JPH11194459A - Photographic emulsifying and dispersing material and silver halide photographic sensitive material containing same - Google Patents

Photographic emulsifying and dispersing material and silver halide photographic sensitive material containing same

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Publication number
JPH11194459A
JPH11194459A JP29871898A JP29871898A JPH11194459A JP H11194459 A JPH11194459 A JP H11194459A JP 29871898 A JP29871898 A JP 29871898A JP 29871898 A JP29871898 A JP 29871898A JP H11194459 A JPH11194459 A JP H11194459A
Authority
JP
Japan
Prior art keywords
metal salt
photographic
water
hydrophobic compound
emulsified dispersion
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
JP29871898A
Other languages
Japanese (ja)
Inventor
Yukio Aogaki
行夫 青柿
Masahiro Fukuoka
正博 福岡
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 JP29871898A priority Critical patent/JPH11194459A/en
Publication of JPH11194459A publication Critical patent/JPH11194459A/en
Pending legal-status Critical Current

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  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a photographic emulsifying and dispersing material small in grain diameter and superior in grain diameter stability over aging dissolution by adding a water-soluble metal salt into a water phase before the end of emulsification and/or into the emulsifying and dispersing material after emulsification. SOLUTION: This emulsifying and dispersing material contains a prescribed amount of a water-soluble uni- or poly-valent metal salt and fine grains of photographic hydrophobic compounds except silver halide, and the water-soluble metal salt is necessary for promoting the action of an anionic surfactant and lowering enough a surface tension as the added amount, and it is concerectly necessary to use the univalent metal in an amount of 70-700 millimol, per 1000 g of the fine particles of the hydrophobic compound, preferably, 280-530 millimol, and, in the case of polyvalent metal, preferably, 7-70 millimol. As for the hydrophobic compounds water-insoluble and/or oil-soluble photographic additives such as various kinds of color couplers, a color non-forming, coupler, a dye, a color mixing preventer and an image stabilizer are exemplified.

Description

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

【0001】[0001]

【発明の属する技術分野】本発明は写真技術に関し、特
に水溶性金属塩を添加することによって、微粒子化と溶
解経時による粒径安定化が達成された写真用疎水性化合
物微粒子の乳化分散物およびその製法、並びにこの乳化
分散物を含んだハロゲン化銀写真感光材料に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to photographic technology, and more particularly to an emulsion dispersion of fine particles of a photographic hydrophobic compound, which has been made finer by adding a water-soluble metal salt to stabilize the particle diameter over time. The present invention relates to a method for producing the same, and a silver halide photographic material containing the emulsified dispersion.

【0002】[0002]

【従来の技術】ハロゲン化銀カラー写真感光材料を露光
後発色現像することにより酸化された芳香族一級アミン
現像薬とカプラーとが反応してインドフェノール、イン
ドアニリン、インダミン、アゾメチン、フェノキサジ
ン、フェナジン及びそれに類する色素ができ、色画像が
形成されることは知られている。この方式においては通
常色再現には減色法が使われ、青、緑、および赤に選択
的に感光するハロゲン化銀乳剤とそれぞれ余色関係にあ
るイエロー、マゼンタ、およびシアンのカラーカプラー
とが使用される。ところで、多層カラー感光材料では、
混色を少なくし、色再現をよくするためにそれぞれのカ
プラーを分離した層に固定することが必要である。この
カプラーの耐拡散化の方法としては多くの方法が知られ
ている。その方法の代表例としては低分子カプラーの分
子中に拡散を防ぐため長鎖の脂肪族基を導入したり、米
国特許第4,080,211号に記載されているように
ポリマー化を行うこと等が挙げられる。
2. Description of the Related Art An oxidized aromatic primary amine developing agent is reacted with a coupler by color development after exposure of a silver halide color photographic light-sensitive material to react with indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine. It is known that a color image can be formed by the formation of a colorant similar thereto. In this method, the color reduction method is usually used for color reproduction, and a silver halide emulsion which is selectively sensitive to blue, green, and red and color couplers of yellow, magenta, and cyan, which have a residual color relationship, are used. Is done. By the way, in the multilayer color photosensitive material,
In order to reduce color mixing and improve color reproduction, it is necessary to fix each coupler in a separate layer. There are many known methods for making the coupler resistant to diffusion. Typical examples of such a method include introducing a long-chain aliphatic group into the molecule of the low-molecular coupler to prevent diffusion, or performing polymerization as described in US Pat. No. 4,080,211. And the like.

【0003】このようなカプラーは、そのままではバイ
ンダー(特にゼラチン)水溶液と混和しないため、通
常、分散物の形で用いられる。このように、水不溶性の
カプラーを水分散物とする方法の例としては、米国特許
第2,322,027号に記載されているような高沸点
の有機溶剤にカプラーを溶かしてゼラチン水溶液中に乳
化分散する方法を挙げることができる。しかしながら、
このようにして得られた疎水性化合物微粒子の乳化分散
物では粒径が大きかったり、また溶解経時によって合一
・凝集等が起って粒径が大きくなり、そのため発色濃度
の低下、塗布(面状)故障の発生という問題があった。
[0003] Such couplers are usually used in the form of a dispersion, because they are not miscible with a binder (especially gelatin) aqueous solution as it is. As described above, as an example of a method of converting a water-insoluble coupler into an aqueous dispersion, a coupler is dissolved in a high boiling organic solvent as described in U.S. Pat. A method of emulsifying and dispersing can be exemplified. However,
The emulsified dispersion of the hydrophobic compound fine particles obtained in this way has a large particle size, and the particle size increases due to coalescence / aggregation due to dissolution aging, so that the color density decreases and the coating (surface) State) There was a problem that a failure occurred.

【0004】[0004]

【発明が解決しようとする課題】したがって、本発明の
目的は粒径が小さく、また粒径の溶解経時安定性(媒体
がゾル状態である時の経時安定性)に優れた乳化分散物
およびこの乳化分散物を含んだハロゲン化銀写真感光材
料を提供することにある。
SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an emulsified dispersion having a small particle size and excellent dissolution stability over time (time stability when the medium is in a sol state), and an emulsion dispersion having the same. An object of the present invention is to provide a silver halide photographic light-sensitive material containing an emulsified dispersion.

【0005】[0005]

【課題を解決するための手段】本発明者等は、鋭意研究
を重ねた結果、前記の課題が水溶性金属塩を乳化終了前
の水相に、および/または乳化後の乳化分散物中に添加
することによって達成されることを見い出し、本発明を
完成するに至った。即ち、本発明は以下の乳化分散物お
よびこの乳化分散物を含んだハロゲン化銀写真感光材料
である。 (1)添加された所定量の水溶性一価または多価の金属
塩を含んで、写真用疎水性化合物微粒子(但し、ハロゲ
ン化銀を除く)が乳化分散されていることを特徴とする
分散物。 (2)金属塩が二価又は三価の金属塩であることを特徴
とする、(1)項に記載の写真用疎水性化合物微粒子の
乳化分散物。 (3)二価又は三価の金属塩がカルシウム塩、マグネシ
ウム塩、バリウム塩およびアルミニウム塩から選ばれる
金属塩の少なくとも一種であることを特徴とする、
(2)項に記載の写真用疎水性化合物微粒子の乳化分散
物。 (4)乳化物中の疎水性化合物微粒子1000gあたり
70ミリモル〜700ミリモルの添加量で添加された水
溶性一価金属塩を含有することを特徴とする写真用疎水
性化合物微粒子(但し、ハロゲン化銀を除く)の乳化分
散物。 (5)金属塩が硝酸塩であることを特徴とする、(1)
〜(4)項のいずれかに記載の写真用疎水性化合物微粒
子の乳化分散物。 (6)支持体上に塗設された親水性コロイド層中に
(1)〜(5)項のいずれかに記載の写真用疎水性化合
物微粒子の乳化分散物を含有することを特徴とするハロ
ゲン化銀写真感光材料。
The present inventors have conducted intensive studies and as a result, the above-mentioned problems have been solved in that the water-soluble metal salt is contained in the aqueous phase before the end of emulsification and / or in the emulsified dispersion after the emulsification. It has been found that this can be achieved by the addition, and the present invention has been completed. That is, the present invention provides the following emulsified dispersion and a silver halide photographic light-sensitive material containing this emulsified dispersion. (1) Dispersion characterized in that photographic hydrophobic compound fine particles (excluding silver halide) are emulsified and dispersed, containing an added predetermined amount of a water-soluble monovalent or polyvalent metal salt. Stuff. (2) The emulsified dispersion of the photographic hydrophobic compound fine particles according to (1), wherein the metal salt is a divalent or trivalent metal salt. (3) the divalent or trivalent metal salt is at least one metal salt selected from calcium salts, magnesium salts, barium salts and aluminum salts,
An emulsified dispersion of the photographic hydrophobic compound fine particles according to item (2). (4) Hydrophobic compound fine particles for photography characterized by containing a water-soluble monovalent metal salt added in an amount of 70 mmol to 700 mmol per 1000 g of hydrophobic compound fine particles in an emulsion (however, halogenated Emulsified dispersion (excluding silver). (5) The metal salt is a nitrate, (1)
An emulsified dispersion of the photographic hydrophobic compound fine particles according to any one of (1) to (4). (6) Halogen characterized in that the hydrophilic colloid layer coated on the support contains an emulsified dispersion of the photographic hydrophobic compound fine particles according to any one of (1) to (5). Silver halide photographic material.

【0006】[0006]

【発明の実施の形態】以下に本発明を詳細に説明する。
本発明における「添加された水溶性金属塩」とは、乳化
終了前の水性媒体中に、または乳化後の乳化分散物中に
添加された水溶性金属塩を意味し、例えば、ゼラチン中
に必然的に含まれる水溶性金属塩が当該ゼラチンの添加
に伴って自動的に(不可避的に)添加される態様は該当
しない。本発明において添加される水溶性金属塩の添加
量は、乳化分散に用いられるアニオン性界面活性剤の作
用を助けて表面張力を十分に下げるに必要な量であり、
具体的には乳化物中の疎水性化合物微粒子1000gあ
たり一価の金属塩では70ミリモル〜700ミリモルが
必要であり、好ましくは280〜530ミリモルであ
る。また、多価金属塩の添加量は7ミリモル〜70ミリ
モルが好ましく、28ミリモル〜53ミリモルが更に好
ましい。本発明において添加された金属塩は乳化分散物
中ではイオンに解離する。一価の金属イオンとしてはK
+ 、Na+ 、Li+ を挙げることができるが、Na+
+ が好ましい。また多価金属イオンとしては二価また
は三価の金属イオンが好ましく、なかでも二価の金属イ
オンが好ましい。
DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The `` added water-soluble metal salt '' in the present invention means a water-soluble metal salt added in an aqueous medium before completion of emulsification, or in an emulsified dispersion after emulsification, and is, for example, necessary in gelatin. The embodiment in which the water-soluble metal salt contained in the mixture is automatically (inevitably) added together with the gelatin is not applicable. The amount of the water-soluble metal salt added in the present invention is an amount necessary to sufficiently reduce the surface tension by assisting the action of the anionic surfactant used for emulsification and dispersion,
Specifically, a monovalent metal salt needs to be 70 mmol to 700 mmol, preferably 280 to 530 mmol, per 1,000 g of the hydrophobic compound fine particles in the emulsion. Further, the addition amount of the polyvalent metal salt is preferably from 7 mmol to 70 mmol, more preferably from 28 mmol to 53 mmol. The metal salt added in the present invention dissociates into ions in the emulsified dispersion. K as a monovalent metal ion
+ , Na + , and Li + , and Na + and K + are preferable. As the polyvalent metal ion, a divalent or trivalent metal ion is preferable, and among them, a divalent metal ion is preferable.

【0007】三価の金属イオンとしてはAl3+が好まし
く、二価の金属イオンとしてはCa2+、Mg2+、Ba2+
が好ましい。一価の金属塩としては硝酸塩、硫酸塩、炭
酸塩やリン酸塩が好ましいが、写真的に悪い影響を与え
ないという点で硝酸塩が特に好ましい。また、多価金属
塩も水溶性金属塩は乳化終了前の水性媒体(水相)に添
加することにより乳化後の粒子径を0.30μm以下、
好ましくは0.25μm以下、更に好ましくは0.05
μm〜0.20μmに微粒子化でき、且つ乳化分散物の
溶解経時による粒子径変化を顕著に減少させることがで
きる。また乳化後に添加することにより、溶解経時によ
る粒子径変化を顕著に減少させることができる。特に、
乳化後に一価または多価の金属塩を添加する方法は溶解
経時による粒子径変化を顕著に減少させることができる
極めて有力な方法であり好ましい。なお、二価または三
価の金属塩は一価の金属塩と比較し、本発明の目的を達
成するのに必要な添加量が少なくてよいという長所があ
る。しかしながら、一方で、二価または三価の金属塩を
使用して得た乳化分散物を用いたハロゲン化銀写真感光
材料を現像処理した場合、該乳化物中から溶出した該二
価または三価の金属塩が現像処理液中に蓄積し、現像主
薬の酸化体および同じく溶出したゼラチンとともに凝集
物を生じる。このため、乳化分散物を得るために使用す
る二価または三価の金属塩の添加量の調節がむずかしい
という難点を含んでいる。一価の金属塩の場合、上記の
問題がないことから、より好ましい。
The trivalent metal ion is preferably Al 3+ , and the divalent metal ion is Ca 2+ , Mg 2+ , Ba 2+
Is preferred. As the monovalent metal salt, a nitrate, a sulfate, a carbonate or a phosphate is preferable, but a nitrate is particularly preferable since it does not adversely affect the photograph. Also, the polyvalent metal salt and the water-soluble metal salt are added to the aqueous medium (aqueous phase) before the completion of the emulsification so that the particle size after emulsification is 0.30 μm or less
Preferably not more than 0.25 μm, more preferably 0.05
It can be micronized to a size of from μm to 0.20 μm, and the change in particle size over time of dissolution of the emulsified dispersion can be significantly reduced. Also, by adding after emulsification, the change in particle size over time with dissolution can be significantly reduced. Especially,
The method of adding a monovalent or polyvalent metal salt after emulsification is an extremely powerful method capable of remarkably reducing the change in particle size over time with dissolution, and is preferred. The divalent or trivalent metal salt has an advantage that the amount of addition required to achieve the object of the present invention may be smaller than that of the monovalent metal salt. However, on the other hand, when a silver halide photographic material using an emulsified dispersion obtained using a divalent or trivalent metal salt is developed, the divalent or trivalent eluted from the emulsion is obtained. Accumulates in the developing solution to form agglomerates with the oxidized form of the developing agent and the gelatin that has also been eluted. For this reason, it is difficult to control the amount of the divalent or trivalent metal salt used to obtain the emulsified dispersion. A monovalent metal salt is more preferable because it does not have the above problems.

【0008】本発明に用いられる疎水性化合物としては
写真技術分野で知られた各種のカラーカプラー、無呈色
カプラー、染料、混色防止剤、画像安定化剤などの水不
溶性および/または油溶性写真用添加剤が挙げられる。
このうち、水不溶性添加剤の代表としては、固体分散染
料が挙げられる。油溶性写真添加剤を溶解させるのに用
いられる高沸点有機溶媒としては、室温で固体でも液体
でもよく例えば特開昭62−172349号に記載され
ている一般式(I)、(II) 、(III) 、(IV)および
(V)で表わされるリン酸エステル類、カルボン酸エス
テル類、アミド類、アニリン類やエーテル類およびその
具体例が好ましい。このように、本発明の写真用疎水性
化合物微粒子の乳化分散物における疎水性化合物微粒子
とは、前記の疎水性化合物自身が微細な粒子として分散
しているものであってもよいし、また単数または複数の
疎水性化合物が室温で固体または液体の高沸点有機溶媒
中に溶解した微細な油滴の形で分散しているものであっ
てもよい。また、疎水性化合物がポリマー中に含浸して
微粒子として分散していてもよい。本発明の乳化分散物
中の写真用疎水性化合物の含有量(濃度)は特に制限は
なく、分散させる写真用疎水性化合物の種類、用途など
により異なり、従来のそのような乳化分散物と特に異な
らない。具体的に例示すると、カプラー、褪色防止剤、
UV吸収剤、混色防止剤等の疎水性化合物の固形分に関
する乳化物中の使用量は、好ましくは2〜20wt%で
ある。さらに本発明の写真用乳化分散物には、その乳化
物の安定性を向上させるため保護コロイド物質(親水性
コロイド)を適宜に添加してもよい。このような保護コ
ロイド物質としては、ゼラチン、誘導体ゼラチン、ポリ
ビニルアルコール、変性ポバールなどがある。本発明写
真用乳化分散物において水(水相)の量は写真用疎水性
化合物などの油相成分及びハロゲン化銀粒子成分以外の
部分の量でありこれは乳化分散物の種類、用途、などに
よって適宜定めることができ、特に制限するのものでは
ないが、好ましくは写真用乳化分散物全量に対し、10
〜90重量%、より好ましくは40〜80重量%であ
る。
As the hydrophobic compound used in the present invention, water-insoluble and / or oil-soluble photographic materials such as various color couplers, colorless couplers, dyes, color mixing inhibitors and image stabilizers known in the photographic art field are used. Additives.
Among these, a typical example of the water-insoluble additive is a solid disperse dye. The high-boiling organic solvent used for dissolving the oil-soluble photographic additive may be a solid or a liquid at room temperature, and may be, for example, any of the general formulas (I), (II) and (II) described in JP-A-62-172349. Phosphoric esters, carboxylic esters, amides, anilines and ethers represented by (III), (IV) and (V) and their specific examples are preferred. As described above, the hydrophobic compound fine particles in the emulsion dispersion of the hydrophobic compound fine particles for photography of the present invention may be those in which the hydrophobic compound itself is dispersed as fine particles, or Alternatively, a plurality of hydrophobic compounds may be dispersed in the form of fine oil droplets dissolved in a solid or liquid high-boiling organic solvent at room temperature. Further, the hydrophobic compound may be impregnated in the polymer and dispersed as fine particles. The content (concentration) of the photographic hydrophobic compound in the emulsified dispersion of the present invention is not particularly limited, and varies depending on the kind of the photographic hydrophobic compound to be dispersed, the use, and the like. No different. Specific examples include a coupler, an anti-fading agent,
The amount of the hydrophobic compound such as a UV absorber and a color mixing inhibitor used in the emulsion with respect to the solid content is preferably 2 to 20% by weight. Further, a protective colloid substance (hydrophilic colloid) may be appropriately added to the emulsion dispersion for photography of the present invention in order to improve the stability of the emulsion. Examples of such protective colloid materials include gelatin, derivative gelatin, polyvinyl alcohol, and denatured poval. In the photographic emulsion dispersion of the present invention, the amount of water (aqueous phase) is an amount of a portion other than an oil phase component such as a photographic hydrophobic compound and a silver halide particle component. Is not particularly limited, but is preferably 10% with respect to the total amount of the photographic emulsified dispersion.
9090% by weight, more preferably 40-80% by weight.

【0009】本発明において好ましく用いられるアニオ
ン性界面活性剤としては次の一般式[I]で示されるも
のから選ばれる。 一般式[I] R−(A)n −B 式中、Rは炭素数4〜24のアルキル基、アルケニル
基、アラルキル基、およびこれらの基の水素原子がフッ
素原子で置換されたフッ化炭化水素基を表わす。Aは二
価の連結基を表わす。nは0又は1を表わす。Bはスル
ホン酸基、スルホン酸エステル基、カルボン酸基、ホス
ホン酸基、ホスホン酸エステル基、ホスファイト基及び
それらの塩を表わす。Bとしては特にスルホン酸基が好
ましい。Aの二価基の具体例を以下に挙げる。
The anionic surfactant preferably used in the present invention is selected from those represented by the following general formula [I]. In the general formula [I] R- (A) n -B formulas, R is an alkyl group having 4 to 24 carbon atoms, an alkenyl group, an aralkyl group, and fluorinated hydrogen atoms of these groups are substituted with fluorine atoms carbide Represents a hydrogen group. A represents a divalent linking group. n represents 0 or 1. B represents a sulfonic acid group, a sulfonic acid ester group, a carboxylic acid group, a phosphonic acid group, a phosphonate ester group, a phosphite group, and salts thereof. B is particularly preferably a sulfonic acid group. Specific examples of the divalent group of A are shown below.

【0010】[0010]

【化1】 Embedded image

【0011】次に本発明に使用されるアニオン性界面活
性剤の具体例を示すがこれに限定されるものではない。
Next, specific examples of the anionic surfactant used in the present invention will be shown, but the present invention is not limited thereto.

【0012】[0012]

【化2】 Embedded image

【0013】[0013]

【化3】 Embedded image

【0014】[0014]

【化4】 Embedded image

【0015】[0015]

【化5】 Embedded image

【0016】アニオン性界面活性剤の使用量としては特
に制限がないが、乳化に用いられるゼラチンに対して
2.5重量%以上が好ましく、更に好ましくは4〜20
重量%である。
The amount of the anionic surfactant used is not particularly limited, but is preferably 2.5% by weight or more, more preferably 4 to 20% by weight, based on the gelatin used for emulsification.
% By weight.

【0017】本発明の感光材料は、本発明の乳化分散物
を含有する支持体上に少なくとも1層有すればよく、乳
化分散物は通常のゼラチンバインダーから成る親水性コ
ロイド層に含有される。本発明の感光材料は黒白感光材
料でもカラー感光材料でもよい。一般的なカラー感光材
料は、支持体上に青感性ハロゲン化銀乳剤層、緑感性ハ
ロゲン化銀乳剤層および赤感性ハロゲン化銀乳剤層を少
なくとも一層ずつ塗設して構成することができるが、そ
の順序はいかなる順でもよい。また、赤外感光性ハロゲ
ン化銀乳剤層を前記感光性乳剤層の少なくとも一つの替
わりに用いることもできる。これらの感光性乳剤層に
は、それぞれの波長域に感度を有するハロゲン化銀乳剤
と、感光する光と補色の関係にある色素を形成するカプ
ラーを含有させることで減色法の色再現を行うことがで
きる。ただし、感光性乳剤層とカプラーの発色色相とは
上記のような対応を持たない構成であってもよい。
The light-sensitive material of the present invention may have at least one layer on a support containing the emulsion of the present invention, and the emulsion is contained in a hydrophilic colloid layer comprising a usual gelatin binder. The light-sensitive material of the present invention may be a black-and-white light-sensitive material or a color light-sensitive material. A general color light-sensitive material can be constituted by coating at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, and at least one red-sensitive silver halide emulsion layer on a support. The order may be any order. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned photosensitive emulsion layers. These light-sensitive emulsion layers contain a silver halide emulsion having sensitivity in each wavelength range and a coupler that forms a dye having a complementary color with the light to be exposed, so that color reproduction by the subtractive color method can be performed. Can be. However, the photosensitive emulsion layer and the color hue of the coupler may not have the above correspondence.

【0018】本発明のハロゲン化銀写真感光材料には、
その他従来公知の写真用素材や添加剤を使用できる。例
えば写真用支持体としては、透過型支持体や反射型支持
体を用いることができる。透過型支持体としては、セル
ローストリアセテートフィルムやポリエチレンテレフタ
レートなどの透過フィルム、更には2,6−ナフタレン
ジカルボン酸(NDCA)とエチレングリコール(E
G)とのポリエステルやNDCAとテレフタル酸とEG
とのポリエステル等に磁性層などの情報記録層を設けた
ものが好ましく用いられる。反射型支持体としては特に
複数のポリエチレン層やポリエステル層でラミネートさ
れ、このような耐水性樹脂層(ラミネート層)の少なく
とも一層に酸化チタン等の白色顔料を含有する反射型支
持体が好ましい。
The silver halide photographic light-sensitive material of the present invention comprises
In addition, conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. Examples of the permeable support include permeable films such as cellulose triacetate film and polyethylene terephthalate, and 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (E).
G) with polyester or NDCA, terephthalic acid and EG
A material in which an information recording layer such as a magnetic layer is provided on polyester or the like is preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable.

【0019】更に前記の耐水性樹脂層中には蛍光増白剤
を含有するのが好ましい。また、蛍光増白剤は感材の親
水性コロイド層中に分散してもよい。蛍光増白剤とし
て、好ましくは、ベンゾオキサゾール系、クマリン系、
ピラゾリン系が用いることができ、更に好ましくは、ベ
ンゾオキサゾリルナフタレン系及びベンゾオキサゾリル
スチルベン系の蛍光増白剤である。使用量は、特に限定
されないが、好ましくは1〜100mg/m2 である。
耐水性樹脂に混合する場合の混合比は、好ましくは樹脂
に対して0.0005〜3重量%であり、更に好ましく
は0.001〜0.5重量%である。反射型支持体とし
ては、透過型支持体、または上記のような反射型支持体
上に、白色顔料を含有する親水性コロイド層を塗設した
ものでもよい。また、反射型支持体は、鏡面反射性また
は第2種拡散反射性の金属表面をもつ支持体であっても
よい。
It is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, benzoxazole type, coumarin type,
A pyrazoline-based fluorescent whitening agent is more preferable, and a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m 2 .
The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by weight, more preferably 0.001 to 0.5% by weight, based on the resin. The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

【0020】本発明に用いるハロゲン化銀乳剤として
は、塩化銀、臭化銀、沃臭化銀、塩(沃)臭化銀乳剤等
が用いられるが、迅速処理性の観点からは、塩化銀含有
率が95モル%以上の塩化銀または塩臭化銀乳剤が好ま
しく、更には塩化銀含有率が98モル%以上のハロゲン
化銀乳剤が好ましい。このようなハロゲン化銀乳剤の中
でも、塩化銀粒子の表面に臭化銀局在相を有するもの
が、高感度が得られ、しかも写真性能の安定化が図れる
ことから特に好ましい。
As the silver halide emulsion for use in the present invention, silver chloride, silver bromide, silver iodobromide, silver chloro (iodo) bromide emulsions and the like can be used. A silver chloride or silver chlorobromide emulsion having a content of 95 mol% or more is preferable, and a silver halide emulsion having a silver chloride content of 98 mol% or more is preferable. Among such silver halide emulsions, those having a silver bromide localized phase on the surface of silver chloride grains are particularly preferable since high sensitivity can be obtained and photographic performance can be stabilized.

【0021】前記の反射型支持体やハロゲン化銀乳剤、
更にはハロゲン化銀粒子中にドープされる異種金属イオ
ン種、ハロゲン化銀乳剤の保存安定剤またはカブリ防止
剤、化学増感法(増感剤)、分光増感法(分光増感
剤)、シアン、マゼンタ、イエローカプラーおよびその
乳化分散法、色像保存性改良剤(ステイン防止剤や褪色
防止剤)、染料(着色層)、ゼラチン種、感材の層構成
や感材の被膜pHなどについては、表1〜2の特許に記
載のものが本発明に好ましく適用できる。
The above-mentioned reflection type support or silver halide emulsion,
Further, different metal ion species doped in silver halide grains, storage stabilizers or antifoggants for silver halide emulsions, chemical sensitization (sensitizer), spectral sensitization (spectral sensitizer), Cyan, magenta, yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (anti-stain and anti-fading agents), dyes (colored layers), gelatin species, layer composition of photosensitive material, coating pH of photosensitive material, etc. As described above, those described in the patents of Tables 1 and 2 can be preferably applied to the present invention.

【0022】[0022]

【表1】 [Table 1]

【0023】[0023]

【表2】 [Table 2]

【0024】本発明において使用されるシアン、マゼン
タおよびイエローカプラーとしては、その他、特開昭6
2−215272号の第91頁右上欄4行目〜121頁
左上欄6行目、特開平2−33144号の第3頁右上欄
14行目〜18頁左上欄末行目と第30頁右上欄6行目
〜35頁右下欄11行目やEP0355,660A2号
の第4頁15行目〜27行目、5頁30行目〜28頁末
行目、45頁29行目〜31行目、47頁23行目〜6
3頁50行目に記載のカプラーも有用である。
The cyan, magenta and yellow couplers used in the present invention are described in
JP-A-2-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; JP-A-2-33144, page 3, upper right column, line 14 to page 18, upper left column last line and page 30, upper right Lines 6 to 35, lower right column, line 11 and EP 0355,660A2, page 4, lines 15 to 27, page 5, line 30 to page 28, last line, page 45, lines 29 to 31 Eyes, page 47, lines 23-6
The couplers described on page 3, line 50 are also useful.

【0025】本発明に用いうる防菌・防黴剤としては特
開昭63−271247号に記載のものが有用である。
感光材料を構成する写真層に用いられる親水性コロイド
としては、ゼラチンが好ましく、特に鉄、銅、亜鉛、マ
ンガン等の不純物として含有される重金属は、好ましく
は5ppm以下、更に好ましくは3ppm以下である。
As the antibacterial and antifungal agents usable in the present invention, those described in JP-A-63-271247 are useful.
Gelatin is preferred as the hydrophilic colloid used in the photographic layer constituting the light-sensitive material. Particularly, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably at most 5 ppm, more preferably at most 3 ppm. .

【0026】本発明の感光材料は、通常のネガプリンタ
ーを用いたプリントシステムに使用される以外に、陰極
線(CRT)やレーザーを用いた走査露光方式にも適し
ている。
The light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) or a laser, in addition to being used for a printing system using a normal negative printer.

【0027】[0027]

【実施例】次に本発明を実施例に基づきさらに詳細に説
明する。 実施例1 下記処方の液と液をホモジナイザーを用いて混合
し、乳化後加水(6610ml)して15kgの乳化分
散物1を調製した。 液(水相) ゼラチン* 1000g 水 4000ml 液(油相) シアンカプラー 1030g 紫外線吸収剤 422g 高沸点有機溶媒(ジブチルフタレート) 620ml 酢酸エチル 1300ml 界面活性剤(前記の化合物例12)(72%) 124ml *ゼラチンはCa2+含量が50ppmのものを使用した。
Next, the present invention will be described in more detail with reference to examples. Example 1 A liquid having the following formulation and a liquid were mixed using a homogenizer, emulsified and then added with water (6610 ml) to prepare an emulsified dispersion 1 of 15 kg. Liquid (aqueous phase) Gelatin * 1000 g Water 4000 ml Liquid (oil phase) Cyan coupler 1030 g Ultraviolet absorber 422 g High boiling organic solvent (dibutyl phthalate) 620 ml Ethyl acetate 1300 ml Surfactant (the above-mentioned compound example 12) (72%) 124 ml * Gelatin having a Ca 2+ content of 50 ppm was used.

【0028】[0028]

【化6】 Embedded image

【0029】[0029]

【化7】 Embedded image

【0030】前記の乳化分散物1において、添加する水
溶性金属塩の種類、添加量、添加時期を変えて種々の乳
化分散物を調製し、その調製直後の粒径と、乳化分散物
を40℃で静置して経時させた後の粒径を光散乱法を利
用して測定し、溶解経時安定性を評価した。各乳化分散
物について得られた粒径の結果を図1〜4に示す。図1
中、ライン1は水溶性金属塩無添加、ライン2は乳化分
散物1の液に硝酸カルシウムを60ミリモル添加した
場合、ライン3は乳化分散物1の液に硝酸マグネシウ
ムを60ミリモル添加した場合の乳化分散直後の粒径
(nm)並びに経時による粒径の変化を示す。
In the above-mentioned emulsified dispersion 1, various emulsified dispersions were prepared by changing the type, amount and timing of the water-soluble metal salt to be added. The particles were allowed to stand at 0 ° C. and aged, and the particle size was measured using a light scattering method to evaluate the stability over time. The particle size results obtained for each emulsified dispersion are shown in FIGS. FIG.
In the line, line 1 was a case where no water-soluble metal salt was added, line 2 was a case where 60 mmol of calcium nitrate was added to the liquid of the emulsified dispersion 1, and line 3 was a case where 60 mmol of magnesium nitrate was added to the liquid of the emulsified dispersion 1. The particle diameter (nm) immediately after emulsification and dispersion and the change of the particle diameter with time are shown.

【0031】図2中、ライン4は乳化分散物1の調製直
後に硝酸マグネシウムを60ミリモル添加した場合、ラ
イン5は乳化分散物1に硝酸カルシウムを60ミリモル
添加した場合、およびライン6は乳化分散物1に硝酸バ
リウムを60ミリモル添加した場合の経時による粒径の
変化を示す。図3は、乳化分散物1の液に添加する硝
酸カルシウムの添加量を変えたときの粒子サイズの変化
を示し、ライン7は硝酸カルシウムを30ミリモル添加
した場合、およびライン8は硝酸カルシウムを120ミ
リモル添加した場合の粒径の変化を示す。
In FIG. 2, line 4 is the case where 60 mmol of magnesium nitrate was added immediately after the preparation of emulsified dispersion 1, line 5 was the case where 60 mmol of calcium nitrate was added to emulsified dispersion 1, and line 6 was the emulsified dispersion. The change in particle size with time when barium nitrate was added to the product 1 in an amount of 60 mmol is shown. FIG. 3 shows the change in the particle size when the amount of calcium nitrate added to the liquid of the emulsified dispersion 1 was changed. Line 7 shows the case where 30 mmol of calcium nitrate was added. The change in particle size when mmol is added is shown.

【0032】図4は、硝酸ナトリウムを乳化分散物1の
調製直後に添加したときの粒径の変化を示し、ライン9
は硝酸ナトリウムを60ミリモル添加した場合、ライン
10は硝酸ナトリウムを300ミリモル添加した場合、
およびライン11は硝酸ナトリウムを600ミリモル添
加した場合の粒径の変化を示す。これらの図1〜4の結
果から以下のことがわかる。即ち、図1の結果から、乳
化分散前の水相に水溶性多価金属塩を添加した場合に、
この金属塩を添加しない場合に比べて粒径が小さく、し
かも溶解経時によっても粒径変化が比較的小さい(経時
安定性に優れた)乳化分散物が得られることがわかる。
図2の結果から、乳化分散物の調製後に水溶性多価金属
塩を添加した場合にも、水溶性多価金属塩を添加しない
場合に比べて、乳化物粒子サイズの経時安定性が顕著に
改良されることがわかる。
FIG. 4 shows the change in particle size when sodium nitrate was added immediately after the preparation of the emulsified dispersion 1, and line 9
Is the case where 60 mmol of sodium nitrate is added, and the line 10 is the case where 300 mmol of sodium nitrate is added.
And Line 11 shows the change in particle size when 600 mmol of sodium nitrate was added. The following can be seen from the results of FIGS. That is, from the results of FIG. 1, when a water-soluble polyvalent metal salt is added to the aqueous phase before emulsification and dispersion,
It can be seen that an emulsified dispersion having a smaller particle size as compared with the case where no metal salt is added and having a relatively small change in particle size even with dissolution aging (excellent in stability over time) can be obtained.
From the results of FIG. 2, the stability of the emulsion particle size over time is remarkable even when the water-soluble polyvalent metal salt is added after the preparation of the emulsified dispersion, as compared with the case where the water-soluble polyvalent metal salt is not added. It can be seen that it is improved.

【0033】図3の結果から、乳化分散前の水相に添加
される水溶性多価金属塩の添加量が増大するにつれて乳
化物の粒子サイズを小さくでき、しかも経時安定性も改
良できることがわかる。図4の結果から、水溶性一価金
属塩の添加量が60ミリモルである場合には経時安定性
の改良効果が比較的小さいのに対して、300ミリモル
添加した場合にその改良効果が顕著になり、600ミリ
モル添加した場合に予想外にも経時安定性が水溶性多価
金属塩を60ミリモル添加したと同程度以上に顕著に改
良されることがわかる。
From the results shown in FIG. 3, it can be seen that as the amount of the water-soluble polyvalent metal salt added to the aqueous phase before emulsification and dispersion increases, the particle size of the emulsion can be reduced and the stability with time can be improved. . From the results in FIG. 4, it is found that the effect of improving the stability over time is relatively small when the amount of the water-soluble monovalent metal salt added is 60 mmol, whereas the effect is significantly improved when the amount is 300 mmol. It can be seen that, when 600 mmol is added, the stability with time is unexpectedly remarkably improved to at least the same level as when 60 mmol of the water-soluble polyvalent metal salt is added.

【0034】実施例2 紙の両面をポリエチレン樹脂で被覆してなる支持体の表
面に、コロナ放電処理を施した後、ドデシルベンゼンス
ルホン酸ナトリウムを含むゼラチン下塗層を設け、更に
下記のハロゲン化銀乳剤層とゼラチン保護層を順次塗設
して、カラー写真感光材料を作製した。
Example 2 After a corona discharge treatment was applied to the surface of a support obtained by coating both sides of a paper with a polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. A silver emulsion layer and a gelatin protective layer were sequentially coated to prepare a color photographic light-sensitive material.

【0035】<ハロゲン化銀乳剤層塗布液の調製>以下
に示す平均粒子サイズとは、いわゆるプロジェクテド・
エリア法によって測定された粒子の面積と同じ円の直径
の平均値を意味する。塩臭化銀乳剤(立方体、平均粒子
サイズ0.50μmの大サイズ乳剤Cと0.41μmの
小サイズ乳剤Cとの1:4混合物(銀モル比)。粒子サ
イズ分布の変動係数は、それぞれ0.09と0.11。
各サイズ乳剤とも臭化銀0.5モル%を、塩化銀を基体
とする粒子表面の一部に局在含有させた)を調製した。
この乳剤には下記に示す赤感性増感色素GおよびHが、
銀1モル当り、大サイズ乳剤に対してはそれぞれ6.0
×10-5モル、また小サイズ乳剤に対してはそれぞれ
9.0×10-5モル添加されている。また、この乳剤の
化学熟成は硫黄増感剤と金増感剤が添加して最適に行わ
れた。
<Preparation of Silver Halide Emulsion Layer Coating Solution> The average grain size shown below is what is called a projected
It means the average value of the diameter of the same circle as the area of the particle measured by the area method. Silver chlorobromide emulsion (cubic, 1: 4 mixture (larger silver ratio) of large-size emulsion C having an average grain size of 0.50 μm and small-size emulsion C having an average grain size of 0.51 μm. Coefficient of variation of grain size distribution is 0 .09 and 0.11.
In each size emulsion, 0.5 mol% of silver bromide was locally contained on a part of the surface of the silver chloride-based grain).
This emulsion contains red-sensitive sensitizing dyes G and H shown below,
6.0 moles per mole of silver for large emulsions
× 10 -5 mol, and 9.0 × 10 -5 mol for small-size emulsions, respectively. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer.

【0036】比較用として乳化分散物1と前記の塩臭化
銀乳剤とを混合溶解した乳剤層塗布液1を調製した。ま
た実施例1で調製されたシアンカプラーの乳化分散物2
(乳化分散物1の液に硝酸カルシウムを60ミリモル
添加したもの)と前記の塩臭化銀乳剤とを混合溶解し、
乳剤層塗布液2を調製した。
For comparison, an emulsion layer coating solution 1 was prepared by mixing and dissolving the emulsified dispersion 1 and the above silver chlorobromide emulsion. Also, an emulsified dispersion 2 of the cyan coupler prepared in Example 1
(A solution obtained by adding 60 mmol of calcium nitrate to the liquid of the emulsified dispersion 1) and the silver chlorobromide emulsion were mixed and dissolved,
An emulsion layer coating solution 2 was prepared.

【0037】[0037]

【化8】 Embedded image

【0038】これらの乳剤層用塗布液1と2をそれぞれ
塗布して作製された感光材料1と2に光楔露光を与えて
現像時間が45秒の迅速カラー現像処理したところ、比
較用乳化分散物1を用いた感光材料1に比べて、本発明
の乳化分散物2を用いた感光材料2の方が高い最大発色
濃度が得られ発色性が改良されたことがわかった。ま
た、同様に硝酸カルシウムの替わりに硝酸マグネシウム
や硝酸バリウムが添加された場合にも、発色性が改良さ
れる。
The photosensitive materials 1 and 2 prepared by coating these emulsion layer coating solutions 1 and 2, respectively, were subjected to light wedge exposure and subjected to rapid color development processing for a development time of 45 seconds. Compared with the photosensitive material 1 using the product 1, the photosensitive material 2 using the emulsified dispersion 2 of the present invention obtained a higher maximum color density and improved color forming properties. Similarly, when magnesium nitrate or barium nitrate is added instead of calcium nitrate, the color developability is improved.

【0039】[0039]

【発明の効果】本発明によって粒径が小さく、しかも溶
解経時による粒径変化の小さな乳化分散物が得られ、ま
たこのカプラー乳化分散物を用いることで発色性が高
く、しかも発色濃度が安定したカラー写真感光材料が得
られる。また、カプラーの替わりに混色防止剤を用いて
本発明に従って調製された乳化分散物では、混色防止能
が増大、ないしは安定的に得られるという効果がある。
According to the present invention, it is possible to obtain an emulsified dispersion having a small particle size and a small change in the particle size with the lapse of time of dissolution, and the use of this coupler emulsified dispersion has a high coloring property and a stable coloring density. A color photographic light-sensitive material is obtained. Further, the emulsified dispersion prepared according to the present invention using a color-mixing inhibitor instead of a coupler has an effect that the color-mixing preventing ability is increased or stably obtained.

【図面の簡単な説明】[Brief description of the drawings]

【図1】乳化分散物を溶解経時させたときの粒子径の変
化を示す。
FIG. 1 shows the change in particle size when an emulsified dispersion is dissolved and aged.

【図2】乳化分散物を溶解経時させたときの粒子径の変
化を示す。
FIG. 2 shows a change in particle diameter when an emulsified dispersion is dissolved and aged.

【図3】乳化分散物を溶解経時させたときの粒子径の変
化を示す。
FIG. 3 shows a change in particle size when an emulsified dispersion is dissolved and aged.

【図4】乳化分散物を溶解経時させたときの粒子径の変
化を示す。
FIG. 4 shows a change in particle size when an emulsified dispersion is dissolved and aged.

Claims (6)

【特許請求の範囲】[Claims] 【請求項1】 添加された所定量の水溶性一価または多
価の金属塩を含んで、写真用疎水性化合物微粒子(但
し、ハロゲン化銀を除く)が乳化分散されていることを
特徴とする分散物。
1. A photographic hydrophobic compound fine particle (excluding silver halide) is emulsified and dispersed, containing a predetermined amount of a water-soluble monovalent or polyvalent metal salt added thereto. Dispersion.
【請求項2】 金属塩が二価又は三価の金属塩であるこ
とを特徴とする、請求項1に記載の写真用疎水性化合物
微粒子の乳化分散物。
2. The emulsified dispersion of fine particles of a photographic hydrophobic compound according to claim 1, wherein the metal salt is a divalent or trivalent metal salt.
【請求項3】 二価又は三価の金属塩がカルシウム塩、
マグネシウム塩、バリウム塩およびアルミニウム塩から
選ばれる金属塩の少なくとも一種であることを特徴とす
る、請求項2に記載の写真用疎水性化合物微粒子の乳化
分散物。
3. The divalent or trivalent metal salt is a calcium salt,
The emulsified dispersion of the photographic hydrophobic compound fine particles according to claim 2, which is at least one kind of a metal salt selected from a magnesium salt, a barium salt, and an aluminum salt.
【請求項4】 乳化物中の疎水性化合物微粒子1000
gあたり70ミリモル〜700ミリモルの添加量で添加
された水溶性一価金属塩を含有することを特徴とする写
真用疎水性化合物微粒子(但し、ハロゲン化銀を除く)
の乳化分散物。
4. A fine particle of a hydrophobic compound 1000 in an emulsion.
Hydrophobic compound fine particles for photography characterized by containing a water-soluble monovalent metal salt added in an amount of 70 to 700 mmol per gram (excluding silver halide)
Emulsified dispersion.
【請求項5】 金属塩が硝酸塩であることを特徴とす
る、請求項1〜4のいずれかに記載の写真用疎水性化合
物微粒子の乳化分散物。
5. The emulsified dispersion of the photographic hydrophobic compound fine particles according to claim 1, wherein the metal salt is a nitrate.
【請求項6】 支持体上に塗設された親水性コロイド層
中に請求項1〜5のいずれかに記載の写真用疎水性化合
物微粒子の乳化分散物を含有することを特徴とするハロ
ゲン化銀写真感光材料。
6. A halogenated composition comprising a hydrophilic colloid layer coated on a support, comprising the emulsified dispersion of the photographic hydrophobic compound fine particles according to claim 1 in a hydrophilic colloid layer. Silver photographic photosensitive material.
JP29871898A 1997-11-06 1998-10-20 Photographic emulsifying and dispersing material and silver halide photographic sensitive material containing same Pending JPH11194459A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP29871898A JPH11194459A (en) 1997-11-06 1998-10-20 Photographic emulsifying and dispersing material and silver halide photographic sensitive material containing same

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP9-304270 1997-11-06
JP30427097 1997-11-06
JP29871898A JPH11194459A (en) 1997-11-06 1998-10-20 Photographic emulsifying and dispersing material and silver halide photographic sensitive material containing same

Publications (1)

Publication Number Publication Date
JPH11194459A true JPH11194459A (en) 1999-07-21

Family

ID=26561633

Family Applications (1)

Application Number Title Priority Date Filing Date
JP29871898A Pending JPH11194459A (en) 1997-11-06 1998-10-20 Photographic emulsifying and dispersing material and silver halide photographic sensitive material containing same

Country Status (1)

Country Link
JP (1) JPH11194459A (en)

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