JP2001098207A - Method for reparation of crystalline fine particle dispersion of organic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for efficiently preparing a crystalline fine particle dispersion of an organic compound such as an organic dyestuff compound which can impart optical and chemical functions. SOLUTION: This process for preparing a crystalline fine particle dispersion of an organic compound comprises a step of preparing a slurry of crystalline coarse particles of the organic compound containing a solvent molecule within the crystals and a step of providing atomization treatment of the slurry of the crystalline coarse particles to obtain a slurry of crystalline fine particles of the organic compound substantially free of the solvent molecule within the crystals.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dispersion of crystalline fine particles of an organic compound, and more particularly, to an organic dye which is advantageously used in the production of a functional material such as a photographic material, an optical filter material or an ink jet recording liquid. The present invention relates to a dispersion of crystalline fine particles of a functional organic compound such as a compound and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, in the production of image recording materials and electronic equipment-related materials, dispersions of crystalline fine particles of organic compounds (solid fine particle dispersions or microcrystals) have been developed for the purpose of imparting optical or chemical functions. (Also referred to as a liquid dispersion). As a dispersion of crystalline fine particles of an organic compound that provides an optical function, a dispersion of crystalline particles of an organic dye compound such as a dye or an organic pigment is used, and is used for manufacturing an ink jet recording liquid or a color material for an optical filter. Used. A colored layer (optical filter layer) provided for the purpose of improving photographic image quality even in the production of silver halide photographic light-sensitive materials (hereinafter, abbreviated as light-sensitive materials).
Crystalline fine particles of an organic dye compound are used for the production of

As an organic compound for imparting a chemical function, JP-A-8-95191 and JP-A-10-195191, which are used in the field of a heat development recording material using an organic silver salt, are used.
There are an organic reducing agent, a color tone agent, and an oxidizing agent disclosed in JP-A-207005, and these organic compounds can be used as a dispersion of crystalline fine particles.

As a method of obtaining a dispersion of crystalline fine particles of an organic compound, a method of making coarse crystals fine by a mechanical method such as ball milling is generally used. It is late and cannot be used advantageously for the industrial production of crystalline particulate dispersions.

On the other hand, as disclosed in Japanese Patent Application Laid-Open No. 6-194763, for an alkali-soluble compound intended to be used in a photographic light-sensitive material, the compound is first converted into an alkali solution, and then the alkali solution is used. pH
A method for obtaining a crystalline fine particle dispersion by lowering the particle size is known. In addition, EP 696758 and EP5
Examples disclosed in JP-A-49486 and JP-A-3-182743 describe a method for obtaining a crystalline fine particle dispersion of a dye by an acid precipitation method only for an alkali-soluble dye. . However, these techniques are based on the premise that an organic compound intended to be obtained as a dispersion is alkali-soluble, and it is necessary to remove a salt to obtain a stable dispersion, and further, the stock solution is greatly diluted. Therefore, a step of concentrating the dispersion is essential. In other words, when this dispersion method is used, compounds that can be subjected to dispersion treatment are limited, so that the degree of freedom in selecting a dispersion is reduced, and a post-process after dispersion is indispensable. There is a problem that rises.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for efficiently producing a crystalline fine particle dispersion of an organic compound capable of imparting optical and chemical functions. is there. Another object of the present invention is to provide a method for producing crystalline fine particles of an organic compound which can be advantageously used particularly for producing a dispersion of crystalline fine particles of an organic dye compound. The present invention also provides a crystalline fine particle dispersion of an organic dye compound that can be advantageously used in the production of a halogenated photographic material exhibiting more excellent photographic properties,
With that purpose.

[0007]

According to the present invention, there is provided a process for preparing a slurry of crystalline coarse particles of an organic compound containing a solvent molecule in a crystal, and subjecting the slurry of crystalline coarse particles to a fine particle treatment. A process for obtaining a slurry of crystalline fine particles of an organic compound substantially free of solvent molecules in the crystal.

[0008] The present invention also resides in a dispersion of crystalline fine particles of an organic compound having an average particle size in the range of 0.10 to 0.60 µm obtained by the production method of the present invention.

In the present invention, the average particle diameter is 0.10 to 0.1.
There is also a dispersion of an organic dye compound comprising needle-like crystalline fine particles of an organic dye compound having a needle ratio in the range of 60 μm and a needle ratio of 2 to 50.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, solvent molecules contained in crystalline coarse particles (coarse crystals) of an organic compound (hereinafter, referred to as “coarse crystals”) are used.
This is also referred to as a crystallization solvent) is a polar or non-polar solvent molecule that is liquid at room temperature, and is preferably a polar solvent molecule. The solvent molecule may be either protic or aprotic. The solvent particles contained in the crystalline coarse particles may be one kind, or two or more (preferably three or less) solvent molecules may be combined and introduced into the crystalline coarse particles.

The aprotic solvent preferably used as the crystallization solvent includes amides having 6 or less carbon atoms [eg, N, N-dimethylformamide (DMF), N, N
N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP)], sulfoxides having 6 or less carbon atoms [for example, N, N-dimethylsulfoxide (DMS)
O), N, N-diethylsulfoxide], 6 carbon atoms
The following sulfones [for example, sulfolane], imidazoles having 6 or less carbon atoms [for example, 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole],
Phosphoramides or phosphites having 6 or less carbon atoms [eg, hexamethylphosphoric triamide (HMPA), hexamethylphosphite triamide], and ureas having 6 or less carbon atoms [eg, tetramethyl Urea]. Further, tetrahydrofuran, dioxane, toluene, and benzene may be used.

Protic solvents preferably used as a crystallization solvent include alcohols having 10 or less carbon atoms [eg, methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol],
Examples thereof include carboxylic acids having 5 or less carbon atoms [for example, formic acid, acetic acid, propionic acid], phenols [for example, phenol, m-cresol, p-cresol], liquid ammonia, and water. These solvents may be used alone or as a mixed solvent with another solvent. When used as a mixed solvent, it may be mixed with the aprotic polar solvent described above, or may be used as a mixture with an organic solvent such as acetone, acetonitrile, and ethyl acetate.

Since the selection of an appropriate crystallization solvent depends on the molecular structure of the organic compound to be used as the dispersion of crystalline fine particles, it cannot be said that any solvent type is generally preferable.
However, usually a protic or aprotic polar solvent is preferred.

The amount of the crystallization solvent contained in the crystalline coarse particles is 0.5 mol or more per 1 mol of the organic compound to be a crystalline fine particle dispersion (when two or more crystal solvent molecules are used, , Meaning their total amount) and 0.5
More preferably, it is in the range of 1.0 to 10 mol.
Most preferably, it is in the range of 10 moles.

The amount of solvent molecules (crystal solvent) contained in the crystalline coarse particles of the organic compound containing solvent molecules in the crystal is as follows:
The value represented by the product of the molecular weight of the solvent molecule and the number of moles of the solvent molecule per mole of the organic compound (hereinafter, referred to as CSP) is preferably 100 or more, and a particularly preferred CSP is a value in the range of 100 to 400. It is. In addition, this CSP is also described in the chemical formula of the organic compound containing the solvent molecule in the crystal, which is listed in this specification.

Crystalline fine particles of an organic compound substantially free of solvent molecules in a crystal as defined in the present invention are defined as the amount of solvent molecules present in a crystal (solvent molecules are molecules of a plurality of types of solvents). In this case, the total amount thereof is less than 0.2 mol per 1 mol of the organic compound. The amount of solvent molecules present in this crystal is 0.1
Mol or less, and particularly preferably 0.05 mol or less.

The kind of the solvent contained in the crystal of the crystalline particles such as the crystalline coarse particles and the amount thereof can be measured by a known method such as an NMR method and a gas chromatography method. In particular, when the crystallization solvent is water of crystallization, it can also be measured by Karl Fischer titration. Which method is appropriate depends on the type of solvent. However, in any measurement, in order to completely remove the solvent adhering to the outer surface of the crystalline particles, it is necessary to previously dry the crystal particles at a temperature in the range of 10 to 50 ° C for 30 to 100 hours.

In the first step of the method for producing a dispersion of crystalline fine particles of an organic compound of the present invention, the preparation of a slurry of crystalline coarse organic compound particles containing a solvent molecule in the crystal, which is a first step,
For example, a method in which a powder crystal or a wet cake of an organic compound to be a crystalline fine particle dispersion is charged into a solvent to be introduced into the crystalline coarse particles and heated or stirred without heating can be used. . The stirring temperature is 0 to 200 ° C, preferably 20 to 120 ° C, and the stirring time is 5 minutes to 20 hours, preferably 30 minutes to 6 hours.
Time. Alternatively, the solvent to be introduced into the crystalline coarse particles may be used as a solvent during the synthesis reaction of the organic compound to be dispersed, whereby the solvent can be contained in the crystalline coarse particles in some cases.

Examples of the organic compound used as the crystalline fine particle dispersion in the present invention include a dye having an optical function such as a color material for an ink jet recording liquid or an optical filter, or a colored layer of a silver halide photographic material. Examples thereof include general organic dye compounds such as pigments, and organic compounds having a chemical function such as an organic reducing agent and an antifoggant in a heat development recording material using an organic silver salt.

Examples of the organic compound having a chemical function include an organic reducing agent used in a heat-source image-sensitive material utilizing an organic silver salt. Examples of such organic reducing agents are disclosed in JP-A-46-6074, JP-A-47-1238, JP-A-47-33621, JP-A-49-46427,
JP-A-49-115540, JP-A-50-14334, JP-A-50-36110, and JP-A-50-147711
Gazette, JP-A-51-32632, JP-A-51-3232
No. 4, No. 51-51933, No. 52-847
No. 27, 55-108654, 56-1
46133, 57-82828, 57
-82829, JP-A-6-3793, U.S. Pat. Nos. 3,679,426 and 3,751,
No. 252, No. 3,751,255, No. 3,761,270, No. 3,782,94
No. 9, No. 3,839,048, No. 3,928,686, No. 5,464,738
The specification is disclosed in German Patent No. 2312328 and European Patent No. 692732. Even when these organic reducing agents are used as crystalline fine particle dispersions,
The production method of the present invention is preferably used. Among these organic reducing agents, bisphenol and chromanol are particularly preferred.

Further, it can be advantageously used for producing a crystalline fine particle dispersion of an organic halide used as an antifogging agent in a photothermographic material using an organic silver salt. Examples of such organic halides are described in JP-A-50-119.
Nos. 624, 50-120328, 51-
121332, 54-58022, 5
JP-A-6-20843, JP-A-56-99335, JP-A-59-90842, JP-A-61-129842, JP-A-62-129845, and JP-A-6-2081.
No. 91, 7-5621, 7-2781, 8-15809, U.S. Pat.
Nos. 0,712, 5,369,000 and 5,464,737. The production method of the present invention is also preferably used when these organic halides are used as a dispersion of crystalline fine particles.

The organic compound to be used as the dispersion of crystalline fine particles used in the present invention preferably has a molecular weight in the range of 200 to 1,000, and more preferably has a molecular weight of 300 to 800.
Is most preferably within the range.

The coarse crystals of the organic compound prepared in the above step in a state where solvent molecules are contained in the crystalline coarse particles preferably have an average particle diameter of 5 μm or more, and more preferably 5 to 1 μm.
Most preferably, it is in the range of 00 μm. Here, the average particle size of the coarse crystals refers to particles 5 in an arbitrary field of view under an optical microscope or an electron microscope in a state where the coarse crystals do not overlap.
It represents the average value of the circle-equivalent diameter of the projected area of each particle that can be calculated by observing 00 particles.

According to the present invention, when applied to an organic dye compound such as a dye or an organic pigment, an optically preferable dispersion of crystalline fine particles can be obtained. The dispersion will be described in detail.

The organic dye compound preferably used in the present invention is represented by the following general formula (1) when it is described as containing a crystal solvent molecule.

[0026]

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In the general formula (1), D represents a compound having a chromophore, X represents a dissociable proton bonded to D directly or via a divalent linking group, or a group having a dissociable proton, y represents an integer of 1 to 7.

In the general formula (1), S _1, S ₂ and... Sc represent different solvent molecules (crystal solvents) taken into the dye crystals. p ₁ and p ₂ and ..., p
_c represents a molar ratio of 0 to 10 each. Where p ₁ ,
p _2, · ·, any of p _c not 0, the c representing the number of solvent species is an integer of 1 or more.

In the present invention, similarly, when it is described as containing a crystal solvent molecule, it is particularly preferable to use a dye represented by the general formula (2).

[0030]

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In the general formula (2), A ₁ represents an acidic nucleus necessary for forming a dye, A ₂ represents an acidic nucleus required for forming a dye, or an aromatic ring or a heterocyclic ring;
L ₁ , L ₂ , L ₃ , L ₄ , and L ₅ each represent a methine group or an azomethine group, and m and n are each 0 or 1.

In the general formula (2), S ₁ and S ₂ represent different crystallization solvents incorporated in the dye crystal. p ₁ and p ₂ each represent a molar ratio from 0 to 10, where p ₁ is 0
is not. If p ₂ is 0 crystal solvent is only one S _1.

Hereinafter, the organic dye compound represented by the general formula (1) will be described in detail.

The compound having a chromophore represented by D can be selected from many well-known dye compounds. Examples of these compounds include oxonol dyes, merocyanine dyes, cyanine dyes, arylidene dyes, heteroarylene dyes, azomethine dyes, triphenylmethane dyes, azo dyes, and anthraquinone dyes. Specifically, compounds described in JP-A-3-259136, page 14, lower left column, line 14 to page 13, lower left column, last line can be mentioned.

The dissociative proton or the group having a dissociable proton of the dye of the formula (1) is preferably in a non-dissociated state during the dispersion treatment (fine-grain treatment).
Examples of these groups include a carboxylic acid group, a sulfonamide group, a sulfamoyl group, a sulfonylcarbamoyl group,
Examples thereof include a carbonylsulfamoyl group and an enol group of an oxonol dye. Particularly, a carboxylic acid group and a sulfonamide group can be mentioned.

In the general formula (2), the acidic nucleus represented by A ₁ is preferably a methylene group or a cyclic ketomethylene group (including a thioketomethylene group) sandwiched between electron-withdrawing groups. Specific examples are shown below, but the specific examples only show keto bodies or analogs thereof.

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In each of the above formulas, R ₁ , R ₂ , R ₃ , R ₄
Represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkenyl group or a hydroxyl group, and R ₅ , R ₆ and R ₇ each represent a hydrogen atom or a substituent. R ₁ and R ₂ , R ₃ and R ₄ , R ₅
And R ₆ , or R ₆ and R ₇ may be linked to each other to form a 5- or 6-membered ring.

The substituents represented by R ₅ , R ₆ and R ₇ must not substantially dissolve the dye of the general formula (2) in water having a pH of from 5 to 7; Is not particularly limited. For example, carboxylic acid group, carbon atom 1
To 10 sulfonamide groups, preferably 1 to 1 carbon atoms
6, a sulfonylcarbamoyl group having 2 to 10 carbon atoms, preferably a sulfonylcarbamoyl group having 2 to 7 carbon atoms (for example, methanesulfonylcarbamoyl) , Propanesulfonylcarbamoyl), a carbonylsulfamoyl group having 2 to 10 carbon atoms, preferably 2 carbon atoms.
To 7 carbonylsulfamoyl groups (for example, acetylsulfamoyl, propionylsulfamoyl), an alkyl group having 1 to 10 carbon atoms, preferably 1 carbon atom
To 6 alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl,
-Hydroxyethyl, 4-carboxybutyl), an alkoxy group having 1 to 10 carbon atoms, preferably 1 carbon atom
To 6 alkoxy groups (eg, methoxy, ethoxy, butoxy), halogen atoms (eg, chlorine, bromine, fluorine), amino groups having 0 to 10 carbon atoms, preferably amino groups having 0 to 6 carbon atoms (eg, Dimethylamino, methylethylamino, diethylamino, ethylbutylamino, carboxyethylamino), an ester group having 2 to 12 carbon atoms, preferably an ester group having 2 to 7 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl), An amide group having 1 to 10 carbon atoms, preferably an amide group having 1 to 6 carbon atoms (eg, acetylamino, benzamide), a carbamoyl group having 1 to 10 carbon atoms,
Preferably, a carbamoyl group having 1 to 6 carbon atoms (for example, carbamoyl, methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, butylcarbamoyl,
Phenylcarbamoyl), a sulfamoyl group having 0 to 10 carbon atoms, preferably a sulfamoyl group having 0 to 6 carbon atoms (for example, methylsulfamoyl, butylsulfamoyl, phenylsulfamoyl), and a carbon atom having 6 to 10 carbon atoms
15 aryl groups, preferably an aryl group having 6 to 10 carbon atoms (for example, phenyl, naphthyl, 4-carboxyphenyl, 3-carboxyphenyl, 3,5-dicarboxyphenyl, 4-methanesulfonamidophenyl,
4-butanesulfonamidophenyl), having 2 to 2 carbon atoms
10 acyl groups, preferably an acyl group having 2 to 7 carbon atoms (eg, acetyl, benzoyl, propanoyl),
A sulfonyl group having 1 to 10 carbon atoms, preferably a sulfonyl group having 1 to 7 carbon atoms (e.g., methylsulfonyl, phenylsulfonyl), a ureido group having 1 to 10 carbon atoms, preferably a 1 to 6 carbon atom Ureido groups (e.g., ureido, methylureide), having 2 to 1 carbon atoms
2, a urethane group having 2 to 7 carbon atoms (for example, methoxycarbonylamino, ethoxycarbonylamino), a cyano group, a hydroxyl group, a nitro group, a heterocyclic group (for example, 5-carboxybenzoxazole as a heterocyclic ring) Ring, pyridine ring, sulfolane ring, furan ring) and the like. These may be further substituted.

The alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ is an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, benzyl, phenethyl, propyl, butyl, isobutyl, pentyl, Hexyl, octyl, nonyl), and may have a substituent (for example, each of the groups described above).

The aryl group represented by R ₁ , R ₂ , R ₃ and R ₄ is preferably an aryl group having 6 to 10 carbon atoms (for example, phenyl or naphthyl), and a substituent (for example, Each group described above).

The heterocyclic ring in the heterocyclic group represented by R ₁ , R ₂ , R ₃ and R ₄ is a 5- or 6-membered heterocyclic ring which may have a condensed ring (for example, oxazole ring, Benzoxazole ring, thiazole ring, imidazole ring, pyridine ring, furan ring, benzofuran ring, thiophene ring, sulfolane ring, pyrazole ring, pyrrole ring, indole ring, chroman ring, coumarin ring, 2H-chromen-2-one ring) It is preferable that it has a substituent (for example, each of the groups described above).

The alkenyl group represented by R ₁ , R ₂ , R ₃ and R ₄ is an alkenyl group having 2 to 10 carbon atoms (for example, vinyl, allyl, 1-propenyl, 2-pentenyl,
3-butadienyl).

A 5-membered ring or 6 formed by connecting R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , or R ₆ and R ₇ to each other;
Examples of the member ring include a pyrrolidine ring, a piperidine ring, a morpholine ring, and a benzene ring.

In the general formula (2), A ₂ represents an acidic nucleus, or an aromatic or heterocyclic ring. As the acidic nucleus, A ₁
Or a cyclic ketomethylene group (including a thioketomethylene group). Examples of the aromatic ring include benzene and naphthalene. The heterocyclic ring is preferably a 5-membered ring or a 6-membered ring, and may have a substituent (for example, each group described above). Further, the substituents may be connected to each other to form a condensed ring. Examples of the condensed ring include the heterocyclic ring represented by R ₁ . Specific examples of the heterocyclic ring are shown below.

[0055]

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In each of the above formulas, R ₈ , R ₉ , R ₁₀ , R
₁₁ represents a hydrogen atom or a substituent (as defined for R ₅ ).

In the general formula (2), L ₁ , L ₂ , L ₃ ,
The methine groups represented by L ₄ and L ₅ may have a substituent (for example, methyl or ethyl), and the substituents are connected to each other to form a 5- or 6-membered ring (for example, a cyclopentene ring). , A cyclohexene ring or an isophorone ring). Further, it may be an azomethine group.

In the general formula (2), A ₁ is preferably a substituted or unsubstituted pyrazolone, barbitur, pyridone or pyrazolopyridone nucleus, more preferably pyridone or pyrazolopyridone nucleus. A ₂ is preferably an aromatic ring or a heterocyclic ring, and most preferably a substituted benzene, a substituted naphthalene, or a substituted heterocyclic ring.

The organic dye compound (dye or pigment) represented by the general formula (2), which is preferably used in the present invention.
Are described below in a format including a crystallization solvent (solvent molecule).

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The organic dye compound (dye or pigment) represented by the general formula (2), which is preferable in the present invention, can be prepared by a method known to those skilled in the art (for example, the corresponding acidic nucleus, ethyl orthoformate, diphenylamidine, 1,1,3,3
-A methine source such as tetramethoxypropane, malonaldehyde dianyl or glutaconaldehyde dianyl,
Condensation reaction with a formyl compound).

The crystalline fine particles of the organic dye compound produced by the present invention have a half width of the absorption peak at the maximum absorption wavelength of 120.
It preferably shows an absorption spectrum of not more than nm,
The half width is more preferably 110 nm or less, and most preferably 100 nm or less.

The organic compound coarse crystal (crystalline coarse particle) containing a solvent molecule in the crystal, which is used in the fine particle forming step, which is the second step of the method for producing the organic compound crystalline fine particles of the present invention, is a fine crystal. As a method of dispersing in a state, a method of mechanically dispersing in the presence of a dispersing agent using a known finely refining means (for example, a commercially available ball mill, sand mill, high-pressure homogenizer, or the like) can be used. As a general method, it is preferable to perform dispersion by a vertical or horizontal sand mill method, and specifically, it is preferable to use a sand grinder mill using an internal rotor or a pulverizer called an ultra-visco mill.

In the sand mill method, a pulverizing medium (a minute rigid body such as a ball or a bead; hereinafter, simply referred to as a medium or a minute rigid medium) is put inside, and the medium is vigorously stirred by a rotor stirring mechanism inserted inside. It is performed by treating the raw slurry with the applied impact, shear and frictional forces. In a commercially available dispersing machine of the sand mill method, the crushed material is continuously circulated or circulated only while the fine medium filled in the crusher is held. A mechanism (media separation mechanism) for separating the crushed material and the micro rigid medium has been devised. As such a media separating mechanism, for example, a method of providing a narrow gap between a fixed ring and a rotating ring on a concentric axis to separate the media (generally called a gap separator or a slit system).
There is also a method of inserting and separating a mesh-shaped or metal plate-punched metal plate into a crusher (generally called a screen method), or a centrifugal method using centrifugal force.

The method for producing crystalline fine particles of the present invention is characterized in that the impact force, shear force,
The principle feature is that the frictional force instantaneously destroys a crude crystal of an organic compound containing a solvent in the crystal and newly precipitates a fine crystal of the organic compound in a dispersion solvent.

In the second step of the production method of the present invention,
It is preferable that the slurry of the crystalline coarse particles of the organic compound is refined in the presence of the dispersant. As the dispersant, known anionic, nonionic or cationic surfactants and polymers can be used, and two or more kinds may be used in combination as appropriate. As the dispersant, commercially available dispersants can be used. For example, Demol N, Demol SNB, Demol EP, etc. manufactured by Kao Corporation can be used.

It is a general method that the dispersant is mixed with the powder or wet cake of the coarse crystals before dispersion and then sent as a slurry to the dispersing machine. A treatment with a solvent may be performed to obtain a pigment powder or a wet cake. During the dispersion treatment, as the fine particles are formed, they can be appropriately added to the dispersion. In addition, for stabilizing the physical properties after dispersion, it can be added after the dispersion treatment. In any case, a solvent (eg, water / alcohol) is commonly used. Before, during or after dispersion, the pH may be controlled with a suitable pH adjuster.

The dispersion of the crystalline fine particles of the organic compound prepared may be stored with stirring or may be kept in a highly viscous state (for example, gelatin may be added) with a hydrophilic colloid in order to suppress sedimentation of the fine particles during storage. Or use it in a jelly state). It is preferable to add a preservative for the purpose of preventing propagation of various bacteria during storage.

In carrying out the fine-graining step in the production of the crystalline fine particles of the organic compound of the present invention, the fine particles are composed of the same kind of organic compound as the organic compound which is a crystalline coarse particle containing solvent molecules, and the solvent molecules are substantially removed. It is desirable to add a small amount of coarse particles of crystalline fine particles not contained in the crystals to the coarse crystalline particles containing solvent molecules, and to perform a fine particle forming step as a mixed slurry. Crystalline fine particles of an organic compound containing substantially no organic solvent in the crystal function as seed crystals of the organic compound crystalline fine particles finally obtained as a dispersion. That is, the organic compound dispersed with the seed crystal as a nucleus grows.

The seed crystal may be obtained by any method known in the art. For example, an organic compound to be dispersed is once dissolved in a readily soluble organic solvent, and is dissolved in another hardly soluble solvent (eg, water). To obtain a crystal dispersion obtained by a conventional dispersion method such as a sand mill method, and centrifugal separation to extract only the ultrafine particles. The microcrystalline particles of the organic compound that does not substantially contain a solvent in the crystals and that are used as seed crystals in the present invention preferably have an average particle diameter in the range of 0.005 to 1.00 μm, and more preferably 0.005 to 1.00 μm. Preferably, it is in the range of 0.10 μm.

The organic compound microcrystals that do not contain a solvent in the crystals, which are seed crystals, have a molar ratio of 0.0
It is preferable to mix and disperse 1% to 20%, and more preferable to mix and disperse 1% to 10%.

In the dispersion of crystalline fine particles of an organic compound obtained by the production method of the present invention, 50% or more, preferably 80% or more, expressed as a percentage based on the number thereof, has a long axis of one microcrystal. Is preferably a needle-like crystal (also referred to as a rod-like crystal) having a value (aspect ratio or needle-like ratio) obtained by dividing the length by its width (aspect ratio or needle-like ratio) of 2 to 50. In particular, the needle ratio is preferably in the range of 2 to 40.

The length of the major axis of the crystalline needle-like fine particles is
The average value is preferably in the range of 0.10 to 2.00 μm, particularly preferably in the range of 0.15 to 1.50 μm. The average length of the width of the crystalline acicular fine particles is preferably in the range of 0.005 to 0.30 μm, and particularly preferably in the range of 0.01 to 0.20 μm.

The needle-like crystals (or rod-like crystals)
It can be confirmed by direct electron microscope observation by a cooling method or electron microscope observation by a carbon replica method.

In the fine particle forming step in the production of the crystalline fine particles of the organic compound of the present invention, fine inorganic crystal particles (substantially containing the solvent molecules within the crystal) are added to the coarse organic compound crystalline particles containing the solvent molecules. It is also desirable to add a small amount of crystalline inorganic fine particles not contained in the mixture and to carry out a fine particle forming step as a mixed slurry.

Examples of fine inorganic crystal particles include colloidal metal oxides such as silica, alumina, and titanium oxide, fine particles of a natural or synthetic mica group,
Mineral fine particles described in Table 1 on page 3 of -5748,
Alternatively, semiconductor fine particles and the like can be used. Depending on the purpose of use, a material that does not absorb visible light may be preferable depending on the purpose of use.

The average particle size of the fine inorganic crystal particles is 0.0
It is preferably in the range of 0.5 to 1.00 μm.
More preferably, the thickness is from 005 to 0.10 μm. These inorganic crystal particles also function as nuclei for the growth of organic compound crystals during the micronization process. Therefore, the generated crystalline fine particles of the organic compound are microcrystals of the organic compound containing the inorganic crystalline fine particles. The inorganic crystalline fine particles may be used by adsorbing an organic compound to be dispersed before dispersion.

The inorganic crystalline fine particles are mixed in an amount corresponding to 0.01 to 50% by weight to the organic compound with respect to the organic compound coarse crystals (crystal coarse particles) containing a solvent in the crystal. And preferably dispersed,
More preferably, they are mixed and dispersed in an amount corresponding to 0%. The inorganic crystalline fine particles are preferably used as a dispersion.

Whether or not the crystalline fine particles of the organic compound include the inorganic crystalline fine particles and the shape of each of the crystalline fine particles can be confirmed by direct electron microscopic observation by a cooling method.

The average particle size of the microcrystalline particles (crystalline fine particles) of the organic compound obtained by the production method of the present invention is 0.6.
It is preferably 0 μm or less, and most preferably 0.40 μm or less. The average particle diameter represents the number average of the circle-equivalent diameter of the projected area of the particles, which is obtained when 500 particles are arbitrarily observed in a viewing region with an electron microscope in a state where the microcrystals do not overlap. .

[0102]

The present invention will be specifically described below with reference to examples.

Example 1 Production of Dye Crystalline Coarse Particles In a mixed solvent of acetic acid and acetic anhydride, Dye A represented by the following formula was obtained as a crystalline coarse particle by a known method. The coarse particles of the dye A are mixed with ethylene glycol to form an ethylene glycol wet cake (including comparative coarse particles).
And A portion of this wet cake, after removing the solvent adhering to the crystalline grit external, ¹ H-NM
When measured by R, it was confirmed that ethylene glycol or another solvent was not contained in the crystal. Further, a part of this wet cake was taken, dispersed in water, and 500 crystalline coarse particles were observed with a microscope to calculate the average particle diameter. The average particle diameter was 10 μm.

[0104]

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The crystalline coarse particles of the dye A were added to ethylene glycol, and a portion of a wet cake of the crystalline coarse particles obtained by stirring at 100 ° C. for 2 hours was collected and dried at room temperature. after, ¹ for the obtained crystalline grit H
As a result of measurement by NMR, the crystalline coarse particles showed that
It was confirmed that the dye was crystalline coarse particles of a dye (corresponding to the above-mentioned dye I-46) in which 2 mol of ethylene glycol was incorporated as a crystalline molecule with respect to the mol. Similarly, a part of the wet cake was collected, dispersed in water, and 500 coarse crystalline particles were observed with a microscope to calculate the average particle diameter. The average particle diameter was 20 μm. The dye concentration (solid content) in the thus obtained wet cake (including the coarse particles of the present invention) was 80% by weight.

[0106] [Example 2] with the compound b ₁ of the formula the preparation following dyes crystalline grit compound b ₂ and each using a 10g and 8g DMF (N, N- dimethylformamide) in a solvent The dye B (solid concentration 7
(0% by weight) of a crystalline coarse particle wet cake (including comparative coarse particles). Take a part of this wet cake,
After removing the solvent adhering to the outside of the crystalline coarse particles,
^{As a result} of measurement by ¹ H-NMR, it was confirmed that DMF or another solvent was not contained in the crystal. A part of this wet cake was taken, dispersed in water, and 500 crystalline coarse particles were observed with a microscope to calculate an average particle diameter. The average particle diameter was 7 μm.

[0107]

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[0108] The same compounds b ₁ and the and 10g compound b ₂
And 8 g of DMAc (N, N-dimethylacetamide)
After collecting a part of the wet cake of the crystalline coarse particles obtained by reacting in the solvent and drying at room temperature, the obtained crystalline coarse particles were measured by ¹ H-NMR. The crystalline coarse particles are N, N-
It was confirmed that 2 mol of dimethylacetamide was a crystalline coarse particle of a dye (corresponding to the above-mentioned dye I-77) in a state of being incorporated as a crystalline molecule. Similarly, a part of the wet cake was collected and dispersed in water, and 500 coarse crystalline particles were observed with a microscope to calculate the average particle diameter. The average particle diameter was 10 μm. The pigment concentration (solid content) in the thus obtained wet cake (including the coarse particles of the present invention) was 75% by weight.

Example 3 Production of Dye Crystalline Fine Particle Dispersion The above-mentioned wet cake of each dye crystal coarse particle was treated as a wet cake without drying, and 4.0 g of a dye solid content was weighed. Water for dispersing the coarse particles and 2.4 g of a 25% by weight solution of Demol SNB (manufactured by Kao Corporation) as a dispersing agent are preliminarily mixed, and then the above-mentioned pigment crystalline coarse particles are added to make a total of 60 g. The resulting mixture was adjusted with water so as to obtain a slurry, and the resulting mixture was mixed well to obtain a pigment crystalline coarse particle slurry.

240 g of zirconia beads were prepared, put into a container for fine particle treatment together with the pigmented crystalline coarse particle slurry, and were subjected to a 1/16 gallon sand grinder mill (manufactured by Imex Co., Ltd.). The container was dispersed while being cooled with water at 1200 rpm. As zirconia beads, those having an average particle size of 1.0 mm were used.

Table 1 shows the dispersion time of each dye.

After the dispersion is completed, the solid content of the dye is 5% by weight.
Was added to obtain a dispersion liquid. DP1 to DP6 were obtained from the dye dispersions shown in Table 1.

[0113]

[Table 1] Table 1 分散 Dispersion Dye Crystal solvent Dispersion Time ──────────────────────────────────── DP1 (Comparative example) A None 3 hours DP2 (Comparative example) ) A None 15 hours ──────────────────────────────────── DP5 (Example of the present invention) I-46 Ethylene glycol 3 hours ＤＰ DP3 (Comparative example) B None 3 hours DP4 (Comparative Example) B None 15 hours ＤＰ DP6 (Example of the present invention) I-77 DMAc 3 hours ───────────────── ──────────────────

Example 4 Evaluation of Dye Dispersion Each of the obtained dispersions of the dyes was fine crystal particles dispersed in the form of fine crystals. When the average particle diameter of the fine particles and the value obtained by dividing the length of the major axis by the width (needle ratio) from the projected area of 500 microcrystals (needle ratio) are 2 or more, And the ratio was determined.

The results are shown in Table 2.

Further, each dispersion was diluted by a certain factor, and a light absorption spectrum was obtained by detecting transmitted light of the dispersion. The maximum absorption wavelength of each dispersion, its absorbance (extinction coefficient), and its half width (nm) were measured and are shown in Table 2. The absorbance was expressed as a relative value with the value measured with DP1 as 100. ¹ H-NMR measurement confirmed that the crystalline fine particles of DP5 and DP6 of the dispersion according to the present invention did not contain a crystal solvent (below the detection limit).

[0117]

[Table 2] Table 2 分散 Average particle size of dispersion Particle ratio Peak wavelength Peak absorbance Half width (μm) (%) (nm) (Relative value) (nm) ────────────────────────── {DP-1 1.05 0 506 100 210 DP-2 0.77 0 520 154 170} {DP-5 0.45 95 525 202 110} {DP-3 1.10 0 576 110 180 DP-4 0.63 0 558 171 130} ─────────── {DP-6 0.44 97 536 228 90} ───

[Explanation of the results in Tables 1 and 2] The dispersion of DP1 and DP3 obtained by subjecting the crystalline coarse particles of Dye A and Dye B, which do not contain a crystallization solvent, to a fine particle treatment for 3 hours is a coarse particle. , The absorbance was low, and the absorption spectrum was broad. On the other hand, the crystalline coarse particles of the dye containing the crystallization solvent
The dispersion of DP5 and DP6 (dispersion according to the present invention) obtained by the time micronization treatment achieves sufficient microcrystallization, and thus has a high absorbance and a narrow half-width of the peak at the maximum wavelength. preferable.

The crystalline coarse particles of Dye A and Dye B containing no crystallization solvent were subjected to a fine treatment for 15 hours to obtain D.
The dispersions of P2 and DP4 have a smaller average particle size, a higher absorbance, and a smaller half-width of the peak at the maximum wavelength than the dispersions (DP1 and DP3) obtained by the micronization treatment for 3 hours. Are still inferior to the dispersions according to the invention (DP5 and DP6).

Example 5 Dispersion DP7 According to the Invention
After obtaining a dispersion DP4 (containing no crystallization solvent) in the same manner as in Example 3, this was centrifuged to remove large particles, and a slurry containing fine particles having an average particle diameter of 0.06 μm was obtained. Obtained. This was DP3M. DP3M was weighed to a dye solid content of 0.2 g, and I
-77 (dye solid content: 3.8 g) crystalline coarse particles (DP
6) Premixed. Further, 2.4 g of a 25% by weight solution of Demol SNB (manufactured by Kao Corporation) as a dispersant and water for dispersing are mixed in advance, and the coarse particles are added thereto.
Water was added and adjusted so that the total would be 60 g, and then mixed well to obtain a slurry. Next, this slurry is DP
The dispersion DP7 according to the present invention was obtained by subjecting the dispersion treatment to the micronization treatment under the same conditions as the micronization treatment conditions of No. 6.

The dispersion DP7 was diluted by a certain factor, and a light absorption spectrum was obtained by detecting transmitted light of the dispersion. The maximum absorption wavelength of each dispersion, its absorbance (extinction coefficient), and its half width (nm) were measured and are shown in Table 3. The absorbance was expressed as a relative value with the value measured with DP1 as 100. ¹ H-NMR measurement confirmed that the crystalline solvent of DP7 did not contain a crystallization solvent (below the detection limit). An electron micrograph was taken of each of the dispersion DP7 by the carbon replica method in the same manner as in Example 4, and the average particle size of the fine particles and the acicular ratio were determined based on the projected area of 500 microcrystals in an arbitrary region. When the needle-like crystal particles described above were present, the ratio was determined. The results are also shown in Table 3.

Example 6 Dispersion DP8 According to the Invention
Manufacture of Nissan Chemical Co., Ltd. Snowtex O (average particle size of 10
20 nm of colloidal silica) with a silica solid content of 0.5 g
Crystallized coarse particles (DP6) of I-77 (dye solid content 4.0 g) containing a crystallization solvent, and water for dispersing and Demol SNB (manufactured by Kao Corporation) as a dispersing agent ) Was mixed in advance, and Snowtex O was added thereto. The mixture was adjusted with water so that the total amount became 60 g, and then mixed well to form a slurry. Next, this slurry is subjected to micronization treatment under the same conditions as the micronization treatment of DP6 to obtain the dispersion DP8 according to the present invention.
I got

An arbitrary 500 of the dispersion was observed with a transmission electron microscope.
By observing the individual microcrystals, it was confirmed that 88% of the pigment crystal fine particles in the dispersion contained one colloidal silica.

The dispersion DP8 was diluted to a constant volume, and a light absorption spectrum was obtained by detecting transmitted light of the dispersion. The maximum absorption wavelength of each dispersion, its absorbance (extinction coefficient), and its half width (nm) were measured and are shown in Table 3. The absorbance was expressed as a relative value with the value measured with DP1 as 100. ¹ H-NMR measurement confirmed that the crystalline solvent of DP8 did not contain a crystallization solvent (lower than the detection limit). Further, an electron micrograph was taken of each of the dispersion DP8 by the carbon replica method in the same manner as in Example 4, and the average particle size of the fine particles and the needle ratio were 2 based on the projected area of 500 microcrystals in an arbitrary region. When the needle-like crystal particles described above were present, the ratio was determined. The results are also shown in Table 3.

[0125]

[Table 3] Table ──────────────────────────────────── Dispersion Average particle size Acicular Particle ratio Peak wavelength Peak absorbance Half width (μm) (%) (nm) (Relative value) (nm) ────────────────────────── {DP-4 0.63 0 558 171 130} {DP-6 0.44 97 536 228 90 DP-7 0.31 91 545 242 85 DP-8 0.22 64 552 254 100} ──────────────────────

[Explanation of Results in Table 3] A dispersion D obtained by co-existing crystalline fine particles of a dye having no crystallization solvent in the fine treatment of the crystalline coarse particles of the dye having a crystallization solvent.
The dispersion DP8 obtained by coexisting fine particles of the inorganic compound in the fine particle treatment of P7 and the crystalline coarse particles of the dye having a crystallization solvent has a smaller average particle diameter than DP6, and has an absorbance. Is also preferred.

The attached drawings show carbon replica photographs of the dye dispersion DP4 (comparative sample), the dye dispersion DP6 (sample of the present invention), and the dye dispersion DP7 (sample of the present invention). As shown. The magnification is 10,000 times, and the diameter of the spherical comparative latex particles visible in the photograph is 0.2 μm.

[Embodiment 7] Hatsumei Kyokai Disclosure Report 98-83
In accordance with the method for producing photosensitive material 1 of Example 1 disclosed in JP-A No. 05-2005, a colored layer for crossover cutting is formed using dye dispersions DP1 to DP8,
8) was produced. Then, the characteristics of each photographic light-sensitive material as a light-sensitive material were evaluated. Table 4 shows the results.
The coating amount of the solid content of the dye dye in the method of forming the crossover cut dye layer was adjusted to be 40 mg per one surface of the support.

The X-ray exposure method, the screen to be used, the method of evaluating the crossover value, and the method of developing the photosensitive material were the same as those of the system 1 of Example 1 described in the above-mentioned published technical report. The sensitivities of the photosensitive materials 1 to 8 were all equal.

[0130]

[Table 4] 材 Sensitive material Dye dispersion Sharpness Crossover value (2 lp / mm) photosensitive material after development ───────────────────────────────── ─── Sensitive material 1 DP1 0.520 18% Dye remains (residual color) Sensitive material 2 DP2 0.565 12% No problem Sensitive material 3 DP3 0.500 20% Dye remains (residual color) Sensitive material 4 DP4 0.595 6% No problem 感 Sensitive material 5 DP5 0.605 4% No problem Sensitive material 6 DP6 0.615 2.5% No problem Sensitive material 7 DP7 0.620 1.5% No problem Sensitive material 8 DP8 0.625 1.0% No problem ─────── ────── ──────────────────────

[Explanation of Results in Table 4] Sensitive materials 5 to 8 using dye dispersions DP5 to DP8 produced by the method of the present invention.
However, it can be seen that a photographic image having high sharpness is given.

[0132]

EFFECT OF THE INVENTION By utilizing the method for producing a crystalline fine particle dispersion of an organic compound according to the present invention, a crystal of an organic compound represented by an organic dye compound can be provided with an optical or chemical function. The conductive fine particle dispersion can be efficiently produced using a general fine particle processing apparatus.

[Brief description of the drawings]

FIG. 1 is a carbon replica photograph of dye crystalline fine particles in a comparative dispersion (DP4).

FIG. 2 Dispersion (DP6) produced by the method according to the invention
It is a carbon replica photograph of the pigment crystalline fine particles in.

FIG. 3 shows a dispersion (DP7) produced by the method according to the invention.
It is a carbon replica photograph of the pigment crystalline fine particles in.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/06 502 G03C 1/06 502 F term (Reference) 2H023 CE00 FD01 2H086 BA45 BA51 BA55 4G065 AB16Y AB21Y AB40Y BB03 CA11 DA09 EA01 FA01 4J037 AA30 DD02 DD04 DD05 DD09 DD23 EE08 EE28 EE29 EE43 FF15 4J039 BE01 BE12 CA05 DA02 EA44 GA24

Claims (13)

[Claims] 1. A step of preparing a slurry of crystalline coarse particles of an organic compound containing a solvent molecule in a crystal, and subjecting the slurry of the crystalline coarse particle to a fine-particle treatment to reduce the solvent molecule in the crystal. A method for producing a dispersion of crystalline fine particles of an organic compound, comprising a step of obtaining a slurry of crystalline fine particles of an organic compound substantially free of organic compound. 2. The method for producing a dispersion of crystalline fine particles of an organic compound according to claim 1, wherein the organic compound is an organic dye compound. 3. The method for producing a dispersion of crystalline fine particles of an organic compound according to claim 1, wherein the solvent molecule is a polar solvent molecule. 4. The method according to claim 1, wherein the fine particles of the same kind of organic compound which do not substantially contain solvent molecules are present in the crystal when the slurry of the crystalline coarse particles of the organic compound is subjected to the atomization treatment. A method for producing a dispersion of crystalline fine particles of an organic compound according to any one of claims 1 to 3. 5. The method according to claim 1, wherein when the slurry of the crystalline coarse particles of the organic compound is subjected to the fine-particle treatment, crystalline fine particles of the inorganic compound substantially containing no solvent molecules are present. 13. A method for producing a dispersion of crystalline fine particles of an organic compound according to any one of the above. 6. The method according to claim 1, wherein an average particle size of the crystalline coarse particles of the organic compound containing a solvent molecule in the crystal is in a range of 5 to 100 μm. A method for producing a dispersion of the crystalline fine particles of the organic compound according to the above. 7. The amount of the solvent molecule contained in the crystalline coarse particles of the organic compound containing a solvent molecule in the crystal is the product of the molecular weight of the solvent molecule and the number of moles of the solvent molecule per mole of the organic compound. The method for producing a dispersion of crystalline fine particles of an organic compound according to any one of claims 1 to 6, wherein the value represented by is in the range of 100 to 400. 8. An average particle size obtained by the production method according to claim 1 is 0.10 to 10.10.
A dispersion of crystalline fine particles of an organic compound having a diameter of 0.60 μm. 9. The dispersion of crystalline fine particles of an organic compound according to claim 8, comprising 50% or more of needle-like crystalline fine particles having a needle-like ratio in the range of 2 to 50, expressed as a percentage based on the number. 10. The full width at half maximum of an absorption peak at the maximum absorption wavelength obtained by the production method according to claim 2 is 120.
A dispersion of crystalline fine particles of an organic dye compound having a diameter of not more than nm. 11. A dispersion of an organic dye compound comprising needle-like crystalline fine particles of an organic dye compound having an average particle diameter in a range of 0.10 to 0.60 μm and a needle ratio in a range of 2 to 50. . 12. The dispersion of crystalline fine particles of an organic dye compound according to claim 11, wherein 50% or more of the crystalline fine particles, expressed as a percentage based on the number, contain inorganic crystal particles. . 13. The dispersion of crystalline fine particles of an organic dye compound according to claim 11, wherein the half width of the absorption peak at the maximum absorption wavelength is 120 nm or less.