 129 was dissolved in 100-Toluene yK@, and 10
The 1-piperidine carbon of 7-layer chloride (capital) d-toluene*W was added. After stirring at room temperature for 1 hour, one precipitate was filtered off, and the filtrate was subjected to S condensation. After eluting the concentrated solution with a mixed solvent of hexane and toluene in a silica gel column Coomad Gras 74, a-k) recrystallization from nitrile, 8. s#f
)! I got a deal. The structure of the target product was confirmed by electrolytic desorption mass spectrometry and Psitonran spectrum.
本俺嘴で使帛されるシアン色素形成カプラーは通常のシ
アン色素形成カプラーで用いられる方法技術が同様に適
用小乗る。典型的には、カプラーをハ請ゲy化鎖乳剤に
配合し、この乳剤をペース上に被覆して写真要素を形成
する。The cyan dye-forming couplers used in this invention are similar to those used in conventional cyan dye-forming couplers. Typically, the coupler is incorporated into a dyed chain emulsion and the emulsion is coated onto a paste to form the photographic element.
写真要素は、単色要素また+1多色要素であることがで
診る。多色要素では1本発明のシアン色素形成カプラー
は、普通赤感乳剤に含有させるが、しかし、非増感乳剤
またはスペクトルの三厘色鎖域の各々に感光性を有する
色素画像形成構成単位を有する。各構成単位はスペクト
ルのある一定領域に対して感光性を有する単孔剤層また
は、多層乳剤層からなることができる0画侭形成構成単
位の層を含めて要素の層は、当業界で知られているよう
に種々の順序で配列することが出来る。典瀝的な多色写
真要素は、少なくとも1つのシアン色素形成カプラーを
有する少なくとも1つの赤感ハーゲン化鎖乳剤層からな
るシアン色素画像形成構成単位(シアン色素形成力グラ
−の少なくとも1つは本発明のカプラーであPl)少な
くとも1つの!ゼンタ色素形成カプラーを有する少なく
とも1つの青感ハロゲン化銀乳剤層からなる黄色素画像
形成構成単位なベースに担持させたものからなる。A photographic element can be a single color element or a +1 multicolor element. In multicolor elements, the cyan dye-forming couplers of this invention are normally incorporated into red-sensitive emulsions, but may also be incorporated into non-sensitized emulsions or dye image-forming units sensitive to each of the triad regions of the spectrum. have The layers of the element, including layers of 0 image side-forming units, each of which may consist of a single pore layer or multiple emulsion layers sensitive to a certain region of the spectrum, are known in the art. They can be arranged in various orders as shown. A typical multicolor photographic element consists of a cyan dye image-forming unit consisting of at least one red-sensitive hagenated chain emulsion layer having at least one cyan dye-forming coupler (at least one of the cyan dye-forming couplers is present). Pl) at least one inventive coupler! It consists of at least one blue-sensitive silver halide emulsion layer having a zenta dye-forming coupler supported on a yellow dye image-forming unit base.
要嵩は、追加の層、例えばフィルタ一層、中間層保護層
、下塗り要部を有することが出来る。The bulk can have additional layers, such as a filter layer, an interlayer protective layer, and a primer layer.
本発明のカプラーを乳剤上含有せしめるには、従来公知
の方法に従えばよい。例えばトリクレジルホスツェート
、ジブチル7タレーF岬の沸点17!$ ℃以上の高沸
点有!I!lII諜、または酢酸ブチル、プ田ピオン蒙
ブチル勢の低沸点溶媒のそれぞれ単独kまたは必要に応
じてそれらの温合flK本発明のカプラーを単独でまた
は併用してWSした後、界面活性剤を含むゼラチン水S
*と混合し1次に高速旋回転tdPサーまたはス四イド
ミルで乳化した後、ハレゲン化銀に添加して本発明に使
用するハロゲン化銀乳剤を調整することが出来る。そし
て本尭−のカプラーを本発明のハロゲン化銀乳剤中に添
加する場合1通常、ハロゲン化銀1モル当り約0.07
〜G、7 sth ル、好ましく Irt 0.1〜0
.4−vルf)範囲で本発明のカプラーが添加される。In order to incorporate the coupler of the present invention into an emulsion, a conventionally known method may be followed. For example, the boiling point of tricresyl phoscetate, dibutyl 7 Talley F cape is 17! Has a high boiling point of over $ ℃! I! After WS of the coupler of the present invention alone or in combination with a low boiling point solvent such as butyl acetate, butyl acetate, butyl acetate, or a mixture thereof as necessary, a surfactant is added. Contains gelatin water S
The silver halide emulsion used in the present invention can be prepared by mixing with * and first emulsifying it in a high-speed rotating tdP rotary rotary tdP mill or a sulfur mill, and then adding it to silver halide. When this coupler is added to the silver halide emulsion of the present invention, it is usually about 0.07 mol per mole of silver halide.
~G, 7 sth le, preferably Irt 0.1-0
.. The couplers of the invention are added in the range 4-vlf).
本@ l! f) Aaゲン化銀乳剤に用いられるハp
ゲン化銀としては、臭化銀、塩化銀、沃臭化銀、塩臭化
銀、塩沃臭化Is等の通常のハロゲン化銀乳剤に使用さ
れる任意のものが包含される。Book@l! f) Hap used in Aa silver generator emulsion
Silver genides include any compounds used in conventional silver halide emulsions, such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and Is chloroiodobromide.
本発明のハロゲン化銀乳剤を構成するハロゲン化銀乳剤
は、通常行なわれる製法をはじめ、種々の製法、例えば
特公昭46−7772号公報に記載されている如き方法
、すなわち溶解度が臭化銀よりも大きい、少なくとも一
部の銀基からなる銀基粒子の乳剤を形成し、次いでこの
粒子の少なくとも一部を臭化銀または沃臭化銀塩に変換
する等の所謂コンパージ冒ン乳剤の製法、あるいは0.
1声以下の平均粒径な有する微粒子状ハーゲン化頷から
なるリップマン乳剤の製法等あらゆる製法によって作成
することができる。The silver halide emulsion constituting the silver halide emulsion of the present invention can be manufactured by various manufacturing methods including the usual manufacturing method, such as the method described in Japanese Patent Publication No. 46-7772, that is, the solubility is higher than that of silver bromide. A method for producing a so-called composite emulsion, which involves forming an emulsion of silver-based grains that are large in size and consisting of at least a portion of silver groups, and then converting at least a portion of the grains into silver bromide or silver iodobromide salt; Or 0.
It can be prepared by any method such as the method for producing a Lippmann emulsion consisting of finely divided hagenated particles having an average grain size of one tone or less.
さらに本発明のハロゲン化銀乳剤は、硫黄増感剤、例え
ばアリルチオカルバミド、チオ尿素、シスチン岬、また
活性あるいは不活性のセレン増感剤、そして還元増感剤
、例えば*1スズ塙、ボリア電ン勢、貴金属増感剤1例
えば金増感剤、具体的にはカリウムオーリチオシアネー
ト、カリウムフルロオーレート、2−オー誼スルホペy
ズチアゾールメチルクpリド等、あるいは例えばルテニ
ウム、四ジウム、イリジウム等の水溶性塩の増感剤、具
体的にはア/4ニウムクロ四バ5f−F、カリウムクW
ロプチラネートおよびナトリウムクロロパラダイr等の
単独であるいは適宜併用で化学的に増感されることがt
きる。Furthermore, the silver halide emulsion of the present invention may contain sulfur sensitizers such as allylthiocarbamide, thiourea, cape cystine, active or inactive selenium sensitizers, and reduction sensitizers such as *1 tin sensitizer, boria Noble metal sensitizers 1 For example, gold sensitizers, specifically potassium aurithiocyanate, potassium fluoroate, 2-ester sulfopene
sensitizers such as dithiazole methylchloride, or water-soluble salts such as ruthenium, tetradium, and iridium, specifically, a/quaternium black tetrachloride 5f-F, potassium tetrachloride, etc.
It can be chemically sensitized by using roptilanate and sodium chloroparadia alone or in combination as appropriate.
Wear.
また本発明のハロゲン化銀乳剤は種々の公知の写真用添
加剤を含有せしめることができる。例えばRe5a+r
d・Disclos釘・(リサーチ・ディスクロージャ
ー)、1978年12月項@ 17643 K記載され
ているが如き写真用添加剤である。Furthermore, the silver halide emulsion of the present invention can contain various known photographic additives. For example, Re5a+r
A photographic additive as described in d. Disclos Nail (Research Disclosure), December 1978 @ 17643 K.
本発明のハpゲン化優は赤感性乳剤に必要な感光波長域
に感光性を付与するために、適当な増感色素の選択によ
り分光増感がなされる。この分光増感色素としては種々
のものが用いられ、これらは1種あるいは2種以上併用
することかで館る。The halogenated emulsion of the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity in the wavelength range required for red-sensitive emulsions. Various spectral sensitizing dyes are used, and these can be used alone or in combination.
本発明において有利に使用される分光増感色素としては
1例えば米IO特許第2,269,234号、同第2.
270,378−41!、閂Iff 2,442,71
0号、同II 2,454,629号、開票2,776
j804!各明細書等に記載されている如き □シア具
ン色素、メ田シアニン色素また+t 複合vアニン色素
を代表的なものとして挙げることができる。Spectral sensitizing dyes that are advantageously used in the present invention include 1, for example, US IO Patent No. 2,269,234;
270,378-41! , Lock Iff 2,442,71
No. 0, II No. 2,454,629, 2,776 votes counted
j804! Typical examples include □ cyanine dyes, Meda cyanine dyes, and +t complex v-anine dyes as described in various specifications.
氷見flRK#Iいることがで會る発色現@Illは好
ましくは芳書族第1級アミン系発色現像主薬を主成分と
するものである。この発色現像主薬の異体何としてはり
−7zニレ/シア建y系のものが代表的であり1例え
ばジエチル−p−78ニレンジアオン塩階塩、モノメチ
ル−p−フェニレンジアンン塙酸塩、ジメチル−T)
= 7 xニレ/シアミン塩−塙、2−アンノー5−ジ
ェチルアZノトルエン塩蒙塩、2−ア2ノー5−(N−
エチル−N−ドブシルアず))−トルエン、2−72ノ
ー5−(N−エチル−N−β−メタンスルホンア之ドエ
チル)アミントルエン硫酸塩、4−(N−エチル−N−
β−メタンスルホンア之ドエチルア々))アニリン、4
−(N−エチル−N−β−ヒトジキシエチルアミノ)ア
ニリン、2−ア々ノー5−(N−エチル−N−β−メト
キシエチル)アミントルエン等が挙げられる。HimiflRK#I is preferably a color developing agent containing an aromatic primary amine color developing agent as a main component. Variants of this color developing agent are representatively -7z elm/shea-based ones; for example, diethyl-p-78 nylene diane salt, monomethyl-p-phenylene diane sulfate, dimethyl-T )
=7
Ethyl-N-dobusylaz))-toluene, 2-72no5-(N-ethyl-N-β-methanesulfonanodoethyl)amine toluene sulfate, 4-(N-ethyl-N-
β-Methanesulfone anodoethyl acetate)) Aniline, 4
-(N-ethyl-N-β-hydoxyethylamino)aniline, 2-arano-5-(N-ethyl-N-β-methoxyethyl)amine toluene, and the like.
現像後は銀およびハーゲ/化鎖な除去するための漂白、
定着または漂白一定着、洗浄および乾燥の通常の工程が
行われる。After development, bleach to remove silver and bald spots.
The usual steps of fixing or bleaching, washing and drying are carried out.
以下実施例により1本発明を具体的に述べるが本発明の
実施の態様がこれにより限定されるものではない。The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto.
実施例(1)
at表に示すような本発明のカプラーおよび下記の比較
カプラー(A)、CB)、(C)を各々0,03七〃ず
つ埴り、その重量と同量の7タル酸ジブチルおよび3倍
量の酢酸エチルとの混合液に加え、ω℃に加温して完全
KfI#解した。この溶液をアルカノールB(アルキル
ナフタレンスルホネート、デュポン社11)およびゼラ
チンの水溶液に加え、コ四イド電ルを用いて乳化し、そ
れぞれのカプラー分散液を作成した0次にこのカプラー
分散液を銀とし0.1毫ルを含む塩臭化銀乳剤(2Dモ
ルーが臭化銀)k添加し、ポリエチレンラミネート紙に
塗布し乾燥して、安定な塗布膜を有する6種類のハ四ゲ
ン化銀カラー写真感光材料(試料番号〔!〕〜〔6〕)
を得た。Example (1) The couplers of the present invention as shown in the AT table and the following comparative couplers (A), CB), and (C) were each weighed in an amount of 0.037, and the same amount of 7-talic acid as the weight was added. The mixture was added to a mixture of dibutyl and 3 times the amount of ethyl acetate and heated to ω°C to completely dissolve KfI. This solution was added to an aqueous solution of alkanol B (alkylnaphthalene sulfonate, DuPont Co., Ltd. 11) and gelatin, and emulsified using cotetrahydride to prepare each coupler dispersion.Next, this coupler dispersion was used as silver. Silver chloride bromide emulsion (2D mole is silver bromide) containing 0.1 mmol was added, coated on polyethylene laminate paper and dried, resulting in six types of silver halide color photographs with stable coating films. Photosensitive materials (sample numbers [!] to [6])
I got it.
U!
比較カプラー〔B〕
比較カプラーCC)
これらの試料を常法に従ってウェッジ露光を行なった後
火の処理を行なりた。但し発色現像l1は、べ/デルア
ル;−ルの添加されたもの(〔発色現像液組成!〕)添
加しないもの(〔発色現像液組成z〕)との二種の組成
について行なった。U! Comparative coupler [B] Comparative coupler CC) These samples were subjected to wedge exposure according to a conventional method and then subjected to fire treatment. However, color development 11 was carried out for two types of compositions: one with added alcohol ([color developer composition!]) and one without ([color developer composition z]).
〔処理〕 処理工1m(30℃) 処理時間 下記にその各処理組成を示す。〔process〕 Treatment process 1m (30℃) Processing time The composition of each treatment is shown below.
〔発色現像1[IIi成!〕 〔発色現像液組成2〕 〔漂白定着液組成〕 得られた試料のそれぞれについて写真脣性を測定した。[Color development 1 [IIi formation! ] [Color developer composition 2] [Bleach-fix solution composition] Photographic sensitivity was measured for each of the obtained samples.
その結果を菖!!!に示す。表中相対感度値は、〔発色
現**組成l〕で処理した時の最大感度値を100とし
て表わした。Check out the results! ! ! Shown below. The relative sensitivity values in the table are expressed with the maximum sensitivity value when processed with [Color Development** Composition 1] as 100.
前記第1表から明らかなように本発明に係るカプラーに
より得られた試料は、ベンジルアルコールの有#IKか
〜わらず良好な、感度、最大濃度が得られ優れているこ
とが判る。As is clear from Table 1, the samples obtained using the coupler according to the present invention are excellent in that good sensitivity and maximum density can be obtained regardless of the presence of benzyl alcohol.
又、発色スペクトルを測定した結果、本発明のカプラー
を用いた色素は、赤領域の比較的長い部分に最大敷板極
大を有し、短波側の吸収は少なく優れた色純度を示すこ
とが判った。Furthermore, as a result of measuring the color spectrum, it was found that the dye using the coupler of the present invention has a maximum plateau in a relatively long part of the red region, and exhibits excellent color purity with little absorption on the short wavelength side. .
II膣例(=)
前記実施例(1)と同様にして得られた試料を用いて色
素画像の耐光性、耐熱性、耐湿性の検討を行なった。II Vaginal Example (=) Using a sample obtained in the same manner as in Example (1) above, the light resistance, heat resistance, and moisture resistance of the dye image were examined.
なお、表中耐光性は、得られた各画倫をキセノン7エー
ドメーターで300時間曝露後の残置濃度を、曝露前の
濃度を100として表わした。また耐湿性は旬℃、相対
湿度70−の条件で3週間保存後の残留111度を、試
験前の濃度を100として表わした。さもに耐熱性は、
77℃の条件下3週間保存後の残音濃度を、試験前の濃
度を!OOとして表わした。(僅LIIIJ11度1.
0)
#x!表から明らかなように、比較カプラー1’A)は
耐光性において優れた性能を有するが、耐熱湿性に問題
があり、比較カプラーCB)、(C)は、耐熱湿性に優
れるが、〔発色現**組成2〕での耐光性に問題がある
。In addition, the light resistance in the table is expressed as the residual concentration after 300 hours of exposure of each obtained image in a xenon 7-ade meter, with the concentration before exposure being 100. Moisture resistance was expressed as a residual temperature of 111 degrees after storage for 3 weeks at a temperature of 70 degrees Celsius and a relative humidity of 70 degrees, with the concentration before the test being 100. In addition, the heat resistance is
After storage for 3 weeks at 77℃, the concentration before the test! Expressed as OO. (Only LIIIJ11 degrees 1.
0) #x! As is clear from the table, comparative coupler 1'A) has excellent light resistance, but has a problem with heat and humidity resistance, and comparative couplers CB) and (C) have excellent heat and humidity resistance, but [color development] **Composition 2] has a problem with light resistance.
一方、本発明に係る例示カプラー(1)、(6)および
〔7〕は、いずれの点でも優れた性能を有するカプラー
であることが判る。On the other hand, it can be seen that the exemplary couplers (1), (6) and [7] according to the present invention are couplers having excellent performance in all respects.
実施例(3)
票3表に示すような本発明のカプラー、前記比較カプラ
ー(A)、 CB’lおよび下記の比較カプラー(D)
を各々0.01%ルずつ取り、その重量と同量のトリク
レジルホスフェートおよび3倍量の酢蒙エチルとの混合
[に加え、ω℃に加温して完全に溶解した。この溶液を
アルカノールBおよびゼラチンの水溶1[K加えて、コ
ロイドオルな用いて乳化し、それぞれのカプラー分散液
を作成した。Example (3) Couplers of the present invention as shown in Table 3, the above comparative coupler (A), CB'l and the following comparative coupler (D)
0.01% of each was added to the mixture with the same amount of tricresyl phosphate and three times the amount of ethyl acetate, and the mixture was heated to ω° C. to completely dissolve. Alkanol B and an aqueous gelatin solution 1[K were added to this solution, and the mixture was emulsified using a colloid to prepare each coupler dispersion.
次にこのカプラー分散液を銀とし0.1モルを含む沃臭
化鎖乳剤(6モル憾が沃化II)に添加し、七ル田−ス
アセテートフィルムベース上KII布L、乾燥して安定
な塗布gな有する6種目のへ四ゲy化銀カラー写真感光
材料(試料番号[13) 4・〔1幻〕を得た。This coupler dispersion was then added to an iodobromide chain emulsion containing 0.1 mol of silver (6 mol of iodide II), dried and stabilized on a KII cloth L on a Shichiruta-suacetate film base. Six kinds of silver tetrageyide color photographic light-sensitive materials (sample number [13) 4.[1]] having a coating strength of 100% were obtained.
比較カプラーCD〕
これらの試料を常法に従りてウェッジ露光を行なりた後
火の処理を行なった。Comparative coupler CD] These samples were subjected to wedge exposure according to a conventional method and then subjected to fire treatment.
処環工II(33℃) 処理時間
〔斃色現像淑組成〕
〔定着液組成〕
□〔安定化tILII1ml!〕
隠ル!リン(37qII水溶11) 1.5m
j得られたシアン発色画倫について写真特性を測定した
。その結果な鎮3表に示す。Processing time (33℃) Processing time [Composition of color developer] [Fixer composition] □ [Stabilized tILII 1ml! ] Hidden! Phosphorus (37qII water soluble 11) 1.5m
j The photographic characteristics of the obtained cyan colored image were measured. The results are shown in Table 3.
813表
第3表から明らかな如く、本発明に係るカプラーを用い
た試料は、感度、発色性に優れていることが判る。As is clear from Table 3 of Table 813, the samples using the coupler according to the present invention were found to be excellent in sensitivity and color development.
また本発明による試料は、分光スペクトルヲ測定した結
果、赤領域の長波長部に最大吸収波長を有し、短波長部
はシャープな切れを示し、比較カプラーに比べ、縁領域
の色再現上好ましい色素画儂を与えることが判った。In addition, as a result of measuring the spectroscopic spectrum, the sample according to the present invention has a maximum absorption wavelength in the long wavelength region of the red region, and a sharp break in the short wavelength region, which is preferable in terms of color reproduction in the edge region compared to the comparative couplers. It was found that it gives a pigmented image.
実施例(4)
実施例(1)で得られた試料〔1〕〜〔6〕をウェッジ
露光を行なった後、実施例(1)の〔発色現像液組成l
〕の現像処■を行った。Example (4) After performing wedge exposure on samples [1] to [6] obtained in Example (1), [color developer composition l] of Example (1) was applied.
).
一方漂白定着1[な下記の組成に代えたもので現像処覇
を行い疲労漂白定着tlKよるシアン色素の退色性を調
べた。On the other hand, development was carried out using bleach-fix 1 (substituted with the following composition) and the fading properties of the cyan dye due to fatigue bleach-fixing tlK were investigated.
現倫処理して得られた試料のシアン色素の最大反射濃度
を測定した。その結果を第4表に示す・尚、最大濃度部
に於ける色素残存率は以下のようKして求めた。The maximum reflection density of the cyan dye of the sample obtained by Genrin treatment was measured. The results are shown in Table 4.The dye residual rate in the maximum density area was determined by K as shown below.
w44表
縞4表より本発明に係るカプラーを用いた試料は疲労漂
白定着液処理でのシアン色素の退色が少ないことが理解
される。W44 Table 4 It can be seen from Table 4 that the sample using the coupler of the present invention shows less fading of the cyan dye when treated with a fatigue bleach-fix solution.
代雅人桑原義 静Shizuo Masato Kuwabara
Claims (1)
/化鎖写真用シアン色素形成カプラー一般式(I) 〇 一歇式(n) kケエル基、アリール基、複素環基、シフ曹アルキル基
、アシル基を表わし、 R1とνは互いに結合して5ま
たは6員環を形成してもよ<、Bsはパラスト基を表わ
し、Xは水素原子または発色現像主薬の雪化体と度広し
て脱離する基を表わす、)[Claims] A cyan dye-forming coupler for photography represented by the following general formulas (1) and (II). represents a heterocyclic group, a Schiff carbon alkyl group, or an acyl group, R1 and ν may be combined with each other to form a 5- or 6-membered ring, Bs represents a palust group, and X represents a hydrogen atom or a color developing agent. )
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13045981A JPS5831334A (en) | 1981-08-19 | 1981-08-19 | Cyan dye forming coupler |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13045981A JPS5831334A (en) | 1981-08-19 | 1981-08-19 | Cyan dye forming coupler |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5831334A true JPS5831334A (en) | 1983-02-24 |
JPS6329732B2 JPS6329732B2 (en) | 1988-06-15 |
Family
ID=15034738
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13045981A Granted JPS5831334A (en) | 1981-08-19 | 1981-08-19 | Cyan dye forming coupler |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5831334A (en) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59198454A (en) * | 1983-04-25 | 1984-11-10 | Konishiroku Photo Ind Co Ltd | Method for forming dye image |
EP0204530A2 (en) | 1985-05-31 | 1986-12-10 | Konica Corporation | Method for forming direct positive color image |
EP0228914A2 (en) | 1985-12-28 | 1987-07-15 | Konica Corporation | Method of processing lightsensitive silver halide color photographic material |
US4745047A (en) * | 1986-01-24 | 1988-05-17 | Fuji Photo Film Co., Ltd. | Color image-forming process |
US4774167A (en) * | 1986-02-24 | 1988-09-27 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic materials wherein the color developer contains low concentrations of benzyl alcohol, hydroxylamine and sulfite |
US4774168A (en) * | 1986-01-24 | 1988-09-27 | Fuji Photo Film Co., Ltd. | Method for forming color image with a color developer not containing benzyl alcohol |
US4835092A (en) * | 1986-02-17 | 1989-05-30 | Fuji Photo Film Co., Ltd. | Method for processing a silver halide color photographic material using a color developer containing a chelating agent in the absence of benzyl alcohol |
US4837132A (en) * | 1986-05-23 | 1989-06-06 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic material using a chelating agent and developer with substantially no benzyl alcohol |
US4840878A (en) * | 1986-01-23 | 1989-06-20 | Fuji Photo Film Co., Ltd. | Method of color image formation using a high chloride emulsion and a developer free of benzyl alcohol |
US4845016A (en) * | 1986-01-29 | 1989-07-04 | Fuji Photo Film Co., Ltd. | Process for processing silver halide color photographic materials using a multistage counterflow stabilization system |
US4851326A (en) * | 1986-02-24 | 1989-07-25 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic materials using developer substantially free of bromide and benzyl alcohol |
US4853321A (en) * | 1986-05-19 | 1989-08-01 | Fuji Photo Film, Co., Ltd. | Method of forming a color image and silver halide color photographic material using developer with substantially no benzyl alcohol and low bromide concentration |
US4892803A (en) * | 1986-01-23 | 1990-01-09 | Fuji Photo Film Co., Ltd. | Color image-forming process compressing developer containing no benzyl alcohol |
US4920042A (en) * | 1986-02-20 | 1990-04-24 | Fuji Photo Film Co., Ltd. | Color image forming process comprising developing with substantially no benzyl alcohol a material having specific sensitizing dyes |
US5001041A (en) * | 1986-01-27 | 1991-03-19 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic material for prints |
US5110713A (en) * | 1987-10-30 | 1992-05-05 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic material |
US5118593A (en) * | 1986-01-29 | 1992-06-02 | Fuji Photo Film Co., Ltd. | Method for color image formation |
-
1981
- 1981-08-19 JP JP13045981A patent/JPS5831334A/en active Granted
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59198454A (en) * | 1983-04-25 | 1984-11-10 | Konishiroku Photo Ind Co Ltd | Method for forming dye image |
JPH0452456B2 (en) * | 1983-04-25 | 1992-08-21 | Konishiroku Photo Ind | |
EP0204530A2 (en) | 1985-05-31 | 1986-12-10 | Konica Corporation | Method for forming direct positive color image |
EP0228914A2 (en) | 1985-12-28 | 1987-07-15 | Konica Corporation | Method of processing lightsensitive silver halide color photographic material |
US4892803A (en) * | 1986-01-23 | 1990-01-09 | Fuji Photo Film Co., Ltd. | Color image-forming process compressing developer containing no benzyl alcohol |
US4840878A (en) * | 1986-01-23 | 1989-06-20 | Fuji Photo Film Co., Ltd. | Method of color image formation using a high chloride emulsion and a developer free of benzyl alcohol |
US4745047A (en) * | 1986-01-24 | 1988-05-17 | Fuji Photo Film Co., Ltd. | Color image-forming process |
US4774168A (en) * | 1986-01-24 | 1988-09-27 | Fuji Photo Film Co., Ltd. | Method for forming color image with a color developer not containing benzyl alcohol |
US5001041A (en) * | 1986-01-27 | 1991-03-19 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic material for prints |
US4845016A (en) * | 1986-01-29 | 1989-07-04 | Fuji Photo Film Co., Ltd. | Process for processing silver halide color photographic materials using a multistage counterflow stabilization system |
US5118593A (en) * | 1986-01-29 | 1992-06-02 | Fuji Photo Film Co., Ltd. | Method for color image formation |
US4835092A (en) * | 1986-02-17 | 1989-05-30 | Fuji Photo Film Co., Ltd. | Method for processing a silver halide color photographic material using a color developer containing a chelating agent in the absence of benzyl alcohol |
US4920042A (en) * | 1986-02-20 | 1990-04-24 | Fuji Photo Film Co., Ltd. | Color image forming process comprising developing with substantially no benzyl alcohol a material having specific sensitizing dyes |
US4851326A (en) * | 1986-02-24 | 1989-07-25 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic materials using developer substantially free of bromide and benzyl alcohol |
US4774167A (en) * | 1986-02-24 | 1988-09-27 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic materials wherein the color developer contains low concentrations of benzyl alcohol, hydroxylamine and sulfite |
US4853321A (en) * | 1986-05-19 | 1989-08-01 | Fuji Photo Film, Co., Ltd. | Method of forming a color image and silver halide color photographic material using developer with substantially no benzyl alcohol and low bromide concentration |
US4837132A (en) * | 1986-05-23 | 1989-06-06 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic material using a chelating agent and developer with substantially no benzyl alcohol |
US5110713A (en) * | 1987-10-30 | 1992-05-05 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic material |
Also Published As
Publication number | Publication date |
---|---|
JPS6329732B2 (en) | 1988-06-15 |
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