JPS6360446A - Silver halide photographic sensitive material dispersed by surfactant - Google Patents

Silver halide photographic sensitive material dispersed by surfactant

Info

Publication number
JPS6360446A
JPS6360446A JP20388886A JP20388886A JPS6360446A JP S6360446 A JPS6360446 A JP S6360446A JP 20388886 A JP20388886 A JP 20388886A JP 20388886 A JP20388886 A JP 20388886A JP S6360446 A JPS6360446 A JP S6360446A
Authority
JP
Japan
Prior art keywords
surfactant
photographic
hlb
surfactants
nonionic
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
JP20388886A
Other languages
Japanese (ja)
Inventor
Noriiku Tachibana
範幾 立花
Eiichi Ueda
栄一 上田
Nobuaki Kagawa
宣明 香川
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 JP20388886A priority Critical patent/JPS6360446A/en
Publication of JPS6360446A publication Critical patent/JPS6360446A/en
Pending legal-status Critical Current

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Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/38Dispersants; Agents facilitating spreading
    • 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

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

Abstract

PURPOSE:To obtain the titled material having improved photographic characteristics by using jointly an anionic surfactant and a nonionic surfactant as the dispersant, and by using at least 2 kinds of the surfactants having differ ent HLB in the nonionic surfactant, thereby dispersing uniformly a hydrophobic photographic additive in the titled material. CONSTITUTION:The material comprises at least one layer of the hydrophilic colloid layer which contains the anionic surfactant the nonionic surfactants having HLB of 1-7 and the nonionic surfactant having HLB of 8-20. As to the surfactant especially, the nonionic surfactant the nonionic surfactant having prescribed HLB which displays the specific characteristics of the surfactant is used, and at least 2 kinds of the nonionic surfactants having different kinds of HLB and the anionic surfactants are jontly used. The excellent effect of the titled material about dispersion power, storing stability for a long period and photographic characteristics is obtd., on comparing with the effect obtd. by merely using the anionic surfactant along with the nonionic surfactant.

Description

【発明の詳細な説明】 [産業上の利用分野] 本発明は、界面活性剤を用いて分散したハロゲン化銀写
真感光材料に関するものであり、更に詳しくは、分散剤
として、アニオン性界面活性剤及び少なくとも2種類の
ノニオン性界面活性剤を用いて疎水性写真添加剤を分散
してなる経時安定性を有するハロゲン化銀写真感光材料
に関するものである。
Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic material dispersed using a surfactant, and more specifically, an anionic surfactant as a dispersant. The present invention also relates to a silver halide photographic material having stability over time, which is obtained by dispersing a hydrophobic photographic additive using at least two types of nonionic surfactants.

[発明の背景] 一般に写真感光材料は、写真用支持体上に親水性コロイ
ドを含む写真構成層が複数設けられている。それらの写
真構成層は、下塗層、中間層、感光層、表面保護層等の
種々の機能を有し、それらの機能を満足させるために各
層には種々の例えば、カプラー、紫外線吸収剤、蛍光増
白剤等の疎水性写真添加剤が含有される。そして該添加
剤の有機溶媒あるいはアクリル酸エステル等の疎水性合
成高分子等を分散物として含んだ親水性コロイド液を塗
布する場合に、しばしば分散剤として、界面活性剤が用
いられる。
[Background of the Invention] Generally, a photographic light-sensitive material has a plurality of photographic constituent layers containing hydrophilic colloids provided on a photographic support. These photographic constituent layers have various functions such as an undercoat layer, an intermediate layer, a photosensitive layer, a surface protective layer, etc., and in order to satisfy these functions, each layer has various functions such as couplers, ultraviolet absorbers, Contains hydrophobic photographic additives such as optical brighteners. When applying a hydrophilic colloid liquid containing an organic solvent for the additive or a hydrophobic synthetic polymer such as an acrylic acid ester as a dispersion, a surfactant is often used as a dispersant.

しかしながら、写真感光材料に用いられる界面活性剤は
写真感度、カブリ、階調、現像進行の速さなどの写真特
性や迅速処理性に必要とする良好な現像処理性(即ち、
フィルム面に対するヌレが良好であること及び泡の付着
がないこと等)に悪影響を及ぼさないことが必要である
ところ、写真感光材料の写真的性質は写真乳剤中に添加
された微量の物質によってもしばしば大きな影3を受け
る事があり、そのため界面活性剤の場合も、分散目的を
充分に満足し且つ写真的に悪い影響のない化合物を見出
すことは容易なことではない。
However, surfactants used in photographic materials have good photographic properties such as photographic sensitivity, fog, gradation, and speed of development, as well as good processing properties (i.e., necessary for rapid processing).
It is necessary that the photographic properties of a photographic light-sensitive material are not affected by a trace amount of substances added to the photographic emulsion. It is often difficult to find a compound that fully satisfies the purpose of dispersion and has no adverse photographic effect even in the case of surfactants.

写真用材料の塗布や分散の目的には、界面活性剤として
、一般にアニオン性界面活性剤が用いられ、ノニオン性
界面活性剤については全く使用されていなかった。その
理由は、第1にノニオン性界面活性剤だけを用いた写真
分散物が、その分散能が不充分で均一な分散物が得られ
ないこと、第2にノニオン性界面活性剤を含有している
ハロゲン化銀写真感光材料を現像処理した場合、該現像
速度が所望のものとはならず、多大の影響を及ぼす欠点
がある9例えば、写真感光材料の種類によって、現像速
度が遅くなり過ぎたり、または現像速度が早すぎたりし
て、良好な写真画像が得られない。そのため、写真特性
に対して不充分でありながらも、仕方なくアニオン性界
面活性剤を使用しているというのが現状であった。
For the purpose of coating and dispersing photographic materials, anionic surfactants are generally used as surfactants, and nonionic surfactants have not been used at all. The reasons for this are: firstly, photographic dispersions using only nonionic surfactants have insufficient dispersing ability and cannot obtain uniform dispersions, and secondly, photographic dispersions containing only nonionic surfactants When a silver halide photographic light-sensitive material is developed, the development speed is not as desired, and there are drawbacks that have a large impact.9 For example, depending on the type of photographic light-sensitive material, the development speed may become too slow or , or the development speed is too fast, making it impossible to obtain good photographic images. Therefore, the current situation is that anionic surfactants have no choice but to be used, even though they are insufficient for photographic properties.

そこで、本発明者等は、先にアニオン性界面活性剤の欠
点を改良し、該アニオン性界面活性剤にノニオン性界面
活性剤を併用することにより、写真特性を損なわずに分
散性並びに経時安定性を有するハロゲン化銀写真感光材
料について特許出願した。
Therefore, the present inventors first improved the drawbacks of anionic surfactants and used a nonionic surfactant in combination with the anionic surfactant to improve dispersibility and stability over time without impairing photographic properties. filed a patent application for a silver halide photographic material with

しかしながら、この特許出願においても、長期間の経時
安定性の点では今だ満足のいくものではなかった。
However, even in this patent application, the long-term stability over time was still unsatisfactory.

[本発明の目的] 本発明者等は、前述の問題点ないし欠点について、種々
、研究を続けた結果、界面活性剤特にノニオン性界面活
性剤について、その特性であるHLBを規定するととも
に、少なくともHLBの異る2種類のノニオン性界面活
性剤を用い、且つアニオン性界面活性剤と併用すること
により、アニオン性界面活性剤とノニオン性界面活性剤
との単なる併用の場合より、分散能、長期経時安定性お
よび写真特性において、道かに優れた効果を有すること
を発見した。
[Object of the present invention] As a result of continuing various studies regarding the above-mentioned problems and drawbacks, the present inventors have defined the HLB, which is the characteristic of surfactants, particularly nonionic surfactants, and at least By using two types of nonionic surfactants with different HLB and in combination with an anionic surfactant, the dispersion ability and long-term effect can be improved compared to the simple combination of an anionic surfactant and a nonionic surfactant. It has been discovered that the method has excellent effects in terms of stability over time and photographic properties.

したがって、本発明は、該知見に基ずいてなされたもの
で、本発明の第一の目的は、良好に分散され、且つ長期
経時安定性を有する疎水性写真用添加剤を含有するハロ
ゲン化銀写真感光材料を提供することにある。
Therefore, the present invention has been made based on this knowledge, and the first object of the present invention is to provide a silver halide containing a hydrophobic photographic additive that is well dispersed and has long-term stability over time. Our objective is to provide photographic materials.

また、本発明の第二の目的は、写真感度、カブリ、l!
皆調、現像進行の速さなどの写真特性に実質的に悪影響
を与えない分散剤を用いて疎水性写真用添加剤を分散し
たハロゲン化銀写真感光材料を提供することにある。
A second object of the present invention is to improve photographic sensitivity, fog, l!
It is an object of the present invention to provide a silver halide photographic material in which a hydrophobic photographic additive is dispersed using a dispersant that does not substantially adversely affect photographic properties such as perfect tone and speed of development.

[本発明の構成コ 本発明の目的は、分散剤としてアニオン性界面活性剤お
よびHLBの異る少なくとも2種類のノニオン性界面活
性剤を用いて分散した疎水性写真用添加剤を含有するハ
ロゲン化銀写真感光材料により達成された。即ち本発明
は、支持体上に、アニオン性界面活性剤およびHLBが
1〜7のノニオン性界面活性剤とHLBが8〜2oのノ
ニオン性界面活性剤とを少なくとも含有する親水性コロ
イド層を少なくとも一層有するハロゲン化銀写真感光材
料である。
[Constitution of the present invention] The object of the present invention is to provide a halogenated photographic additive containing a hydrophobic photographic additive dispersed using an anionic surfactant and at least two types of nonionic surfactants having different HLBs as dispersants. This was achieved using silver photographic materials. That is, the present invention provides at least a hydrophilic colloid layer containing at least an anionic surfactant, a nonionic surfactant with an HLB of 1 to 7, and a nonionic surfactant with an HLB of 8 to 2o on a support. This is a silver halide photographic light-sensitive material having one layer.

本発明に係る分散剤として用いられるアニオン性界面活
性剤には、下記の一般式[I]〜[VI]で表わされる
ものが挙げられるが、これらのものは、特に好ましく用
いられるものである。
Examples of the anionic surfactant used as a dispersant according to the present invention include those represented by the following general formulas [I] to [VI], and these surfactants are particularly preferably used.

一般式[11 [式中、Rは水素原子又はメチル基を表わし、R,及び
R2はそれぞれ同じでも異ってもよい水素原子又は炭素
原子数1〜18のアルキル基を表わし、 Wは−COO
M、  −3o、M。
General formula [11 [In the formula, R represents a hydrogen atom or a methyl group, R and R2 each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, which may be the same or different, and W is -COO
M, -3o, M.

−OPO(OM)2を表わし、またMは水素原子または
カチオンを表わす。IolはO〜50の整数またnlは
O〜4の整数を表わす。] 一般式[+1] R1→Cf70+CH2CHOh−CH2抽W[式中、
Rは水素原子又はメチル基を表わし、R3は炭素原子数
6〜20のアルキル基またはアルケニル基を表わし、 
Wは−COOM、−3Os M、−0PO(OM)2を
表わし、またMは水素原子またはカチオンを表わす、f
f12はO〜50の整数を表わし、R2は0〜4の整数
を、またaはOまたは1の整数を表わす。] 一般式[II+ ] [式中、R4およびR6はそれぞれ炭素原子数6〜18
のアルキル基を表わし、またMは水素原子またはカチオ
ンを表わす。コ 一般式[] %式% [式中、R8は炭素原子数6〜20のアルキル基を表わ
し、R2は炭素原子数1〜4のアルキル基を表わし、X
は−COOMまたは一5o3!Jを表わし、またMは水
素原子またはカチオンを表わす。n、は1〜4の整数を
表わす、] 一般式[V] [式中、R6およびR9はそれぞれ炭素原子数6〜20
のアルキル基を表わし、またMは水素原子またはカチオ
ンを表わす。〕 一般式[VI] [式中、R3゜、R11およびR12はそれぞれ炭素原
子数1〜16のアルキル基を表わし、またMは水素原子
またはカチオンを表わす。] R1乃至R+2で表わされるそれぞれのアルキル基は置
換基を有するものも含み、この場合、炭素原子数にはそ
の置換基を含めない。カチオンとしては、ナトリウムイ
オン、カリウムイオン、アンモニウムイオン等が挙げら
れる。
-OPO(OM)2, and M represents a hydrogen atom or a cation. Iol represents an integer of 0 to 50, and nl represents an integer of 0 to 4. ] General formula [+1] R1→Cf70+CH2CHOh-CH2 extraction W [in the formula,
R represents a hydrogen atom or a methyl group, R3 represents an alkyl group or alkenyl group having 6 to 20 carbon atoms,
W represents -COOM, -3Os M, -0PO(OM)2, and M represents a hydrogen atom or a cation, f
f12 represents an integer of O to 50, R2 represents an integer of 0 to 4, and a represents an integer of O or 1. ] General formula [II+ ] [In the formula, R4 and R6 each have 6 to 18 carbon atoms
represents an alkyl group, and M represents a hydrogen atom or a cation. General formula [ ] % Formula % [In the formula, R8 represents an alkyl group having 6 to 20 carbon atoms, R2 represents an alkyl group having 1 to 4 carbon atoms, and
-COOM or one 5o3! J represents a hydrogen atom or a cation. n represents an integer of 1 to 4, General formula [V] [wherein R6 and R9 each have 6 to 20 carbon atoms]
represents an alkyl group, and M represents a hydrogen atom or a cation. ] General formula [VI] [In the formula, R3°, R11 and R12 each represent an alkyl group having 1 to 16 carbon atoms, and M represents a hydrogen atom or a cation. ] Each of the alkyl groups represented by R1 to R+2 includes those having a substituent, and in this case, the number of carbon atoms does not include the substituent. Examples of cations include sodium ions, potassium ions, ammonium ions, and the like.

一般式CI]乃至一般式[VT]で表わされるもののう
ち、特に好ましいのは一敗式[I]、一般式[I+ ]
および一般式[V]で表わされるものである。
Among those represented by the general formula CI] to the general formula [VT], particularly preferred are the Ichiro formula [I] and the general formula [I+]
and is represented by the general formula [V].

次に具体的化合物の例を挙げるがこれらに限定されるも
のではない。
Examples of specific compounds will be listed next, but the invention is not limited to these.

(以下余白) 1、+J2s−0+CHzC1(20h (C1h+3
SO3KC+aHs3−OfCI(2CH20?i; 
(CII2i 5O5Na(、,1(250503Na C12H25−MC1hC1bOf SO3NaC12
H25−C−0+CHtCHiO%5OsNaa−10 a−11 D C)l。
(Left below) 1, +J2s-0+CHzC1(20h (C1h+3
SO3KC+aHs3-OfCI(2CH20?i;
(CII2i 5O5Na(,,1(250503Na C12H25-MC1hC1bOf SO3NaC12
H25-C-0+CHtCHiO%5OsNaa-10 a-11 D C)l.

CI2Cl2)125 CHzCHiCOOHC9l−
1141−0−C−CHz CJl+++−OC−CH−5O3NaCsll + 
+ 0COCH−5OJaC1ot(210COCR2 2H5 C4)IgCHCLO[:OCI 5OJa■ a−15a−16 本発明で用いられる2種類のノニオン性界面活性剤とし
ては、グリフインによるHLB値が1〜7で、実質的に
水に溶解しないもの、即ち疎水性のものとHLB値が8
〜20で、実質的に水溶性のもの乃至親水性のものとを
組合せたノニオン性界面活性剤であって、特にグリフイ
ンによるHLB値がそれぞれ1〜7および8〜20の範
囲のものが好ましく、これらの範囲にあれば、特にその
式構造は問わない。 また、該界面活性剤は、25℃で
液体状態のものが特に好ましいが、25℃で固体であっ
ても分散状態で液体になるものであれば、本発明の範囲
のものとして使用することができる。更に、これら2種
類のノニオン性界面活性剤のHLB値の差が2以上であ
るのが好ましい。
CI2Cl2)125 CHzCHiCOOHC9l-
1141-0-C-CHz CJl+++-OC-CH-5O3NaCsll +
+ 0COCH-5OJaC1ot(210COCR2 2H5 C4)IgCHCLO[:OCI 5OJa■ a-15a-16 The two types of nonionic surfactants used in the present invention have an HLB value of 1 to 7 according to griffin, and are substantially water-resistant. Those that do not dissolve in water, that is, those that are hydrophobic and have an HLB value of 8
~20, and is a combination of a substantially water-soluble or hydrophilic nonionic surfactant, and particularly preferred is a nonionic surfactant with an HLB value of 1 to 7 and a range of 8 to 20, respectively, according to griffin. As long as it falls within these ranges, its formula structure is not particularly limited. Further, it is particularly preferable that the surfactant be in a liquid state at 25°C, but even if it is solid at 25°C, any surfactant that becomes liquid in a dispersed state may be used within the scope of the present invention. can. Furthermore, it is preferable that the difference in HLB value between these two types of nonionic surfactants is 2 or more.

HLB値が20を越えるものでは、良好な分散性を得る
ことができないばかりではなく経済的にも好ましくない
If the HLB value exceeds 20, it is not only impossible to obtain good dispersibility but also economically unfavorable.

本発明で用いられるノニオン性界面活性剤について、具
体的化合物を挙げるが、ここに挙げたものは、最も好ま
しいものの一例であって、本発明をこれに限定するもの
ではない。
Concerning the nonionic surfactant used in the present invention, specific compounds are listed, but those listed here are examples of the most preferred ones, and the present invention is not limited thereto.

まず、HLBが1〜7のノニオン性界面活性剤の具体例
を挙げる。
First, specific examples of nonionic surfactants having an HLB of 1 to 7 will be given.

N−1ソルビタンモノラウレート N−2ソルビタンモノオレエート N−3ソルビタンドール油脂肪酸エステルN−4ソルビ
タンヒマシ油脂肪酸エステルN−5ポリオキシエチレン
オレエート N−6ポリオキシエチレンオリーブ油脂肪酸エステルの
うちエチレンオキサイド鎖 (以下nと略す)が5以下のもの N−7グリセリルモノカブリレート N−8グリセリルモノオレエート N−9グリセリルモノイソステアレートN−10ジグリ
セリルモノオレエート N−11ポリオキシエチレングリセリルモノオレエート
 (n=1〜6) N−12ポリオヤシエチレンノニルフェニルエーテル(
n;2〜6) N−13ポリオキシエチレンオレイルエーテル(n;2
〜6) N−14ポリオキシエチレンソルビトール脂肪酸エステ
ル(n=2〜6) N−15グリセリルモノアルキルエーテル(アルキル基
の炭素原子が8〜18個) N−16ポリプロピレンオキシド N−17オキシエチレン・オキシプロピレンブロックポ
リマ−(エチレンオキシド 重量% 5%) 次ぎに、HLBが8〜20のノニオン性界面活性剤の具
体例を挙げる。
N-1 Sorbitan monolaurate N-2 Sorbitan monooleate N-3 Sorbitandole oil fatty acid ester N-4 Sorbitan castor oil fatty acid ester N-5 Polyoxyethylene oleate N-6 Among polyoxyethylene olive oil fatty acid esters, ethylene Items with 5 or less oxide chains (hereinafter abbreviated as n) N-7 Glyceryl monocabrilate N-8 Glyceryl monooleate N-9 Glyceryl monoisostearate N-10 Diglyceryl monooleate N-11 Polyoxyethylene glyceryl Monooleate (n=1-6) N-12 polyoxyethylene nonylphenyl ether (
n; 2-6) N-13 polyoxyethylene oleyl ether (n; 2
~6) N-14 polyoxyethylene sorbitol fatty acid ester (n=2-6) N-15 glyceryl monoalkyl ether (alkyl group has 8 to 18 carbon atoms) N-16 polypropylene oxide N-17 oxyethylene oxy Propylene block polymer (ethylene oxide weight% 5%) Next, specific examples of nonionic surfactants having an HLB of 8 to 20 will be given.

n  IC+aH3tO−+f:)I2CH20+To
Hn−2C16)1370fCH2CH20+T−oH
l  3   ClaH3sO(CH2CH20+−r
−38n  4   G+21hsO−fC)I2CH
2吐+Jn −9 C++tlz3COO−fCH2CH20rroHC+
 7835に00 +C1hClbOtTb)lポリオ
キシエチレン・ソルビタンモノラウレートn−12(n
=20) CI 28(:ON [+CHzC:H20+ToH]
 2オキシエチレン・オキシプロピレンブロックポリマ
−(エチレンオキシド重量% 40%)本発明で用いら
れる分散剤において、アニオン性界面活性剤とノニオン
性界面活性剤との添加割合は、重量比で、1:99〜9
9.5:0.5、好ましくは、2080〜99:lの範
囲で用いられ、このうち2種類のノニオン性界面活性剤
の重量比は、HLBにおいて(1〜7)/(8〜20)
が1:99〜99:1である。また疎水性写真用添加剤
に対しては、添加剤量の0.1〜15重量の範囲で用い
られる。
n IC+aH3tO-+f:)I2CH20+To
Hn-2C16) 1370fCH2CH20+T-oH
l 3 ClaH3sO(CH2CH20+-r
-38n 4 G+21hsO-fC)I2CH
2 discharge + Jn -9 C++tlz3COO-fCH2CH20rroHC+
7835 to 00 +C1hClbOtTb)l Polyoxyethylene sorbitan monolaurate n-12(n
=20) CI 28(:ON [+CHzC:H20+ToH]
2-oxyethylene/oxypropylene block polymer (ethylene oxide weight% 40%) In the dispersant used in the present invention, the addition ratio of anionic surfactant and nonionic surfactant is 1:99 to 1:99 by weight. 9
9.5:0.5, preferably in the range of 2080 to 99:l, and the weight ratio of the two types of nonionic surfactants is (1 to 7)/(8 to 20) in HLB.
is 1:99 to 99:1. For hydrophobic photographic additives, the amount used is from 0.1 to 15% by weight of the additive.

本発明において、前記分散剤を用いて分散することので
きる疎水性写真用添加剤は、黒白用ハロゲン化銀写真感
光材料、ハロゲン化銀カラー写真感光材料等の写真感光
材料の製造に用いられるもので、例えば、疎水性カプラ
ー、紫外線吸収剤、酸化防止剤、蛍光増白剤、カブリ防
止剤、スティン防止剤、フィルター染料、ハレーション
防止染料等の染料、硬膜剤等の写真性能を発揮するのに
必要な添加剤を挙げることができる。
In the present invention, hydrophobic photographic additives that can be dispersed using the dispersant are those used in the production of photographic materials such as black and white silver halide photographic materials and silver halide color photographic materials. For example, dyes such as hydrophobic couplers, ultraviolet absorbers, antioxidants, optical brighteners, anti-fogging agents, anti-stain agents, filter dyes, anti-halation dyes, and hardeners that exhibit photographic performance. Additives necessary for this can be mentioned.

代表的な疎水性色素画像形成カプラーについては、各種
のものが用いられるが、以下に疎水性のカプラーの一例
を挙げる。
Various types of typical hydrophobic dye image-forming couplers are used, and examples of hydrophobic couplers are listed below.

イエロー色素形成カプラー (’L マゼンタ色士形成カプラー 2A−1 I r′t しL t トA−5 t t )A−8 シアン色素形成カプラー 0ば H L OOH L マスク形成カラードカプラー t DIRカプラー(現像抑制剤放出カプラー)dH5 N−4 本発明の疎水性写真用添加剤として用いられる紫外線吸
収剤としては、代表的には下記のものを挙げることがで
きる。
Yellow dye-forming coupler ('L Magenta color-forming coupler 2A-1 I r't L t A-5 t t ) A-8 Cyan dye-forming coupler 0ba H L OOH L Mask-forming colored coupler t DIR coupler ( Development inhibitor releasing coupler) dH5 N-4 As the ultraviolet absorber used as the hydrophobic photographic additive of the present invention, the following can be typically mentioned.

I し4H9(L) ■0 TJI”I U −8CN (CH2−CH−(:H2)2N  CH−CH−(:
H−CN CN 本発明の疎水性写真用添加剤として用いられる酸化防止
剤としては、代表的には次のものを挙げることかできる
I shi4H9(L) ■0 TJI"I U -8CN (CH2-CH-(:H2)2N CH-CH-(:
H-CN CN Typical antioxidants used as the hydrophobic photographic additive of the present invention include the following.

O−1 O−2 CH O−3 O−4 H3 下記に代表的な室光増白剤(BL)、染料(F)の具体
例を示す。
O-1 O-2 CH O-3 O-4 H3 Specific examples of typical room light brighteners (BL) and dyes (F) are shown below.

BL−1 BL−2 C2H。BL-1 BL-2 C2H.

次に本発明の分散剤を用いて疎水性写真用添加剤を親水
性コロイドバインダー中に分散する代表的な方法につい
て述べる。親水性コロイドバインダーに疎水性写真用添
加剤を分散するには、まず該疎水性写真用添加剤を低沸
点有機溶媒、例えば、酢酸エチル、メタノール、エタノ
ール等に溶解する。この際疎水性写真用添加剤を溶解す
るのを促進するために高沸点有機溶媒、例えば、ジブチ
ルフタレート、トリクレジルホスフェート、ジノニルフ
ェノール、ジエチルラウリルアミド、ジエチレングリコ
ールブチルアセテート等を加えることができる。このよ
うにして溶解した疎水性写真用添加剤を親水性コロイド
バインダー中に分散させるには、常法に従って、本発明
の界面活性剤を用い例えばミキサー、ホモジナイザー、
コロイドミル、超音波分散機を用いて親木性コロイド中
に分散される。親木性コロイドとしては通常写真用のバ
インダーとして用いられるものがすべて用いられる。
Next, a typical method for dispersing a hydrophobic photographic additive into a hydrophilic colloid binder using the dispersant of the present invention will be described. To disperse a hydrophobic photographic additive in a hydrophilic colloid binder, the hydrophobic photographic additive is first dissolved in a low boiling organic solvent such as ethyl acetate, methanol, ethanol, or the like. At this time, a high boiling point organic solvent such as dibutyl phthalate, tricresyl phosphate, dinonylphenol, diethyl laurylamide, diethylene glycol butyl acetate, etc. can be added to promote dissolution of the hydrophobic photographic additive. To disperse the hydrophobic photographic additive thus dissolved into the hydrophilic colloid binder, the surfactant of the present invention is used in a conventional manner, for example, using a mixer, homogenizer, etc.
It is dispersed into a woody colloid using a colloid mill or an ultrasonic dispersion machine. As the wood-philic colloid, all those commonly used as binders for photography can be used.

本発明の分散物は従来公知の分散方法と同様の方法によ
って親木性コロイドバインダーあるいはハロゲン化銀写
真乳剤と混合されて写真用塗布液が調整される。
The dispersion of the present invention is mixed with a wood-philic colloid binder or a silver halide photographic emulsion to prepare a photographic coating solution by a method similar to a conventionally known dispersion method.

本発明の界面活性剤は、ハロゲン化銀写真乳剤層の他に
保護層、中間層、フィルター層、ハレーション防止層、
バック層、下引層等の補助層を適用する際、これらの補
助層材料中に用いることができる。
In addition to the silver halide photographic emulsion layer, the surfactant of the present invention can be used in protective layers, intermediate layers, filter layers, antihalation layers,
When applying auxiliary layers such as backing layers and subbing layers, it can be used in these auxiliary layer materials.

本発明の界面活性剤は、ハロゲン化銀写真感光材料とし
て、特にハロゲン化銀カラー写真感光材料を用いる場合
には、青感性乳剤層、緑感性乳剤層、赤感性乳剤層の各
乳剤層、黄色フィルター層、各種中間層、最外層として
保護層、紫外線吸収層等のハロゲン化銀カラー写真感光
材料の構成層中に用いられる。
The surfactant of the present invention is used as a silver halide photographic material, especially when a silver halide color photographic material is used. It is used in constituent layers of silver halide color photographic materials such as filter layers, various intermediate layers, protective layers as outermost layers, and ultraviolet absorbing layers.

[実施例] 以下、実施例により本発明を具体的に述べるが、本発明
の実施の態様はこれにより限定されるものではない。
[Examples] The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto.

実施例1 表1に記載された疎水性写真用添加剤の各化合物、アニ
オン性界面活性剤の各化合物およびノニオン性界面活性
剤の各化合物を、各々含む下記組成の混合物および比較
用混合物を40tにて、ホモジナイザーにより激しく攪
拌し、それぞれ表1に記載の試料(本発明)1〜17お
よび比較18.19.20を得た。
Example 1 40 tons of a mixture and a comparative mixture having the following compositions each containing each compound of a hydrophobic photographic additive, each compound of an anionic surfactant, and each compound of a nonionic surfactant listed in Table 1. The mixture was vigorously stirred using a homogenizer to obtain samples 1 to 17 (invention) and comparative samples 18, 19, and 20 listed in Table 1, respectively.

疎水性写真用添加剤    表1記載の量ジブチルフタ
レート3g ゼラチン             5gアニオン性界
面活性剤   表1記載の量)ILB値1〜7のノニオ
ン 性界面活性剤       表1記載の量)ILB値8
〜200ノニオ ン性界面活性剤      表1記載の食酢酸エチル 
         10cc水           
        1ooIIlfL得られた分散物は、
コールタ−カウンターN4(コールタ−社製)を用いて
分散物の粒径を測定し、30℃での分散直後、5時間後
、60時間後の粒径変化を観測した。表1から明らかな
ように、本発明(試料1〜17)のものは、比較(試料
18.19.20)のものに比べ、時間経過(60時間
)に対する粒径変化が殆どなく、したがって長時間分散
安定性を有することがわかる。
Hydrophobic photographic additives Amounts listed in Table 1 Dibutyl phthalate 3g Gelatin 5g Anionic surfactants Amounts listed in Table 1) Nonionic surfactants with an ILB value of 1 to 7) Amounts listed in Table 1) ILB value 8
~200 Nonionic surfactant Ethyl acetate listed in Table 1
10cc water
1ooIIlfL The obtained dispersion is
The particle size of the dispersion was measured using a Coulter Counter N4 (manufactured by Coulter Inc.), and changes in particle size were observed immediately after dispersion at 30°C, 5 hours later, and 60 hours later. As is clear from Table 1, the particles of the present invention (samples 1 to 17) showed almost no change in particle size over time (60 hours) compared to the comparative samples (samples 18, 19, and 20), and therefore It can be seen that it has time dispersion stability.

(以下余白) 実施例2 実施例1で得られた分散物のうち、試料4〜6の全量を
カラードマゼンタカプラー(L−6)およびDIRカプ
ラー(N−1)を含む緑感性沃臭化銀乳剤(6,0モル
%の沃化銀を含有)500gに添加してハレーション防
止層を有するトリアセテートベースに銀量が5 m g
 / d m ’になるように塗布し乾燥した。得られ
た本発明の試料を試料(1)〜(3)とする、上記分散
物試料の代りに、同じ〈実施例1で得られた比較試料1
5を上記と同様の方法により塗布、乾燥し、比較試料(
A)を作成した。 前記試料(1)〜(3)および(A
)をウェッジ露光し、下記に示す処理工程に従って処理
した。またこの処理工程において用いた処理液は下記に
示す通りである。
(Space below) Example 2 Among the dispersions obtained in Example 1, the entire amount of Samples 4 to 6 was replaced with green-sensitive silver iodobromide containing a colored magenta coupler (L-6) and a DIR coupler (N-1). 5 mg of silver on a triacetate base with an antihalation layer added to 500 g of emulsion (containing 6.0 mol % silver iodide)
/ d m' and dried. The obtained samples of the present invention are referred to as samples (1) to (3). Instead of the above dispersion sample, the same <comparative sample 1 obtained in Example 1>
5 was applied and dried in the same manner as above, and a comparative sample (
A) was created. The samples (1) to (3) and (A
) was wedge exposed and processed according to the processing steps shown below. Further, the treatment liquid used in this treatment step is as shown below.

[処理工程] 発色現像     38℃    3分 O秒漂白定着
     25℃    1分30秒水   洗   
    25℃      2分  0秒[発色現像液
組成] 水を加えて11とし水酸化カリウムを用いてp)Iを1
0.0に調整する。
[Processing process] Color development 38°C 3 minutes O seconds bleach fixing 25°C 1 minute 30 seconds Washing with water
25°C 2 minutes 0 seconds [Color developer composition] Add water to 11 and use potassium hydroxide to adjust p)I to 1
Adjust to 0.0.

[漂白定着液] た。[Bleach-fix solution] Ta.

本発明の分散剤を使用して分散したハロゲン化銀写真感
光材料について、その写真特性のうち、感度、カブリの
結果を表2に示す。
Among the photographic properties of the silver halide photographic material dispersed using the dispersant of the present invention, the results of sensitivity and fog are shown in Table 2.

感度はカブリ+0.5の濃度の試料(A)の感度を10
0とした相対感度で示した。
The sensitivity is 10 the sensitivity of sample (A) with a density of fog + 0.5.
The relative sensitivity is expressed as 0.

表−2 表2から明らかな如く、本発明のものは、比較(A)の
ものより、高感度であるにもかかわらずカブリが少ない
上、均質な画像が得られることを示している。
Table 2 As is clear from Table 2, the samples of the present invention produce less fog and more homogeneous images than those of Comparative (A) despite having higher sensitivity.

[本発明の効果] 前述の如く、本発明では、分散剤として、アニオン性界
面活性剤およびノニオン性界面活性剤を併用すると共に
、該ノニオン性界面活性剤において、少なくともHLB
の異なる2 fffi類の界面活性剤を用いることによ
り、疎水性写真用添加剤を均一に分散することができる
と共に、写真特性に優れた良質の写真画像を得ることが
できるという格別顕著な効果を有するものである。
[Effects of the present invention] As described above, in the present invention, an anionic surfactant and a nonionic surfactant are used together as a dispersant, and the nonionic surfactant has at least HLB
By using two types of fffi surfactants with different characteristics, it is possible to uniformly disperse hydrophobic photographic additives, and at the same time, it is possible to obtain high-quality photographic images with excellent photographic properties, which is a particularly remarkable effect. It is something that you have.

以上 出願人        小西六写真工業株式会社代理人
弁理士         中 島 幹 雄外1名
Applicant: Konishiroku Photo Industry Co., Ltd. Representative Patent Attorney Miki Nakajima Yugai (1 person)

Claims (1)

【特許請求の範囲】 支持体上に、アニオン性界面活性剤および HLBの異る少なくとも2種類のノニオン性界面活性剤
を含有する親水性コロイド層を少なくとも一層有するハ
ロゲン化銀写真感光材料。
[Scope of Claims] A silver halide photographic material having, on a support, at least one hydrophilic colloid layer containing an anionic surfactant and at least two types of nonionic surfactants having different HLBs.
JP20388886A 1986-09-01 1986-09-01 Silver halide photographic sensitive material dispersed by surfactant Pending JPS6360446A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP20388886A JPS6360446A (en) 1986-09-01 1986-09-01 Silver halide photographic sensitive material dispersed by surfactant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP20388886A JPS6360446A (en) 1986-09-01 1986-09-01 Silver halide photographic sensitive material dispersed by surfactant

Publications (1)

Publication Number Publication Date
JPS6360446A true JPS6360446A (en) 1988-03-16

Family

ID=16481378

Family Applications (1)

Application Number Title Priority Date Filing Date
JP20388886A Pending JPS6360446A (en) 1986-09-01 1986-09-01 Silver halide photographic sensitive material dispersed by surfactant

Country Status (1)

Country Link
JP (1) JPS6360446A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5356768A (en) * 1990-10-29 1994-10-18 Minnesota Mining And Manufacturing Company Light-sensitive silver halide color photographic elements containing surfactants with a combined HLB greater than 20
US5576161A (en) * 1994-08-12 1996-11-19 Konica Corporation Silver halide light-sensitive photographic material and method of processing thereof
EP1530079A1 (en) * 2003-10-24 2005-05-11 Konica Minolta Medical & Graphic, Inc. Silver salt photothermographic dry imaging material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5329715A (en) * 1976-08-31 1978-03-20 Fuji Photo Film Co Ltd Photographic light sensitive material
JPS5348734A (en) * 1976-10-15 1978-05-02 Mitsubishi Paper Mills Ltd Multiilayer color silver halide photographic material
JPS5711341A (en) * 1980-06-25 1982-01-21 Fuji Photo Film Co Ltd Photographic sensitive material
JPS6076741A (en) * 1983-10-03 1985-05-01 Fuji Photo Film Co Ltd Photosensitive silver halide material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5329715A (en) * 1976-08-31 1978-03-20 Fuji Photo Film Co Ltd Photographic light sensitive material
JPS5348734A (en) * 1976-10-15 1978-05-02 Mitsubishi Paper Mills Ltd Multiilayer color silver halide photographic material
JPS5711341A (en) * 1980-06-25 1982-01-21 Fuji Photo Film Co Ltd Photographic sensitive material
JPS6076741A (en) * 1983-10-03 1985-05-01 Fuji Photo Film Co Ltd Photosensitive silver halide material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5356768A (en) * 1990-10-29 1994-10-18 Minnesota Mining And Manufacturing Company Light-sensitive silver halide color photographic elements containing surfactants with a combined HLB greater than 20
US5576161A (en) * 1994-08-12 1996-11-19 Konica Corporation Silver halide light-sensitive photographic material and method of processing thereof
EP1530079A1 (en) * 2003-10-24 2005-05-11 Konica Minolta Medical & Graphic, Inc. Silver salt photothermographic dry imaging material
US7097962B2 (en) 2003-10-24 2006-08-29 Konica Minoltn Medical & Graphic, Inc. Silver salt photothermographic dry imaging material

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