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JPH045372B2 - - Google Patents
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JPH045372B2 - - Google Patents

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Publication number
JPH045372B2
JPH045372B2 JP26929084A JP26929084A JPH045372B2 JP H045372 B2 JPH045372 B2 JP H045372B2 JP 26929084 A JP26929084 A JP 26929084A JP 26929084 A JP26929084 A JP 26929084A JP H045372 B2 JPH045372 B2 JP H045372B2
Authority
JP
Japan
Prior art keywords
group
atom
general formula
layer
groups
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.)
Expired
Application number
JP26929084A
Other languages
Japanese (ja)
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JPS61145554A (en
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed filed Critical
Priority to JP26929084A priority Critical patent/JPS61145554A/en
Priority to US06/805,120 priority patent/US4684603A/en
Priority to DE8585308980T priority patent/DE3576579D1/en
Priority to EP19850308980 priority patent/EP0185506B1/en
Publication of JPS61145554A publication Critical patent/JPS61145554A/en
Publication of JPH045372B2 publication Critical patent/JPH045372B2/ja
Granted legal-status Critical Current

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Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3003Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
    • G03C7/3005Combinations of couplers and photographic additives
    • G03C7/3008Combinations of couplers having the coupling site in rings of cyclic compounds and photographic additives
    • G03C7/301Combinations of couplers having the coupling site in pyrazoloazole rings and photographic additives
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392Additives
    • G03C7/39208Organic compounds
    • G03C7/39284Metallic complexes

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Description

【発明の詳现な説明】[Detailed description of the invention]

〔産業䞊の利甚分野〕 本発明はハロゲン化銀カラヌ写真感光材料に関
し、特に色再珟性の改良されたハロゲン化銀カラ
ヌ写真感光材料に関する。 〔埓来技術〕 ハロゲン化銀カラヌ写真感光材料を甚いお色玠
画像を圢成する方法ずしおは、写真甚カプラヌず
発色珟像䞻薬の酞化䜓ずの反応により、色玠を圢
成する方法が挙げられ、通垞の色再珟を行うため
の写真甚カプラヌずしおは、マれンタ、む゚ロヌ
およびシアンの各カプラヌが、たた発色珟像䞻薬
ずしおは芳銙族第玚アミン系発色珟像䞻薬がそ
れぞれ賞甚されおおり、マれンタおよびむ゚ロヌ
の各カプラヌず芳銙族第玚アミン系発色珟像䞻
薬の酞化䜓ずの反応により、アゟメチン色玠等の
色玠が圢成され、シアンカプラヌず芳銙族第玚
アミン系発色珟像䞻薬の酞化䜓ずの反応により、
むンドアニリン色玠等の色玠が圢成される。 これらのうち、マれンタ色画像を圢成するため
には、−ピラゟロン、シアノアセトプノン、
むンダゟロン、ピラゟロベンズむミダゟヌル、ピ
ラゟロトリアゟヌル系カプラヌ等が䜿甚される。 埓来マれンタ色画像圢成カプラヌずしお、実甚
されおいたものは殆ど−ピラゟロン系カプラヌ
であ぀た。−ピラゟロン系カプラヌから圢成さ
れる色画像は光や熱に察する堅牢性が優れおいる
が、この色玠の色調は十分なものではなく、
430n付近に黄色成分を有する䞍芁吞収が存圚
し、たた、550n付近の可芖光の吞収スペクト
ルもブロヌドなため、色濁りの原因ずなり写真画
像は鮮やかさに欠けるものずな぀おいた。 この䞍芁吞収がないカプラヌずしお米囜特蚱
3725067号、特開昭59−162548号、同59−171956
号等に蚘茉されおいる1H−ピラゟロ−
−−トリアゟヌル型カプラヌ、1H−むミダ
ゟ−−ピラゟヌル型カプラヌ、1H−
ピラゟロ−−ピラゟヌル型カプラヌ、
又は、1H−ピラゟロ−テトラゟヌ
ル型カプラヌは、特に優れたものである。 しかしながら、これらのカプラヌから圢成され
る色玠画像の光に察する堅牢性は著しく䜎い。感
光材料、特に盎接芳賞する事に適した感光材料
に、これらのカプラヌを䜿甚した堎合には、画像
を蚘録、保存するずいう写真材料ずしおの本質的
な必芁条件を損なう事ずなる。 埓぀お実甚化に難点のあるものであ぀た。そこ
で耐光性を向䞊する方法ずしおプノヌル系又は
プニル゚ヌテル系の酞化防止剀を䜿甚するこず
が特開昭59−125732号に蚘茉されおいる。 しかしながら、この方法によ぀おは十分な耐光
性向䞊効果が埗られおいなか぀た。䞀方、䞀般匏
〔XI〕及び〔XII〕で瀺される化合物は、耐光性向
䞊効果が著しい。しかしながら写真画像の長期保
存又は加熱による着色汚染が増加するずいう
欠点を有しおいた。たた写真性胜階調性も十
分に満足されるものではなか぀た。 特に䜎濃床郚脚郚が、軟調であるずいう欠
点を有しおいた。埓぀おこれらの欠点が、いずれ
もなく、か぀耐光性のよいマれンタ画像を圢成す
るこずができる写真感光材料が望たれおいた。 〔発明の目的〕 本発明の目的は、マれンタ画像の色再珟性、マ
れンタ色画像の光堅牢性が良く、か぀熱による着
色汚染の増加がなく、写真性胜階調も良奜な
ハロゲン化銀写真感光材料を提䟛するこずにあ
る。 〔発明の構成〕 前蚘本発明の目的は、䞋蚘䞀般匏〔〕で衚さ
れるカプラヌの少なくずも぀ず、䞋蚘䞀般匏
〔XI〕で衚される化合物及び〔XII〕で衚される化
合物の少なくずも぀ずを含有するこずを特城ず
するハロゲン化銀写真感光材料によ぀お達成され
た。 䞀般匏〔〕 匏䞭、R1は環に盎結する根元原子が炭玠原子
であり、か぀、該炭玠原子に結合する氎玠原子が
個だけである眮換基を衚し、R2はR1ずは異な
る眮換基を衚す。たたは氎玠原子たたは発色珟
像䞻薬の酞化䜓ずの反応により離脱しうる眮換基
を衚す。 䞀般匏〔XI〕 䞀般匏〔XII〕 匏䞭、X1X2およびX4は、それぞれ酞玠原子
を衚す。X3はヒドロキシル基を、は硫黄原子
を、R1R2およびR3は、それぞれ氎玠原子又は
アルキル基を衚す。䜆し、R1R2R3のうち少
なくずも二぀はアルキル基を衚す。R4〜R9は、
アルキル基、アリヌル基、アルコキシ基、アリヌ
ルオキシ基、アルコキシカルボニル基、アリヌル
オキシカルボニル基、アシル基、アシルアミノ
基、アルキルアミノ基、カルバモむル基、スルフ
アモむル基、スルホンアミド基、スルホニル基た
たはシクロアルキル基を衚す。たた、お互いに連
結しお員たたは員の環を圢成しおもよい。
は金属原子を衚す。および
は、それぞれ〜の敎数を衚す。 次に本発明を具䜓的に説明する。 本発明に係る前蚘䞀般匏〔〕 䞀般匏〔〕 で衚されるマれンタカプラヌに斌いお、前蚘R1
の衚す眮換基ずしおは、䟋えばそれぞれ環に盎結
する根元原子が炭玠原子であり、か぀該炭玠原子
に結合する氎玠原子が個だけである、アルキル
基、シクロアルキル基、アルケニル基、シクロア
ルケニル基、アルキニル基、ヘテロ環基、スピロ
化合物残基、有橋炭化氎玠化合物残基が挙げられ
る。 R1で衚されるアルキル基ずしおは、炭玠数
〜32のもの、アルケニル基、アルキニル基ずしお
は炭玠数〜32のもの、シクロアルキル基、シク
ロアルケニル基ずしおは炭玠数〜12、特に〜
のものが奜たしい。 たた、これらアルキル基、アルケニル基、アル
キニル基、シクロアルキル基、シクロアルケニル
基は眮換基䟋えばアリヌル、シアノ、ハロゲン
原子、ヘテロ環、シクロアルキル、シクロアルケ
ニル、スピロ環化合物残基、有橋炭化氎玠化合物
残基の他、アシル、カルボキシル、カルバモむ
ル、アルコキシカルボニルの劂くカルボニル基を
介しお眮換するもの、曎にはヘテロ原子を介しお
眮換するもの、具䜓的にはヒドロキシル、アルコ
キシ、アリヌルオキシ等の酞玠原子を介しお眮換
するもの、ニトロ、アミノゞアルキルアミノ等
を含む、スルフアモむルアミノ、アルコキシカ
ルボニルアミノ、アリヌルオキシカルボニルアミ
ノ、アシルアミノ、スルホンアミド、むミド、り
レむド等の窒玠原子を介しお眮換するもの、アル
キルチオ、アリヌルチオ、ヘテロ環チオ、スルホ
ニル、スルフむニル、スルフアモむル等の硫黄原
子を介しお眮換するもの、ホスホニル等の燐原子
を介しお眮換するもの等を有しおいおもよい。 具䜓的には䟋えばむ゜プロピル基、sec−ブチ
ル基、sec−アミル基、−゚チルプロピル基、
−゚チルペンチル基、−ヘキシルノニル基、
−ヘプチルデシル基、ゞフルオロメチル基、
−゚トキシトリデシル基、−メトキシむ゜プロ
ピル基、−プニルむ゜プロピル基、−
〔4′−4″−ドデシルオキシベンれンスルホンアミ
ドプニル〕む゜プロピル基、シクロプロピル
基、シクロペンチル基、シクロヘキシル基等が挙
げられる。 R1で衚されるヘテロ環基ずしおは〜員の
ものが奜たしく、眮換されおいおもよく、又、瞮
合しおいおもよい。 R1で衚されるスピロ化合物残基ずしおは、䟋
えばスピロ3.3ヘプタン−−むル等が挙げ
られる。 の衚す発色珟像䞻薬の酞化䜓ずの反応により
離脱しうる眮換基ずしおは、䟋えばハロゲン原子
塩玠原子、臭玠原子、北玠原子等の他、炭玠
原子、酞玠原子、硫黄原子たたは窒玠原子を介し
お眮換する基が挙げられる。 炭玠原子を介しお眮換する基ずしおは、カルボ
キシル基の他、䟋えば䞀般匏 R1及びR2は前蚘R1及びR2ず同矩であり、R3及
びR4は氎玠原子、アリヌル基、アルキル基又は
ヘテロ環基を衚す。で瀺される基、ヒドロキシ
メチル基、トリプニルメチル基が挙げられる。 酞玠原子を介しお眮換する基ずしおは、䟋えば
アルコキシ基、アリヌルオキシ基、ヘテロ環オキ
シ基、アシルオキシ基、スルホニルオキシ基、ア
ルコキシカルボニルオキシ基、アリヌルオキシカ
ルボニル基、アルキルオキサリルオキシ基、アル
コキシオキサリチルオキシ基が挙げられる。 該アルコキシ基は曎に眮換基を有しおもよく、
䟋えば゚トキシ基、−プノキシ゚トキシ基、
−シアノ゚トキシ基、プネチルオキシ基、
−クロロベンゞルオキシ基等が挙げられる。 該アリヌルオキシ基ずしおはプノキシ基が奜
たしく、該アリヌル基は曎に眮換基を有しおいお
もよい。具䜓的にはプノキシ基、−メチルフ
゚ノキシ基、−ドデシルプノキシ基、−メ
タンスルホンアミドプノキシ基、−〔α−
3′−ペンタデシルプノキシブタンアミド〕
プノキシ基、ヘキサデシルカルバモむルメトキ
シ基、−シアノプノキシ基、−メタンスル
ホニルプノキシ基、−ナフチルオキシ基、
−メトキシプノキシ基等が挙げられる。 該ヘテロ環オキシ基ずしおは〜員のヘテロ
環オキシ基が奜たしく、瞮合環であ぀おもよく、
又、眮換基を有しおいおもよい。具䜓的には、
−プニルテトラゟリルオキシ基、−ベンゟチ
アゟリルオキシ基等が挙げられる。 該アシルオキシ基ずしおは、䟋えばアセトキシ
基、ブタノむルオキシ基等のアルキルカルボニル
オキシ基、シンナモむルオキシ基の劂きアルケニ
ルカルボニルオキシ基、ベンゟむルオキシ基の劂
きアリヌルカルボニルオキシ基が挙げられる。 該スルホニルオキシずしおは、䟋えばブタンス
ルホニルオキシ基、メタンスルホニルオキシ基が
挙げられる。 該アルコキシカルボニルオキシ基ずしおは、䟋
えば゚トキシカルボニルオキシ基、ベンゞルオキ
シカルボニルオキシ基が挙げられる。 該アリヌルオキシカルボニル基ずしおはプノ
キシカルボニルオキシ基等が挙げられる。 該アルキルオキサリルオキシ基ずしおは、䟋え
ばメチルオキシサリルオキシ基が挙げられる。 該アルコキシオキサリルオキシ基ずしおは、゚
トキシオキサリルオキシ基等が挙げられる。 硫黄原子を介しお眮換する基ずしおは、䟋えば
アルキルチオ基、アリヌルチオ基、ヘテロ環チオ
基、アルコキシカルボニルチオ基が挙げられる。 該アルキルチオ基ずしおは、ブチルチオ基、
−シアノ゚チルチオ基、プネチルチオ基、ベン
ゞルチオ基等が挙げられる。 該アリヌルチオ基ずしおは、プニルチオ基、
−メタンスルホンアミドプニルチオ基、−
ドデシルプネチルチオ基、−ノナフルオロペ
ンタンアミドプネチルチオ基、−カルボキシ
プニルチオ基、−゚トキシ−−−ブチル
プニルチオ基等が挙げられる。 該ヘテロ環チオ基ずしおは、䟋えば−プニ
ル−−テトラゟリル−−チオ
基、−ベンゟチアゟリルチオ基等が挙げられ
る。 䞊蚘窒玠原子を介しお眮換する基ずしおは、䟋
えば䞀般匏
[Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material with improved color reproducibility. [Prior Art] A method for forming a dye image using a silver halide color photographic light-sensitive material includes a method in which a dye is formed by a reaction between a photographic coupler and an oxidized form of a color developing agent. Magenta, yellow and cyan couplers are used as photographic couplers for reproduction, and aromatic primary amine color developing agents are used as color developing agents. A dye such as an azomethine dye is formed by the reaction between the coupler and an oxidized form of an aromatic primary amine color developing agent, and a reaction between the cyan coupler and an oxidized form of an aromatic primary amine color developing agent forms a dye such as an azomethine dye.
Pigments such as indoaniline dyes are formed. Among these, in order to form a magenta image, 5-pyrazolone, cyanoacetophenone,
Indazolone, pyrazolobenzimidazole, pyrazolotriazole couplers, etc. are used. Most of the conventional magenta color image forming couplers that have been put to practical use have been 5-pyrazolone couplers. Color images formed from 5-pyrazolone couplers have excellent fastness to light and heat, but the color tone of this dye is not sufficient;
Unnecessary absorption with a yellow component exists near 430 nm, and the visible light absorption spectrum near 550 nm is also broad, causing color turbidity and resulting in photographic images lacking in vividness. U.S. patent for coupler without unnecessary absorption
3725067, JP 59-162548, JP 59-171956
1H-pyrazolo[3,2-
c]-s-triazole type coupler, 1H-imidazo[1,2-b]-pyrazole type coupler, 1H-
pyrazolo[1,5-b]-pyrazole coupler,
Alternatively, 1H-pyrazolo[1,5-d]tetrazole type couplers are particularly excellent. However, the light fastness of dye images formed from these couplers is significantly lower. When these couplers are used in photosensitive materials, especially photosensitive materials suitable for direct viewing, they impair the essential requirement of photographic materials, which is to record and preserve images. Therefore, it was difficult to put it into practical use. Therefore, as a method of improving light resistance, the use of phenol-based or phenyl ether-based antioxidants is described in JP-A-59-125732. However, this method did not provide a sufficient effect of improving light resistance. On the other hand, the compounds represented by the general formulas [XI] and [XII] have a remarkable effect of improving light resistance. However, this method has the drawback of increasing color staining due to long-term storage (or heating) of photographic images. Furthermore, photographic performance (gradation) was not fully satisfactory. In particular, the low density portion (leg portion) had a drawback of being soft in tone. Therefore, there has been a desire for a photographic light-sensitive material that is free from any of these drawbacks and is capable of forming magenta images with good light resistance. [Object of the Invention] The object of the present invention is to provide a silver halide that has good color reproducibility of magenta images, good light fastness of magenta images, no increase in color contamination due to heat, and good photographic performance (gradation). Our objective is to provide photographic materials. [Structure of the Invention] The object of the present invention is to at least one of the couplers represented by the following general formula [] and at least one of the compounds represented by the following general formula [XI] and [XII]. This was achieved using a silver halide photographic material characterized by containing . General formula [] In the formula, R 1 represents a substituent whose root atom directly connected to the ring is a carbon atom and there is only one hydrogen atom bonded to the carbon atom, and R 2 represents a substituent different from R 1 . represent. Further, X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. General formula [XI] General formula [XII] In the formula, X 1 , X 2 and X 4 each represent an oxygen atom. X 3 represents a hydroxyl group, Y represents a sulfur atom, and R 1 , R 2 and R 3 each represent a hydrogen atom or an alkyl group. However, at least two of R 1 , R 2 and R 3 represent an alkyl group. R4 to R9 are
Represents an alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acylamino group, alkylamino group, carbamoyl group, sulfamoyl group, sulfonamide group, sulfonyl group or cycloalkyl group . Alternatively, they may be connected to each other to form a 5- or 6-membered ring. M
represents a metal atom. a, b, c, d, e and f
each represents an integer from 0 to 4. Next, the present invention will be specifically explained. The above general formula according to the present invention [] General formula [] In the magenta coupler represented by R 1
Examples of substituents represented by include alkyl groups, cycloalkyl groups, alkenyl groups, and cycloalkenyl groups in which the root atom directly connected to the ring is a carbon atom, and only one hydrogen atom is bonded to the carbon atom. , an alkynyl group, a heterocyclic group, a spiro compound residue, and a bridged hydrocarbon compound residue. The alkyl group represented by R 1 has 1 carbon number
~32, alkenyl groups, alkynyl groups with 2 to 32 carbon atoms, cycloalkyl groups, cycloalkenyl groups with 3 to 12 carbon atoms, especially 5 to 32 carbon atoms.
7 is preferred. In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents (e.g., aryl, cyano, halogen atom, heterocycle, cycloalkyl, cycloalkenyl, spirocyclic compound residue, bridged hydrocarbon In addition to compound residues, those substituted via a carbonyl group such as acyl, carboxyl, carbamoyl, and alkoxycarbonyl, and those substituted via a hetero atom, specifically oxygen atoms such as hydroxyl, alkoxy, and aryloxy. Those substituted through a nitrogen atom such as nitro, amino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido, etc. , alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, sulfamoyl, etc., which are substituted through a sulfur atom, and phosphonyl, which is substituted through a phosphorus atom.Specifically, for example, Isopropyl group, sec-butyl group, sec-amyl group, 1-ethylpropyl group,
1-ethylpentyl group, 1-hexylnonyl group,
1-heptyldecyl group, difluoromethyl group, 1
-Ethoxytridecyl group, 1-methoxyisopropyl group, 1-phenylisopropyl group, 2-
[4′-(4″-dodecyloxybenzenesulfonamido)phenyl] Examples include isopropyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc. The heterocyclic group represented by R 1 is a 5- to 7-membered one. is preferable, and may be substituted or fused. Examples of the spiro compound residue represented by R 1 include spiro[3.3]heptan-1-yl. Examples of substituents that can be removed by reaction with the oxidized product of the color developing agent include halogen atoms (chlorine, bromine, fluorine, etc.), as well as substituents via carbon, oxygen, sulfur, or nitrogen atoms. Examples of groups substituted via a carbon atom include carboxyl groups, as well as groups of the general formula (R 1 and R 2 have the same meanings as R 1 and R 2 above, and R 3 and R 4 represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group.) Enylmethyl group is mentioned. Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyl groups, alkyloxalyloxy groups, and alkoxyoxalicyloxy groups. Examples include groups. The alkoxy group may further have a substituent,
For example, ethoxy group, 2-phenoxyethoxy group,
2-cyanoethoxy group, phenethyloxy group, p
-chlorobenzyloxy group and the like. The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent. Specifically, phenoxy group, 3-methylphenoxy group, 3-dodecylphenoxy group, 4-methanesulfonamidophenoxy group, 4-[α-
(3′-pentadecylphenoxy)butanamide]
Phenoxy group, hexadecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-naphthyloxy group, p
-methoxyphenoxy group and the like. The heterocyclic oxy group is preferably a 5- to 7-membered heterocyclic oxy group, and may be a fused ring,
Moreover, it may have a substituent. Specifically, 1
-phenyltetrazolyloxy group, 2-benzothiazolyloxy group and the like. Examples of the acyloxy group include acetoxy groups, alkylcarbonyloxy groups such as butanoyloxy groups, alkenylcarbonyloxy groups such as cinnamoyloxy groups, and arylcarbonyloxy groups such as benzoyloxy groups. Examples of the sulfonyloxy include a butanesulfonyloxy group and a methanesulfonyloxy group. Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group. Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group. Examples of the alkyloxalyloxy group include methyloxysalyloxy group. Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group. Examples of the group substituted via a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkoxycarbonylthio group. As the alkylthio group, butylthio group, 2
-cyanoethylthio group, phenethylthio group, benzylthio group, etc. As the arylthio group, phenylthio group,
4-methanesulfonamidophenylthio group, 4-
Examples include dodecylphenethylthio group, 4-nonafluoropentanamidephenethylthio group, 4-carboxyphenylthio group, and 2-ethoxy-5-t-butylphenylthio group. Examples of the heterocyclic thio group include 1-phenyl-1,2,3,4-tetrazolyl-5-thio group and 2-benzothiazolylthio group. Examples of the group substituting via the nitrogen atom include the general formula

〔実斜䟋〕〔Example〕

以䞋に具䜓的実斜䟋を瀺しお本発明を曎に詳し
く説明するが、本発明の実斜の態様は、これによ
り限定されない。 実斜䟋  前蚘䟋瀺マれンタカプラヌ11の40をゞオクチ
ルフタレヌト40ml及び酢酞゚チル100mlの混合溶
媒に溶解し、この溶液をドデシルベンれンスルホ
ン酞ナトリりムを含むれラチン氎溶液300ml
に添加した埌、ホモゞナむザヌにお分散し埗られ
た分散液を緑感性塩臭化銀乳剀500Ag量30
含有に混合し、これに塗垃助剀を加えお塗垃液
を調補した。次いで、この塗垃液をポリ゚チレン
被芆玙支持䜓䞊に塗垃し、曎にこの塗垃局䞊に、
−2′−ヒドロキシ−3′5′−ゞ−−アミルフ
゚ニルベンゟトリアゟヌル、れラチン、延展剀
及び硬膜剀を含有する塗垃液を塗蚭し保護膜ずし
た。 この際、−2′−ヒドロキシ−3′5′−ゞ−
−アミルプニルベンゟトリアゟヌルは、
mgm2、れラチンは15mgm2の付量ずなるよ
うに塗蚭し、ハロゲン化銀写真感光材料を䜜補し
詊料比范ずした。 次に比范詊料の乳剀局に、本発明に係る金属
錯䜓−をカプラヌに察しモル比で0.4添加し
た以倖は、比范詊料ず同䞀の詊料を䜜補し
た。 曎に詊料のマれンタカプラヌを、本発明に係
るマれンタカプラヌ19、40、、比范マれンタカ
プラヌ及び比范マれンタカプラヌに代えた以
倖は詊料ず同䞀の詊料〜を䜜補した。 これらの詊料に感光蚈小西六写真工業(æ ª)補、
KS−型を甚いおセンシトメトリヌ甚光楔露
光を行぀た埌、次の凊理を行぀た。 凊理工皋 凊理枩床 凊理時間 発色珟像 32.8℃ 分30秒 挂癜定着 32.8℃ 分30秒 æ°Ž 掗 32.8℃ 分30秒 䞊蚘凊理工皋に甚いた凊理液組成は以䞋の通り
である。 発色珟像液組成 −アミノ−−メチル−−゚チル−−β
−メタンスルホンアミド゚チルアニリン硫酞塩
 ベンゞルアルコヌル 15ml ヘキサメタ燐酞ナトリりム 2.5 無氎亜硫酞ナトリりム 18.5 臭化ナトリりム 0.7 臭化カリりム 0.5 硌砂 39.1 氎を加えおずし、氎酞化ナトリりムを甚い
おPH10.3に調敎する。 挂癜定着液組成 ゚チレンゞアミン四酢酞 鉄アンモニりム 61.0 ゚チレンゞアミン四酢酞 アンモニりム氎塩 5.0 チオ硫酞アンモニりム 124.5 メタ重亜硫酞ナトリりム 13.5 無氎亜硫酞ナトリりム 2.7 氎を加えおずする。 凊理埌、埗られた詊料の耐光性、保存による着
色汚染以埌、黄色ステむンず呌ぶの増加床、
及び脚郚階調性を以䞋の芁領で枬定した。 〔耐光性詊隓退色率枬定〕 各詊料に圢成された色玠画像にアンダヌグラス
屋倖曝露台を甚いお500時間倪陜光を曝射した時
の退色率D0−D0×100、D0初濃床1.0、 退色埌の濃床を枬定した。 これらの結果を衚に瀺す。 〔黄色ステむン詊隓〕 各詊料を77℃、加湿なしの恒枩局に20日間保存
した。保存前埌での各詊料の癜色郚の青色光反射
濃床の差増加濃床を枬定した。 〔脚郚階調ガンマ倀枬定〕 り゚ツゞ露光した各詊料の濃床0.3ず濃床0.8の
間の傟きガンマ倀を枬定した。 γ0.5logE0.8−logE0.3 E0.8濃床0.8を䞎える露光量 E0.3濃床0.3を䞎える露光量 これらの詊隓結果を衚に瀺す。
The present invention will be explained in more detail with reference to specific examples below, but the embodiments of the present invention are not limited thereto. Example 1 40 g of the above exemplary magenta coupler 11 was dissolved in a mixed solvent of 40 ml of dioctyl phthalate and 100 ml of ethyl acetate, and this solution was dissolved in 300 ml of a 5% aqueous gelatin solution containing sodium dodecylbenzenesulfonate.
The resulting dispersion was dispersed using a homogenizer, and the resulting dispersion was mixed with 500 g of green-sensitive silver chlorobromide emulsion (Ag amount: 30 g).
(containing), and a coating aid was added thereto to prepare a coating solution. Next, this coating solution was coated on a polyethylene-coated paper support, and further on this coated layer,
A coating solution containing 2-(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole, gelatin, a spreading agent, and a hardening agent was applied to form a protective film. At this time, 2-(2'-hydroxy-3',5'-di-t
-amyl phenyl) benzotriazole is 5
mg/dm 2 , and gelatin was applied in an amount of 15 mg/dm 2 to prepare a silver halide photographic material, which was designated as Sample 1 (comparison). Next, Sample 2, which was the same as Comparative Sample 1, was prepared, except that Metal Complex B-4 according to the present invention was added to the emulsion layer of Comparative Sample 1 at a molar ratio of 0.4 to the coupler. Further, Samples 3 to 7 were prepared which were the same as Sample 2 except that the magenta coupler in Sample 2 was replaced with magenta couplers 19, 40, and 7 according to the present invention, comparative magenta coupler 1, and comparative magenta coupler 2. A sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.,
After performing optical wedge exposure for sensitometry using a KS-7 model, the following processing was performed. Processing process Processing temperature Processing time Color development 32.8°C 3 minutes 30 seconds Bleach-fixing 32.8°C 1 minute 30 seconds Water washing 32.8°C 3 minutes 30 seconds The composition of the processing solution used in the above processing step is as follows. (Color developer composition) 4-amino-3-methyl-N-ethyl-N-(β
-methanesulfonamidoethyl)aniline sulfate
5g Benzyl alcohol 15ml Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 18.5g Sodium bromide 0.7g Potassium bromide 0.5g Borax 39.1g Add water to make 1, and adjust the pH to 10.3 using sodium hydroxide. (Bleach-fix solution composition) Iron ammonium ethylenediaminetetraacetate 61.0g Ethylenediaminetetraacetic acid diammonium dihydrate 5.0g Ammonium thiosulfate 124.5g Sodium metabisulfite 13.5g Anhydrous sodium sulfite 2.7g Add water to make 1. After treatment, the light resistance of the obtained sample, the degree of increase in color staining (hereinafter referred to as yellow stain) due to storage,
and leg gradation were measured as follows. [Lightfastness test (fading rate measurement)] Fading rate (D 0 − D / D 0 ×100, D0 initial density (1.0), D density after fading) were measured. These results are shown in Table 1. [Yellow stain test] Each sample was stored at 77°C in a constant temperature bath without humidification for 20 days. The difference in blue light reflection density (increase in density) of the white part of each sample before and after storage was measured. [Measurement of leg gradation (gamma value)] The slope (gamma value) between density 0.3 and density 0.8 of each wedge-exposed sample was measured. γ=0.5/logE 0.8 −logE 0.3 E 0.8 : Exposure amount that gives a density of 0.8 E 0.3 : Exposure amount that gives a density of 0.3 These test results are shown in Table 1.

【衚】 退色率の数倀は小さい皋、耐光性が良いこずを
瀺す。 衚から本発明に係る金属錯䜓を甚いた詊料は
耐光性が良いこずがわかる。又、比范カプラヌを
甚いた比范詊料及びでは黄色ステむンの増
加、或いは脚郚階調の軟調化が珟れる。 本発明のマれンタカプラヌず金属錯䜓の組合せ
により、耐光性、黄色ステむン、脚郚階調性のい
づれもが良奜な写真画像が埗られる。 実斜䟋  ポリ゚チレン被芆玙からなる支持䜓䞊に、䞋蚘
の各局を支持䜓偎から順次塗蚭し、倚色甚ハロゲ
ン化銀写真感光材料を䜜補した。 第局青感性ハロゲン化銀乳剀局 む゚ロヌカプラヌずしおα−ピバリル−α−
−ベンゞル−−ゞオキ゜むミダゟリ
ゞン−−むル−−クロロ−−〔γ−
−ゞ−−アミルプノキシブチルアミ
ド〕アセトニリドをmgm2、青感性ハロゲ
ン化銀乳剀を銀に換算しおmgm2、
−ゞ−−ブチルプノヌル−3′5′−ゞ−
−アミル−4′−ヒドロキシベンゟ゚ヌトを
mgm2、ゞオクチルフタレヌトをmgm2
およびれラチンを16mgm2の塗垃付量ずなる
様に塗蚭した。 第局䞭間局 れラチンをmgm2の塗垃付量ずなる様に
塗蚭した。 第局緑感性ハロゲン化銀乳剀局 前蚘䟋瀺マれンタカプラヌ20をmgm2、
緑感性塩臭化銀乳剀を銀に換算しおmg
m2、ゞオクチルフタレヌトをmgm2および
れラチンを16mgm2の塗垃付量ずなる様に塗
蚭した。 第局䞭間局 玫倖線吞収剀−2′−ヒドロキシ−3′5′−
ゞ−−アミルプニルベンゟトリアゟヌル
をmgm2、−2′−ヒドロキシ−3′5′−
ゞ−−ブチルプニルベンゟトリアゟヌル
をmgm2、ゞオクチルフタレヌトをmg
m2およびれラチンを14mgm2の塗垃付量ず
なる様に塗蚭した。 第局赀感性ハロゲン化銀乳剀局 シアンカプラヌずしお−ゞクロロ−
−メチル−−〔α−−ゞ−−アミル
プノキシブチルアミド〕プノヌルを
mgm2、−−ペンタ
フルオロプニルアシルアミノ−−クロロ
−−〔α−−ゞ−−アミルプノキ
シペンチルアミド〕プノヌルをmg
m2、ゞオクチルフタレヌトをmgm2および
赀感性塩臭化銀乳剀を銀に換算しおmgm2
の塗垃付量ずなる様に塗蚭した。 第局䞭間局 玫倖線吞収剀ずしお−2′−ヒドロキシ−
3′5′−ゞ−−アミルプニルベンゟトリ
アゟヌルをmgm2、−2′−ヒドロキシ
−3′5′−ゞ−−ブチルプニルベンゟト
リアゟヌルをmgm2、ゞオクチルフタレヌ
トをmgm2およびれラチンをmgm2の
塗垃付量ずなる様に塗蚭した。 第局保護局 れラチンをmgm2の塗垃付量ずなる様に
塗蚭した。 かくしお䜜補した詊料を詊料ずする。 次に詊料の第局におけるマれンタカプラヌ
及び金属錯䜓の組合せが衚に瀺すようにした以
倖は詊料ず同䞀の詊料〜25を䜜補した。 かくしお䜜補した詊料に実斜䟋ず同䞀の露光
凊理を行぀た。䜆し、マれンタの単色詊料を埗る
べく緑色光を甚いお光楔露光した。凊理埌に埗ら
れた各詊料に぀いお、実斜䟋ず同様に耐光性、
黄色ステむン、脚郚階調性の枬定を行぀た。 その結果を衚に瀺す。
[Table] The smaller the fading rate value, the better the light resistance. Table 1 shows that the samples using the metal complex according to the present invention have good light resistance. Further, in Comparative Samples 6 and 7 using comparative couplers, an increase in yellow stain or a softening of the leg gradation appears. By combining the magenta coupler of the present invention and the metal complex, photographic images with good light fastness, yellow stain, and leg gradation can be obtained. Example 2 A multicolor silver halide photographic material was prepared by sequentially coating the following layers on a support made of polyethylene-coated paper from the support side. 1st layer: blue-sensitive silver halide emulsion layer α-pivalyl-α- as a yellow coupler
(1-benzyl-2,4-dioxoimidazolidin-3-yl)-2-chloro-5-[γ-(2,
4-di-t-amylphenoxy)butyramide] acetonilide at 8 mg/dm 2 , blue-sensitive silver halide emulsion at 3 mg/dm 2 in terms of silver, 2,4
-di-t-butylphenol-3',5'-di-t
-amyl-4'-hydroxybenzoate 3
mg/dm 2 , dioctyl phthalate 3 mg/dm 2
And gelatin was coated at a coating amount of 16 mg/dm 2 . 2nd layer: Intermediate layer Gelatin was coated at a coating amount of 4 mg/dm 2 . Third layer: green-sensitive silver halide emulsion layer: 4 mg/dm 2 of the above-mentioned exemplary magenta coupler 20,
2 mg/d of green-sensitive silver chlorobromide emulsion converted to silver
m 2 , 4 mg/dm 2 of dioctyl phthalate and 16 mg/dm 2 of gelatin were coated. 4th layer: Intermediate layer UV absorber 2-(2'-hydroxy-3',5'-
3 mg/dm 2 of di-t-amyl phenyl)benzotriazole, 2-(2'-hydroxy-3',5'-
3 mg/dm 2 of di-t-butylphenyl)benzotriazole and 4 mg/dm of dioctyl phthalate.
dm 2 and gelatin were coated at a coating amount of 14 mg/dm 2 . 5th layer: red-sensitive silver halide emulsion layer 2,4-dichloro-3 as cyan coupler
-Methyl-6-[α-(2,4-di-t-amylphenoxy)butyramide]phenol
mg/dm 2 , 2-(2,3,4,5,6-pentafluorophenyl)acylamino-4-chloro-5-[α-(2,4-di-t-amylphenoxy)pentylamide]phenol 3mg/d
m 2 , 2 mg/dm 2 of dioctyl phthalate and 3 mg/dm 2 of red-sensitive silver chlorobromide emulsion in terms of silver.
The coating was applied so that the coating amount was as follows. 6th layer: Intermediate layer 2-(2'-hydroxy-
2 mg/dm 2 of 3',5'-di-t-amylphenyl)benzotriazole, 2 mg/dm2 of 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, and 2 mg/dm2 of dioctyl phthalate. and gelatin were coated at a coating amount of 2 mg/dm 2 and 6 mg/dm 2 . 7th layer: Protective layer Gelatin was coated at a coating amount of 9 mg/dm 2 . The sample thus prepared is designated as sample 8. Next, Samples 9 to 25 were prepared which were the same as Sample 8 except that the combinations of magenta coupler and metal complex in the third layer of Sample 8 were as shown in Table 2. The sample thus prepared was subjected to the same exposure treatment as in Example 1. However, in order to obtain a magenta monochromatic sample, light wedge exposure was performed using green light. For each sample obtained after the treatment, light resistance,
Yellow stain and leg gradation were measured. The results are shown in Table 2.

【衚】【table】

衚から明らかな様に、比范金属錯䜓や比范カ
プラヌを甚いた堎合には、黄色ステむンの増加あ
るいは、脚郚階調の䜎䞋が起こる。 しかしながら本発明の詊料では、これらの欠点
がいづれもない詊料が埗られる。この効果は本発
明に係るカプラヌず本発明に係る金属錯䜓の組合
せにより初めお発揮されるものであり、予想され
なか぀たこずである。 たた本発明の詊料では、耐光性が良く、たた色
再珟性の良い鮮明なマれンタ画像が埗られた。 実斜䟋  䞋匕加工したセルロヌストリアセテヌトフむル
ムからなり、ハレヌシペン防止局黒色コロむド
銀0.40及びれラチン3.0を含有する。を有す
る透明支持䜓䞊に、䞋蚘の各局を順番に塗蚭する
事により、詊料26を䜜補した。 第局赀感性ハロゲン化銀乳剀局の䜎感床局 AgBrIからなる乳剀乳剀を赀感性に色
増感したもの1.8ず、0.8の−ヒドロキシ
−−β−メトキシ゚チルアミノカルボニル
メトキシ−−〔Ύ−−ゞ−−アミ
ルプノキシブチル〕−−ナフトアミド
−ず称す、0.075の−ヒドロキシ−
−〔−−ヒドロキシ−−アセトアミド
−−ゞスルホ−−ナフチルアゟプ
ノキシ〕−−〔Ύ−−ゞ−−アミル
プノキシブチル〕−−ナフトアミドゞナ
トリりムCC−ずいう、0.015の−ヒ
ドロキシ−−〔Ύ−−ゞ−−アミル
プノキシ−−ブチル〕ナフトアミド、
0.07の−オクタデシルスクシンむミド−
−−プニル−−テトラゟリルチオ−
−むンダノン−ずいうを0.65のトリ
クレゞルホスプヌトTCPずいうに溶解
し、1.85のれラチンを含む氎溶液䞭に乳化分
散した分散物を含有しおいる赀感光性ハロゲン
化銀乳剀局の䜎感床局。 第局赀感光性ハロゲン化銀乳剀局の高感床局 AgBrIからなる乳剀乳剀を赀感性に色
増感したもの1.2ず、0.21のシアンカプラ
ヌ−ず、0.02のカラヌドシアンカプ
ラヌCC−を溶解した0.23のTCPに溶
解し、1.2のれラチンを含む氎溶液䞭に乳化
分散した分散物を含有しおいる赀感光性ハロゲ
ン化銀乳剀局の高感床局。 第局䞭間局 0.8のれラチンず、0.07の−ゞ−
−オクチルハむドロキノンHQ−ずい
うを溶解した0.04のゞブチルフタレヌト
DBPずいうを含有する䞭間局。 第局緑感光性ハロゲン化銀乳剀局の䜎感床局
乳剀を緑感性に色増感したもの0.80ず、
0.80の䟋瀺化合物20、0.01の化合物−
を溶解した0.95のゞ゚チルラりリル酞ア
ミドを2.2のれラチンを含む氎溶液䞭に乳化
分散した分散物を含有しおいる緑感光性ハロゲ
ン化銀乳剀局の䜎感床局。 第局緑感光性ハロゲン化銀乳剀局の高感床局
乳剀を緑感性に色増感した1.8の乳剀ず、
0.20の䟋瀺化合物20を溶解した0.25のゞ゚
チルラりリル酞アミドを1.9のれラチンを含
む氎溶液䞭に乳化分散した分散物を含有しおい
る緑感光性ハロゲン化銀乳剀局の高感床局。 第局黄色フむルタヌ 0.15の黄色コロむド銀ず、0.2の色汚染
防止剀HQ−を溶解した0.11のDBP
ず、1.5のれラチンを含有する黄色フむルタ
ヌ局。 第局青感光性ハロゲン化銀乳剀局の䜎感床局
乳剀を青感性に色増感したもの0.2ず、1.5
のα−ピバロむル−α−−ベンゞル−
−プニル−−ゞオキ゜むミダゟリゞン
−−むル−−クロロ−−〔α−ドデシル
オキシカルボニル゚トキシカルボニル〕アセ
トアニラむド−ずいうを溶解した0.6
のTCPを1.9のれラチンを含む氎溶液䞭に
乳化分散した分散物を含有しおいる青感光性ハ
ロゲン化銀乳剀局の䜎感床局。 第局青感光性ハロゲン化銀乳剀局の高感床局 AgI2モルを含むAgBrIからなる乳剀を青
感性に色増感したもの0.9ず、1.30のむ゚
ロヌカプラヌ−を溶解した0.65の
TCPを1.5のれラチンを含む氎溶液䞭に乳化
分散した分散物を含有しおいる青感光性ハロゲ
ン化銀乳剀局の高感床局。 第局保護局 0.23のれラチン保護局。 このようにしお䜜成した詊料26に぀いお、緑感
性乳剀局に衚に瀺す金属錯䜓をカプラヌに察し
お40モル添加したこずのみ代え、詊料27〜30を
䜜成した。 さらに詊料29の第局及び第局の高沞点有機
溶媒のゞ゚チルラりリル酞アミドを、トリオクチ
ルホスプヌト及びゞオクチルフタレヌトに代え
た詊料31、32を䜜成した。 このようにしお䜜成した各詊料26〜32を緑色光
を甚いおり゚ツゞ露光した埌、䞋蚘珟像凊理を行
぀た。 珟像凊理工皋 発色珟像 38℃ 分15秒 挂 癜 38℃ 分30秒 æ°Ž 掗 38℃ 分15秒 安定化 38℃ 分30秒 也 燥 各凊理工皋においお䜿甚した凊理液組成は䞋蚘
の通りである。 〔発色珟像液〕 −アミノ−−メチル−−゚チル−−β
−ヒドロキシル゚チルアニリン硫酞塩 4.75 無氎亜硫酞ナトリりム 4.25 ヒドロキシルアミン・1/2ç¡«é…žå¡© 2.0 無氎炭酞カリりム 37.5 臭化ナトリりム 1.3 ニトリロ䞉酢酞・ナトリりム塩氎塩
2.5 氎酞化カリりム 1.0 氎を加えおずし、PH10.02に調敎する。 〔挂癜液〕 ゚チレンゞアミン四酢酞鉄 アンモニりム塩 100 ゚チレンゞアミン四酢酞 アンモニりム塩 10 臭化アンモニりム 150 氷酢酞 10ml 氎を加えおずし、アンモニア氎を甚いおPH
6.0に調敎する。 〔定着液〕 チオ硫酞アンモニりム 175 無氎亜硫酞ナトリりム 8.5 メタ重亜硫酞ナトリりム 2.3 氎を加えおずし、酢酞を甚いおPH6.0に
調敎する。 〔安定液〕 ホルマリン37氎溶液 1.5ml コニダツクス小西六写真工業(æ ª)補 7.5ml 氎を加えおずする。 この様にしお埗られた各詊料を実斜䟋ず同様
に耐光性、黄色ステむン、階調性を枬定した。 その結果を衚に瀺す。
As is clear from Table 2, when a comparative metal complex or a comparative coupler is used, an increase in yellow stain or a decrease in leg gradation occurs. However, the samples of the present invention do not have any of these drawbacks. This effect was exhibited for the first time by the combination of the coupler according to the present invention and the metal complex according to the present invention, and was unexpected. In addition, the sample of the present invention had good light resistance and a clear magenta image with good color reproducibility was obtained. Example 3 The following layers were coated in order on a transparent support made of subbed cellulose triacetate film and having an antihalation layer (containing 0.40 g of black colloidal silver and 3.0 g of gelatin). , Sample 26 was prepared. 1st layer: Low-speed layer of red-sensitive silver halide emulsion layer 1.8 g of an emulsion (emulsion) made of AgBrI sensitized to red sensitivity and 0.8 g of 1-hydroxy-4-(β-methoxyethylamino carbonylmethoxy)-N-[Ύ-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide (referred to as C-1), 0.075 g of 1-hydroxy-
4-[4-(1-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo)phenoxy]-N-[ÎŽ-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide disodium (referred to as CC-1), 0.015 g of 1-hydroxy-2-[ÎŽ-(2,4-di-t-amylphenoxy)-n-butyl]naphthamide,
0.07g of 4-octadecylsuccinimide-2
-(1-phenyl-5-tetrazolylthio)-1
- A red-sensitive silver halide containing a dispersion of indanone (referred to as D-1) dissolved in 0.65 g of tricresyl phosphate (referred to as TCP) and emulsified and dispersed in an aqueous solution containing 1.85 g of gelatin. A low-speed layer of the emulsion layer. 2nd layer: High-sensitivity layer of red-sensitive silver halide emulsion layer 1.2 g of a red-sensitized emulsion (emulsion) consisting of AgBrI, 0.21 g of cyan coupler (C-1), and 0.02 g High sensitivity of red-sensitive silver halide emulsion layer containing a dispersion of colored cyan coupler (CC-1) dissolved in 0.23 g of TCP and emulsified in an aqueous solution containing 1.2 g of gelatin. layer. 3rd layer: middle layer 0.8g gelatin and 0.07g 2,5-di-
An intermediate layer containing 0.04 g of dibutyl phthalate (referred to as DBP) in which t-octylhydroquinone (referred to as HQ-1) was dissolved. 4th layer: 0.80 g of the low-speed layer emulsion of the green-sensitive silver halide emulsion layer color-sensitized to green sensitivity;
0.80g of Exemplified Compound 20, 0.01g of Compound (D-
A low-sensitivity layer of a green-sensitive silver halide emulsion layer containing a dispersion obtained by emulsifying and dispersing 0.95 g of diethyl lauryl amide dissolved in 1) in an aqueous solution containing 2.2 g of gelatin. 5th layer: 1.8 g of an emulsion obtained by color-sensitizing the high-sensitivity layer emulsion of the green-sensitive silver halide emulsion layer to green sensitivity;
A high-sensitivity layer of a green-sensitive silver halide emulsion layer containing a dispersion obtained by emulsifying and dispersing 0.25 g of diethyl lauryl amide in which 0.20 g of Exemplified Compound 20 is dissolved in an aqueous solution containing 1.9 g of gelatin. 6th layer: Yellow filter 0.15g yellow colloidal silver and 0.11g DBP dissolved in 0.2g color stain inhibitor (HQ-1)
and a yellow filter layer containing 1.5g of gelatin. 7th layer: 0.2g of the low-speed layer emulsion of the blue-sensitive silver halide emulsion layer color-sensitized to blue sensitivity, and 1.5g of the blue-sensitive silver halide emulsion layer.
g of α-pivaloyl-α-(1-benzyl-5
-Phenyl-2,4-dioxoimidazolidin-3-yl)-2-chloro-5-[α-dodecyloxycarbonyl)ethoxycarbonyl]acetanilide (referred to as Y-1) was dissolved in 0.6
A low-sensitivity layer of a blue-sensitive silver halide emulsion layer containing a dispersion in which 1.9 g of TCP is emulsified and dispersed in an aqueous solution containing 1.9 g of gelatin. 8th layer: High-sensitivity layer of blue-sensitive silver halide emulsion layer 0.9 g of a blue-sensitized emulsion of AgBrI containing 2 mol% of AgI and 1.30 g of yellow coupler (Y-1) are dissolved. 0.65g
A high-sensitivity blue-sensitive silver halide emulsion layer containing a dispersion of TCP emulsified in an aqueous solution containing 1.5 g of gelatin. 9th layer: Protective layer 0.23g gelatin protective layer. Samples 27 to 30 were prepared with the exception of sample 26 prepared in this manner, except that 40 mol % of the metal complex shown in Table 3 was added to the coupler in the green-sensitive emulsion layer. Furthermore, Samples 31 and 32 were prepared by replacing diethyl lauryl amide as the high-boiling organic solvent in the fourth and fifth layers of Sample 29 with trioctyl phosphate and dioctyl phthalate. After each of the samples 26 to 32 thus prepared was wedge exposed using green light, the following development treatment was performed. Development processing process Color development 38℃ 3 minutes 15 seconds Bleaching 38℃ 6 minutes 30 seconds Washing with water 38℃ 3 minutes 15 seconds Stabilization 38℃ 1 minute 30 seconds Drying The processing solution composition used in each processing step is as follows. It is. [Color developer] 4-amino-3-methyl-N-ethyl-N-(β
-hydroxylethyl)aniline sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g Potassium hydroxide 1.0g Add water to make 1 and adjust the pH to 10.02. [Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100g Ethylenediaminetetraacetic acid diammonium salt 10g Ammonium bromide 150g Glacial acetic acid 10ml Add water to make 1, and adjust the pH using ammonia water.
= 6.0. [Fixer] Ammonium thiosulfate 175g Anhydrous sodium sulfite 8.5g Sodium metabisulfite 2.3g Add water to make 1, and adjust to PH=6.0 using acetic acid. [Stabilizer] Formalin (37% aqueous solution) 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5ml Add water to make 1. The light resistance, yellow stain, and gradation of each sample thus obtained were measured in the same manner as in Example 1. The results are shown in Table 3.

【衚】 衚から明らかなように、本発明の詊料では耐
光性が良く黄色ステむンの増加やガンマ倀の劣化
の少ない良奜なマれンタ画像が埗られる。たた色
再珟の良い鮮明な画像が埗られた。
[Table] As is clear from Table 3, the samples of the present invention have good light resistance and can provide good magenta images with little increase in yellow stain and little deterioration in gamma value. In addition, clear images with good color reproduction were obtained.

Claims (1)

【特蚱請求の範囲】  䞋蚘䞀般匏〔〕で衚されるカプラヌの少な
くずも぀ず、䞋蚘䞀般匏〔XI〕で衚される化合
物及び〔XII〕で衚される化合物の少なくずも぀
ずを含有するこずを特城ずするハロゲン化銀写真
感光材料。 䞀般匏〔〕 〔匏䞭、R1は環に盎結する根元原子が炭玠原子
であり、か぀、該炭玠原子に結合する氎玠原子が
個だけである眮換基を衚し、R2はR1ずは異な
る眮換基を衚す。たたは氎玠原子たたは発色珟
像䞻薬の酞化䜓ずの反応により離脱しうる眮換基
を衚す。〕 䞀般匏〔XI〕 䞀般匏〔XII〕 〔匏䞭、X1X2およびX4は、それぞれ酞玠原子
を衚す。X3はヒドロキシル基を、は硫黄原子
を、R1R2およびR3は、それぞれ氎玠原子又は
アルキル基を衚す。䜆し、R1R2R3のうち少
なくずも二぀はアルキル基を衚す。R4〜R9は、
アルキル基、アリヌル基、アルコキシ基、アリヌ
ルオキシ基、アルコキシカルボニル基、アリヌル
オキシカルボニル基、アシル基、アシルアミノ
基、アルキルアミノ基、カルバモむル基、スルフ
アモむル基、スルホンアミド基、スルホニル基た
たはシクロアルキル基を衚す。たた、お互いに連
結しお員たたは員の環を圢成しおもよい。
は金属原子を衚す。および
は、それぞれ〜の敎数を衚す。〕
[Scope of Claims] 1 Contains at least one coupler represented by the following general formula [] and at least one of the compounds represented by the following general formula [XI] and [XII] A silver halide photographic material characterized by: General formula [] [In the formula, R 1 represents a substituent whose root atom directly connected to the ring is a carbon atom and there is only one hydrogen atom bonded to the carbon atom, and R 2 represents a substituent different from R 1 represents. Further, X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. ] General formula [XI] General formula [XII] [In the formula, X 1 , X 2 and X 4 each represent an oxygen atom. X 3 represents a hydroxyl group, Y represents a sulfur atom, and R 1 , R 2 and R 3 each represent a hydrogen atom or an alkyl group. However, at least two of R 1 , R 2 and R 3 represent an alkyl group. R4 to R9 are
Represents an alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acylamino group, alkylamino group, carbamoyl group, sulfamoyl group, sulfonamide group, sulfonyl group or cycloalkyl group . Alternatively, they may be connected to each other to form a 5- or 6-membered ring. M
represents a metal atom. a, b, c, d, e and f
each represents an integer from 0 to 4. ]
JP26929084A 1984-12-12 1984-12-19 Silver halide photographic sensitive material Granted JPS61145554A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP26929084A JPS61145554A (en) 1984-12-19 1984-12-19 Silver halide photographic sensitive material
US06/805,120 US4684603A (en) 1984-12-12 1985-12-04 Light-sensitive silver halide color photographic material
DE8585308980T DE3576579D1 (en) 1984-12-12 1985-12-10 LIGHT SENSITIVE PHOTOGRAPHIC SILVER HALOGENID MATERIAL.
EP19850308980 EP0185506B1 (en) 1984-12-12 1985-12-10 Light-sensitive silver halide photographic material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP26929084A JPS61145554A (en) 1984-12-19 1984-12-19 Silver halide photographic sensitive material

Publications (2)

Publication Number Publication Date
JPS61145554A JPS61145554A (en) 1986-07-03
JPH045372B2 true JPH045372B2 (en) 1992-01-31

Family

ID=17470286

Family Applications (1)

Application Number Title Priority Date Filing Date
JP26929084A Granted JPS61145554A (en) 1984-12-12 1984-12-19 Silver halide photographic sensitive material

Country Status (1)

Country Link
JP (1) JPS61145554A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01131560A (en) * 1987-08-05 1989-05-24 Konica Corp Silver halide photographic sensitive material having superior color reproducibility
JP2711452B2 (en) * 1987-08-13 1998-02-10 コニカ株匏䌚瀟 Silver halide photographic material with excellent color reproduction

Also Published As

Publication number Publication date
JPS61145554A (en) 1986-07-03

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