JP2004240445A - Method for emulsifying and dispersing hydrophobic photographically useful compound - Google Patents

Method for emulsifying and dispersing hydrophobic photographically useful compound Download PDF

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JP2004240445A
JP2004240445A JP2004093250A JP2004093250A JP2004240445A JP 2004240445 A JP2004240445 A JP 2004240445A JP 2004093250 A JP2004093250 A JP 2004093250A JP 2004093250 A JP2004093250 A JP 2004093250A JP 2004240445 A JP2004240445 A JP 2004240445A
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water
dispersing
dispersion
photographic
hydrophobic
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Naoyuki Kawanishi
直之 川西
Masataka Ogawa
雅隆 小川
Atsushi Hayakawa
篤 早川
Kazuhiko Fujiwara
一彦 藤原
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material containing a fine dispersion of a hydrophobic photographically useful compound excellent in suitability to manufacture. <P>SOLUTION: This invention relates to a method for dispersing a water-insoluble phase substantially comprising a hydrophobic photographically useful compound having a melting point of <100°C and an aqueous solution of an organic solvent having a high boiling point in water or in a hydrophilic colloidal composition, the method includes a step of dispersing the hydrophobic photographically useful compound in water or in a hydrophilic colloidal composition at a temperature close to the melting point of the compound to obtain a dispersion, a step of cooling the dispersion to 5-60°C, and a step of storing the dispersion, and the water-insoluble phase is prepared and used in such a way that the viscosity of the water-insoluble phase at the storage temperature of the dispersion becomes 100 to <1,000,000 P at a shear rate of 10 s<SP>-1</SP>. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

本発明は、ハロゲン化銀写真感光材料に用いられる写真用有用化合物の分散方法に関し、更に詳しくは、疎水性写真用有用化合物を水中または親水性コロイド組成物中に安定に乳化する方法に関する。   The present invention relates to a method for dispersing a useful photographic compound for use in a silver halide photographic light-sensitive material, and more particularly to a method for stably emulsifying a hydrophobic photographic useful compound in water or a hydrophilic colloid composition.

写真感光材料では、支持体上に疎水性写真用有用化合物を含有する親水性コロイド層を有する。   The photographic light-sensitive material has a hydrophilic colloid layer containing a hydrophobic photographic useful compound on a support.

疎水性写真用有用化合物とは、例えば画像形成用カプラー、カラードカプラー現像抑制剤放出カプラー、退色防止剤、カブリ防止剤、紫外線吸収剤、写真用染料または混色防止剤などである。一般的に疎水性写真用有用化合物を写真感光材料中に組み込む方法には、オイルプロテクト法と呼ばれる高沸点有機溶媒にこれらの化合物を溶解して乳化分散する方法、または有機溶媒を用いずに固体状態で直接分散する方法、或いは特許文献1(英国特許1,193,349)、非特許文献1(RD−16,468)、特許文献2(米国特許2,870,012号)、特許文献3(欧州特許361,322号)、特許文献4(同347,837号)等各明細書に示されるように、水混和性有機溶媒や塩基性水溶液に疎水性写真用有用化合物を溶解した後に水中で微粒子として析出分散させる方法が取られてきた。
英国特許1,193,349号明細書 米国特許2,870,012号明細書 欧州特許361,322号明細書 欧州特許347,837号明細書 リサーチ・ディスクロージャーNo.16,468
Useful hydrophobic photographic compounds include, for example, image-forming couplers, colored couplers development inhibitor releasing couplers, fading inhibitors, antifoggants, ultraviolet absorbers, photographic dyes or color mixing inhibitors. In general, useful hydrophobic photographic compounds are incorporated into photographic light-sensitive materials by dissolving and emulsifying these compounds in a high-boiling organic solvent called the oil protection method, or solid without using an organic solvent. A method of directly dispersing in a state, or Patent Document 1 (British Patent 1,193,349), Non-Patent Document 1 (RD-16,468), Patent Document 2 (US Pat. No. 2,870,012), Patent Document 3 (European Patent No. 361,322), Patent Document 4 (No. 347,837), etc. As shown in each specification, a hydrophobic photographic useful compound is dissolved in a water-miscible organic solvent or a basic aqueous solution and then dissolved in water. The method of precipitating and dispersing as fine particles has been used.
British Patent 1,193,349 US Patent 2,870,012 European Patent 361,322 Specification European Patent No. 347,837 Research Disclosure No. 16,468

いずれの方法においても、高価な写真用化合物を有効に活用するためには、分散質単位重量当りの表面積を増やすべく1μm未満の微粒子に分散する必要があり、粒子数と界面積の増大に伴って分散物の経時安定性が悪くなることは一般的なコロイド分散物の宿命に外れず、写真性能上の品質ばかりでなく、粗大粒子の発生や疎水性化合物の結晶化に伴うブツなどが塗布品質を悪化させていた。   In any method, in order to effectively use expensive photographic compounds, it is necessary to disperse in fine particles of less than 1 μm in order to increase the surface area per unit weight of the dispersoid, and as the number of particles and the interfacial area increase. The deterioration of the stability of the dispersion over time does not deviate from the fate of general colloidal dispersions, and not only the quality in photographic performance, but also the application of coarse particles and crystallization of hydrophobic compounds due to crystallization of hydrophobic compounds. The quality was deteriorating.

これらの問題点は、特に上記分散物の貯蔵中に発現し、ゼラチンを含む場合にはゼラチン水溶液のゲル化温度未満の貯蔵、ならびにゲルの溶融点以上での貯蔵のいずれの期間中にも起こりうるために、管理上の経時期間を制限したり、場合によってはせっかく調製した分散物を破棄せざる得ない不経済な状況が発生していた。   These problems are manifested especially during storage of the above dispersion, and when gelatin is included, it occurs during both periods of storage below the gelation temperature of the aqueous gelatin solution and storage above the melting point of the gel. As a result, there was an uneconomic situation in which the time period for management was limited, and in some cases the prepared dispersion had to be discarded.

本発明は上記従来の問題を解決すべく、その目的は、分散時の微粒子性能を維持しつつ、経時保存での粒子成長や粗大粒子あるいは析出結晶物の発生を伴わない分散物を得ることのできる乳化方法の提供にある。   In order to solve the above-mentioned conventional problems, the object of the present invention is to obtain a dispersion that does not involve particle growth during storage over time or generation of coarse particles or precipitated crystals while maintaining fine particle performance during dispersion. An emulsification method is provided.

本発明者らは、鋭意検討の結果、下記により本発明の上記の目的を達成できることを見い出した。   As a result of intensive studies, the present inventors have found that the above object of the present invention can be achieved by the following.

(1)実質的に、融点が100℃未満の疎水性写真用有用化合物と高沸点有機溶媒水溶液とのみを含む水不溶性相を水中又は親水性コロイド組成物中に分散させる方法であって、
疎水性写真用有用化合物をその融点近傍の温度で水中又は親水性コロイド組成物中に分散して分散物を得る工程、
分散物を5℃〜60℃に冷却する工程、および
その後分散物を保存する工程を含み、かつ、
分散物の保存温度での前記水不溶性相の粘度が、10sec -1の剪断速度において100Poise 以上、1,000,000Poise 未満になるように水不溶性相を調製,使用することを特徴とする疎水性写真用有用化合物の乳化分散方法。
(2)水不溶性相が、疎水性写真用有用化合物と高沸点有機溶媒水溶液とのみを含むことを特徴とする、上記(1)に記載の疎水性写真用有用化合物の乳化分散方法。
(3)疎水性写真用有用化合物が、色素像供与レドックス化合物、ステイン防止剤、カブリ防止剤、紫外線吸収剤、退色防止剤、混色防止剤、造核剤、色素画像安定化剤、ハロゲン化銀溶剤、漂白促進剤、フィルター用色素及びこれらの前駆体、染料、顔料、増感剤、硬膜剤、増白剤、減感剤、現像剤、帯電防止剤、酸化防止剤、現像薬スカベンジャー、媒染剤、または、これらを分散するための媒体として用いられる分散用オイルあるいは分散用ポリマーであることを特徴とする、上記(1)または(2)に記載の疎水性写真用有用化合物の乳化分散方法。
(4)分散物を5℃〜40℃に冷却することを特徴とする、上記(1)〜(3)のいずれかに記載の疎水性写真用有用化合物の乳化分散方法。
によって達成される。
(1) A method of substantially dispersing a water-insoluble phase containing only a hydrophobic useful photographic compound having a melting point of less than 100 ° C. and a high-boiling organic solvent aqueous solution in water or a hydrophilic colloid composition,
A step of dispersing a hydrophobic photographic useful compound in water or a hydrophilic colloid composition at a temperature near its melting point to obtain a dispersion;
Cooling the dispersion to 5 ° C. to 60 ° C., and then storing the dispersion, and
Hydrophobic, characterized in that the water-insoluble phase is prepared and used so that the viscosity of the water-insoluble phase at the storage temperature of the dispersion is not less than 100 Poise and less than 1,000,000 Poise at a shear rate of 10 sec −1 . A method for emulsifying and dispersing useful photographic compounds.
(2) The method for emulsifying and dispersing a hydrophobic photographic useful compound as described in (1) above, wherein the water-insoluble phase contains only the hydrophobic photographic useful compound and a high-boiling organic solvent aqueous solution.
(3) Hydrophobic photographic useful compounds include dye image donating redox compounds, stain inhibitors, antifoggants, UV absorbers, fading inhibitors, color mixing inhibitors, nucleating agents, dye image stabilizers, silver halides Solvents, bleach accelerators, filter dyes and their precursors, dyes, pigments, sensitizers, hardeners, brighteners, desensitizers, developers, antistatic agents, antioxidants, developer scavengers, A method for emulsifying and dispersing a hydrophobic photographic useful compound according to (1) or (2) above, which is a mordant or a dispersing oil or a dispersing polymer used as a medium for dispersing them. .
(4) The method for emulsifying and dispersing a useful hydrophobic photographic compound as described in any one of (1) to (3) above, wherein the dispersion is cooled to 5 to 40 ° C.
Achieved by:

本発明によれば、疎水性写真用有用化合物の分散物粒子を安定に得ることが可能になり、長期の経時保存性が付与され、製造適性に優れる。さらには、本発明は汎用的に疎水性写真用有用化合物の結晶化を防止できる方法を提供するために、これらの化合物の分子設計を行う上での自由度が増し、写真性能やコストメリットが得られる。   According to the present invention, it becomes possible to stably obtain dispersion particles of a hydrophobic photographic useful compound, impart long-term storage stability, and excellent manufacturing suitability. Furthermore, since the present invention provides a method for preventing the crystallization of useful compounds for hydrophobic photographic use for general purposes, the degree of freedom in molecular design of these compounds is increased, and photographic performance and cost merit are improved. can get.

以下に本発明の内容を詳細な説明する。   The contents of the present invention will be described in detail below.

本発明は、疎水性写真用有用化合物(以下、疎水性化合物、又は写真用化合物ということもある。)を微粒子かつ濃厚に分散する場合に有効である。具体的には、平均粒子径が1μm未満、分散質の体積分率が10%以上の分散を行う際に効果が著しい。本発明における乳化分散物は、一般的に沸点約175℃以上の高沸点有機溶媒或いは、沸点約30℃ないし約150℃の低沸点有機溶媒を夫々単独もしくは両者を任意の割合で混合して用いることにより疎水性化合物を溶解した後に、水中又は親水性コロイド組成物中に分散させることで得られる。しかしながら、このような乳化分散物を調製する過程、ならびに出来上がった乳化分散物を貯蔵する過程において、水不溶性相より疎水性化合物が結晶化して粗大な粒子へと成長することがしばしば経験されていた。この原因は、一般的に画像形成カプラーなどの疎水性写真用有用化合物の分子量が500以上と大きく、且つ分子構造が極めて複雑なために有機溶媒に安定に溶存しにくいことが挙げられる。さらに、近年写真感光材料に求められる鮮鋭性や粒状性などの画像品質を達成するためは、写真用化合物を高密度に感光材料膜中に組み込む必要があり、そのためには乳化分散物中の粒子内部の写真用化合物の濃度が飽和溶解度以上に設定されることが珍しくなくなっていることに原因する。この様な条件の乳化分散物を貯蔵すると、各々の分散粒子内で写真用化合物の結晶化が進行し、ついには分散物全体が析出した状態に推移してしまう。この乳化分散物を含む写真乳剤を塗布するとブツなどの欠陥が多発し、商品としての価値を損なうことは言うまでもない。   The present invention is effective when a hydrophobic photographic useful compound (hereinafter, sometimes referred to as a hydrophobic compound or a photographic compound) is dispersed finely and densely. Specifically, the effect is remarkable when performing dispersion with an average particle size of less than 1 μm and a volume fraction of the dispersoid of 10% or more. In the emulsified dispersion of the present invention, generally, a high boiling point organic solvent having a boiling point of about 175 ° C. or higher, or a low boiling point organic solvent having a boiling point of about 30 ° C. to about 150 ° C. is used alone or in a mixture of both at an arbitrary ratio. In this way, the hydrophobic compound is dissolved and then dispersed in water or a hydrophilic colloid composition. However, in the process of preparing such an emulsified dispersion and the process of storing the finished emulsified dispersion, it has often been experienced that the hydrophobic compound crystallizes from the water-insoluble phase and grows into coarse particles. . This is because, in general, the useful molecular weight for hydrophobic photography such as an image forming coupler has a large molecular weight of 500 or more and the molecular structure is extremely complicated, so that it is difficult to stably dissolve in an organic solvent. Furthermore, in order to achieve the image quality such as sharpness and graininess required for photographic photosensitive materials in recent years, it is necessary to incorporate photographic compounds in the photosensitive material film at a high density, and for this purpose, particles in an emulsified dispersion are required. This is because it is not rare that the concentration of the internal photographic compound is set higher than the saturation solubility. When an emulsified dispersion under such conditions is stored, crystallization of the photographic compound proceeds in each dispersed particle, and eventually the whole dispersion is shifted to a precipitated state. Needless to say, when a photographic emulsion containing this emulsified dispersion is applied, defects such as bumps occur frequently and the value as a product is impaired.

我々は、結晶化しやすい組成の水不溶性相を分散した乳化物の析出機構の詳細を解析した結果、水不性相の粘度が大きく影響することを解明した。即ち、過飽和度が高く結晶核が容易に発生する状況にあっても、水不溶性相の粘度が十分に高ければ溶質分子の運動が制限され、結晶成長速度が緩慢になる。水不溶性相の粘度が十分に高いと、乳化分散物の通常の貯蔵期間中に著しい結晶成長は起こらないために、実質的に塗布品質の悪化をまねくことは避けられる。種々の写真用化合物と有機溶媒の組成において、3カ月程度の貯蔵期間を維持するためには、水不溶性相の粘度が剪断速度が10sec-1において、少なくとも100Poise以上なければならないことが実証された。 As a result of analyzing the details of the precipitation mechanism of an emulsion in which a water-insoluble phase having a composition that tends to crystallize is dispersed, we have clarified that the viscosity of the water-insoluble phase is greatly affected. That is, even in a situation where the degree of supersaturation is high and crystal nuclei are easily generated, if the viscosity of the water-insoluble phase is sufficiently high, the movement of solute molecules is limited, and the crystal growth rate becomes slow. If the viscosity of the water-insoluble phase is sufficiently high, significant crystal growth does not occur during the normal storage period of the emulsified dispersion, so that substantial deterioration of the coating quality is avoided. In various photographic compound and organic solvent compositions, it has been demonstrated that the viscosity of the water-insoluble phase must be at least 100 Poise or higher at a shear rate of 10 sec −1 in order to maintain a shelf life of about 3 months. .

水不溶性相のこの粘度域を実現するためには、3つの方法がある。第1には通常、水不溶性相を構成する写真用有用化合物、高沸点有機溶媒、低沸点有機溶媒に加えて、合成ポリマーなどの高分子を増粘剤として添加して見掛け粘度を高くする方法。第2には、初期の水不溶性相は低沸点有機溶媒を多量に含有し、従って粘度が低い状態にあるが、分散中もしくは分散直後に低沸点溶媒を除去することによって溶質濃度を高め、粘度を増大させる方法。第3には、写真用化合物の融点が100℃未満の場合に、その融点近傍の温度で乳化分散し、後に通常の貯蔵温度である5℃〜60℃、好ましくは5℃〜40℃に冷却することによって、水不溶性相の粘度を増大させる方法が挙げられる。我々の研究結果によると、上記のいずれの方法を用いても剪断速度10sec-1における貯蔵温度での水不溶性相の粘度が100Poise以上であれば、3ケ月の貯蔵期間中に塗布品質を悪化させるような析出物の生成は認められなかった。ただし、第3の融点近傍の温度で乳化分散する手段は、写真用化合物そのものによって融点が決まってしまうために、他の2つの方法と比べて汎用的な方法ではないと言えよう。 There are three ways to achieve this viscosity range of the water-insoluble phase. First, a method of increasing the apparent viscosity by adding a polymer such as a synthetic polymer as a thickener in addition to a useful photographic compound, a high-boiling organic solvent, and a low-boiling organic solvent that usually constitute a water-insoluble phase. . Second, the initial water-insoluble phase contains a large amount of low-boiling organic solvent, and thus has a low viscosity, but the solute concentration is increased by removing the low-boiling solvent during or immediately after dispersion, thereby increasing the viscosity. How to increase. Third, when the melting point of the photographic compound is less than 100 ° C., it is emulsified and dispersed at a temperature in the vicinity of the melting point, and then cooled to a normal storage temperature of 5 ° C. to 60 ° C., preferably 5 ° C. to 40 ° C. By doing so, a method for increasing the viscosity of the water-insoluble phase can be mentioned. According to our research results, if any of the above methods is used and the viscosity of the water-insoluble phase at the storage temperature at a shear rate of 10 sec -1 is 100 Poise or more, the coating quality deteriorates during the storage period of 3 months. Such a precipitate was not observed. However, it can be said that the means for emulsifying and dispersing at a temperature near the third melting point is not a general-purpose method compared to the other two methods because the melting point is determined by the photographic compound itself.

本発明における水不溶性相の粘度はキャピラリー型、二重円筒型など剪断速度が規定できる粘度測定方法ならばいずれの方法を用いても測定可能であるが、特にコーンプレート型のE型粘度計が剪断速度10sec-1において、1から10万Poiseの粘度を簡便かつ正確に評価できる点で好ましい。また、この粘度は乳化分散を行った後では水不溶性相が微粒子に分割されて測定不可能となるために、予め乳化分散を行う前に測定し、本発明の粘度になるように処方設計をする必要がある。 The viscosity of the water-insoluble phase in the present invention can be measured by any method that can regulate the shear rate, such as a capillary type or a double cylinder type. A shear rate of 10 sec −1 is preferable in that a viscosity of 1 to 100,000 Poise can be easily and accurately evaluated. In addition, since the water-insoluble phase is divided into fine particles and cannot be measured after emulsification and dispersion, the viscosity is measured before emulsification and dispersion, and the formulation design is made so that the viscosity of the present invention is obtained. There is a need to.

剪断速度10sec -1における水不溶性相の粘度は、高ければ高いほど写真用化合物の分子運動を緩慢にし、従って結晶化を防止する効果は高くなるが、極端に高粘度にした結果、固体状態に近づくと実用的に様々な障害が発生する。例えば、本発明における第1の増粘剤を添加する方法については、水不溶性相の粘度が高くなり過ぎると乳化分散性が悪化し微粒子が得られない。また、本発明における第2の低沸点有機溶媒を除去する方法についても、写真用化合物が画像形成用カプラーやカブリ防止剤のごとく写真感光材料中で化学反応を伴って機能を発揮する場合には、水不溶性相の粘度の上昇とともに写真的な活性が低下する問題が発生する。 The higher the viscosity of the water-insoluble phase at a shear rate of 10 sec −1 , the slower the molecular motion of the photographic compound, and thus the higher the effect of preventing crystallization, but as a result of extremely high viscosity, Various obstacles occur practically when approaching. For example, regarding the method of adding the first thickener in the present invention, if the viscosity of the water-insoluble phase becomes too high, the emulsifying dispersibility deteriorates and fine particles cannot be obtained. Further, regarding the method for removing the second low-boiling organic solvent in the present invention, when a photographic compound exhibits a function with a chemical reaction in a photographic photosensitive material such as an image-forming coupler or an antifoggant. However, there is a problem that the photographic activity is lowered with an increase in viscosity of the water-insoluble phase.

以上の観点より、剪断速度10sec -1における水不溶性相の粘度には上限が存在し、本発明における粘度は、100Poise 以上1,000,000Poise未満を範囲とし好ましくは100Poise以上100,000Poise 未満、さらに好ましくは1,000Poise 以上100,000Poise 未満とする。 From the above viewpoint, there is an upper limit to the viscosity of the water-insoluble phase at a shear rate of 10 sec −1, and the viscosity in the present invention is in the range of 100 Poise or more and less than 1,000,000 Poise, preferably 100 Poise or more and less than 100,000 Poise, Preferably it is 1,000 Poise or more and less than 100,000 Poise.

本発明に用いられる水不溶性相の増粘剤は、少なくとも一種の繰り返し単位からなる水不溶性かつ有機溶媒可溶性であれば、いかなる重合体でもよい。これらを形成する繰り返し単位の種類としては、アクリル酸エステル類、メタクリル酸エステル類、ビニルエステル類、アクリルアミド類、メタクリルアミド類、オレフィン類、ビニルエーテル類などが挙げられる。   The water-insoluble phase thickener used in the present invention may be any polymer as long as it is water-insoluble and organic solvent-soluble consisting of at least one repeating unit. Examples of the repeating unit forming these include acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, methacrylamides, olefins, vinyl ethers, and the like.

また、本発明における重合体は、単一種類の繰り返し単位をもつホモポリマーであっても、2種類以上の繰り返し単位で構成される共重合体やブロック共重合体であってもよい。   In addition, the polymer in the present invention may be a homopolymer having a single type of repeating unit or a copolymer or block copolymer composed of two or more types of repeating units.

重合体の分子量や重合度は高いほど増粘作用が高まり、水不溶性への添加量が少なくても所望の粘度が得られるので好ましいが、その反面、溶解性が低下するために、重合体の種類によって適当な値に設定しなければならない。重合体のガラス転移温度は乳化分散物の保存温度以上であることが、増粘剤として水不溶性相内の粘性を一定に保つ観点で重要であり、好ましくは40℃以上、さらに好ましくは60℃以上であることが望まれる。   The higher the molecular weight and the degree of polymerization of the polymer, the higher the thickening action, and the desired viscosity can be obtained even if the amount added to water insolubility is small, but on the other hand, the solubility is lowered. It must be set to an appropriate value depending on the type. It is important for the glass transition temperature of the polymer to be equal to or higher than the storage temperature of the emulsified dispersion from the viewpoint of keeping the viscosity in the water-insoluble phase constant as a thickener, preferably 40 ° C or higher, more preferably 60 ° C. It is desirable that it is the above.

以下に本発明に用いられる増粘剤の具体例の一部を記すが、本発明は、これらに限定されるものではない。   Some specific examples of the thickener used in the present invention will be described below, but the present invention is not limited thereto.

(P−1) ポリ(2−tert−ブチルフェニルアクリレート)
(P−2) ポリ(4−tert−ブチルフェニルアクリレート)
(P−3) ポリメチルメタクリレート
(P−4) ポリエチルメタクリレート
(P−5) ポリメチルクロロアクリレート
(P−6) ポリ(N−sec −ブチルアクリルアミド)
(P−7) ポリ(N−tert−ブチルアクリルアミド)
(P−8) ポリ(N−tert−ブチルメタクリルアミド)
(P−9) ポリ(4−ビフェニルアクリレート)
(P−10) ポリ(2−クロロフェニルアクリレート)
(P−11) ポリ(4−シアノベンジルアクリレート)
(P−12) ポリ(3−メトキシカルボニルフェニルアクリレート)
(P−13) ポリビニル−tert−ブチレート
(P−14) ポリ(エチルフルオロメタクリレート)
(P−15) メチルメタクリレート−塩化ビニル共重合体(70:30)
(P−16) メチルメタクリレート−スチレン共重合体(90:10)
(P−17) 塩化ビニル−酢酸ビニル共重合体(65:35)
(P−18) メチルメタクリレート−フェニルビニルケトン共重合体(70:30)
(P−19) メチルメタクリレート−アクリル酸共重合体(95:5)
(P−20) メチルメタクリレート−アクリルニトリル共重合体(70:30)
(P−21) メチルメタクリレート−スチレン−ビニルスホンアミド共重合体(70:20:10)
(P−22) n−ブチルメタクリレート−メチルメタクリレート−ベンジルメタクリレート−アクリル酸共重合体(35:35:25:5)
(P−23) n−ブチルメタクリレート−メチルメタクリレート−アクリルアミド共重合体(35:35:30)
(P−24) n−ブチルメタクリレート−メチルメタクリレート−塩化ビニル共重合体(37:36:27)
低沸点有機溶媒は公知の方法で除去することができる。例えば米国特許第2,322,027号、同2,801,171号、同2,949,360号、同3,396,027号等各明細書に示されるように、ゼラチンのようなゲル化温度を有する親水性コロイド水溶液を用いた乳化分散物の場合、ゲル化温度以下で分散物をヌーデル状に押し出して水洗することによって低沸点有機溶媒の除去が行われる。又は、特開昭60−158437号明細書における限外濾過膜を用いる方法や、米国特許第5,024,929号ならびに同5,108,611号各明細書に示される透析膜を用いる方法が挙げられる。さらには、特公昭61−56010号公報のごとく減圧操作や加熱操作によって、低沸点有機溶媒を蒸発させて取り除く方法も可能である。
(P-1) Poly (2-tert-butylphenyl acrylate)
(P-2) Poly (4-tert-butylphenyl acrylate)
(P-3) Polymethylmethacrylate (P-4) Polyethylmethacrylate (P-5) Polymethylchloroacrylate (P-6) Poly (N-sec-butylacrylamide)
(P-7) Poly (N-tert-butylacrylamide)
(P-8) Poly (N-tert-butylmethacrylamide)
(P-9) Poly (4-biphenyl acrylate)
(P-10) Poly (2-chlorophenyl acrylate)
(P-11) Poly (4-cyanobenzyl acrylate)
(P-12) Poly (3-methoxycarbonylphenyl acrylate)
(P-13) Polyvinyl-tert-butylate (P-14) Poly (ethyl fluoromethacrylate)
(P-15) Methyl methacrylate-vinyl chloride copolymer (70:30)
(P-16) Methyl methacrylate-styrene copolymer (90:10)
(P-17) Vinyl chloride-vinyl acetate copolymer (65:35)
(P-18) Methyl methacrylate-phenyl vinyl ketone copolymer (70:30)
(P-19) Methyl methacrylate-acrylic acid copolymer (95: 5)
(P-20) Methyl methacrylate-acrylonitrile copolymer (70:30)
(P-21) Methyl methacrylate-styrene-vinyl sulfonamide copolymer (70:20:10)
(P-22) n-butyl methacrylate-methyl methacrylate-benzyl methacrylate-acrylic acid copolymer (35: 35: 25: 5)
(P-23) n-butyl methacrylate-methyl methacrylate-acrylamide copolymer (35:35:30)
(P-24) n-butyl methacrylate-methyl methacrylate-vinyl chloride copolymer (37:36:27)
The low boiling point organic solvent can be removed by a known method. For example, as shown in US Pat. Nos. 2,322,027, 2,801,171, 2,949,360, 3,396,027, etc., gelation such as gelatin In the case of an emulsified dispersion using a hydrophilic colloid aqueous solution having a temperature, the low boiling point organic solvent is removed by extruding the dispersion into a nudell form at a gelling temperature or lower and washing with water. Alternatively, a method using an ultrafiltration membrane in JP-A-60-158437, or a method using a dialysis membrane shown in US Pat. Nos. 5,024,929 and 5,108,611, respectively. Can be mentioned. Furthermore, a method of evaporating and removing the low boiling point organic solvent by a decompression operation or a heating operation as disclosed in Japanese Patent Publication No. 61-56010 is also possible.

この内、減圧操作と加熱操作を組み合わせる方法においては、化学工学協会編集の「化学工学便覧」(丸善株式会社)に記載の様々な分子蒸留ならびに蒸発装置を単独あるいは組み合わせて使用することが出来るが、いずれにおいても加熱された乳化分散物の温度と減圧度によって蒸発速度が決まり、操作時間によって低沸点有機溶媒の除去率が変化する。この時、乳化分散物の温度が高すぎたり、操作時間が長かったりすると、分散物が熱劣化を起こして粗大粒子へと成長したり、写真化合物が分解したりするので注意が必要である。従って、乳化分散物の温度は60℃未満、好ましくは50℃未満に保たれることが望まれる。この温度条件における操作時間は、60分未満、さらに好ましくは30分未満である。   Among these, in the method of combining the decompression operation and the heating operation, various molecular distillation and evaporation apparatuses described in “Chemical Engineering Handbook” (Maruzen Co., Ltd.) edited by the Chemical Engineering Association can be used alone or in combination. In any case, the evaporation rate is determined by the temperature of the heated emulsified dispersion and the degree of pressure reduction, and the removal rate of the low-boiling organic solvent varies depending on the operation time. At this time, if the temperature of the emulsified dispersion is too high or if the operation time is long, the dispersion will be thermally deteriorated to grow into coarse particles, or photographic compounds will be decomposed. Therefore, it is desired that the temperature of the emulsified dispersion is kept below 60 ° C, preferably below 50 ° C. The operation time in this temperature condition is less than 60 minutes, more preferably less than 30 minutes.

この温度と操作時間の範囲で本発明の目的とする水不溶性相の高い粘度域を実現するためには、水不溶性相の組成によっても様々に変化するが、加熱した乳化分散の温度における低沸点有機溶媒の蒸気圧の少なくとも80%未満、好ましくは蒸気圧の50%未満、さらに好ましくは蒸気圧の30%未満に減圧条件を設定することが必要である。   In order to achieve the high viscosity range of the water-insoluble phase, which is the object of the present invention, within this temperature and operating time range, it varies depending on the composition of the water-insoluble phase. It is necessary to set the decompression condition to at least less than 80% of the vapor pressure of the organic solvent, preferably less than 50% of the vapor pressure, more preferably less than 30% of the vapor pressure.

本発明において使用することができる疎水性写真用有用化合物とは、写真用途に有用な任意の有機化合物及び無機化合物を意味する。水不溶性相に添加する疎水性写真用有用化合物の濃度は、重量%として10〜90、好ましくは50〜80である。本発明においては、油溶性の有機写真用物質を使用することが好ましい。ここで油溶性とは、室温(20℃)において、有機溶剤に3重量%以上溶解するものを言う。又、有機溶剤としては、「溶剤ハンドブック」等に記載の有機溶媒を意味し、それらの例としては、メタノール、エタノール、イソプロパノール、ブタノール、酢酸エチル、酢酸ブチル、アセトン、メチルエチルケトン、テトラヒドロフラン、シクロヘキサノン、ベンゼン、トルエン、ジオキサン、アセトニトリル、ジクロルメタン、クロロホルムなどを挙げることができる。   Hydrophobic photographic useful compounds that can be used in the present invention mean any organic and inorganic compounds useful for photographic applications. The concentration of the useful hydrophobic photographic compound added to the water-insoluble phase is 10 to 90, preferably 50 to 80, by weight. In the present invention, it is preferable to use an oil-soluble organic photographic substance. Here, oil-soluble means a substance that dissolves 3% by weight or more in an organic solvent at room temperature (20 ° C.). The organic solvent means an organic solvent described in “Solvent Handbook” and the like, and examples thereof include methanol, ethanol, isopropanol, butanol, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, tetrahydrofuran, cyclohexanone, and benzene. , Toluene, dioxane, acetonitrile, dichloromethane, chloroform and the like.

本発明の分散物に使用し得る疎水性写真用有用化合物としては、色素像形成カプラー、色素像供与レドックス化合物、ステイン防止剤、カブリ防止剤、紫外線吸収剤、退色防止剤、混色防止剤、造核剤、色素画像安定化剤、ハロゲン化銀溶剤、漂白促進剤、フィルター用色素及びこれらの前駆体、染料、顔料、増感剤、硬膜剤、増白剤、減感剤、現像剤、帯電防止剤、酸化防止剤、現像薬スカベンジャー、媒染剤、及びこれらを分散するための媒体として用いられる分散用オイルや分散用ポリマーなどであり、これらの化合物の記載としては、リサーチ・ディスクロージャーNo.17643、No.18716、No.307105号などが挙げられる。   Useful hydrophobic photographic compounds that can be used in the dispersion of the present invention include dye image-forming couplers, dye image-donating redox compounds, stain inhibitors, antifoggants, ultraviolet absorbers, fading inhibitors, color mixing inhibitors, Nucleating agents, dye image stabilizers, silver halide solvents, bleach accelerators, filter dyes and their precursors, dyes, pigments, sensitizers, hardeners, brighteners, desensitizers, developers, Antistatic agents, antioxidants, developer scavengers, mordants, and dispersing oils and dispersing polymers used as a medium for dispersing them. Examples of these compounds include Research Disclosure No. 17643, no. 18716, no. No. 307105.

本発明を実施するために使用する分散機としては、大きな剪断力を有する高速攪拌型分散機、高強度の超音波エネルギーを与える分散機などがある。具体的には、コロイドミル、ホモジナイザー、毛細管式乳化装置、液体サイレン、電磁歪式超音波発生機、ポールマン笛を有する乳化装置などがある。本発明で使用するのに好ましい高速攪拌型分散機は、ディゾルバー、ポリトロン、ホモミキサー、ホモブレンダー、ケデイーミル、ジェットアジターなど、分散作用する要部が液中で高速回転(500〜15,000rpm。好ましくは2,000〜4,000rpm)するタイプの分散機である。本発明で使用する高速攪拌型分散機は、ディゾルバーないしは高速インペラー分散機とも呼ばれ、特開昭55−129136号にも記載されているように、高速で回転する軸に鋸歯状のプレートを交互に上下方向に折り曲げたインペラーを着装して成るものも好ましい一例である。   Examples of the disperser used for carrying out the present invention include a high-speed stirring disperser having a large shearing force and a disperser that provides high-intensity ultrasonic energy. Specifically, there are a colloid mill, a homogenizer, a capillary emulsifying device, a liquid siren, an electromagnetic distortion ultrasonic generator, an emulsifying device having a Paulman whistle, and the like. A high-speed stirring type disperser preferable for use in the present invention is a high-speed rotation (500 to 15,000 rpm) in a liquid in which main parts such as a dissolver, polytron, homomixer, homoblender, ket mill, and jet agitator are dispersed. Preferably, it is a disperser of the type of 2,000 to 4,000 rpm. The high-speed stirring type disperser used in the present invention is also called a dissolver or a high-speed impeller disperser. As described in Japanese Patent Laid-Open No. 55-129136, serrated plates are alternately arranged on a shaft that rotates at high speed. It is also a preferable example that is formed by wearing an impeller bent vertically.

本発明に従って疎水性化合物を含む乳化分散物を調製する際には、種々のプロセスに従うことができる。疎水性化合物を有機溶媒に溶解するときは、後述の高沸点有機物質、水非混和性低沸点有機溶媒または水混和性有機溶媒の中から任意に選択された一種、又は二種以上の任意の複数成分混和物に溶解し、次いで界面活性化合物の存在化で、水中あるいは親水性コロイド水溶液中に分散せしめる。疎水性化合物を含む水不溶性相と水性相との混合方法としては、攪拌下に水性相中に水不溶性相を加えるいわゆる順混合法でも、その逆の逆混合法でも良いが、とりわけ逆混合法の内の一種である転相法が、より微細な水性分散物を与える点で好ましい。   In preparing an emulsified dispersion comprising a hydrophobic compound according to the present invention, various processes can be followed. When the hydrophobic compound is dissolved in an organic solvent, one kind arbitrarily selected from the following high-boiling organic substances, water-immiscible low-boiling organic solvents or water-miscible organic solvents, or any two or more kinds of arbitrary substances Dissolve in the multi-component mixture and then disperse in water or aqueous hydrophilic colloid in the presence of a surface active compound. The mixing method of the water-insoluble phase containing the hydrophobic compound and the aqueous phase may be a so-called forward mixing method in which the water-insoluble phase is added to the aqueous phase with stirring, or a reverse mixing method, and the reverse mixing method. Of these, the phase inversion method is preferred because it gives a finer aqueous dispersion.

本発明においては、疎水性化合物を水中又は親水性コロイド組成物中のいずれにおいても分散することができるが、親水性コロイド組成物に分散することが好ましい。   In the present invention, the hydrophobic compound can be dispersed either in water or in the hydrophilic colloid composition, but is preferably dispersed in the hydrophilic colloid composition.

本発明に用いられる親水性コロイドとしては、通常ハロゲン化銀写真感光材料に使用される結合剤または保護コロイドが用いられる。これらは、ゼラチンを用いるのが有用であるが、それ以外の親水性コロイドも用いることができる。例えば、ゼラチン誘導体、ゼラチンと他の高分子とのグラフトポリマー、アルブミン、カゼイン等の蛋白質;ヒドロキシセルロース、カルボキシメチルセルロース、セルロース燐酸エステル類等のごときセルロース誘導体;アルギン酸ソーダ、澱粉誘導体などの糖誘導体;ポリビニールアルコール、ポリビニールアルコール部分アセタール、ポリ−N−ビニルピロリドン、ポリアクリル酸、ポリメタクリル酸、ポリアクリルアミド、ポリビニルイミダゾール、ポリビニルピラゾール等の単一あるいは共重合体のごとき多種の合成親水性高分子物質を用いることができる。   As the hydrophilic colloid used in the present invention, a binder or a protective colloid usually used for a silver halide photographic light-sensitive material is used. For these, gelatin is useful, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxycellulose, carboxymethylcellulose, and cellulose phosphates; sugar derivatives such as sodium alginate and starch derivatives; Various synthetic hydrophilic polymer materials such as mono- or copolymers such as vinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. Can be used.

水中油滴分散法に用いられる高沸点溶媒の例は米国特許第2,322,027号、国際公開WO91/17480号各明細書などに記載されており、フタル酸エステル類、リン酸またはホスホン酸のエステル類、安息香酸エステル類、アミド類、アルコール類またはフェノール類、脂肪属カルボン酸エステル類、アニリン誘導体、炭化水素類などが挙げられる。   Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027, International Publication No. WO91 / 17480, etc., and phthalates, phosphoric acid or phosphonic acid Esters, benzoic acid esters, amides, alcohols or phenols, aliphatic carboxylic acid esters, aniline derivatives, hydrocarbons and the like.

以下、本発明を実施例により詳細に説明するが、本発明はこれらに限定されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

(実施例−1)
下記のI−1およびII−1〜II−8液を用いて、以下の方法により乳化物A−1〜A−8を調製した。
(Example-1)
Emulsions A-1 to A-8 were prepared by the following method using the following I-1 and II-1 to II-8 solutions.

I−1液:石灰処理ゼラチン溶液(10%) 1000g
II−1液:下記カプラー(Y−1) 100g
燐酸トリクレジル 50g
酢酸エチル 50g
ドデシルベンゼンスルホン酸ナトリウム 10g
II−2液:下記カプラー(Y−1) 100g
燐酸トリクレジル 50g
酢酸エチル 50g
ドデシルベンゼンスルホン酸ナトリウム 10g
P−1(MW=7万) 5g
II−3液:下記カプラー(Y−1) 100g
燐酸トリクレジル 50g
酢酸エチル 50g
ドデシルベンゼンスルホン酸ナトリウム 10g
P−1(MW=7万) 10g
II−4液:下記カプラー(Y−1) 100g
燐酸トリクレジル 50g
酢酸エチル 50g
ドデシルベンゼンスルホン酸ナトリウム 10g
P−1(MW=7万) 25g
II−5液:下記カプラー(Y−1) 100g
燐酸トリクレジル 50g
酢酸エチル 50g
ドデシルベンゼスルホン酸ナトリウム 10g
P−1(MW=7万) 40g
II−6液:下記カプラー(Y−1) 100g
燐酸トリクレジル 50g
酢酸エチル 50g
ドデシルベンゼンスルホン酸ナトリウム 10g
P−7(MW=10万) 30g
II−7液:下記カプラー(Y−1) 100g
燐酸トリクレジル 50g
酢酸エチル 50g
ドデシルベンゼンスルホン酸ナトリウム 10g
P−16(MW=6万) 30g
II−8液:下記カプラー(Y−1) 100g
燐酸トリクレジル 50g
酢酸エチル 50g
ドデシルベンゼンスルホン酸ナトリウム 10g
P−21(MW=7万) 30g
I-1 liquid: Lime-processed gelatin solution (10%) 1000 g
II-1 solution: 100 g of the following coupler (Y-1)
Tricresyl phosphate 50g
50 g of ethyl acetate
Sodium dodecylbenzenesulfonate 10g
II-2 solution: 100 g of the following coupler (Y-1)
Tricresyl phosphate 50g
50 g of ethyl acetate
Sodium dodecylbenzenesulfonate 10g
P-1 (MW = 70,000) 5g
II-3 solution: 100 g of the following coupler (Y-1)
Tricresyl phosphate 50g
50 g of ethyl acetate
Sodium dodecylbenzenesulfonate 10g
P-1 (MW = 70,000) 10g
II-4 solution: 100 g of the following coupler (Y-1)
Tricresyl phosphate 50g
50 g of ethyl acetate
Sodium dodecylbenzenesulfonate 10g
P-1 (MW = 70,000) 25g
II-5 solution: 100 g of the following coupler (Y-1)
Tricresyl phosphate 50g
50 g of ethyl acetate
10g sodium dodecyl benzene sulfonate
P-1 (MW = 70,000) 40g
II-6 liquid: 100 g of the following coupler (Y-1)
Tricresyl phosphate 50g
50 g of ethyl acetate
Sodium dodecylbenzenesulfonate 10g
P-7 (MW = 100,000) 30g
II-7 liquid: 100 g of the following coupler (Y-1)
Tricresyl phosphate 50g
50 g of ethyl acetate
Sodium dodecylbenzenesulfonate 10g
P-16 (MW = 60,000) 30g
II-8 solution: 100 g of the following coupler (Y-1)
Tricresyl phosphate 50g
50 g of ethyl acetate
Sodium dodecylbenzenesulfonate 10g
P-21 (MW = 70,000) 30g

Figure 2004240445
Figure 2004240445

乳化方法はI液およびII液を60℃で混合溶解し、2リッターの容器内で直径5cmのディゾルバー翼を5000rpmの回転数で、平均粒子径がおよそ0.15μmになるように20〜30分間攪拌した。平均粒子径の測定には、動的光散乱法を用いた野崎産業のNICOMP Model370を使用した。   In the emulsification method, liquid I and liquid II are mixed and dissolved at 60 ° C., and a dissolver blade having a diameter of 5 cm is mixed in a 2 liter container at a rotational speed of 5000 rpm for 20 to 30 minutes so that the average particle diameter is approximately 0.15 μm. Stir. For measurement of the average particle size, NICOM Model Model 370 of Nozaki Sangyo using the dynamic light scattering method was used.

以上8種の乳化物を冷却してゲル化させ、5℃で長期保存した場合のカプラーの結晶化の度合いを調べた。II液の粘度の測定には、東京計器社製のE型粘度計を用い、5℃の恒温室内で実施した。カプラーの結晶化は、40℃に溶解した乳化物を100gサンプリングし、公称ポア径が3μmのポール社製エポセルフィルターを用いて吸引濾過を行いフィルター上に蓄積した濾過残渣の重量を求めて比較した。   The above eight emulsions were cooled and gelled, and the degree of crystallization of the couplers when stored at 5 ° C. for a long time was examined. The viscosity of the II liquid was measured in a thermostatic chamber at 5 ° C. using an E-type viscometer manufactured by Tokyo Keiki Co., Ltd. For coupler crystallization, 100 g of the emulsion dissolved at 40 ° C. is sampled, suction filtered using a Paul Epocel filter with a nominal pore diameter of 3 μm, and the weight of the filtration residue accumulated on the filter is compared. did.

結果は第1表に示すとおりであり、ポリマーを添加していない比較例のA−1ならびにポリマーの添加量が少なく粘度が100Poise に満たないA−2やA−3においては、著しいカプラーの結晶化が認められるのに対し、本発明による乳化物A−4〜A−8は長期にわたっても僅かな結晶化が起こっているにすぎない。これにより、本発明による優れた乳化物の安定性が例証される。   The results are as shown in Table 1. In the comparative example A-1 to which no polymer was added, and in the case of A-2 and A-3 in which the amount of polymer added was small and the viscosity was less than 100 poise, remarkable coupler crystals In contrast, the emulsions A-4 to A-8 according to the present invention are only slightly crystallized over a long period of time. This illustrates the excellent emulsion stability according to the invention.

Figure 2004240445
Figure 2004240445

(実施例−2)
上記のI−I液および下記のII−9液を用いて、以下の方法により乳化物A−9を調製した。
(Example-2)
Emulsion A-9 was prepared by the following method using the above-mentioned II solution and the following II-9 solution.

II−9液:上記カプラー(Y−1) 100g
燐酸トリクレジル 100g
ドデシルベンゼンスルホン酸ナトリウム 10g
乳化方法はI液およびII液をそれぞれ60℃と80℃で混合溶解し、70℃の温水ジャケットで保温した2リッターの容器内で直径5cmのディゾルバー翼を6000rpmの回転数で、平均粒子径がおよそ0.15μmになるように40分間攪拌した。
II-9 solution: 100 g of the above coupler (Y-1)
Tricresyl phosphate 100g
Sodium dodecylbenzenesulfonate 10g
In the emulsification method, liquid I and liquid II were mixed and dissolved at 60 ° C. and 80 ° C., respectively, and a dissolver blade having a diameter of 5 cm was placed at a rotational speed of 6000 rpm in a 2 liter container kept warm by a 70 ° C. hot water jacket. It stirred for 40 minutes so that it might be set to about 0.15 micrometer.

平均粒子径およびII液の粘度の測定、ならびにカプラーの結晶化の評価は実施例−1と同様に行った。   Measurement of the average particle diameter and the viscosity of the II liquid, and evaluation of coupler crystallization were carried out in the same manner as in Example-1.

実施例−1の乳化物A−1と比較した結果を第2表に示す。カプラーY−1の融点はおよそ90℃であるが、高沸点溶媒の燐酸トリクレジルの存在化では、70℃でも安定な溶液状態に47。実施例−1の乳化物と比較して攪拌回転数を上げても目的の平均粒子径に到達するのに10分以上余分に掛かった。II−9液が非常に高粘なために、分散作用が低下していると推定される。70℃においては1Poise未満の粘性であるが、5℃では5千倍以上に増加する。従って、カプラーの結晶化については、5℃での粘度が100Poiseをはるかに上回っているために極めて安定であることが第2表より明確に示される。   The result compared with the emulsion A-1 of Example-1 is shown in Table 2. The melting point of coupler Y-1 is about 90 ° C., but the presence of tricresyl phosphate, a high-boiling solvent, gives a stable solution state even at 70 ° C. 47. Even if the stirring rotation speed was increased as compared with the emulsion of Example-1, it took 10 minutes or more to reach the target average particle diameter. It is presumed that the dispersion action is reduced because the II-9 solution is very viscous. At 70 ° C., the viscosity is less than 1 Poise, but at 5 ° C., it increases to 5,000 times or more. Thus, Table 2 clearly shows that the crystallization of the coupler is very stable because the viscosity at 5 ° C is much higher than 100 Poise.

Figure 2004240445
Figure 2004240445

(実施例−3)
下記のI−2液およびII−10液を用いて、以下の方法により乳化物を調製した。
(Example-3)
An emulsion was prepared by the following method using the following liquid I-2 and liquid II-10.

I−2液:石灰処理ゼラチン溶液(12%) 6000g
II−10液:下記カプラー(C−1) 600g
燐酸トリクレジル 300g
酢酸エチル 300g
ドデシルベンゼンスルホン酸ナトリウム 60g
I-2 solution: lime-processed gelatin solution (12%) 6000 g
II-10 liquid: 600 g of the following coupler (C-1)
300 g of tricresyl phosphate
300 g of ethyl acetate
60g sodium dodecylbenzenesulfonate

Figure 2004240445
Figure 2004240445

乳化方法はI液およびII液を60℃で混合溶解し、10リッターの容器内で直径7cmのディゾルバー翼を4000rpmの回転数で、平均粒子径がおよそ0.2μmになるように20〜30分間攪拌した。その後、出来上がった乳化物を1000gづつ採取し、ロータリーエバポレーターを用いて50〜400torrの減圧下で50℃に加熱して酢酸エチルの除去を行い、最終的にB−2〜B−6の乳化物を得た。   In the emulsification method, liquid I and liquid II were mixed and dissolved at 60 ° C., and a dissolver blade having a diameter of 7 cm in a 10-liter container was rotated at 4000 rpm for 20 to 30 minutes so that the average particle diameter was about 0.2 μm. Stir. Thereafter, 1000 g of the completed emulsion was collected and heated to 50 ° C. under a reduced pressure of 50 to 400 torr using a rotary evaporator to remove ethyl acetate, and finally the emulsion of B-2 to B-6. Got.

50℃における酢酸エチルの蒸気圧は約300torrである。減圧度をそれぞれ400torrと300torrに設定したB−2ならびにB−3では十分な溶媒除去が行えなかったが、酢酸エチルの蒸気圧の三分の一未満に減圧したB−5とB−6では10%以下の残存溶媒率が得られた。   The vapor pressure of ethyl acetate at 50 ° C. is about 300 torr. B-2 and B-3, which were set to 400 torr and 300 torr respectively, could not remove the solvent sufficiently, but B-5 and B-6, which were reduced to less than one third of the vapor pressure of ethyl acetate, A residual solvent ratio of 10% or less was obtained.

平均粒子径およびII液の粘度の測定、ならびにカプラーの結晶化の評価は実施例−1と同様に行った。酢酸エチルの濃度は、水溶液試料で検量したガスクロマトグラフによって求めた。   Measurement of the average particle diameter and the viscosity of the II liquid, and evaluation of coupler crystallization were carried out in the same manner as in Example-1. The concentration of ethyl acetate was determined by a gas chromatograph calibrated with an aqueous solution sample.

結果を第3表に示すが、B−1〜B−6と溶媒の除去率が高くなるにつれて、II液の粘度は上昇する。同時にカプラーの結晶化の度合いは低下し、粘度が100Poiseを越えるB−5より、90日間の長期冷蔵を経ても塗布故障を引き起こすようなブツの発生は認められなかった。これにより、乳化物中の低沸点有機溶媒を除去し水不溶性相の粘度を上昇させる本発明の第2の方法を用いることによ、優れた経時安定性が付与されることが例証される。   The results are shown in Table 3. As the removal rate of B-1 to B-6 and the solvent increases, the viscosity of the II liquid increases. At the same time, the degree of crystallization of the coupler decreased, and from B-5 with a viscosity exceeding 100 Poise, no occurrence of defects that would cause a coating failure was observed even after 90 days of long-term refrigeration. This demonstrates that excellent aging stability is imparted by using the second method of the present invention to remove the low boiling organic solvent in the emulsion and increase the viscosity of the water insoluble phase.

Figure 2004240445
Figure 2004240445

以上実施例により詳細に説明したように、本発明によれば、疎水性写真用有用化合物の分散物粒子を安定に得ることが可能になり、長期の経時保存性が付与され、製造適性に優れる。さらには、本発明は汎用的に疎水性写真用有用化合物の結晶化を防止できる方法を提供するために、これらの化合物の分子設計を行う上での自由度が増し、写真性能やコストメリットが得られる。   As described in detail in the above examples, according to the present invention, it becomes possible to stably obtain a dispersion particle of a hydrophobic photographic useful compound, imparting long-term storage stability, and excellent manufacturing suitability. . Furthermore, since the present invention provides a method for preventing the crystallization of useful compounds for hydrophobic photographic use for general purposes, the degree of freedom in molecular design of these compounds is increased, and photographic performance and cost merit are improved. can get.

Claims (4)

実質的に、融点が100℃未満の疎水性写真用有用化合物と高沸点有機溶媒水溶液とのみを含む水不溶性相を水中又は親水性コロイド組成物中に分散させる方法であって、
疎水性写真用有用化合物をその融点近傍の温度で水中又は親水性コロイド組成物中に分散して分散物を得る工程、
分散物を5℃〜60℃に冷却する工程、および
その後分散物を保存する工程を含み、かつ、
分散物の保存温度での前記水不溶性相の粘度が、10sec -1の剪断速度において100Poise 以上、1,000,000Poise 未満になるように水不溶性相を調製,使用することを特徴とする疎水性写真用有用化合物の乳化分散方法。
A method of substantially dispersing a water-insoluble phase containing only a hydrophobic useful photographic compound having a melting point of less than 100 ° C. and a high-boiling organic solvent aqueous solution in water or a hydrophilic colloid composition,
A step of dispersing a hydrophobic photographic useful compound in water or a hydrophilic colloid composition at a temperature near its melting point to obtain a dispersion;
Cooling the dispersion to 5 ° C. to 60 ° C., and then storing the dispersion, and
Hydrophobic, characterized in that the water-insoluble phase is prepared and used so that the viscosity of the water-insoluble phase at the storage temperature of the dispersion is not less than 100 Poise and less than 1,000,000 Poise at a shear rate of 10 sec −1 . A method for emulsifying and dispersing useful photographic compounds.
水不溶性相が、疎水性写真用有用化合物と高沸点有機溶媒水溶液とのみを含むことを特徴とする、請求項1に記載の疎水性写真用有用化合物の乳化分散方法。 The method for emulsifying and dispersing a hydrophobic photographic useful compound according to claim 1, wherein the water-insoluble phase contains only the hydrophobic photographic useful compound and a high-boiling organic solvent aqueous solution. 疎水性写真用有用化合物が、色素像供与レドックス化合物、ステイン防止剤、カブリ防止剤、紫外線吸収剤、退色防止剤、混色防止剤、造核剤、色素画像安定化剤、ハロゲン化銀溶剤、漂白促進剤、フィルター用色素及びこれらの前駆体、染料、顔料、増感剤、硬膜剤、増白剤、減感剤、現像剤、帯電防止剤、酸化防止剤、現像薬スカベンジャー、媒染剤、または、これらを分散するための媒体として用いられる分散用オイルあるいは分散用ポリマーであることを特徴とする、請求項1または2に記載の疎水性写真用有用化合物の乳化分散方法。 Useful hydrophobic photographic compounds include dye image donating redox compounds, anti-stain agents, anti-fogging agents, UV absorbers, anti-fading agents, anti-color mixing agents, nucleating agents, dye image stabilizers, silver halide solvents, bleaching Accelerators, dyes for filters and their precursors, dyes, pigments, sensitizers, hardeners, brighteners, desensitizers, developers, antistatic agents, antioxidants, developer scavengers, mordants, or The method for emulsifying and dispersing a useful hydrophobic photographic compound according to claim 1, wherein the oil is a dispersing oil or a dispersing polymer used as a medium for dispersing them. 分散物を5℃〜40℃に冷却することを特徴とする、請求項1〜3のいずれかに記載の疎水性写真用有用化合物の乳化分散方法。 The method of emulsifying and dispersing a useful hydrophobic photographic compound according to any one of claims 1 to 3, wherein the dispersion is cooled to 5 to 40 ° C.
JP2004093250A 1995-02-24 2004-03-26 Method for emulsifying and dispersing hydrophobic photographically useful compound Pending JP2004240445A (en)

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