JP3177809B2 - Silver halide color photographic materials - Google Patents

Silver halide color photographic materials

Info

Publication number
JP3177809B2
JP3177809B2 JP33205793A JP33205793A JP3177809B2 JP 3177809 B2 JP3177809 B2 JP 3177809B2 JP 33205793 A JP33205793 A JP 33205793A JP 33205793 A JP33205793 A JP 33205793A JP 3177809 B2 JP3177809 B2 JP 3177809B2
Authority
JP
Japan
Prior art keywords
silver halide
emulsion
grains
silver
gelatin
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 - Fee Related
Application number
JP33205793A
Other languages
Japanese (ja)
Other versions
JPH07191425A (en
Inventor
貞康 石川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
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 by Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to JP33205793A priority Critical patent/JP3177809B2/en
Priority to DE69421790T priority patent/DE69421790D1/en
Priority to EP94309680A priority patent/EP0660176B1/en
Publication of JPH07191425A publication Critical patent/JPH07191425A/en
Application granted granted Critical
Publication of JP3177809B2 publication Critical patent/JP3177809B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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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
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/07—Substances influencing grain growth during silver salt formation
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/16—Methine and polymethine dyes with an odd number of CH groups with one CH group
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
    • G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions
    • G03C2001/0055—Aspect ratio of tabular grains in general; High aspect ratio; Intermediate aspect ratio; Low aspect ratio
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions
    • G03C2001/0058—Twinned crystal
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • G03C2001/0156—Apparatus or processes for the preparation of emulsions pAg value; pBr value; pCl value; pI value
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03535—Core-shell grains
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/0357—Monodisperse emulsion
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03594—Size of the grains

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【産業上の利用分野】本発明は、写真の分野において有
用なハロゲン化銀カラー写真感光材料に関する。更に詳
しくは、高感度で、潜像保存性に優れたハロゲン化銀カ
ラー写真感光材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material useful in the field of photography. More specifically, the present invention relates to a silver halide color photographic material having high sensitivity and excellent latent image preservability.

【０００２】[0002]

【従来の技術】近年、コンパクトカメラ及び自動焦点１
眼レフカメラ、更にはレンズ付きフィルム等の普及によ
り、高感度でかつ画質の優れたハロゲン化銀カラー写真
感光材料の開発が強く望まれている。そのために、写真
用のハロゲン化銀乳剤に対する性能改良の要求はますま
す厳しく、高感度、優れた粒状性、及び優れたシャープ
ネス等の写真性能に対して、より高水準の要求がなされ
ている。2. Description of the Related Art In recent years, compact cameras and auto-focus cameras 1
With the spread of eye reflex cameras, films with lenses, and the like, the development of silver halide color photographic materials having high sensitivity and excellent image quality has been strongly desired. Therefore, demands for improved performance of photographic silver halide emulsions are becoming more severe, and higher levels of demands are made on photographic performance such as high sensitivity, excellent graininess, and excellent sharpness.

【０００３】かかる要求に対して、例えば、米国特許第
4,434,226号、同4,439,520号、同4,414,310号、同4,43
3,048号、同4,414,306号、同4,459,353号等に平板状ハ
ロゲン化銀粒子(以下、単に〔平板粒子〕ともいう)を使
用した技術が開示されており、増感色素による色増感効
率の向上を含む感度の向上、感度／粒状性の改良、平板
粒子の特異的な光学的性質によるシャープネスの向上、
カバーリングパワーの向上などの利点が知られている。
しかしながら、近年の高水準の要求に応えるには不十分
であり、より一層の性能向上が望まれている。In response to such a request, for example, US Pat.
4,434,226, 4,439,520, 4,414,310, 4,43
No. 3,048, No. 4,414,306, No. 4,459,353 and the like, a technique using tabular silver halide grains (hereinafter, also simply referred to as `` tabular grains '') is disclosed, and the improvement of the color sensitization efficiency by a sensitizing dye is disclosed. Increasing sensitivity, improving sensitivity / granularity, improving sharpness due to specific optical properties of tabular grains,
Advantages such as an improvement in covering power are known.
However, it is not enough to meet recent high-level demands, and further improvement in performance is desired.

【０００４】高感度という点では、これまで様々な解
析、技術開発が行われてきた。乳剤の感度に係わる非効
率因子としては種々あるが、１つの因子である自由電子
と正孔の再結合を防止するという観点では、還元増感を
施すことが有効であることが古くから知られている。In terms of high sensitivity, various analyzes and technical developments have been made. There are various inefficiency factors relating to the sensitivity of emulsions, but it has long been known that reduction sensitization is effective in preventing recombination of free electrons and holes, which is one factor. ing.

【０００５】ジャーナル オブ フォトグラフィックサイ
エンス(Journal of Photographic Science)第25巻、p.1
9〜27(1977)及びフォトグラフィック サイエンス アン
ド エンジニアリング(Photographic Science and Engin
eering)第23巻、p113〜117(1979)の記載が示すとおり、
適切に施された還元増感核はフォトグラフィッシュ コ
レスポンデンツ(Photographishe Korrespondenz)第1
巻、p20〜(1957)及びフォトグラフィック サイエンス
アンド エンジニアリング(Photographic Science and E
ngineering)第19巻、p49〜55(1975)の報文の中でMichel
lとLoweが述べているように、露光時に以下の式で示さ
れる反応を通し増感に寄与すると考えられている。[0005] Journal of Photographic Science, Vol. 25, p. 1
9-27 (1977) and Photographic Science and Engin
eering) Volume 23, p113-117 (1979),
Properly applied reduction sensitization nuclei are the first in Photographicish Korrespondenz
Volume, p20- (1957) and Photographic Science
And Engineering (Photographic Science and E
Michel in the report of Volume 19, p49-55 (1975)
As described by l and Lowe, it is considered that the compound contributes to sensitization through a reaction represented by the following formula at the time of exposure.

【０００６】 ＡｇＸ ＋ ｈν → ｅ- ＋ ｈ+ (1) Ａｇ2 ＋ ｈ+ → Ａｇ+ ＋ Ａｇ (2) Ａｇ → Ａｇ+ ＋ ｅ- (3) ここに、h+及びe-は露光で生じた自由正孔及び自由電
子、hvは光子、Ag2は還元増感核を示す。この理論が正
しいと仮定すると、還元増感核は電子が正孔と再結合す
ることによって生じる効率低下を防止し高感度化に寄与
すると考えられる。[0006] AgX + hν → e - + h + (1) Ag 2 + h + → Ag + + Ag (2) Ag → Ag + + e - (3) Here, h +, e - occurs at exposure Free holes and free electrons, hv indicates a photon, and Ag 2 indicates a reduction sensitization nucleus. Assuming that this theory is correct, it is considered that the reduction sensitization nucleus prevents a decrease in efficiency caused by the recombination of electrons with holes and contributes to an increase in sensitivity.

【０００７】しかし、フォトグラフィック サイエンス
アンド エンジニアリング(Photographic Science and E
ngineering)第16巻、p35〜42(1971)及び同第23巻、p113
〜117(1979)によれば還元増感核は正孔をトラップする
だけでなく電子をトラップする性格を有しており、上述
の理論だけでは必ずしも十分な説明はできない。However, photographic science
And Engineering (Photographic Science and E
ngineering) Volume 16, p35-42 (1971) and Volume 23, p113
According to 117117 (1979), the reduction sensitization nucleus has the property of trapping not only holes but also electrons, and cannot be sufficiently explained by the above theory alone.

【０００８】以上述べてきたハロゲン化銀粒子固有の感
光核とは異なり、分光増感されたハロゲン化銀の色増感
領域での還元増感の働きは感光過程の複雑さゆえにその
予測がまことに困難である。Unlike the above-described photosensitive nuclei peculiar to silver halide grains, the reduction sensitization in the color sensitized region of spectrally sensitized silver halide is not exactly predicted due to the complexity of the photosensitive process. Have difficulty.

【０００９】分光増感されたハロゲン化銀乳剤において
は、固有感光領域と異なり光を吸収するのは増感色素で
あり、感光の初期過程は(1)式の代わりに(4)式によって
示される。In the spectrally sensitized silver halide emulsion, the sensitizing dye absorbs light differently from the intrinsic photosensitive region, and the initial process of exposure is represented by the formula (4) instead of the formula (1). It is.

【００１０】 Ｄｙｅ ＋ ｈν → Ｄｙｅ+ ＋ ｅ- (4) 右辺で示される色素正孔(Ｄｙｅ+)及び電子(ｅ-)がハロ
ゲン化銀粒子に伝達されるかどうかは色素の性質による
ところが大きい。色素正孔に注目したとき、一般的には
色素正孔が粒子内部に伝達されない方が増感効率がよい
とされている。[0010] Dye + hν → Dye + + e - (4) dye hole (Dye +) and electrons represented by the right-hand side (e -) Whether is transmitted to the silver halide grains is largely due to the nature of the dye . When attention is paid to dye holes, it is generally considered that the sensitization efficiency is better if the dye holes are not transmitted to the inside of the grains.

【００１１】このことは、たとえばフォトグラフィック
サイエンス アンド エンジニアリング(Photographic S
cience and Engineering)第24巻、p138〜143(1980)の中
で色素の酸化電位(Ｅｏｘ)と関連づけて議論されてい
る。This is, for example, the case of Photographic S & E.
Science and Engineering, Vol. 24, pp. 138-143 (1980), in connection with the oxidation potential (Eox) of the dye.

【００１２】しかし、インターナショナル コングレス
オブ フォトグラフィック サイエンス(International C
ongress of Photographic Science)要旨集、p159〜162
(1978)及びフォトグラフィック サイエンス アンド エ
ンジニアリング(PhotographicScience and Engineerin
g)第17巻、p235〜244(1973)は露光時に生じた色素正孔
(Ｄｙｅ+)がハロゲン化銀粒子表面にとどまるような増
感色素は表面にあるカブリ核や還元増感核を漂白するこ
とを示唆しており、最も一般的な表面潜像型の乳剤にお
いては表面の潜像が漂白されむしろ減感を招くことも予
想される。However, International Congress
Of Photographic Science (International C
ongress of Photographic Science) Abstracts, pp. 159-162
(1978) and PhotographicScience and Engineerin
g) Volume 17, p235-244 (1973) is dye holes generated during exposure
Sensitizing dyes in which (Dye +) stays on the surface of silver halide grains indicate that the fogging nuclei and reduction sensitizing nuclei on the surface are bleached, and in the most common surface latent image type emulsions, It is also expected that the latent image on the surface will be bleached, rather causing desensitization.

【００１３】しかしながら、これまで述べてきたよう
に、分光増感された系において還元増感をハロゲン化銀
粒子表面あるいは内部のいづれに施せばよいのか、また
どのような色素と組み合わせたときその効果が発揮され
るかは未だ知られていない。However, as described above, whether reduction sensitization should be performed on the surface or inside of silver halide grains in a spectrally sensitized system, and what kind of dye should be used when combined with reduction sensitization It is not yet known whether it will be exerted.

【００１４】還元増感の方法として、ハロゲン化銀粒子
表面に施すものやハロゲン化銀粒子の成長中に施す方
法、あるいは種晶を粒子成長に用いる場合には、その種
晶にあらかじめ還元増感を施しておく方法が知られてい
る。As a method of reduction sensitization, a method applied to the surface of silver halide grains, a method applied during the growth of silver halide grains, or a seed crystal used for grain growth, the reduction sensitization of the seed crystal in advance. There is a known method for performing the above.

【００１５】粒子表面に施す方法は他の増感法(例えば
金化合物、硫黄化合物)と併用すると、好ましくないか
ぶりの増加が著しく、実用上不適である。それに比べハ
ロゲン化銀粒子成長中に還元増感を施す方法は、換言す
れば粒子内部に還元増感を施す方法は、他の増感法と併
用しても上記のような欠点はない。When the method of applying to the grain surface is used in combination with other sensitizing methods (for example, a gold compound and a sulfur compound), an undesirable increase in fogging is remarkable, which is not suitable for practical use. On the other hand, the method of performing reduction sensitization during the growth of silver halide grains, in other words, the method of performing reduction sensitization inside the grains does not have the above-mentioned disadvantages even when used in combination with other sensitization methods.

【００１６】例えばこのような方法は特開昭48-87825
号、特開昭57-179835号に記載されている。しかしこれ
らの特許には、ハロゲン化銀の固有感度の向上は報告さ
れているが、分光増感した系については触れられていな
い。これは、前述のように、ハロゲン化銀表面にとどま
っている色素正孔が、表面の潜像を破壊するためであろ
うと予想される。粒子内部にある還元増感核は、表面の
色素正孔を有効にトラップしないため、その還元増感の
効果がみられないものと思われる。For example, such a method is disclosed in JP-A-48-87825.
And JP-A-57-179835. However, although these patents report an improvement in the intrinsic sensitivity of silver halide, they do not mention a spectrally sensitized system. It is expected that this is because, as described above, dye holes remaining on the silver halide surface destroy the latent image on the surface. Since the reduction sensitization nucleus inside the grain does not effectively trap the dye holes on the surface, it is considered that the effect of the reduction sensitization is not seen.

【００１７】従って、還元増感と金・硫黄増感の併用に
よる表面潜像型ハロゲン化銀の高感度化を達成するため
には、特に分光感度の向上という立場からみて、次の問
題点があることが知られていた。Therefore, in order to increase the sensitivity of the surface latent image type silver halide by the combined use of reduction sensitization and gold / sulfur sensitization, the following problems arise, especially from the standpoint of improving the spectral sensitivity. It was known that there was.

【００１８】１.粒子内部に還元増感を施した場合、多
くの場合、分光増感については効果がない。一方で、表
面に還元増感を施した場合、分光増感上の分光増感上の
効果についてもまだ確証はない ２.粒子表面に還元増感を施した場合、高かぶりの発生
のため金・硫黄増感との併用が難しい 以上の点に対しては、特開平2-105139号、同2-108038
号、同2-125247号、同2-127636号、同2-130545号、同2-
150837号、同2-168247号、同2-235043号、同4-232945
号、同4-32832号等において、特に分光増感されたハロ
ゲン化銀乳剤における高感度化、保存性改良、圧力特性
改良等の技術について開示されている。1. When reduction sensitization is performed inside grains, spectral sensitization has no effect in many cases. On the other hand, when reduction sensitization is applied to the surface, the effect on spectral sensitization on spectral sensitization is not yet confirmed. 2. When reduction sensitization is applied to the particle surface, gold is generated due to high fog. -It is difficult to use together with sulfur sensitization. For the above points, see JP-A-2-105139 and 2-108038.
Nos. 2-125247, 2-127636, 2-130545, 2-
No. 150837, No. 2-168247, No. 2-35043, No. 4-232945
And Nos. 4-32832 disclose techniques for increasing the sensitivity, improving storage stability, improving pressure characteristics, and the like, particularly in spectrally sensitized silver halide emulsions.

【００１９】しかしながら、これらの技術は、露光後
に、高温、高湿度下で長時間保存された後の減感が大き
く、実用に耐え得るものではなかった。However, these techniques have a large desensitization after being stored for a long time at high temperature and high humidity after exposure, and have not been practically usable.

【００２０】[0020]

【発明が解決しようとする課題】本発明の課題は、上記
問題点を改良して、高感度で、かつ潜像保存性(露光後
に、高温、高湿度下で長時間保存された後の感度の安定
性)に優れたハロゲン化銀カラー写真感光材料を提供す
ることにある。SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned problems, to provide a high sensitivity and a latent image preservability (the sensitivity after long-term storage at high temperature and high humidity after exposure). To provide a silver halide color photographic light-sensitive material having excellent stability.

【００２１】[0021]

【課題を解決するための手段】本発明の上記課題は以下
の構成により達成される。The above object of the present invention is achieved by the following constitution.

【００２２】支持体上に少なくとも１層のハロゲン化銀
乳剤層を有するハロゲン化銀カラー写真感光材料におい
て、該乳剤層の少なくともいずれか１層のハロゲン化銀
乳剤層に含まれるハロゲン化銀粒子の全投影面積の50％
以上が、主平面に平行な双晶面を偶数枚有するアスペク
ト比５未満の平板状ハロゲン化銀粒子からなり、該粒子
が以下の(Ａ)〜(Ｃ)の要件を満たすことを特徴とする平
板状ハロゲン化銀粒子を含有するハロゲン化銀カラー写
真感光材料。In a silver halide color photographic material having at least one silver halide emulsion layer on a support, silver halide grains contained in at least one of the silver halide emulsion layers of the emulsion layer 50% of total projected area
The above consists of tabular silver halide grains having an even number of twin planes parallel to the main plane and having an aspect ratio of less than 5, and the grains satisfy the following requirements (A) to (C). A silver halide color photographic light-sensitive material containing tabular silver halide grains.

【００２３】(Ａ)粒径の変動係数が20％以下であり、
(Ｂ)主平面に平行な双晶面間距離の変動係数(ｘ)と、粒
子の厚さの変動係数(ｙ)との間に0.7≦ｙ/ｘ≦2.0の関
係を有し、(Ｃ)粒子内部に還元増感されている。(A) the coefficient of variation of the particle size is 20% or less,
(B) has a relationship of 0.7 ≦ y / x ≦ 2.0 between the variation coefficient (x) of the twin plane distance parallel to the main plane and the variation coefficient (y) of the grain thickness, and (C) ) Reduction sensitization inside the grains.

【００２４】以下、本発明について詳細に述べる。Hereinafter, the present invention will be described in detail.

【００２５】本発明のハロゲン化銀乳剤に含まれるハロ
ゲン化銀粒子は平板粒子である。平板粒子とは、結晶学
的には双晶に分類される。The silver halide grains contained in the silver halide emulsion of the present invention are tabular grains. Tabular grains are crystallographically classified as twins.

【００２６】双晶とは、一つの粒子内に一つ以上の双晶
面を有するハロゲン化銀結晶であるが、双晶の形態の分
類はクラインとモイザーによる報文フォトグラフィッシ
ェコレスポンデンツ(Photographishe Korrespondenz)第
99巻、p100、同第100巻、p57に詳しく述べられている。[0026] Twins are silver halide crystals having one or more twin planes in one grain, and the classification of twin morphology is based on the report by Klein and Moiser. Korrespondenz)
It is described in detail in Vol. 99, p100, Vol. 100, p57.

【００２７】本発明における平板粒子は、主平面に平行
な双晶面を偶数枚有する。双晶面は透過型電子顕微鏡に
より観察することができる。具体的な方法は次の通りで
ある。まず、含有される平板粒子が、支持体上にほぼ主
平面が平行に配向するようにハロゲン化銀写真乳剤を塗
布し、試料を作成する。これをダイヤモンド・カッター
を用いて切削し、厚さ0.1μm程度の薄切片を得る。この
切片を透過型電子顕微鏡で観察することにより双晶面の
存在を確認することができる。The tabular grains in the present invention have an even number of twin planes parallel to the main plane. The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First, a silver halide photographic emulsion is coated on a support so that the contained tabular grains are substantially parallel to the main plane to prepare a sample. This is cut using a diamond cutter to obtain a thin section having a thickness of about 0.1 μm. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed.

【００２８】本発明において双晶面間距離とは、上記の
透過型電子顕微鏡を用いた切片の観察において、主平面
に対しほぼ垂直に切断された断面を示す平板粒子を任意
に1000個以上選び、主平面に平行な偶数枚の双晶面の
内、最も距離の短い２枚の双晶面間距離をそれぞれの粒
子について求め、加算平均することにより得られる。In the present invention, the distance between twin planes refers to a value obtained by arbitrarily selecting 1,000 or more tabular grains having a cross section substantially perpendicular to the main plane in the observation of the slice using the above-mentioned transmission electron microscope. The distance between the two twin planes having the shortest distance among the even twin planes parallel to the principal plane is obtained for each particle, and is obtained by averaging.

【００２９】本発明で言う双晶面間距離の変動係数(ｘ)
とは、平板粒子の双晶面間距離のバラツキの程度を表
し、双晶面間距離の標準偏差を双晶面間距離の平均値で
割った値のパーセント表示値である。The coefficient of variation (x) of the distance between twin planes referred to in the present invention.
The term “indicates the degree of variation in the distance between twin planes of tabular grains, and is a percentage value of a value obtained by dividing the standard deviation of the distance between twin planes by the average value of the distance between twin planes.

【００３０】本発明において、双晶面間距離の平均は0.
01μm〜0.05μmが好ましく、更に好ましくは0.013μm〜
0.03μmである。In the present invention, the average of the distance between twin planes is equal to 0.
01 μm to 0.05 μm is preferable, and more preferably 0.013 μm to
0.03 μm.

【００３１】本発明の平板粒子の厚さは、前述の透過型
電子顕微鏡を用いた切片の観察により、同様にしてそれ
ぞれの粒子について厚さを求め、加算平均することによ
り得られる。平板粒子の厚さは0.05μm〜1.5μmが好ま
しく、更に好ましくは0.15μm〜1.0μmである。The thickness of the tabular grain of the present invention can be obtained by observing a section using a transmission electron microscope as described above, similarly obtaining the thickness of each grain, and performing averaging. The thickness of the tabular grains is preferably from 0.05 μm to 1.5 μm, more preferably from 0.15 μm to 1.0 μm.

【００３２】本発明で言う平板粒子の厚さの変動係数
(ｙ)とは、平板粒子の厚さのバラツキの程度を表し、粒
子厚さの標準偏差を厚さの平均値で割った値のパーセン
ト表示値である。Coefficient of variation of tabular grain thickness referred to in the present invention
(y) represents the degree of variation in the thickness of tabular grains, and is expressed as a percentage of the value obtained by dividing the standard deviation of the grain thickness by the average thickness.

【００３３】本発明の平板粒子は、双晶面間距離の変動
係数(ｘ)と、厚さの変動係数(ｙ)との間に0.7≦ｙ/ｘ≦
2.0の関係を有し、更に好ましくは、0.8≦ｙ/ｘ≦1.6の
関係を有し、最も好ましくは0.9≦ｙ/ｘ≦1.3の関係を
有するものである。The tabular grains of the present invention have a coefficient of variation of 0.7 ≦ y / x ≦ t between the variation coefficient (x) of the distance between twin planes and the variation coefficient (y) of the thickness.
It has a relationship of 2.0, more preferably has a relationship of 0.8 ≦ y / x ≦ 1.6, and most preferably has a relationship of 0.9 ≦ y / x ≦ 1.3.

【００３４】本発明の平板粒子は、アスペクト比(粒径
／粒子厚さ)が５未満のものを言うが4.0以下が好まし
い。The tabular grains of the present invention have an aspect ratio (particle size / grain thickness) of less than 5, but preferably 4.0 or less.

【００３５】本発明においてハロゲン化銀粒子の粒径
は、該ハロゲン化銀粒子の投影面積の円相当直径(該ハ
ロゲン化銀粒子と同じ投影面積を有する円の直径)で示
されるが、0.1〜5.0μmが好ましく、更に好ましくは0.2
〜2.0μmである。In the present invention, the grain size of the silver halide grains is represented by the equivalent circle diameter of the projected area of the silver halide grains (the diameter of a circle having the same projected area as the silver halide grains). 5.0 μm is preferred, and more preferably 0.2 μm.
2.02.0 μm.

【００３６】粒径は、例えば該粒子を電子顕微鏡で１万
倍から７万倍に拡大して撮影し、そのプリント上の粒子
直径または投影時の面積を実測することによって得るこ
とができる（測定粒子個数は無差別に1000個以上あるこ
ととする）。The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 70,000 and measuring the particle diameter or the area at the time of projection on the print (measurement). The number of particles shall be indiscriminately 1000 or more).

【００３７】ここに、平均粒径ｒは、粒径riを有する粒
子の頻度niとri3との積ni×ri3が最大となるときの粒径
riと定義する（有効数字３桁、最小桁数字は４捨５入す
る）。Here, the average particle diameter r is the particle diameter at which the product ni × ri 3 of the frequency ni and ri 3 of the particles having the particle diameter ri becomes maximum.
Defined as ri (three significant digits, the smallest digit is rounded off to the nearest 5).

【００３８】本発明のハロゲン化銀粒子は、単分散のハ
ロゲン化銀乳剤からなる。ここで単分散のハロゲン化銀
乳剤としては、平均粒径ｒを中心に±20％の粒径範囲内
に含まれるハロゲン化銀重量が、全ハロゲン化銀粒子重
量の60％以上であるものが好ましく、より好ましくは70
％以上、更に好ましくは80％以上である。The silver halide grains of the present invention comprise a monodispersed silver halide emulsion. Here, as the monodispersed silver halide emulsion, the one in which the weight of silver halide contained in a range of ± 20% of the particle size around the average particle size r is 60% or more of the total weight of silver halide particles. Preferred, more preferably 70
%, More preferably 80% or more.

【００３９】本発明の高度の単分散乳剤は、 （標準偏差／平均粒径）×100 ＝ 粒径分布(粒径の変動
係数) 〔％〕 によって分布の広さを定義したとき20％以下のものであ
り、更に好ましくは15％以下、最も好ましくは12％以下
のものである。ここに平均粒径および標準偏差は、上記
定義した粒径ｒiから求めるものとする。The highly monodispersed emulsion of the present invention has a particle size distribution (coefficient of variation of particle size) [%] of (standard deviation / average particle size). And more preferably at most 15%, most preferably at most 12%. Here, the average particle diameter and the standard deviation are determined from the particle diameter ri defined above.

【００４０】本発明において、双晶面間距離は、核形成
時の過飽和状態に影響を及ぼす因子、例えばゼラチン濃
度、ゼラチン種、温度、沃素イオン濃度、pBr、pＨ、イ
オン供給速度、撹拌回転数等の諸因子の組み合わせにお
いて適切に選択することにより制御することができる。
一般に核形成を高過飽和状態で行なうほど、双晶面間距
離を狭くすることができる。In the present invention, the distance between twin planes is a factor affecting the supersaturation state at the time of nucleation, for example, gelatin concentration, gelatin species, temperature, iodine ion concentration, pBr, pH, ion supply speed, stirring speed. Can be controlled by appropriately selecting a combination of various factors such as
In general, the more the nucleation is performed in a supersaturated state, the narrower the distance between twin planes can be.

【００４１】過飽和因子に関しての詳細は、例えば特開
昭63-92924号、あるいは特開平1-213637号等の記述を参
考にすることができる。The details of the supersaturation factor can be referred to, for example, the descriptions in JP-A-63-92924 and JP-A-1-213637.

【００４２】本発明のハロゲン化銀粒子は、粒子内部に
還元増感されている。還元増感された粒子内部とは、粒
子全体の体積で90％より内側であり、好ましくは70％よ
り内側の部分のことである。The silver halide grains of the present invention are reduction sensitized inside the grains. The inside of the reduction-sensitized grain is a portion inside 90%, preferably inside 70% by volume of the whole grain.

【００４３】還元増感は、ハロゲン化銀乳剤又は粒子成
長のための混合溶液に還元剤を添加することによって行
われる。あるいは、ハロゲン化銀乳剤又は粒子成長のた
めの混合溶液をpAg７以下の低pＡｇ下で、又はpＨ７以
上の高pＨ条件下で熟成又は粒子成長させることによっ
て行なわれる。これらの方法を組み合わせて行なう方法
は、本発明の好ましい態様である。Reduction sensitization is carried out by adding a reducing agent to a silver halide emulsion or a mixed solution for grain growth. Alternatively, it is carried out by ripening or grain growing a silver halide emulsion or a mixed solution for grain growth under a low pAg of 7 or less, or under a high pH condition of 7 or more. A method performed by combining these methods is a preferred embodiment of the present invention.

【００４４】還元剤として好ましいものとして二酸化チ
オ尿素、アスコルビン酸及びその誘導体、第１錫塩が挙
げられる。他の適当な還元剤としては、ボラン化合物、
ヒドラジン誘導体、ホルムアミジンスルフィン酸、シラ
ン化合物、アミン及びポリアミン類及び亜硫酸塩等が挙
げられる。添加量は、ハロゲン化銀１モル当たり10-2〜
10-8モルが好ましい。Preferred reducing agents include thiourea dioxide, ascorbic acid and its derivatives, and stannous salts. Other suitable reducing agents include borane compounds,
Examples include hydrazine derivatives, formamidinesulfinic acid, silane compounds, amines and polyamines, and sulfites. The addition amount is 10 -2 to 1 mol per mol of silver halide.
10 -8 mol is preferred.

【００４５】低pAg熟成を行なうためには、銀塩を添加
することができるが、水溶性銀塩が好ましい。水溶性銀
塩としては硝酸銀が好ましい。熟成時のpAgは７以下が
適当であり、好ましくは６以下、更に好ましくは１〜３
である(ここで、pAg＝−log〔Ag+〕である)。[0045] In order to perform low-pAg ripening, can be added a silver salt, have preferred water-soluble silver salt. Silver nitrate is preferred as the water-soluble silver salt. The pAg at the time of aging is suitably 7 or less, preferably 6 or less, and more preferably 1-3.
(Where pAg = −log [Ag + ]).

【００４６】高pＨ熟成は、例えばハロゲン化銀乳剤あ
るいは粒子成長の混合溶液にアルカリ性化合物を添加す
ることによって行われる。アルカリ性化合物としては、
例えば水酸化ナトリウム、水酸化カリウム、炭酸ナトリ
ウム、炭酸カリウム、アンモニア等を用いることができ
る。ハロゲン化銀形成にアンモニア性硝酸銀を添加する
方法においては、アンモニアの効果が低下するため、ア
ンモニアを除くアルカリ性化合物が好ましく用いられ
る。The high pH ripening is carried out, for example, by adding an alkaline compound to a silver halide emulsion or a mixed solution for grain growth. As the alkaline compound,
For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and the like can be used. In the method of adding ammoniacal silver nitrate to silver halide formation, an alkaline compound other than ammonia is preferably used because the effect of ammonia is reduced.

【００４７】還元増感のための銀塩、アルカリ性化合物
の添加方法としては、ラッシュ添加でもよいし、あるい
は一定時間をかけて添加してもよい。この場合には、一
定流量で添加してもよいし、関数様に流量を変化させて
添加してもよい。また、何回かに分割して必要量を添加
してもよい。可溶性銀塩及び／又は可溶性ハロゲン化物
の反応容器中への添加に先立ち、反応容器中に存在せし
めていてもよいし、あるいは可溶性ハロゲン化物溶液中
に混入し、ハロゲン化物とともに添加してもよい。更に
は、可溶性銀塩、可溶性ハロゲン化物とは別個に添加を
行なってもよい。As a method for adding a silver salt or an alkaline compound for reduction sensitization, rush addition or addition over a certain period of time may be used. In this case, the addition may be performed at a constant flow rate, or may be performed by changing the flow rate like a function. Further, the required amount may be added several times. Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, it may be present in the reaction vessel, or may be mixed in a soluble halide solution and added together with the halide. Further, it may be added separately from the soluble silver salt and the soluble halide.

【００４８】本発明のハロゲン化銀乳剤の作成において
は、種粒子から成長させる方法が好ましく用いられる。
具体的には、反応容器に予め保護コロイドを含む水溶液
及び種粒子を存在させ、必要に応じて銀イオン、ハロゲ
ンイオン、あるいはハロゲン化銀微粒子を供給して種粒
子を結晶成長させて得るものである。ここで種粒子は当
該分野でよく知られているシングル・ジェット法、コン
トロールド・ダブルジェット法等により調製することが
できる。種粒子のハロゲン組成は任意であり、臭化銀、
沃化銀、塩化銀、沃臭化銀、塩沃化銀、塩臭化銀、塩沃
臭化銀のいずれであってもよいが、臭化銀、沃臭化銀が
好ましく、沃臭化銀の場合は、平均沃化銀含有率は１モ
ル％〜20モル％が好ましい。In the preparation of the silver halide emulsion of the present invention, a method of growing from seed grains is preferably used.
Specifically, an aqueous solution containing a protective colloid and seed particles are pre-existing in a reaction vessel, and silver ions, halogen ions, or silver halide fine particles are supplied as necessary to grow the seed particles to obtain crystals. is there. Here, the seed particles can be prepared by a single jet method, a controlled double jet method, or the like well known in the art. The halogen composition of the seed grains is arbitrary, and silver bromide,
Any of silver iodide, silver chloride, silver iodobromide, silver chloroiodide, silver chlorobromide and silver chloroiodobromide may be used, but silver bromide and silver iodobromide are preferred, and iodobromide is preferred. In the case of silver, the average silver iodide content is preferably from 1 mol% to 20 mol%.

【００４９】種粒子から結晶成長させる形態において、
低pAg熟成は種乳剤の形成後、すなわち種粒子の脱塩直
前〜脱塩後までの工程の間に硝酸銀を添加して熟成させ
ることが好ましい。特に種粒子の脱塩後に硝酸銀を添加
して熟成させるのが好ましく、熟成温度は40℃以上、50
℃〜80℃が好ましい。熟成時間は、30分以上、50〜150
分が好ましく用いられる。In the form of crystal growth from seed particles,
The low pAg ripening is preferably performed by adding silver nitrate after the formation of the seed emulsion, that is, during the steps from immediately before desalting to after the desalting of the seed grains. It is particularly preferable to ripen by adding silver nitrate after desalting of the seed particles, and the ripening temperature is 40 ° C. or higher, 50 ° C.
C. to 80C is preferred. Aging time is more than 30 minutes, 50-150
Minutes are preferably used.

【００５０】種粒子から成長させる形態において、高p
Ｈ熟成を行なう場合は、成長後の粒子の体積に対して、
70％に相当する部分が成長するまでにpＨ７以上の環境
を少なくとも１回は経て粒子成長させる必要があり、成
長後の粒子の体積に対して、50％に相当する部分が成長
するまでにpＨ７以上の環境を少なくとも１回は経て粒
子成長させることが更に好ましく、成長後の粒子の体積
に対して、40％に相当する部分が成長するまでにpＨ８
以上の環境を少なくとも１回は経て粒子成長させること
が特に好ましい。In the form of growing from seed particles, high p
When H ripening is performed, the volume of the grown particles is
It is necessary to grow the particles at least once through an environment having a pH of 7 or more before the portion corresponding to 70% grows, and the pH is increased until the portion corresponding to 50% grows with respect to the volume of the grown particles. More preferably, the particles are grown at least once through the above environment, and the pH is increased until a portion corresponding to 40% of the volume of the grown particles grows.
It is particularly preferable to carry out the particle growth at least once through the above environment.

【００５１】本発明のハロゲン化銀乳剤は酸化剤を用い
ることができる。酸化剤としては以下のものを使用する
ことができる。An oxidizing agent can be used in the silver halide emulsion of the present invention. The following oxidizing agents can be used.

【００５２】過酸化水素(水)及びその付加物：H2O2、Na
BO2、H2O2−3H2O2、Na4P2O7−2H2O2、2Na2SO4−H2O2−2H
2Oなど。ペルオキシ酸塩：K2S2O3、K2C2O3、K4P2O3、K2
〔Ti(O2)C2O4〕-3H2Oなど。Hydrogen peroxide (water) and its adducts: H 2 O 2 , Na
BO 2, H 2 O 2 -3H 2 O 2, Na 4 P 2 O 7 -2H 2 O 2, 2Na 2 SO 4 -H 2 O 2 -2H
2 O etc. Peroxy acid salts: K 2 S 2 O 3, K 2 C 2 O 3, K 4 P 2 O 3, K 2
[Ti (O 2 ) C 2 O 4 ] -3H 2 O and the like.

【００５３】過酢酸、オゾン、沃素、臭素、チオスルホ
ン酸系化合物などが挙げられる。Examples include peracetic acid, ozone, iodine, bromine and thiosulfonic acid compounds.

【００５４】本発明で用いる酸化剤の添加量は、還元剤
の種類、還元増感条件、酸化剤の添加時期、添加条件に
よりその量に影響を受けるが、用いた還元剤１モル当た
り10-2〜10-5モルが好ましい。[0054] The amount of oxidizing agent used in the present invention, the kind of the reducing agent, reduction sensitization conditions, timing of addition of oxidizing agent, is influenced in an amount by adding conditions, the reducing agent per mole 10 using - 2-10 -5 mol are preferred.

【００５５】酸化剤の添加時期は、ハロゲン化銀乳剤製
造工程中であればどこでもよい。還元剤の添加に先立っ
て添加することもできる。The oxidizing agent may be added at any time during the silver halide emulsion manufacturing process. It can be added prior to the addition of the reducing agent.

【００５６】また、酸化剤を添加した後に、過剰な酸化
剤を中和するために新たに還元性物質を添加することも
できる。これらの還元性物質としては、上記酸化剤を還
元し得る物質であり、スルフィン酸類、ジ及びトリヒド
ロキシベンゼン類、クロマン類、ヒドラジン及びヒドラ
ジド類、p-フェニレンジアミン類、アルデヒド類、アミ
ノフェノール類、エンジオール類、オキシム類、還元性
糖類、フェニドン類、亜硫酸塩、アスコルビン酸誘導体
などがある。これらの還元性物質の添加量は、用いる酸
化剤の量１モル当たり10-3〜103モルが好ましい。After the oxidizing agent is added, a reducing substance may be newly added to neutralize the excess oxidizing agent. These reducing substances are substances capable of reducing the oxidizing agent, and include sulfinic acids, di- and trihydroxybenzenes, chromans, hydrazines and hydrazides, p-phenylenediamines, aldehydes, aminophenols, Examples include enediols, oximes, reducing sugars, phenidones, sulfites, and ascorbic acid derivatives. The amount of the reducing substance is preferably an amount per mole 10-3 to 3 moles of the oxidizing agent to be used is.

【００５７】本発明のハロゲン化銀粒子は、実質的に沃
臭化銀からなるが、本発明の効果を損なわない範囲で塩
化銀を含有させることができる。The silver halide grains of the present invention are substantially composed of silver iodobromide, but can contain silver chloride as long as the effects of the present invention are not impaired.

【００５８】本発明のハロゲン化銀粒子は、粒子内部に
５モル％以上の沃化銀を含有する沃臭化銀相を有するこ
とが好ましく、10モル％〜40モル％の沃化銀を含有する
沃臭化銀相を有することが更に好ましい。沃臭化銀相を
有する粒子内部とは、粒子全体の体積で90％より内側で
あり、好ましくは50％より内側である。The silver halide grains of the present invention preferably have a silver iodobromide phase containing 5 mol% or more of silver iodide inside the grains, and contain 10 mol% to 40 mol% of silver iodide. It is more preferred to have a silver iodobromide phase. The inside of the grain having the silver iodobromide phase is more than 90%, preferably more than 50% by volume of the whole grain.

【００５９】本発明のハロゲン化銀粒子は、沃化銀が粒
子内部に集中している、いわゆるコア/シェル型粒子が
好ましい。The silver halide grains of the present invention are preferably so-called core / shell grains in which silver iodide is concentrated inside the grains.

【００６０】本発明のハロゲン化銀粒子は、平均沃化銀
含有率が１モル％〜20モル％である沃臭化銀から成るこ
とが好ましく、更に好ましくは３〜15モル％である。The silver halide grains of the present invention preferably comprise silver iodobromide having an average silver iodide content of 1 mol% to 20 mol%, more preferably 3 to 15 mol%.

【００６１】本発明のハロゲン化銀乳剤の形成手段とし
ては、当該分野でよく知られている種々の方法を用いる
ことができる。すなわち、シングル・ジェット法、コン
トロールド・ダブルジェット法、コントロールド・トリ
プルジェット法等を任意に組み合わせて使用することが
できるが、本発明の高度な単分散粒子を得るためには、
ハロゲン化銀粒子の生成される液相中のpＡｇをハロゲ
ン化銀粒子の成長速度に合わせてコントロールすること
が重要である。pＡｇ値としては7.0〜10.5の領域を使用
し、好ましくは7.5〜10.0、8.0〜9.5の領域を使用する
ことが特に好ましい。As a means for forming the silver halide emulsion of the present invention, various methods well known in the art can be used. That is, a single jet method, a controlled double jet method, a controlled triple jet method, etc. can be used in any combination, but in order to obtain the highly monodispersed particles of the present invention,
It is important to control the pAg in the liquid phase in which the silver halide grains are formed in accordance with the growth rate of the silver halide grains. As the pAg value, a range of 7.0 to 10.5 is used, and it is particularly preferable to use a range of 7.5 to 10.0 and 8.0 to 9.5.

【００６２】添加速度の決定に当たっては、特開昭54-4
8521号、 特開昭58-49938号を参考にできる。In determining the addition rate, refer to JP-A-54-4
No. 8521 and JP-A-58-49938 can be referred to.

【００６３】本発明のハロゲン化銀粒子の製造時に、ア
ンモニア、チオエーテル、チオ尿素等の公知のハロゲン
化銀溶剤を存在させることもできるし、ハロゲン化銀溶
剤を使用しなくても良い。In the production of the silver halide grains of the present invention, a known silver halide solvent such as ammonia, thioether, thiourea or the like may be present, or a silver halide solvent may not be used.

【００６４】本発明のハロゲン化銀粒子は、潜像が主と
して表面に形成される粒子あるいは主として粒子内部に
形成される粒子いずれであっても良い。The silver halide grains of the present invention may be either grains whose latent image is mainly formed on the surface or grains mainly formed inside the grain.

【００６５】本発明のハロゲン化銀粒子は、分散媒の存
在下に即ち、分散媒を含む溶液中で製造される。ここ
で、分散媒を含む水溶液とは、ゼラチンその他の親水性
コロイドを構成し得る物質(バインダーとなり得る物質
など)により保護コロイドが水溶液中に形成されている
ものをいい、好ましくはコロイド状の保護ゼラチンを含
有する水溶液である。The silver halide grains of the present invention are produced in the presence of a dispersion medium, that is, in a solution containing the dispersion medium. Here, the aqueous solution containing the dispersion medium refers to an aqueous solution in which a protective colloid is formed in an aqueous solution by a substance capable of forming a hydrophilic colloid (e.g., a substance that can serve as a binder), and preferably a colloidal protective substance. It is an aqueous solution containing gelatin.

【００６６】本発明を実施する際、上記保護コロイドと
してゼラチンを用いる場合は、ゼラチンは石灰処理され
たものでも、酸を使用して処理されたものでもどちらで
もよい。ゼラチンの製法の詳細はアーサー・グアイス
著、ザ・マクロモレキュラー・ケミストリー・オブ・ゼ
ラチン、(アカデミック・プレス、1964年発行)に記載が
ある。When gelatin is used as the protective colloid in the practice of the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in Arthur Guice's, The Macromolecular Chemistry of Gelatin, (Academic Press, 1964).

【００６７】保護コロイドとして用いることができるゼ
ラチン以外の親水性コロイドとしては、例えばゼラチン
誘導体、ゼラチンと他の高分子とのグラフトポリマー、
アルブミン、カゼイン等の蛋白質；ヒドロキシエチルセ
ルロース、カルボキシメチルセルロース、セルロース硫
酸エステル類等の如きセルロース誘導体、アルギン酸ソ
ーダ、澱粉誘導体などの糖誘導体；ポリビニルアルコー
ル、ポリビニルアルコール部分アセタール、ポリ-N-ビ
ニルピロリドン、ポリアクリル酸、ポリメタクリル酸、
ポリアクリルアミド、ポリビニルイミダゾール、ポリビ
ニルピラゾール等の単一あるいは共重合体の如き多種の
合成親水性高分子物質がある。Examples of hydrophilic colloids other than gelatin that can be used as the protective colloid include gelatin derivatives, graft polymers of gelatin and other polymers,
Proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, and polyacryl Acid, polymethacrylic acid,
There are various kinds of synthetic hydrophilic high molecular substances such as single or copolymer such as polyacrylamide, polyvinylimidazole, polyvinylpyrazole and the like.

【００６８】ゼラチンの場合は、パギー法においてゼリ
ー強度200以上のものを用いることが好ましい。In the case of gelatin, it is preferable to use a gelatin having a jelly strength of 200 or more in a puggy method.

【００６９】本発明のハロゲン化銀粒子は、粒子を形成
する過程および／または 成長させる過程で、カドミウ
ム塩、亜鉛塩、鉛塩、タリウム塩、鉄塩、ロジウム塩、
イリジウム塩、インジウム塩(錯塩を含む)から選ばれる
少なくとも１種を用いて金属イオンを添加し、粒子内部
及び／又は粒子表面にこれらの金属元素を含有させるこ
とができる。The silver halide grains of the present invention can be used in the step of forming grains and / or in the course of growing the grains, in the presence of cadmium salts, zinc salts, lead salts, thallium salts, iron salts, rhodium salts,
Metal ions can be added using at least one selected from iridium salts and indium salts (including complex salts), and these metal elements can be contained inside the particles and / or on the surface of the particles.

【００７０】本発明のハロゲン化銀粒子は、ハロゲン化
銀粒子の成長終了後に、不要な可溶性塩類を除去したも
のであってもよいし、あるいは含有させたままのもので
も良い。The silver halide grains of the present invention may be those from which unnecessary soluble salts have been removed after the growth of the silver halide grains has been completed, or may be those which are still contained.

【００７１】また、特開昭60-138538号記載の方法のよ
うに、ハロゲン化銀成長の任意の点で脱塩を行なう事も
可能である。該塩類を除去する場合には、リサーチ・デ
ィスクロージャー（Research Disclosure、以下RDと略
す）17643号II項に記載の方法に基づいて行なうことが
できる。さらに詳しくは、沈澱形成後、あるいは物理熟
成後の乳剤から可溶性塩を除去するためには、ゼラチン
をゲル化させて行なうヌーデル水洗法を用いても良く、
また無機塩類、アニオン性界面活性剤、アニオン性ポリ
マー（たとえばポリスチレンスルホン酸）、あるいはゼ
ラチン誘導体（たとえばアシル化ゼラチン、カルバモイ
ル化ゼラチンなど）を利用した沈澱法（フロキュレーシ
ョン）を用いても良い。It is also possible to perform desalting at any point during silver halide growth, as in the method described in JP-A-60-138538. The removal of the salts can be performed based on the method described in Research Disclosure (hereinafter abbreviated as RD) No. 17643, section II. More specifically, in order to remove soluble salts from the emulsion after the formation of the precipitate or after the physical ripening, a Nudel washing method performed by gelling gelatin may be used,
Further, a precipitation method (flocculation) using an inorganic salt, an anionic surfactant, an anionic polymer (eg, polystyrene sulfonic acid), or a gelatin derivative (eg, acylated gelatin, carbamoylated gelatin, etc.) may be used.

【００７２】本発明のハロゲン化銀粒子は、常法により
化学増感することができる。すなわち、硫黄増感、セレ
ン増感、金その他の貴金属化合物を用いる貴金属増感法
などを単独でまたは組み合わせて用いることができる。The silver halide grains of the present invention can be chemically sensitized by a conventional method. That is, sulfur sensitization, selenium sensitization, a noble metal sensitization method using gold or another noble metal compound, or the like can be used alone or in combination.

【００７３】本発明のハロゲン化銀粒子は、写真業界に
おいて増感色素として知られている色素を用いて所望の
波長域に光学的に増感できる。増感色素は、単独で用い
てもよいが２種類以上を組み合わせて用いても良い。増
感色素と共にそれ自身分光増感作用をもたない色素、あ
るいは可視光を実質的に吸収しない化合物であって、増
感色素の増感作用を強める強色増感剤を乳剤中に含有さ
せても良い。The silver halide grains of the present invention can be optically sensitized to a desired wavelength region using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye which has no spectral sensitizing effect by itself together with the sensitizing dye or a compound which does not substantially absorb visible light and which enhances the sensitizing effect of the sensitizing dye is contained in the emulsion. May be.

【００７４】本発明のハロゲン化銀粒子には、カブリ防
止剤、安定剤などを加えることができる。The silver halide grains of the present invention may contain an antifoggant, a stabilizer and the like.

【００７５】本発明に使用されるバインダーとしては、
ゼラチンを用いるのが有利である。乳剤層、その他の親
水性コロイド層は、硬膜することができ、また、可塑
剤、水不溶性または可溶性合成ポリマーの分散物（ラテ
ックス）を含有させることができる。The binder used in the present invention includes:
Advantageously, gelatin is used. Emulsion layers and other hydrophilic colloid layers can be hardened and can contain plasticizers, dispersions (latexes) of water-insoluble or soluble synthetic polymers.

【００７６】本発明のハロゲン化銀カラー写真感光材料
の乳剤層にはカプラーが用いられる。さらに色補正の効
果を有している競合カプラーおよび現像主薬の酸化体と
のカップリングによって現像促進剤、現像剤、ハロゲン
化銀溶剤、調色剤、硬膜剤、カブリ剤、カブリ防止剤、
化学増感剤、分光増感剤および減感剤のような写真的に
有用なフラグメントを放出する化合物を用いることがで
きる。A coupler is used in the emulsion layer of the silver halide color photographic light-sensitive material of the present invention. Further, a development accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, an antifogging agent, and a coupling with a competing coupler having a color correcting effect and an oxidized form of a developing agent,
Compounds that release photographically useful fragments can be used, such as chemical sensitizers, spectral sensitizers, and desensitizers.

【００７７】本発明のハロゲン化銀カラー写真感光材料
には、フィルター層、ハレーション防止層、イラジイエ
ーション防止層等の補助層を設けることができる。これ
らの層中および／または乳剤層中には現像処理中に感光
材料から流出するか、もしくは漂白される染料が含有さ
れても良い。The silver halide color photographic light-sensitive material of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer and an anti-irradiation layer. In these layers and / or the emulsion layers, dyes which flow out of the light-sensitive material or are bleached during the development processing may be contained.

【００７８】本発明のハロゲン化銀カラー写真感光材料
には、マット剤、滑剤、画像安定剤、ホルマリンスカベ
ンジャー、紫外線吸収剤、蛍光増白剤、界面活性剤、現
像促進剤や現像遅延剤を添加できる。The silver halide color photographic light-sensitive material of the present invention contains a matting agent, a lubricant, an image stabilizer, a formalin scavenger, an ultraviolet absorber, a fluorescent brightener, a surfactant, a development accelerator and a development retarder. it can.

【００７９】本発明に使用される支持体としては、ポリ
エチレン等をラミネートした紙、ポリエチレンテレフタ
レートフィルム、バライタ紙、三酢酸セルロース等を用
いることができる。As the support used in the present invention, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate and the like can be used.

【００８０】[0080]

【実施例】以下、実施例を挙げて本発明を詳細に説明す
るが、本発明の態様はこれに限定されない。EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

【００８１】実施例１ 〔双晶種乳剤Ｔ−１の調製〕以下に示す方法によって、
２枚の平行な双晶面を有した種乳剤を調製した。Example 1 [Preparation of twin seed emulsion T-1]
A seed emulsion having two parallel twin planes was prepared.

【００８２】 (Ａ液) オセインゼラチン 80.0ｇ 臭化カリウム 47.4ｇ HO(CH2CH2O)m〔CH(CH3)CH2O〕19.8(CH2CH2O)nH (m＋n＝9.77) の10重量％メタノール溶液 0.48ml 蒸留水で8000.0mlに仕上げる (Ｂ液) 硝酸銀 1200.0ｇ 蒸留水で1600.0mlに仕上げる (Ｃ液) オセインゼラチン 32.2ｇ 臭化カリウム 790.0ｇ 沃化カリウム 70.34ｇ 蒸留水で1600.0mlに仕上げる (Ｄ液) アンモニア水 470.0ml 40℃で激しく攪拌したＡ液に、Ｂ液とＣ液をダブルジェ
ット法により7.7分間で添加し核の生成を行なった。こ
の間、pBrは1.60に保った。その後、30分間かけて、温
度を20℃に下げた。さらにＤ液を1分間で添加し、引き
続き5分間の熟成を行なった。熟成時のKBr濃度は0.03mo
l／l、アンモニア濃度は0.66mol／lであった。(Solution A) Ossein gelatin 80.0 g Potassium bromide 47.4 g HO (CH 2 CH 2 O) m [CH (CH 3 ) CH 2 O] 19.8 (CH 2 CH 2 O) n H ( m + n = 9.77) 10% by weight methanol solution 0.48 ml Make up to 8000.0 ml with distilled water (Solution B) 1200.0 g silver nitrate Make up to 1600.0 ml with distilled water (Solution C) 32.2 g of ossein gelatin 790.0 g of potassium iodide 70.34 g Finish to 1600.0 ml with distilled water (solution D) 470.0 ml ammonia water Solution B and solution C were added to solution A, which was vigorously stirred at 40 ° C, by a double jet method for 7.7 minutes to generate nuclei. During this time, pBr was kept at 1.60. Thereafter, the temperature was reduced to 20 ° C. over 30 minutes. Further, the solution D was added for 1 minute, and then ripening was performed for 5 minutes. KBr concentration at aging is 0.03mo
l / l and the ammonia concentration were 0.66 mol / l.

【００８３】熟成終了後、pＨを6.0に調整し、常法に従
って脱塩を行なった。脱塩後の乳剤に、10重量％のゼラ
チン水溶液を加え、60℃で30分間撹拌分散させた後、蒸
留水を加えて5360ｇの乳剤として仕上げた。After completion of the ripening, the pH was adjusted to 6.0, and desalting was performed according to a conventional method. To the emulsion after desalting, a 10% by weight aqueous solution of gelatin was added, and the mixture was stirred and dispersed at 60 ° C. for 30 minutes. Then, distilled water was added to complete the emulsion as 5360 g.

【００８４】この種乳剤粒子を電子顕微鏡観察したとこ
ろ、互いに平行な２枚の双晶面を有する平板状粒子であ
った。When the seed emulsion grains were observed with an electron microscope, they were tabular grains having two twin planes parallel to each other.

【００８５】この種乳剤粒子の平均粒径は0.217μm、２
枚の平行な双晶面を有する粒子は、全粒子の75％(個数
比)であった。The average grain size of the seed emulsion grains is 0.217 μm,
The number of grains having parallel twin planes was 75% (number ratio) of all grains.

【００８６】〔低pAg熟成を施した、双晶種乳剤Ｔ−２
の調製〕種乳剤Ｔ−１の製造方法において、脱塩後の乳
剤に、10重量％のゼラチン水溶液1884mlを加え、60℃で
15分間撹拌分散させた後、21ｇの硝酸銀を含む水溶液13
0mlを添加して乳剤のpAg値を1.88に調整し、引き続き60
℃で80分間撹拌熟成させた。その後、14.5ｇの臭化カリ
ウムを含む水溶液193mlを添加し、乳剤温度を40℃に下
げて蒸留水を加え5360ｇの乳剤として仕上げた。[Twin seed emulsion T-2 which had been subjected to low pAg ripening]
Preparation of Seed Emulsion T-1 In the method for producing seed emulsion T-1, 1884 ml of a 10% by weight aqueous gelatin solution was added to the emulsion after desalting,
After stirring and dispersing for 15 minutes, an aqueous solution 13 containing 21 g of silver nitrate 13
0 ml was added to adjust the pAg value of the emulsion to 1.88, followed by 60
The mixture was aged by stirring at 80 ° C. for 80 minutes. Thereafter, 193 ml of an aqueous solution containing 14.5 g of potassium bromide was added, the temperature of the emulsion was lowered to 40 ° C., and distilled water was added to complete 5360 g of an emulsion.

【００８７】この種乳剤粒子を電子顕微鏡観察したとこ
ろ、互いに平行な２枚の双晶面を有する平板状粒子であ
った。When the seed emulsion grains were observed with an electron microscope, the grains were tabular grains having two twin planes parallel to each other.

【００８８】この種乳剤粒子の平均粒径は0.217μm、２
枚の平行な双晶面を有する粒子は、全粒子の75％(個数
比)であった。 〔本発明乳剤ＥＭ−１の作成〕以下に示す７種類の溶液
(溶液Ａには、低pAg熟成を施した種乳剤Ｔ−２を含む)
を用いて、本発明の平板乳剤ＥＭ−１を調製した。The average grain size of the seed emulsion grains is 0.217 μm, 2
The number of grains having parallel twin planes was 75% (number ratio) of all grains. [Preparation of Emulsion EM-1 of the Present Invention] Seven types of solutions shown below
(Solution A contains seed emulsion T-2 subjected to low pAg ripening)
Was used to prepare a tabular emulsion EM-1 of the present invention.

【００８９】 (溶液Ａ) オセインゼラチン 67.0ｇ 蒸留水 3176.0ml HO(CH2CH2O)m〔CH(CH3)CH2O〕19.8(CH2CH2O)nH (m＋n＝9.77) の10重量%メタノール溶液 2.50ml 種乳剤(Ｔ−２) 98.51ｇ 蒸留水で3500mlに仕上げる (溶液Ｂ) 0.5Ｎ硝酸銀水溶液 948ml (溶液Ｃ) 臭化カリウム 52.88ｇ オセインゼラチン 35.55ｇ 蒸留水で948mlに仕上げる (溶液Ｄ) 3.5Ｎ硝酸銀水溶液 4471ml (溶液Ｅ) 臭化カリウム 1862.2ｇ オセインゼラチン 200ｇ 蒸留水で4471mlに仕上げる (溶液Ｆ) ３重量％のゼラチンと、沃化銀粒子(平均粒径0.05μm)から成る 微粒子乳剤(*) 2465.5ｇ *調製法を以下に示す。(Solution A) 67.0 g of ossein gelatin distilled water 3176.0 ml HO (CH 2 CH 2 O) m [CH (CH 3 ) CH 2 O] 19.8 (CH 2 CH 2 O) n H ( m + n = 9.77) 10% by weight methanol solution 2.50 ml Seed emulsion (T-2) 98.51 g Make up to 3500 ml with distilled water (Solution B) 0.5N silver nitrate aqueous solution 948 ml (Solution C) Potassium bromide 52.88 g Ossein gelatin 35.55 g Distilled water (Solution D) 3.5N silver nitrate aqueous solution 4471 ml (solution E) potassium bromide 1862.2 g ossein gelatin 200 g finish to 4471 ml with distilled water (solution F) 3% by weight of gelatin and silver iodide particles (average particle size) Fine particle emulsion (*) having a diameter of 0.05 µm) (2465.5 g) * The preparation method is described below.

【００９０】0.06モルの沃化カリウムを含む6.0重量％
のゼラチン溶液5000mlに、7.06モルの硝酸銀と、7.06モ
ルの沃化カリウムを含む水溶液各々2000mlを、10分間か
けて添加した。微粒子形成中のpＨは硝酸を用いて2.0
に、温度は40℃に制御した。粒子形成後に、炭酸ナトリ
ウム水溶液を用いてpＨを6.0に調整した。仕上がり重量
は12.53kgであった。6.0% by weight containing 0.06 mol of potassium iodide
2,000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added to 5000 ml of the gelatin solution over 10 minutes. The pH during fine particle formation was 2.0
In addition, the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. The finished weight was 12.53 kg.

【００９１】(溶液Ｇ) 1.75Ｎ臭化カリウム水溶液 反応容器に溶液Ａを添加し、激しく撹拌しながら、溶液
Ｂ〜溶液Ｆを表１に示した組み合わせに従って同時混合
法により添加を行ない、種結晶を成長させ、コア／シェ
ル型ハロゲン化銀乳剤を調製した。(Solution G) 1.75N Aqueous potassium bromide solution Solution A was added to a reaction vessel, and while vigorously stirring, solutions B to F were added by the simultaneous mixing method according to the combination shown in Table 1, and the seed crystal was added. Was grown to prepare a core / shell type silver halide emulsion.

【００９２】ここで、(1)溶液Ｂ、溶液Ｃ及び溶液Ｆの
添加速度、(2)溶液Ｄ、溶液Ｅ及び溶液Ｆの添加速度、
(3)溶液Ｄ及び溶液Ｅの添加速度は、それぞれハロゲン
化銀粒子の臨界成長速度に見合ったように時間に対して
関数様に変化させ、成長している種結晶以外に小粒子の
発生及びオストワルド熟成により多分散化しないように
適切な添加速度にコントロールした。Here, (1) solution B, solution C and solution F addition rates, (2) solution D, solution E and solution F addition rates,
(3) The addition rates of the solution D and the solution E are changed in a function-wise manner with respect to time so as to correspond to the critical growth rate of the silver halide grains. An appropriate addition rate was controlled so as not to be polydispersed by Ostwald ripening.

【００９３】また、結晶成長の全域に渡って、反応容器
内の溶液温度を75℃、pAgを8.8にコントロールした。pA
gコントロールのために、必要に応じて溶液Ｇを添加し
た。The solution temperature in the reaction vessel was controlled at 75 ° C. and the pAg was controlled at 8.8 over the entire area of crystal growth. pA
Solution g was added as needed for g control.

【００９４】反応溶液の添加時間に対するその時点での
粒径、及び表面を形成するハロゲン化銀相の沃化銀含有
率を表１に示した。Table 1 shows the grain size at that time with respect to the addition time of the reaction solution, and the silver iodide content of the silver halide phase forming the surface.

【００９５】粒子成長後に、特願平3-41314号に記載の
方法に従い脱塩処理を施し、その後ゼラチンを加え再分
散し、40℃にてpＨを5.80、pAgを8.06に調整した。得ら
れた乳剤粒子の電子顕微鏡写真から、平均粒径1.23μ
m、平均アスペクト比2.0、粒径分布12.0％の平板粒子で
あることが確認された。After grain growth, desalting was carried out according to the method described in Japanese Patent Application No. 3-41314, and gelatin was added and redispersed. The pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C. From the electron micrograph of the obtained emulsion particles, the average particle size is 1.23μ.
m, the average aspect ratio was 2.0, and the particle size distribution was 12.0%.

【００９６】[0096]

【表１】 [Table 1]

【００９７】〔本発明乳剤ＥＭ−２の調製〕乳剤ＥＭ−
１の製造方法において、種乳剤Ｔ−１を使用し、結晶成
長のための溶液の添加開始から65分の時点で、2.0ｇの
水酸化カリウムを含む水溶液10mlを添加して反応系内の
乳剤のpＨ値を8.7に調整し、それ以外は乳剤ＥＭ−１と
同様の製造方法により、乳剤ＥＭ−２を調製した。結晶
成長のための反応溶液の添加終了時点では、乳剤のpＨ
値は5.8に下がっていた。[Preparation of Emulsion EM-2 of the Invention] Emulsion EM-
In the production method 1, the seed emulsion T-1 was used, and at 65 minutes after the start of the addition of the solution for crystal growth, 10 ml of an aqueous solution containing 2.0 g of potassium hydroxide was added to the emulsion in the reaction system. Was adjusted to 8.7, and emulsion EM-2 was prepared in the same manner as in preparation of emulsion EM-1. At the end of the addition of the reaction solution for crystal growth, the pH of the emulsion is
The value has dropped to 5.8.

【００９８】得られた乳剤粒子の走査型電子顕微鏡写真
から、平均粒径1.24μm、平均アスペクト比2.1、粒径分
布12.5％の平板粒子であることが確認された。From the scanning electron micrograph of the obtained emulsion grains, it was confirmed that the grains were tabular grains having an average particle size of 1.24 μm, an average aspect ratio of 2.1 and a particle size distribution of 12.5%.

【００９９】さらに、乳剤ＥＭ−１の製造方法におい
て、種乳剤Ｔ−１を使用し、結晶成長中のpAg値を11.0
にコントロールし、それ以外は乳剤ＥＭ−１と同様の製
造方法により、比較用乳剤ＥＭ−３を調製した。Further, in the method for producing the emulsion EM-1, the seed emulsion T-1 was used, and the pAg value during crystal growth was 11.0.
EM-3 was prepared in the same manner as in the preparation of emulsion EM-1.

【０１００】さらに、乳剤ＥＭ−２の製造方法におい
て、結晶成長中に水酸化カリウムの添加を行なわず、そ
れ以外は乳剤ＥＭ−２と同様の製造方法により、比較用
の乳剤ＥＭ−４を調製した。Further, in the method for producing emulsion EM-2, a comparative emulsion EM-4 was prepared by the same production method as emulsion EM-2 except that potassium hydroxide was not added during crystal growth. did.

【０１０１】さらに、種乳剤、種乳剤の低pAg熟成条
件、結晶成長中の高pＨ熟成の有無、結晶成長中の水酸
化カリウムの添加位置、結晶成長中のpAgコントロール
値等を変化させて、乳剤ＥＭ−５〜ＥＭ−９を調整し
た。Further, the seed emulsion, the low pAg ripening conditions of the seed emulsion, the presence / absence of high pH ripening during the crystal growth, the position of potassium hydroxide addition during the crystal growth, the pAg control value during the crystal growth, etc. were changed. Emulsions EM-5 to EM-9 were prepared.

【０１０２】双晶面間距離及び粒子厚さの決定あたっ
て、透過型電子顕微鏡は日本電子(株)製JEM-2000FXを用
い、加速電圧200KV、温度-120℃で観察した。In determining the distance between twin planes and the grain thickness, observation was performed with a transmission electron microscope using JEM-2000FX manufactured by JEOL Ltd. at an acceleration voltage of 200 KV and a temperature of -120 ° C.

【０１０３】乳剤ＥＭ−１〜ＥＭ−９の調製条件及び得
られた結果を表２にまとめた。Table 2 summarizes the conditions for preparing emulsions EM-1 to EM-9 and the results obtained.

【０１０４】[0104]

【表２】 [Table 2]

【０１０５】表中、KOH添加位置は〔KOHを添加した時点
の粒子の体積／結晶成長後の粒子の体積〕×100を表わ
す。ｙ／ｘは、[粒子厚さの変動係数(ｙ)／双晶面間距
離の変動係数(ｘ)]を示す。In the table, the KOH addition position represents [volume of particles at the time of adding KOH / volume of particles after crystal growth] × 100. y / x represents [variation coefficient of grain thickness (y) / variation coefficient of twin plane distance (x)].

【０１０６】表２からわかるように、結晶成長中のpAg
値を11.0以上の値でコントロールした乳剤は、粒径分布
が広がり、かつｙ／ｘ値が大きくなってしまう。このこ
とは、粒径分布の広がりとともに、粒子厚さのバラツキ
が大きくなっていることを示している。一方、結晶成長
中のpAg値を8.8にコントロールした乳剤は、粒径分布が
狭く、かつｙ／ｘ値も小さい粒径分布の広がりと粒子厚
さのバラツキが結晶成長時のpAg値に依存することは非
常に興味深い発見であった。As can be seen from Table 2, pAg during crystal growth
An emulsion whose value is controlled at a value of 11.0 or more has a wide particle size distribution and a large y / x value. This indicates that the dispersion of the particle thickness increases with the spread of the particle size distribution. On the other hand, in the emulsion in which the pAg value during crystal growth is controlled to 8.8, the grain size distribution is narrow and the y / x value is small. The spread of the grain size distribution and the variation in grain thickness depend on the pAg value during crystal growth. That was a very interesting discovery.

【０１０７】実施例２(ハロゲン化銀カラー写真感光材
料試料の作成) 乳剤ＥＭ−１〜ＥＭ−９に、金−硫黄増感を最適に施
し、これらの乳剤を用いてトリセチルセルロースフィル
ム支持体上に下記に示すような組成の各層を順次支持体
側から形成して、本発明のハロゲン化銀カラー写真感光
材料を作成した。Example 2 (Preparation of silver halide color photographic material sample) Emulsions EM-1 to EM-9 were optimally subjected to gold-sulfur sensitization, and these emulsions were used to prepare a tricetyl cellulose film support. Each layer having the following composition was formed in this order from the support side to prepare a silver halide color photographic light-sensitive material of the present invention.

【０１０８】以下の全ての記載において、ハロゲン化銀
写真感光材料中の添加量は、特に記載のない限り1ｍ2当
たりのグラム数を示す。また、ハロゲン化銀及びコロイ
ド銀は、銀に換算して示し、増感色素は、ハロゲン化銀
1モル当たりのモル数で示した。In all the following descriptions, the amount of addition in the silver halide photographic light-sensitive material indicates the number of grams per 1 m 2 unless otherwise specified. Further, silver halide and colloidal silver are shown in terms of silver, and the sensitizing dye is silver halide.
It was shown in moles per mole.

【０１０９】本発明のハロゲン化銀カラー写真感光材料
試料101(本発明の乳剤ＥＭ−１を使用)の構成は以下の
通りである。The constitution of the silver halide color photographic light-sensitive material sample 101 of the present invention (using the emulsion EM-1 of the present invention) is as follows.

【０１１０】 試料101 第１層：ハレーション防止層 黒色コロイド銀 0.16 紫外線吸収剤(ＵＶ-１) 0.20 高沸点溶媒(ＯＩＬ-１) 0.16 ゼラチン 1.60 第２層：中間層 化合物(ＳＣ-１) 0.14 高沸点溶媒(ＯＩＬ-２) 0.17 ゼラチン 0.80 第３層：低感度赤感性層 沃臭化銀乳剤Ａ 0.15 沃臭化銀乳剤Ｂ 0.35 増感色素(ＳＤ-１) 2.0×10-4 増感色素(ＳＤ-２) 1.4×10-4 増感色素(ＳＤ-３) 1.4×10-5 増感色素(ＳＤ-４) 0.7×10-4 シアンカプラー(Ｃ-１) 0.53 カラードシアンカプラー(ＣＣ-１) 0.04 ＤＩＲ化合物(Ｄ-１) 0.025 高沸点溶媒(ＯＩＬ-３) 0.48 ゼラチン 1.09 第４層：中感度赤感性層 沃臭化銀乳剤Ｂ 0.30 沃臭化銀乳剤Ｃ 0.34 増感色素(ＳＤ-１) 1.7×10-4 増感色素(ＳＤ-２) 0.86×10-4 増感色素(ＳＤ-３) 1.15×10-5 増感色素(ＳＤ-４) 0.86×10-4 シアンカプラー(Ｃ-１) 0.33 カラードシアンカプラー(ＣＣ-１) 0.013 ＤＩＲ化合物(Ｄ-１) 0.02 高沸点溶媒(ＯＩＬ-１) 0.16 ゼラチン 0.79 第５層：高感度赤感性層 乳剤ＥＭ−１ 0.95 増感色素(ＳＤ-１) 1.0×10-4 増感色素(ＳＤ-２) 1.0×10-4 増感色素(ＳＤ-３) 1.2×10-5 シアンカプラー(Ｃ-２) 0.14 カラードシアンカプラー(ＣＣ-１) 0.016 高沸点溶媒(ＯＩＬ-１) 0.16 ゼラチン 0.79 第６層：中間層 化合物(ＳＣ-１) 0.09 高沸点溶媒(ＯＩＬ-２) 0.11 ゼラチン 0.80 第７層：低感度緑感性層 沃臭化銀乳剤Ａ 0.12 沃臭化銀乳剤Ｂ 0.38 増感色素（ＳＤ-４） 4.6×10-5 増感色素（ＳＤ-５） 4.1×10-4 マゼンタカプラー(Ｍ-１) 0.14 マゼンタカプラー(Ｍ-２) 0.14 カラードマゼンタカプラー(ＣＭ-１) 0.06 高沸点溶媒(ＯＩＬ-４) 0.34 ゼラチン 0.70 第８層：中間層 ゼラチン 0.41 第９層：中感度緑感性層 沃臭化銀乳剤Ｂ 0.30 沃臭化銀乳剤Ｃ 0.34 増感色素（ＳＤ-６） 1.2×10-4 増感色素（ＳＤ-７） 1.2×10-4 増感色素（ＳＤ-８） 1.2×10-4 マゼンタカプラー(Ｍ-１) 0.04 マゼンタカプラー(Ｍ-２) 0.04 カラードマゼンタカプラー(ＣＭ-１) 0.017 ＤＩＲ化合物(Ｄ-２) 0.025 ＤＩＲ化合物(Ｄ-３) 0.002 高沸点溶媒(ＯＩＬ-４) 0.12 ゼラチン 0.50 第10層：高感度緑感性層 沃臭化銀乳剤Ｄ 0.95 増感色素（ＳＤ-６） 7.1×10-5 増感色素（ＳＤ-７） 7.1×10-5 増感色素（ＳＤ-８） 7.1×10-5 マゼンタカプラー(Ｍ-１) 0.09 カラードマゼンタカプラー(ＣＭ-１) 0.011 高沸点溶媒(ＯＩＬ-４) 0.11 ゼラチン 0.79 第11層：イエローフィルター層 黄色コロイド銀 0.08 化合物(ＳＣ-１) 0.15 高沸点溶媒(ＯＩＬ-２) 0.19 ゼラチン 1.10 第12層：低感度青感性層 沃臭化銀乳剤Ａ 0.12 沃臭化銀乳剤Ｂ 0.24 沃臭化銀乳剤Ｃ 0.12 増感色素（ＳＤ-９） 6.3×10-5 増感色素（ＳＤ-10） 1.0×10-5 イエローカプラー(Ｙ-１) 0.50 イエローカプラー(Ｙ-２) 0.50 ＤＩＲ化合物(Ｄ-４) 0.04 ＤＩＲ化合物(Ｄ-５) 0.02 高沸点溶媒(ＯＩＬ-２) 0.42 ゼラチン 1.40 第13層：高感度青感性層 沃臭化銀乳剤Ｃ 0.15 沃臭化銀乳剤Ｅ 0.80 増感色素(ＳＤ-９) 8.0×10-5 増感色素(ＳＤ-11) 3.1×10-5 イエローカプラー(Ｙ-１) 0.12 高沸点溶媒(ＯＩＬ-２) 0.05 ゼラチン 0.79 第14層：第１保護層 沃臭化銀乳剤(平均粒径0.08μm、沃化銀含有率1.0モル％) 0.40 紫外線吸収剤(ＵＶ-１) 0.065 高沸点溶媒(ＯＩＬ-１) 0.07 高沸点溶媒(ＯＩＬ-３) 0.07 ゼラチン 0.65 第15層：第２保護層 アルカリ可溶性マット剤(平均粒径２μm) 0.15 ポリメチルメタクリレート(平均粒径３μm) 0.04 滑り剤(ＷＡＸ-１) 0.04 ゼラチン 0.55 尚上記組成物の他に、塗布助剤Ｓｕ−１、分散助剤Ｓｕ
−２、粘度調整剤、硬膜剤Ｈ−１、Ｈ−２、安定剤ＳＴ
−１、かぶり防止剤ＡＦ−１、平均分子量：10,000及び
平均分子量：1,100,000の２種のＡＦ−２、及び防腐剤
ＤＩ−１を添加した。Sample 101 First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound (SC-1) 0.14 High Boiling point solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: Low-sensitivity red-sensitive layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.35 Sensitizing dye (SD-1) 2.0 × 10 -4 Sensitizing dye ( SD-2) 1.4 × 10 -4 sensitizing dye (SD-3) 1.4 × 10 -5 sensitizing dye (SD-4) 0.7 × 10 -4 cyan coupler (C-1) 0.53 colored cyan coupler (CC-1) ) 0.04 DIR compound (D-1) 0.025 High boiling solvent (OIL-3) 0.48 Gelatin 1.09 Fourth layer: Medium-speed red-sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD- 1) 1.7 × 10 -4 sensitizing dye (SD-2) 0.86 × 10 -4 sensitizing dye (SD-3) 1.15 × 10 -5 sensitizing dye (SD-4) 0.86 × 10 -4 cyan coupler (C -1) 0.33 colored cyan coupler (CC- 1) 0.013 DIR compound (D-1) 0.02 High boiling solvent (OIL-1) 0.16 Gelatin 0.79 Fifth layer: Highly sensitive red-sensitive layer Emulsion EM-1 0.95 Sensitizing dye (SD-1) 1.0 × 10 -4 increase Sensitizing dye (SD-2) 1.0 × 10 -4 Sensitizing dye (SD-3) 1.2 × 10 -5 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.016 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 Sixth layer: Intermediate layer Compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 Seventh layer: Low sensitivity green-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.38 Sensitizing dye (SD-4) 4.6 × 10 -5 Sensitizing dye (SD-5) 4.1 × 10 -4 Magenta coupler (M-1) 0.14 Magenta coupler (M-2) 0.14 Colored magenta coupler (CM-1) 0.06 High boiling point solvent (OIL-4) 0.34 Gelatin 0.70 8th layer: Intermediate layer Gelatin 0.41 9th layer: Medium sensitivity green-sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye SD-6) 1.2 × 10 -4 Sensitizing dye (SD-7) 1.2 × 10 -4 Sensitizing dye (SD-8) 1.2 × 10 -4 Magenta coupler (M-1) 0.04 Magenta coupler (M-2) 0.04 Colored magenta coupler (CM-1) 0.017 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling solvent (OIL-4) 0.12 Gelatin 0.50 10th layer: Highly sensitive green-sensitive layer Silver iodobromide Emulsion D 0.95 Sensitizing dye (SD-6) 7.1 × 10 -5 sensitizing dye (SD-7) 7.1 × 10 -5 sensitizing dye (SD-8) 7.1 × 10 -5 Magenta coupler (M-1) 0.09 Colored magenta coupler (CM-1) 0.011 High boiling solvent (OIL-4) 0.11 Gelatin 0.79 Layer 11: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling solvent (OIL-2) 0.19 Gelatin 1.10 12 layer: low sensitivity blue-sensitive layer silver iodobromide emulsion A 0.12 silver iodobromide emulsion B 0.24 silver iodobromide emulsion C 0.12 sensitizing dye (SD-9) 6.3 × 10 -5 sensitizing dye SD-10) 1.0 × 10 -5 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D-5) 0.02 High boiling solvent (OIL-2) 0.42 Gelatin 1.40 13th layer: High-sensitivity blue-sensitive layer Silver iodobromide emulsion C 0.15 Silver iodobromide emulsion E 0.80 Sensitizing dye (SD-9) 8.0 × 10 -5 Sensitizing dye (SD-11) 3.1 × 10 − 5 Yellow coupler (Y-1) 0.12 High boiling solvent (OIL-2) 0.05 Gelatin 0.79 14th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 Ultraviolet absorber (UV-1) 0.065 High boiling solvent (OIL-1) 0.07 High boiling solvent (OIL-3) 0.07 Gelatin 0.65 15th layer: 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethyl Methacrylate (average particle size: 3 μm) 0.04 Slip agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aid Su-1, dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, an antifoggant AF-1, two kinds of AF-2 having an average molecular weight of 10,000 and an average molecular weight of 1,100,000, and a preservative DI-1 were added.

【０１１１】上記試料に用いた乳剤は、下記のとおりで
ある。各乳剤は、金・硫黄増感を最適に施した。The emulsions used in the above samples are as follows. Each emulsion was optimally subjected to gold / sulfur sensitization.

【０１１２】[0112]

【表３】 [Table 3]

【０１１３】[0113]

【化１】 Embedded image

【０１１４】[0114]

【化２】 Embedded image

【０１１５】[0115]

【化３】 Embedded image

【０１１６】[0116]

【化４】 Embedded image

【０１１７】[0117]

【化５】 Embedded image

【０１１８】[0118]

【化６】 Embedded image

【０１１９】[0119]

【化７】 Embedded image

【０１２０】[0120]

【化８】 Embedded image

【０１２１】[0121]

【化９】 Embedded image

【０１２２】[0122]

【化１０】 Embedded image

【０１２３】[0123]

【化１１】 Embedded image

【０１２４】乳剤ＥＭ−２〜ＥＭ−９についても、表４
に示すとおり、試料101の乳剤ＥＭ−１に変えてこれら
の各乳剤を用いる事により、同様にハロゲン化銀カラー
写真感光材料試料102〜109を作成した。Table 4 also shows emulsions EM-2 to EM-9.
As shown in Table 1, silver halide color photographic light-sensitive material samples 102 to 109 were prepared in the same manner by using each of these emulsions instead of the emulsion EM-1 of the sample 101.

【０１２５】[0125]

【表４】 [Table 4]

【０１２６】得られた各試料について、通常のウェッジ
露光を与え、下記の処理工程に従って現像処理を行っ
た。Each of the obtained samples was subjected to ordinary wedge exposure, and developed according to the following processing steps.

【０１２７】 処理工程 １．発色現像 ３分15秒 38.0±0.1℃ ２．漂 白 ６分30秒 38.0±3.0℃ ３．水 洗 ３分15秒 24〜41℃ ４．定 着 ６分30秒 38.0±3.0℃ ５．水 洗 ３分15秒 24〜41℃ ６．安 定 ３分15秒 38.0±3.0℃ ７．乾 燥 50℃以下 各処理工程において使用した処理液組成は下記の通りで
ある。Processing Steps 1. Color development 3 minutes 15 seconds 38.0 ± 0.1 ℃ 2. Bleaching 6 minutes 30 seconds 38.0 ± 3.0 ℃ 3. Rinse 3 minutes and 15 seconds 24 to 41 ° C 4. 6 minutes and 30 seconds 38.0 ± 3.0 ℃ 5. Rinse 3 minutes and 15 seconds 24 to 41 ° C 6. Stability 3 minutes 15 seconds 38.0 ± 3.0 ℃ 7. Drying 50 ° C or less The composition of the processing solution used in each processing step is as follows.

【０１２８】 〈発色現像液〉 4-アミノ-3-メチル-N-エチル-N-(β-ヒドロキシエチル) アニリン・硫酸塩 4.75ｇ 無水亜硫酸ナトリウム 4.25ｇ ヒドロキシルアミン・1/2硫酸塩 2.0ｇ 無水炭酸カリウム 37.5ｇ 臭化ナトリウム 1.3ｇ ニトリロ三酢酸・三ナトリウム塩(一水塩) 2.5ｇ 水酸化カリウム 1.0ｇ 水を加えて１リットルとし、pＨ＝10.1に調整する。<Color developing solution> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid / trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter, and adjust the pH to 10.1.

【０１２９】 〈漂白液〉 エチレンジアミン四酢酸鉄アンモニウム塩 100.0ｇ エチレンジアミン四酢酸二アンモニウム塩 10.0ｇ 臭化アンモニウム 150.0ｇ 氷酢酸 10.0ｇ 水を加えて１リットルとし、アンモニア水を用いてpＨ＝6.0に調整する。<Bleaching solution> Iron ammonium ethylenediaminetetraacetate 100.0 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter, and the pH was adjusted to 6.0 using aqueous ammonia. I do.

【０１３０】 〈定着液〉 チオ硫酸アンモニウム 175.0ｇ 無水亜硫酸ナトリウム 8.5ｇ メタ亜硫酸ナトリウム 2.3ｇ 水を加えて１リットルとし、酢酸を用いてpＨ＝6.0に調整する。<Fixing Solution> 175.0 g of ammonium thiosulfate 8.5 g of anhydrous sodium sulfite 2.3 g of sodium metasulfite 2.3 g of water was added to make 1 liter, and the pH was adjusted to 6.0 using acetic acid.

【０１３１】 〈安定液〉 ホルマリン(37％水溶液) 1.5ml コニダックス(コニカ〔株〕製) 7.5ml 水を加えて１リットルとする。<Stable liquid> Formalin (37% aqueous solution) 1.5 ml Konidax (manufactured by Konica Corporation) 7.5 ml Water was added to make up to 1 liter.

【０１３２】得られた各試料について、赤色光(Ｒ)を用
いてセンシトメトリー用ウエッジ露光(1/200")を施し、
相対感度、及び潜像保存性の評価を行なった。Each of the obtained samples was subjected to wedge exposure for sensitometry (1/200 ") using red light (R).
The relative sensitivity and the storage stability of the latent image were evaluated.

【０１３３】その結果を以下表５に示す。The results are shown in Table 5 below.

【０１３４】即の相対感度は、露光後1分以内にカラー
現像処理を開始し、Ｄmin(最小濃度)＋0.15の濃度を与
える露光量の逆数の相対値として求め、試料101の感度
を100とする値で示した(100に対して、値が大きいほど
高感度であることを示す)。 潜像保存性は、露光後
に、50℃で相対湿度80％で7日間放置した後、カラー現
像処理を行い、試料101の即の相対感度を100とする値に
対して各試料の相対感度を求めた。The immediate relative sensitivity is determined as the reciprocal of the exposure amount that gives a density of Dmin (minimum density) +0.15 after the color development process is started within 1 minute after the exposure. (A value greater than 100 indicates higher sensitivity). Latent image storability is as follows. After exposure, the sample is left at 50 ° C. at a relative humidity of 80% for 7 days, and then subjected to color development processing. I asked.

【０１３５】[0135]

【表５】 [Table 5]

【０１３６】表５に示す結果から明らかなように、本発
明の乳剤を含む本発明の試料101、試料102及び試料107
〜109は、高感度で潜像保存性が改良されている。As is clear from the results shown in Table 5, Samples 101, 102 and 107 of the present invention containing the emulsion of the present invention.
Nos. To 109 have high sensitivity and improved latent image storability.

【０１３７】これらの中でも、本発明のベストの組み合
わせを満たす乳剤ＥＭ−９を用いた試料109が特に優れ
ている。Among these, the sample 109 using the emulsion EM-9 satisfying the best combination of the present invention is particularly excellent.

【０１３８】表５にみられるように、本発明における粒
径分布、及びｙ／ｘ効果は、即の感度に現れている。As shown in Table 5, the particle size distribution and the y / x effect in the present invention are immediately apparent.

【０１３９】一方、粒子内部の還元増感の効果は、潜像
保存後の感度に現れていることがわかる。上述のごと
く、本発明は、感度、潜像保存性に優れるハロゲン化銀
写真乳剤及びハロゲン化銀カラー写真感光材料を得るこ
とができる。On the other hand, it can be seen that the effect of reduction sensitization inside the grains appears in the sensitivity after storage of the latent image. As described above, the present invention can provide a silver halide photographic emulsion and a silver halide color photographic light-sensitive material excellent in sensitivity and storage stability of a latent image.

【０１４０】[0140]

【発明の効果】本発明によるハロゲン化銀カラー写真感
光材料は、高感度で、かつ潜像保存性(露光後に、高
温、高湿度下で長時間保存された後の感度の安定性)に
優れた効果を有する。The silver halide color photographic light-sensitive material according to the present invention has high sensitivity and excellent latent image storability (stable stability after long-term storage at high temperature and high humidity after exposure). Has the effect.

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 支持体上に少なくとも１層のハロゲン化
銀乳剤層を有するハロゲン化銀カラー写真感光材料にお
いて、該乳剤層の少なくともいずれか１層のハロゲン化
銀乳剤層に含まれるハロゲン化銀粒子の全投影面積の50
％以上が、主平面に平行な双晶面を偶数枚有するアスペ
クト比５未満の平板状ハロゲン化銀粒子からなり、該粒
子が以下の(Ａ)〜(Ｃ)の要件を満たすことを特徴とする
平板状ハロゲン化銀粒子を含有するハロゲン化銀カラー
写真感光材料。(Ａ)粒径の変動係数が20％以下であり、
(Ｂ)主平面に平行な双晶面間距離の変動係数(ｘ)と、粒
子の厚さの変動係数(ｙ)との間に0.7≦ｙ/ｘ≦2.0の関
係を有し、(Ｃ)粒子内部に還元増感されている。1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide contained in at least one of the emulsion layers is a silver halide emulsion layer. 50 of the total projected area of the particle
% Or more are tabular silver halide grains having an even number of twin planes parallel to the main plane and having an aspect ratio of less than 5, and the grains satisfy the following requirements (A) to (C). Silver halide color photographic material containing tabular silver halide grains. (A) the coefficient of variation of the particle size is 20% or less,
(B) has a relationship of 0.7 ≦ y / x ≦ 2.0 between the variation coefficient (x) of the twin plane distance parallel to the main plane and the variation coefficient (y) of the grain thickness, and (C) ) Reduction sensitization inside the grains.
JP33205793A 1993-12-27 1993-12-27 Silver halide color photographic materials Expired - Fee Related JP3177809B2 (en)

Priority Applications (3)

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JP33205793A JP3177809B2 (en) 1993-12-27 1993-12-27 Silver halide color photographic materials
DE69421790T DE69421790D1 (en) 1993-12-27 1994-12-22 Silver halide color photographic light-sensitive material
EP94309680A EP0660176B1 (en) 1993-12-27 1994-12-22 Silver halide color photographic light-sensitive material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP33205793A JP3177809B2 (en) 1993-12-27 1993-12-27 Silver halide color photographic materials

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JPH07191425A JPH07191425A (en) 1995-07-28
JP3177809B2 true JP3177809B2 (en) 2001-06-18

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JP2649843B2 (en) * 1989-06-21 1997-09-03 富士写真フイルム株式会社 Method for producing silver halide emulsion and silver halide X-ray photographic material containing this emulsion
JPH0566510A (en) * 1991-09-06 1993-03-19 Konica Corp Silver halide photographic emulsion

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JPH07191425A (en) 1995-07-28
EP0660176A2 (en) 1995-06-28
DE69421790D1 (en) 1999-12-30
EP0660176B1 (en) 1999-11-24

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