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JPH0223330A - Production of silver halide emulsion - Google Patents

Production of silver halide emulsion

Info

Publication number
JPH0223330A
JPH0223330A JP17187688A JP17187688A JPH0223330A JP H0223330 A JPH0223330 A JP H0223330A JP 17187688 A JP17187688 A JP 17187688A JP 17187688 A JP17187688 A JP 17187688A JP H0223330 A JPH0223330 A JP H0223330A
Authority
JP
Japan
Prior art keywords
water
silver halide
halide emulsion
photographic
concentrate
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.)
Pending
Application number
JP17187688A
Other languages
Japanese (ja)
Inventor
Fumitaka Terai
文隆 寺井
Hiroyuki Yamagami
博之 山上
Nobuhiko Uchino
内野 暢彦
Masaki Okazaki
正樹 岡崎
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.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
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 Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Priority to JP17187688A priority Critical patent/JPH0223330A/en
Publication of JPH0223330A publication Critical patent/JPH0223330A/en
Pending legal-status Critical Current

Links

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
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)

Abstract

PURPOSE:To prevent the generation of a lumpy or stripe like coating trouble by making a water-insoluble photographic additive together with an easily water-dispersible or an easily water-dissoluble photographic additive to a flake like concentrate, followed by dispersing it into water, and then, incorporating the obtd. dispersion in the silver halide emulsion. CONSTITUTION:The photographic additive which is substantially insoluble in the water, together with one or more kinds of the easily water-dispersible or the easily water-dissoluble photographic additives are dissolved in an org. solvent, while heating, and then the solvent of an obtd. solution is evaporated to form the flake-like concentrate, and further, the concentrate is dispersed in the water, followed by incorporating the obtd. dispersion in the silver halide emulsion. The evaporating condition for making the flake-like concentrate lies in a temp. of less than the decomposition temp. of the photographic additive under a prescribed reduced pressure. Thus, as the org. solvent is not directly added to the emulsion, and the additional amount of a surfactant is small, the coating trouble caused by the generation of a precipitate etc., at the time of coating the emulsion is prevented.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明はハロゲン化銀乳剤の製造方法に関するものであ
る。特に実質的に水不溶性の写真用添加剤の結晶状態を
変えることにより、水性分散体としてハロゲン化銀乳剤
に添加する方法に関するものである。
DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a silver halide emulsion. In particular, it relates to a method of adding a substantially water-insoluble photographic additive to a silver halide emulsion as an aqueous dispersion by changing its crystalline state.

(従来の技術〕 従来ハロゲン化銀写真乳剤に種々の水不溶性写真用添加
剤を添加する場合、有機溶媒に溶解した水不溶性の写真
用添加剤のRf&を水又はアニオン界面活性剤を含有す
る水溶液又は水性バインダを含有する水溶液又は親水性
コロイド溶液中に添加し、再結晶化し、分散されやすい
結晶状態にして分散し、咳分散液をハロゲン化銀乳剤に
添加する方法が用いられていた。
(Prior Art) Conventionally, when various water-insoluble photographic additives are added to silver halide photographic emulsions, Rf& of the water-insoluble photographic additives dissolved in an organic solvent is mixed with water or an aqueous solution containing an anionic surfactant. Alternatively, a method has been used in which the cough dispersion is added to an aqueous solution or a hydrophilic colloid solution containing an aqueous binder, recrystallized, and dispersed in an easily dispersed crystalline state, and then the cough dispersion is added to a silver halide emulsion.

その際分11を作るのに機械的に分散する方法を用いた
ものとして、例えば米国特許第3,788.857号明
細書、特開昭50−11419号公報、米甲特許第3.
660.101号明細書、特公昭49−46416号公
報があった。
Examples of methods using a mechanical dispersion method to make the portion 11 include, for example, U.S. Pat.
660.101 and Japanese Patent Publication No. 49-46416.

又前記同様に再結晶化させた後、有機溶媒を除去して水
中での分散液を形成させる方法を用いたものとして、特
開昭49−128725号明細書があった。
Furthermore, JP-A-49-128725 discloses a method in which a dispersion in water is formed by recrystallizing in the same manner as described above and then removing the organic solvent.

更に又、前記とは全く異なり、実質的に有機溶媒および
/又は界面活性剤が存在しない条件下でpH6〜8.6
0〜80°Cの条件下で水中にて実質的に水不溶性の写
真用添加剤を機械的に分散し、得られた分散物をハロゲ
ン化銀乳剤に添加する方法がある(特公昭61−452
17号公報)。
Furthermore, completely different from the above, pH 6 to 8.6 under conditions substantially free of organic solvent and/or surfactant.
There is a method in which a substantially water-insoluble photographic additive is mechanically dispersed in water at a temperature of 0 to 80°C, and the resulting dispersion is added to a silver halide emulsion (Japanese Patent Publication No. 1983-1999). 452
Publication No. 17).

〔発明が解決しようとする課題〕[Problem to be solved by the invention]

しかしながら、種々の水不溶性写真用添加物を有機溶媒
に溶解する場合、特に有機溶媒に対して難溶性の写真用
添加剤を使用する場合は、多量の有機溶媒をハロゲン化
銀乳剤に添加することになり、その際凝集物が生成する
という問題やハロゲン化銀乳剤を塗布するときに塊り状
や筋状の塗布故障が生じるなどの欠点があった。
However, when dissolving various water-insoluble photographic additives in organic solvents, especially when using photographic additives that are poorly soluble in organic solvents, it is necessary to add a large amount of organic solvent to the silver halide emulsion. In this case, there were problems such as the formation of aggregates and the occurrence of lump-like or streak-like coating failures when coating the silver halide emulsion.

また、前記同様に再結晶化させた後、有機溶媒を除去し
て、水中での分散液を形成させる方法は、有機溶媒を除
去する工程として蒸発あるいは膜分離を用いるので、蒸
発処理後の溶液の濃度のバラツキ・及び組成物の分解が
起き、又膜分離法を用いる場合は膜分離後の溶液濃度の
バラツキが起きるといった問題点があり、かつ製造工程
も複雑になる欠点があった。
In addition, the method of recrystallizing in the same way as above and then removing the organic solvent to form a dispersion in water uses evaporation or membrane separation as the process for removing the organic solvent, so the solution after evaporation treatment is There are problems such as variations in the concentration of the solution and decomposition of the composition, and when a membrane separation method is used, variations in the concentration of the solution after membrane separation occur, and the manufacturing process is also complicated.

また、特公昭61−45217号公報に示される方法は
優れた方法であるが、写真用添加剤によっては分散され
ないで、粗大結晶(5〜30μ)のま−残るものもある
。すなわち、何らかの方法で結晶状態を変えないと機械
的に分散出来ない写真用添加剤があることが判った。
Although the method disclosed in Japanese Patent Publication No. 61-45217 is an excellent method, some photographic additives are not dispersed and remain as coarse crystals (5 to 30 .mu.m). In other words, it has been found that there are some photographic additives that cannot be mechanically dispersed unless the crystalline state is changed in some way.

本出願人は上記問題点を解消し、塊状や筋状の塗布故障
を生じることなく、添加液の濃度のバラツキや組成の分
解もなく、水不溶性写真用添加剤を容易に分散し、乳剤
に添加出来るハロゲン化銀乳剤の製造方法として、先に
、実質的に水不溶性の写真用添加剤を、有機溶媒と、親
水基として40i−−O503なる基を有する界面活性
剤と、そして必要に応じて少量の塩基又は塩基及び酸を
加えた混合液に加熱溶解し、その溶解液を水中に滴下再
結晶させた後、分散機で分散させ、該分散液をハロゲン
化乳剤に添加することを特徴とするハロゲン化銀乳剤の
製造方法を提案した。
The present applicant has solved the above problems, and can easily disperse water-insoluble photographic additives into emulsions without causing coating failures such as lumps or streaks, without variations in the concentration of the additive solution, and without decomposition of the composition. As a method for producing a silver halide emulsion that can be added, first, a substantially water-insoluble photographic additive is mixed with an organic solvent, a surfactant having a 40i--O503 group as a hydrophilic group, and, if necessary, It is characterized by heating and dissolving in a small amount of a base or a mixture of a base and an acid, dropping the solution into water to recrystallize it, dispersing it with a dispersion machine, and adding the dispersion to the halogenated emulsion. We proposed a method for producing silver halide emulsions.

上記の方法は優れた方法であるが、ハロゲン化銀乳剤に
添加する溶解液は有機溶剤を含んでおり、塗布の際に筋
状又は塊状の塗布故障の原因となることがあった。これ
を更に改善するため有機溶媒を含まないことが望まれて
いた。
Although the above-mentioned method is an excellent method, the solution added to the silver halide emulsion contains an organic solvent, which may cause streak-like or lump-like coating failures during coating. In order to further improve this problem, it has been desired to not include an organic solvent.

本発明の目的は上記問題点を解消し、塊状や筋状の塗布
故障を生じることなく、添加液の濃度のバラツキや分解
もなく、水不溶性写真用添加剤を有機溶媒を含むことな
く添加出来るハロゲン化銀乳剤の製造方法を提供するも
のである。
The purpose of the present invention is to solve the above-mentioned problems, and to make it possible to add water-insoluble photographic additives without containing organic solvents, without causing coating failures such as lumps or streaks, without variations in concentration or decomposition of the additive solution. A method for producing a silver halide emulsion is provided.

(課題を解決するための手段及び作用]本発明の上記目
的は、実質的に水不溶性の写真用添加剤を11以上の水
晶分散性又は水易溶解性の写真用添加剤と共に有機溶媒
で加熱溶解し、完溶後該溶解液の溶媒を蒸発させてフレ
ーク状濃縮物にした後、該フレーク状濃縮物を水中に分
散し、該分散液をハロゲン化銀乳剤に添加することを特
徴とするハロゲン化銀乳剤の製造方法によって達成され
る。
(Means and effects for solving the problems) The above object of the present invention is to heat a substantially water-insoluble photographic additive together with 11 or more crystal-dispersible or easily water-soluble photographic additives in an organic solvent. It is characterized by dissolving, and after complete dissolution, evaporating the solvent of the solution to form a flake-like concentrate, dispersing the flake-like concentrate in water, and adding the dispersion to a silver halide emulsion. This is achieved by a method for producing a silver halide emulsion.

本発明について更に詳しく説明すると、本発明に用いる
ことのできる実質的に水不溶性の写真用添加剤としては
、固形の添加剤であり、具体的には、次のようなものが
ある。分光増感色素、カブリ防止剤、カラーカプラー、
染料、増感剤、硬膜剤、紫外線吸収剤、帯電防止剤、増
白剤、減感剤、現像剤、褪色防止剤、媒染剤などである
To explain the present invention in more detail, the substantially water-insoluble photographic additives that can be used in the present invention are solid additives, and specifically include the following. Spectral sensitizing dyes, antifoggants, color couplers,
These include dyes, sensitizers, hardeners, ultraviolet absorbers, antistatic agents, brighteners, desensitizers, developers, anti-fading agents, and mordants.

これらの添加剤については、RESEARCHDTSC
LOSURE vol、176 RD−17643pa
ge22〜31(December1978)に記載さ
れている。
For these additives, RESEARCHDTSC
LOSURE vol, 176 RD-17643pa
ge22-31 (December 1978).

例えば、分光増悪剤としては、シアニン色素、メロシア
ニン色素、ヘミシアニン色素、ローダシアニン色素、オ
キソノール色素、ヘミオキソノール色素等のメチン色素
及びスチリル色素を挙げることができる。これらの色素
でもアニオン系色素、例えば置換基としてスルホ基また
はスルホアルキル基を1個、好ましくは2個以上有した
色素などが有効である。
For example, examples of the spectral aggravating agent include methine dyes and styryl dyes such as cyanine dyes, merocyanine dyes, hemicyanine dyes, rhodacyanine dyes, oxonol dyes, and hemioxonol dyes. Among these dyes, anionic dyes such as dyes having one, preferably two or more sulfo groups or sulfoalkyl groups as substituents are effective.

分光増感剤としては、前記の刊行物以外に次のようなも
のに記載されたものが用いられる。ドイツ特許9290
80号、米国特許2493748号、同2503776
号、同2519001号、同2912329号、同36
56959号、同3672897号、同3694217
号、同4025349号、同4046572号、同26
88545号、同2977229号、同3397060
号、同3522052号、同3527641号、同36
17293号、同3628964号、同3666480
号、同3672898号、同3679428号、同37
03377号、同3814609号、同3837862
号、同4026707号、英国特許1242588号、
同1344281号、同1507803号、特公昭44
−14030号、同52−24844号、同43−49
36号、同53−12375号、特開昭52−1106
18号、同52−109925号、同50−80827
号各公報に記載されている。
As the spectral sensitizer, in addition to the above-mentioned publications, those described in the following publications can be used. German patent 9290
No. 80, U.S. Patent No. 2493748, U.S. Patent No. 2503776
No. 2519001, No. 2912329, No. 36
No. 56959, No. 3672897, No. 3694217
No. 4025349, No. 4046572, No. 26
No. 88545, No. 2977229, No. 3397060
No. 3522052, No. 3527641, No. 36
No. 17293, No. 3628964, No. 3666480
No. 3672898, No. 3679428, No. 37
No. 03377, No. 3814609, No. 3837862
No. 4026707, British Patent No. 1242588,
No. 1344281, No. 1507803, Special Publication No. 1977
-14030, 52-24844, 43-49
No. 36, No. 53-12375, JP-A No. 52-1106
No. 18, No. 52-109925, No. 50-80827
It is stated in each publication.

分光増感剤以外のものとしては、次の様なものを挙げる
ことができる。すなわち、ベンゾトリアゾール化合物、
4−チアゾリドン化合物、ベンゾフェノン化合物、桂皮
酸エステル化合物、ブタジェン化合物、ペンヅオキサゾ
ール化合物、カチオン性ポリマー、クロム塩、アルデヒ
ド類、N−メチロール化合物、ジオキサン誘導体、活性
ビニル化合物、活性ハロゲン化合物、ムコハロゲン酸類
、ニトロインダゾール類、トリアゾール類、ベンゾトリ
アゾール類、ベンズイミダゾール類、メルカプトチアゾ
ール類、メルカプトベンゾチアゾール類、テトラアザイ
ンデン類、5−ピラゾロンカプラーピラゾロンベンツイ
ミダゾールカプラー、アシルアセトアミドカプラー、ナ
フトールカプラー、フェノールカプラーなどを挙げるこ
とができる。
Examples of substances other than spectral sensitizers include the following. That is, benzotriazole compounds,
4-thiazolidone compounds, benzophenone compounds, cinnamic acid ester compounds, butadiene compounds, penduoxazole compounds, cationic polymers, chromium salts, aldehydes, N-methylol compounds, dioxane derivatives, active vinyl compounds, active halogen compounds, mucohalogen acids , nitroindazoles, triazoles, benzotriazoles, benzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, tetraazaindenes, 5-pyrazolone couplers, pyrazolone benzimidazole couplers, acylacetamide couplers, naphthol couplers, phenol couplers, etc. can be mentioned.

ハロゲン化銀乳剤に添加される実質的に水不溶性の写真
用添加剤の量は、添加剤の種類やハロゲン化銀景などに
よって一義的にのべることはできないが、従来の方法に
て添加される量とほぼ同等量用いることができる。
The amount of the substantially water-insoluble photographic additive added to the silver halide emulsion cannot be determined unambiguously depending on the type of additive and the silver halide pattern, but it can be added by conventional methods. Approximately the same amount can be used.

しかしながら、本発明は水不溶性の写真用添加剤がシア
ニン色素類に属する写真用分光増感色素の場合効果的で
ある。
However, the present invention is effective when the water-insoluble photographic additive is a photographic spectral sensitizing dye belonging to cyanine dyes.

その例として、 (以後これを色素Aという) が挙げられる。As an example, (Hereafter, this will be referred to as dye A) can be mentioned.

本発明において水晶分散性又は水易溶解性の写真用添加
剤とは、水中にて湿潤剤や分散剤を用いなくても容易に
機械的な攪拌により分散又は溶解が可能な写真用添加剤
で、 例えば 等が挙げられる。
In the present invention, a quartz crystal dispersible or easily water-soluble photographic additive is a photographic additive that can be easily dispersed or dissolved in water by mechanical stirring without using a wetting agent or dispersant. , for example.

本発明に用いられる有機溶媒としては、アルコール類に
属する有機溶媒が好ましい。脂肪族飽和アルコール、脂
肪族不飽和アルコール、脂環式アルコール、芳香族アル
コール、複素環アルコール等があるが、特に芳香族1級
アルコール又はハロゲン化アルコールが好ましい。
As the organic solvent used in the present invention, organic solvents belonging to alcohols are preferable. Examples include aliphatic saturated alcohols, aliphatic unsaturated alcohols, alicyclic alcohols, aromatic alcohols, heterocyclic alcohols, and aromatic primary alcohols or halogenated alcohols are particularly preferred.

例えばベンジルアルコール(CaHsC)ItOtl)
 、フッ化アルコールが挙げられる。
For example, benzyl alcohol (CaHsC)
, fluorinated alcohol.

本発明に用いられるハロゲン化銀乳剤には、ハロゲン化
銀として臭化銀、沃臭化銀、沃塩臭化銀、塩臭化銀、塩
化銀などのいずれを用いてもよい。
In the silver halide emulsion used in the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloride, etc. may be used as the silver halide.

ハロゲン化銀の粒子サイズとしては、特に問わないが3
μ以下が好ましい。これらのハロゲン化銀乳剤は、次の
文献に記載された方法によって容易に調製することがで
きる。P、GIafkides著Chimie  et
  Physique  Photographiqu
e  (Paul  Monte1社刊、1967年)
 、G、F、Duffin著Photograhic 
Emulsion ChevAiStry (The 
Focal Press刊、1966年) 、V、L、
Zelikman et at著Making and
 CoatingPhotographic Elll
ulsion(The Focal Press刊、1
964年)などに記載されている。
The grain size of silver halide is not particularly limited, but it is 3
It is preferably less than μ. These silver halide emulsions can be easily prepared by the method described in the following literature. Chimie et by P, GIafkides
Physique Photography
e (Paul Monte1, 1967)
, Photographic by G.F. Duffin
Emulsion ChevAiStry (The
Focal Press, 1966), V.L.
Making and by Zelikman et at
CoatingPhotographic Ell
ulsion (The Focal Press, 1
964), etc.

すなわち、酸性法、中性法、アンモニア法等のいずれで
もよ(、また可溶性銀塩と可溶性ハロゲン塩を反応させ
る形式としては片側混合法、同時混合法、それらの組合
せなどのいずれを用いてもよい。
In other words, any of the acidic method, neutral method, ammonia method, etc. may be used (and the method for reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc.). good.

粒子を恨イオン過剰の下において形成させる方法(いわ
ゆる逆混合法)を用いることもできる。
It is also possible to use a method in which particles are formed under an excess of negative ions (so-called back-mixing method).

同時混合法の一つの形式としてハロゲン化銀の生成され
る液相中のPAgを一定に保つ方法、すなわちいわゆる
コンドロールド・ダブルジェット法を用いることもでき
る。
As one type of simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

この方法によると、結晶形が規則的で粒子サイズが均一
に近いハロゲン化銀乳剤かえられる。
According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

別々に形成した2種以上のハロゲン化銀乳剤を混合して
用いてもよい。
Two or more types of silver halide emulsions formed separately may be mixed and used.

ハロゲン化銀粒子形成または物理熟成の過程において、
カドミウム塩、亜鉛塩、鉛塩、タリウム塩、イリジウム
塩またはその錯塩、ロジウム塩またはその錯塩、鉄塩ま
たは鉄錯塩などを共存させてもよい。
In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

本発明に用いられるハロゲン化銀乳剤には、その他種々
の添加剤を用いることができる。すなわち、硫黄増感剤
、還元増悪剤、貴金属増感剤などの増悪剤、安定剤、界
面活性剤、硬膜剤、増粘剤、染料、紫外線吸収剤、帯電
防止剤、増白剤、減感剤、現像剤、褪色防止剤、媒染剤
などを用いることができる。更に、カラーカプラーなど
のカプラーをオイル中に分散して用いることもできる。
Various other additives can be used in the silver halide emulsion used in the present invention. In other words, sulfur sensitizers, reduction aggravators, noble metal sensitizers and other sensitizers, stabilizers, surfactants, hardeners, thickeners, dyes, ultraviolet absorbers, antistatic agents, brighteners, and thinners. Sensitizers, developers, anti-fading agents, mordants, etc. can be used. Furthermore, a coupler such as a color coupler can also be used by dispersing it in oil.

これらの添加剤については、R[!5EARCHDIS
CLOSURE(RD−17643) 、vol、17
6 、 Page22〜31(Dec−ember 1
978) 、THE! THEORY OF TH[!
 PH0TOGRAPHICPROCESS (4th
 [!d、) T、LJames I(1977、M−
acmillan Publishing Co、 I
nc、)などに具体的に記載されている。
For these additives, R[! 5EARCHDIS
CLOSURE (RD-17643), vol, 17
6, Pages 22-31 (Dec-ember 1
978), THE! THEORY OF TH[!
PH0TOGRAPHIC PROCESS (4th
[! d,) T, LJames I (1977, M-
Acmillan Publishing Co, I
nc, ) etc.

本発明のハロゲン化銀乳剤に用いられるバインダーとし
ては、ゼラチンが好ましいが、ゼラチンの他にフタル化
ゼラチンなどの誘導体ゼラチン、アルブミン、寒天、ア
ラビアゴム、セルローズ誘導体、ポリ酢酸ビニル、ポリ
アクリルアミド、ポリビニルアルコールなどが用いられ
る。
The binder used in the silver halide emulsion of the present invention is preferably gelatin, but in addition to gelatin, derivative gelatin such as phthalated gelatin, albumin, agar, gum arabic, cellulose derivatives, polyvinyl acetate, polyacrylamide, polyvinyl alcohol etc. are used.

本発明におけるハロゲン化銀乳剤の製造方法としては、
先ず、タンク内に秤量した有機溶媒を入れ、実質的に水
不溶性の写真用添加剤を1種以上の水易分散性の写真用
添加剤と共に該有機溶媒に添加し、70〜90°Cにて
加熱溶解する。溶解タンクとしては撹拌翼は例えば攪拌
軸に4枚羽根を備えたタービン翼で、その直径とタンク
内径との比はl;5〜2:5程度で、タービン翼の直径
と、タンクの底部とタービン翼との間隙の比は2:1〜
1;1程度、タービン翼の直径とタンク内の静止液深さ
の比は1:1〜1;3程度に設定することが望ましい。
The method for producing the silver halide emulsion in the present invention includes:
First, a weighed amount of organic solvent is placed in a tank, a substantially water-insoluble photographic additive is added to the organic solvent along with one or more water-readily dispersible photographic additives, and the temperature is heated to 70-90°C. Heat and dissolve. For the melting tank, the stirring blade is, for example, a turbine blade with four blades on the stirring shaft, and the ratio of its diameter to the tank inner diameter is about 5 to 2:5, and the ratio between the diameter of the turbine blade and the bottom of the tank is The gap ratio between the turbine blade and the turbine blade is 2:1~
It is desirable to set the ratio between the diameter of the turbine blade and the depth of the static liquid in the tank to be about 1:1 to 1:3.

但しこの場合攪拌翼はタービン翼だけに限られず、パド
ル翼、プロペラ翼、デイシルバー翼等を用いてもよい。
However, in this case, the stirring blade is not limited to a turbine blade, and paddle blades, propeller blades, day silver blades, etc. may also be used.

尚少量調整の場合はマグネテインクスターラを使用する
ことが出来る。
For small quantity adjustment, a magnetic stirrer can be used.

この場合、有機溶媒に対して親水性基として−so、、
−osotなる基を有する界面活性剤を加えてもよい。
In this case, -so, as a hydrophilic group toward organic solvents,
A surfactant having a group -osot may also be added.

咳界面活性剤としては、陰イオン界面活性剤としてアル
キル硫酸塩、アルキルスルホン酸塩、アルキルアリール
スルホン酸塩、スルホコハク酸エステル塩等がある。
Examples of cough surfactants include anionic surfactants such as alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, and sulfosuccinate ester salts.

特に が好ましい。especially is preferred.

本発明において有機溶媒に、親水性基として一3OS、
−0502なる基を有する界面活性剤を添加混合する場
合、有機溶媒と界面活性剤の種類によっても異なるが、
両者を混合させた溶液で溶解する場合は、界面活性剤の
添加量は写真用添加剤の総量に対して5〜50重量%を
添加すると分散性向上効果は増大する。
In the present invention, in the organic solvent, -3OS, as a hydrophilic group,
When adding and mixing a surfactant having a -0502 group, although it varies depending on the type of organic solvent and surfactant,
When the two are dissolved in a mixed solution, the effect of improving dispersibility is increased by adding the surfactant in an amount of 5 to 50% by weight based on the total amount of photographic additives.

次に、前記のように完溶した後の該溶解液中の有機溶媒
を蒸発させてフレーク状i4縮物にするが、蒸発条件と
しては写真用添加剤の分解温度以下で適当な残圧条件で
蒸発を行わせることが好ましい。
Next, the organic solvent in the solution after complete dissolution as described above is evaporated to form a flaky i4 condensate.The evaporation conditions are below the decomposition temperature of the photographic additive and under an appropriate residual pressure. Preferably, the evaporation is carried out at .

フレーク状′a縮物中の残存溶媒は写真用添加剤総量に
対して1重量%以下とする。
The amount of residual solvent in the flaky condensate is 1% by weight or less based on the total amount of photographic additives.

得られたフレーク状結晶は水易分散性添加剤との共晶化
物となるため水中への分散性に優れたものとなる。
The obtained flake-like crystals become a eutectic product with the water-easily dispersible additive, and therefore have excellent dispersibility in water.

その様にして出来たフレーク状a縮物を水に添加し、4
0〜60°Cの加温条件下でpl+6.5〜7.5にI
N。
Add the flaky agglomerate thus obtained to water,
I at pl+6.5-7.5 under heating conditions of 0-60°C
N.

NaOHを用いて調整した後、高速攪拌機で分散すこの
場合用いる高速撹拌機としては第1図(a)(b)に示
すようにタンク1内に分散させる液2を入れ、攪拌翼3
としてデイシルバー翼を用いることが好ましい。
After adjusting with NaOH, dispersion is carried out using a high-speed stirrer.The high-speed stirrer used in this case is as shown in Fig. 1 (a) and (b).
It is preferable to use daysilver blades as the blade.

デイシルバー翼の直径とタンク内径との比は1:5〜2
:5程度、デイシルバー翼の直径と、タンク底部とデイ
シルバー翼との間隙との比2:l〜1:1程度、デイシ
ルバー翼の直径とタンク内静止液との比1:1〜1:3
程度が好ましい。
The ratio of the diameter of the Daysilver blade to the inner diameter of the tank is 1:5 to 2.
: About 5, the ratio of the diameter of the daysilver blade and the gap between the bottom of the tank and the daysilver blade is about 2:1 to 1:1, and the ratio of the diameter of the daysilver blade to the stationary liquid in the tank is 1:1 to 1. :3
degree is preferred.

該分散液はそのまま直接ハロゲン化銀乳剤に添加しても
良いし、−旦保護コロイドと混合した後溶液状態で添加
してしも、又ゲル状態にして添加しても十分な写真性能
を得ることが出来る。
The dispersion may be added directly to the silver halide emulsion as it is, or it may be mixed with a protective colloid and then added in the form of a solution, or it may be added in the form of a gel to obtain sufficient photographic performance. I can do it.

本発明の好ましい実施態様としては次のようである。Preferred embodiments of the present invention are as follows.

(1)特許請求の範囲第1項において、該実質的に水不
溶性の写真用添加剤が、シアニン色素類に属する写真用
分光増感色素であることを特徴とするハロゲン化銀乳剤
の製造方法。
(1) A method for producing a silver halide emulsion according to claim 1, characterized in that the substantially water-insoluble photographic additive is a photographic spectral sensitizing dye belonging to cyanine dyes. .

(2、特許請求の範囲第1項又は実施態様(])におい
て、−3Oa+−0303なる基を有する界面活性剤の
添加量が写真用添加剤の総量に対して5〜50重量%で
あることを特徴とするハロゲン化銀乳剤の製造方法。
(2. In Claim 1 or Embodiment (]), the amount of the surfactant having a -3Oa+-0303 group is 5 to 50% by weight based on the total amount of photographic additives. A method for producing a silver halide emulsion characterized by:

〔実 施 例〕〔Example〕

実施例−1 実質的に水不溶性の写真用添加剤として前記した色素A
 1 、59gを、水易分散性の写真用添加剤として前
記した色素88.12g、前記した色素C0,3gと共
に、有機溶媒としてフッ化アルコール100gに添加し
、80〜85°Cに加熱し、タービン翼で攪拌しながら
20分間溶解を行う。
Example-1 Dye A described above as a substantially water-insoluble photographic additive
1.59 g was added to 100 g of fluorinated alcohol as an organic solvent along with 88.12 g of the above-mentioned dye as a water easily dispersible photographic additive and 0.3 g of the above-mentioned dye C, and heated to 80-85 ° C. Melting is carried out for 20 minutes while stirring with a turbine blade.

完溶した後80″C,1〜2mHHの直空中で1時間溶
媒の蒸発を行い、フレーク状i1縮物を作る。この際フ
レーク状濃縮物の残留溶媒は写真用添加剤総量に対して
1重量%以下とする。得られたフレーク状結晶は水易分
散性添加剤と共晶化物となるため水中への分散性に優れ
たものとなる。
After complete dissolution, the solvent is evaporated in direct air at 80"C and 1 to 2 mHH for 1 hour to produce a flake-like condensate. At this time, the residual solvent in the flake-like concentrate is 1% of the total amount of photographic additives. % by weight or less.The resulting flaky crystals form a eutectic product with the water-easily dispersible additive, resulting in excellent dispersibility in water.

次にこのフレーク状濃縮物を水500m lに添加し、
1N、NaollでpHを7に調整し、温度50℃の条
件下で高速攪拌機として第1図に示すようなデイシルバ
ー翼を用い300Or、ρ、sで約2時間かけて分散を
行った。
This flaky concentrate was then added to 500 ml of water,
The pH was adjusted to 7 with 1N Naoll, and dispersion was carried out over a period of about 2 hours at a temperature of 50° C. using a Daysilver blade as shown in FIG. 1 as a high-speed stirrer at 300 Or, ρ, s.

比較例−1 実質的に水不溶性の写真用添加剤として前記した色素A
1.59gのみをフッ化アルコール16gに添加し、8
0〜85°Cに加熱し、タービン翼で攪拌しながら20
分間溶解を行う。
Comparative Example-1 Dye A described above as a substantially water-insoluble photographic additive
Add only 1.59g to 16g of fluorinated alcohol, 8
Heat to 0-85°C and stir with a turbine blade for 20 minutes.
Perform lysis for minutes.

完溶した後80″C,1〜2mmHgの真空中で1時間
溶媒の蒸発を行い、フレーク状濃縮物を作る。この際フ
レーク状濃縮物の残留溶媒は写真用添加剤に対して1重
量%以下とする。
After complete dissolution, the solvent is evaporated in a vacuum at 80"C and 1 to 2 mmHg for 1 hour to produce a flake concentrate. At this time, the residual solvent in the flake concentrate is 1% by weight based on the photographic additive. The following shall apply.

次にこのフレーク状濃縮物を水易分散性の写真用添加剤
として前記した色素B 8.12g、前記した色素C0
,3grと共に水500s+ 1.に添加し、実施例−
1と同条件で分散を行った。
Next, this flake-like concentrate was used as a water easily dispersible photographic additive.
, 500s+ water with 3gr 1. Example-
Dispersion was performed under the same conditions as 1.

実施例−1の分散物と比較例−1の分散物を400倍の
光学類V&鏡で観察したところ、実施例−1は1μ以下
の粒子に分散が完結していたが、比較例−1は粗大結晶
(10〜70μレベル)が顕微鏡視野の10′gを占め
ていた。
When the dispersion of Example-1 and the dispersion of Comparative Example-1 were observed with a 400x optical V&mirror, dispersion in Example-1 was completed to particles of 1 μ or less, but in Comparative Example-1 Coarse crystals (10-70μ level) occupied 10'g of the microscopic field of view.

本発明の方法は分散の方法として優れたものである。The method of the present invention is an excellent dispersion method.

〔発明の効果] 上記に示すように、本発明の製造方法はハロゲン化銀乳
剤には直接有機溶媒を加えることがなく、又界面活性剤
の添加量も少量であるので乳剤塗布時における析出物等
による塗布故障を生じることがない。又添加液の濃度の
バラツキや組成の分解もなく水不溶性写真用添加剤を有
機溶媒を含むことなくハロゲン化銀乳剤に添加出来る製
造方法を提供出来た。
[Effects of the Invention] As shown above, the production method of the present invention does not require adding an organic solvent directly to the silver halide emulsion, and the amount of surfactant added is small, so that no precipitates are formed during emulsion coating. There is no possibility of coating failure due to etc. Furthermore, it has been possible to provide a manufacturing method in which a water-insoluble photographic additive can be added to a silver halide emulsion without containing an organic solvent without causing variations in concentration or decomposition of the composition of the additive solution.

【図面の簡単な説明】[Brief explanation of the drawing]

第1図は本発明の分散液の製造に用いる高速攪拌機の設
置状態の側面図(a)及び高速撹拌機のデイシルバー翼
の斜視図(ハ)である。 1・・・タンク 2・・・分散させる液 3・・・デイシルバー翼 ・撹拌軸 31・ ・ディスク 第 図 32、33 ・羽根 (q)
FIG. 1 is a side view (a) of the installed state of a high-speed stirrer used for producing the dispersion of the present invention, and a perspective view (c) of the day silver blade of the high-speed stirrer. 1...Tank 2...Liquid to be dispersed 3...Daysilver blade/stirring shaft 31...Disc Fig. 32, 33 -Veil (q)

Claims (1)

【特許請求の範囲】[Claims] (1)実質的に水不溶性の写真用添加剤を、1種以上の
水晶分散性又は水易溶解性の写真用添加剤と共に有機溶
媒で加熱溶解し、完溶後該溶解液の有機溶媒を蒸発させ
てフレーク状濃縮物にした後、該フレーク状濃縮物を水
中に分散し、該分散液をハロゲン化銀乳剤に添加するこ
とを特徴とするハロゲン化銀乳剤の製造方法。
(1) A substantially water-insoluble photographic additive is heated and dissolved in an organic solvent together with one or more crystal dispersible or easily water-soluble photographic additives, and after complete dissolution, the organic solvent of the solution is removed. A method for producing a silver halide emulsion, which comprises evaporating to form a flake concentrate, dispersing the flake concentrate in water, and adding the dispersion to a silver halide emulsion.
JP17187688A 1988-07-12 1988-07-12 Production of silver halide emulsion Pending JPH0223330A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP17187688A JPH0223330A (en) 1988-07-12 1988-07-12 Production of silver halide emulsion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP17187688A JPH0223330A (en) 1988-07-12 1988-07-12 Production of silver halide emulsion

Publications (1)

Publication Number Publication Date
JPH0223330A true JPH0223330A (en) 1990-01-25

Family

ID=15931432

Family Applications (1)

Application Number Title Priority Date Filing Date
JP17187688A Pending JPH0223330A (en) 1988-07-12 1988-07-12 Production of silver halide emulsion

Country Status (1)

Country Link
JP (1) JPH0223330A (en)

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