KR20080032233A - Process for production of organic particles, process for production of organic particle dispersion compositions, and jet-printing inks containing organic particle dispersion compositions obtained by the process - Google Patents

Abstract

A process for the production of organic particles which comprises mixing at least three components, i.e., a solution of an organic material in a good solvent, a solvent which is compatible with the good solvent and acts as a poor solvent for the organic material, and a solution containing a high-molecular dispersant to form particles of the organic material in the mixed solution.

Description

TECHNICAL FOR PRODUCTION OF ORGANIC PARTICLES, PROCESS FOR PRODUCTION OF ORGANIC PARTICLE DISPERSION COMPOSITIONS, AND JET-PRINTING INKS CONTAINING ORGANIC PARTICLE DISPERSION COMPOSITIONS OBTAINED BY THE PROCESS}

The present invention relates to a method for producing organic particles in which organic particles are produced in the presence of a polymer dispersant. Moreover, it is related with the manufacturing method of the organic particle-dispersion composition which concentrated this organic particle | grain liquid. More specifically, nano-size organic particles are produced in a mono-dispersed state, and the change in particle diameter and dispersibility when the nanoparticle liquid is concentrated can be suppressed and can be easily redispersed even when aggregated by concentration. A method for producing organic particles and a method for producing organic particle dispersion composition. Moreover, it is related with the inkjet ink for ink using the organic-particle dispersion composition obtained by the said manufacturing method.

In recent years, research has been conducted to reduce the size of particles. In particular, studies are being conducted to reduce the size to nanometer size (for example, in the range of 10 to 100 nm), which is difficult to manufacture by a grinding method, a precipitation method, or the like. In addition, it is attempted to make the particles having high monodispersibility (in the present invention, the degree to which the particle diameters are aligned) after small size at nanometer size.

The size of such nanometer-sized fine particles differs from the size of larger bulk particles, the size of smaller molecules and atoms, and is located in the middle of them. Therefore, it is pointed out that it is possible to derive new characteristics which were not previously expected. Moreover, if this monodispersity can be improved, the characteristic can also be stabilized. The potential of such nanoparticles is expected in various fields, and research is being actively conducted in a wide range of fields such as biochemistry, new materials, electronic devices, light emitting display devices, printing, and medical care.

In particular, organic nanoparticles composed of organic compounds have a high potential as a functional material because the organic compounds themselves have a variety. For example, polyimide is used in many fields in that it is a chemically and mechanically stable material such as heat resistance, solvent resistance, and mechanical properties, and has excellent electrical insulation. In the material which made the polyimide microparticles | fine-particles, new utilization is expanded by the combination of the characteristic and shape of a polyimide. For example, as a proposed technique for the use of finely divided polyimide, an additive of a powder toner for image formation (Patent Document 1) and the like has been proposed.

Among organic nanoparticles, organic pigments include, for example, paints, printing inks, electrophotographic toners, inkjet inks, color filters, and the like, and are now important materials indispensable in life. . Among them, high performance is required, and pigments for ink jet inks and pigments for color filters are particularly important in practical use.

Dye has been used conventionally about the color material of inkjet ink, but there exists a problem in water resistance and light resistance, and a pigment is used in order to improve it. The image obtained by the pigment ink has the advantage that it is excellent in light resistance and water resistance compared with the image by dye ink. However, it is difficult to make monodispersity high in the nanometer size which can permeate the space | gap of a paper surface, and there exists a problem that adhesiveness with respect to paper is inferior.

Moreover, with the high pixel of a digital camera, the thinning of the color filter used for optical elements, such as a CCD sensor, and a display element is desired. Organic pigments are used for color filters, but since the thickness of the filter largely depends on the particle diameter of the organic pigment, production of microparticles stable at a nanometer size level and monodisperse is desired.

Regarding the production of the organic particles, a gas phase method (a method of subliming a sample in an inert gas atmosphere and recovering the particles on a substrate), a liquid phase method (for example, a sample dissolved in a good solvent may be used for stirring conditions or temperature). The reprecipitation method which obtains microparticles | fine-particles by injecting into the poor solvent controlled, the laser ablation method (the method which refine | miniaturizes the particle | grains by irradiating a laser and abrading to the sample disperse | distributed in the solution), etc. are researched. Moreover, the production example which tried monodisperse to the desired size by these methods is reported. (See patent documents 2-4, etc.).

Among them, the reprecipitation method is a method for producing organic particles excellent in simplicity and productivity, but is still not enough as a particle manufacturing method having high industrial utility. For example, there has not been enough research on how to separate and recover the organic particles prepared by the reprecipitation method. In the reprecipitation method, the prepared organic particles are obtained in a state of being dispersed in a lean solvent. Even if the desired organic particles can be prepared in the dispersion, it is practical to use the process of concentrating and separating and recovering the particle size, deteriorating the monodispersibility of the particles, or requiring a large cost for the recovery. Can not. In Patent Document 5, it is described that the effect of preventing the reagglomeration of the pigment particles by miniaturizing the pigment particles by including the dispersant in either the good solvent or the poor solvent. However, this method also relates to the formation of pigment particles, and it cannot be said that industrial practical use is possible in view of concentration and separation.

Patent Document 1: Japanese Patent Application Laid-Open No. 11-237760

Patent Document 2: Japanese Patent Publication No. 2002-092700

Patent document 3: Unexamined-Japanese-Patent No. 6-79168

Patent Document 4: Japanese Unexamined Patent Publication No. 2004-91560

Patent Document 5: Japanese Unexamined Patent Publication No. 2003-26972

Disclosure of the Invention

An object of this invention is to provide the manufacturing method of the organic particle which has a fine particle diameter by monodispersion. In more detail, the manufacturing method of the organic particle | grains which can simplify a concentration process, can suppress the change of the particle size and monodispersibility when it concentrates, and can be redispersed easily also when it aggregates by concentration, and An object of the present invention is to provide a method for producing an organic particle dispersion composition obtained by concentrating it. Another object of the present invention is to provide organic particles having excellent monodispersibility and fine enough, industrially available industrial use, a concentrated organic particle dispersion composition containing the same, and ink jet recording ink using the same.

According to the present invention, the following means are provided:

(1) between a solution of an organic material dissolved in a good solvent, a solvent which is compatible with the good solvent and becomes a poor solvent for the organic material, and a solution containing a polymer dispersant. At least 3 types are mixed and the said organic material is produced as particle | grains in the liquid mixture, The manufacturing method of the organic particle | grains characterized by the above-mentioned.

(2) The method for producing organic particles according to (1), wherein the organic material is an organic pigment.

(3) The method for producing organic particles according to (1) or (2), wherein the poor solvent is an aqueous solvent.

(4) The method for producing organic particles according to any one of (1) to (3), wherein the polymer dispersant is a polymer dispersant having a mass average molecular weight of 1000 or more.

(5) The method for producing organic particles according to any one of (1) to (4), wherein the organic material is produced as nano-dispersed monodisperse nanoparticles in the presence of the polymer dispersant.

(6) The method for producing organic particles according to any one of (1) to (5), wherein the polymer dispersant is polyvinylpyrrolidone, polyacrylamide, or polyethyleneimine.

(7) The organic particle dispersion liquid is manufactured by the manufacturing method in any one of (1)-(6), and this concentrates to predetermined density | concentration, The manufacturing method of the organic particle dispersion composition.

(8) An inkjet recording ink, comprising an organic particle dispersion composition produced by the production method described in (7).

(9) The inkjet recording ink according to (8), wherein the average particle diameter of the organic particles contained in the organic particle dispersion composition is 1 to 100 nm.

The above and other features and advantages of the present invention will become more apparent from the following description when considered in conjunction with the accompanying drawings.

1: A is sectional drawing which shows preferable embodiment of the manufacturing apparatus used in the manufacturing method of the organic particle of this invention.

FIG. 1B is an enlarged partial cross-sectional view schematically showing the mixing chamber by a partial cross section as one embodiment of the manufacturing apparatus of FIG. 1A.

FIG. 1C is an enlarged partial cross-sectional view schematically showing the mixing chamber by a partial cross section as another embodiment of the manufacturing apparatus of FIG. 1A.

2 is a cross-sectional view schematically showing another preferred embodiment of the production apparatus used in the method for producing organic particles of the present invention.

3 is a cross-sectional view schematically showing still another preferred embodiment of the production apparatus used in the method for producing organic particles of the present invention.

It is explanatory drawing which shows the example of 1 structure of the ultrafiltration apparatus used in the manufacturing method of the organic particle of this invention.

In the drawings, the symbols of the main members are described below.

11 containers

11a liquid bath (solvent)

11b face value

12 stirring wings

13 Mixing Room

14a, 14b supply pipe

14c, 14d supply line opening

15 shafts

16 motor

17 Casing (Mixed Wall)

18 holes (round holes)

19a, 19b stirring wing

21 containers (stirrer outer wall)

21a stirring tank

22 stirring wings

23 exhaust pipe

24a, 24b, 24c supply pipe

25 shafts

50 stirring device

31, 32, 33 supply port

36 outlet

40 seal plate

41, 42 stirring blade

46 outer magnet

48, 49 motor

81 Storage Container

82 Circulation Pumps

83 Ultrafiltration Module

84 Supplemental pure water flow meter

85 Permeate Flow Meter

86 Reverse Cleaning Pump

Implement the invention  Best form for

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

[Organic materials]

In the manufacturing method of the organic particle | grains of this invention, if an organic material can precipitate and produce as organic particle | grains, there will be no restriction | limiting in particular. As an organic material, For example, high molecular compounds, such as an organic pigment, an organic pigment, a fullerene, polydiacetylene, and a polyimide, aromatic hydrocarbon or aliphatic hydrocarbon (for example, aromatic hydrocarbon or aliphatic hydrocarbon which has orientation, Or aromatic hydrocarbons or aliphatic hydrocarbons having sublimation), and organic pigments, organic pigments, or high molecular compounds are preferred, and organic pigments are particularly preferred. Moreover, you may combine these.

The organic pigment which can be used by the manufacturing method of the organic particle of this invention is not limited in color, For example, perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthrone, Benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, thioindigo, isoindolin, isoindolinone, pyrantrone Or isobioanthrone pigments, or mixtures thereof.

More specifically, for example, perylene pigments such as CI pigment red 190 (CI number 71140), CI pigment red 224 (CI number 71127), CI pigment violet 29 (CI number 71129), and CI pigment orange 43 (CI No. 71105), or perinone pigments such as CI Pigment Red 194 (CI. No. 71100), CI Pigment Violet 19 (CI No. 73900), CI Pigment Violet 42, CI Pigment Red 122 (CI No. 73915), CI Pigment Red 192, Quinacridone pigments of CI pigment red 202 (CI number 73907), CI pigment red 207 (CI number 73900, 73906), or CI pigment red 209 (CI number 73905), CI pigment red 206 (CI number 73900/73920), Anthraquinone pigments, such as quinacridone quinone pigments, such as CI pigment orange 48 (CI number 73900/73920) or CI pigment orange 49 (CI number 73900/73920), CI pigment yellow 147 (CI number 60645), CI Antanthron pigments such as pigment red 168 (CI number 59300), CI pigment brown 25 CI Pigment Violet 32 (CI No. 12517), CI Pigment Yellow 180 (CI No. 21290), CI Pigment Yellow 181 (CI No. 11777), CI Pigment Orange 62 (CI No. 11775), or CI Pigment Red Benzimidazolone pigments such as 185 (CI number 12516), CI pigment yellow 93 (CI number 20710), CI pigment yellow 94 (CI number 20038), CI pigment yellow 95 (CI number 20034), CI pigment yellow 128 ( CI number 20037), CI pigment yellow 166 (CI number 20035), CI pigment orange 34 (CI number 21115), CI pigment orange 13 (CI number 21110), CI pigment orange 31 (CI number 20050), CI pigment red 144 ( CI No. 20735), CI Pigment Red 166 (CI No. 20730), CI Pigment Red 220 (CI No. 20055), CI Pigment Red 221 (CI No. 20065), CI Pigment Red 242 (CI No. 20067), CI Pigment Red 248, Disazo condensed pigments such as CI pigment red 262 or CI pigment brown 23 (CI No. 20060), CI pigment Disazo pigments such as low 13 (CI number 21100), CI pigment yellow 83 (CI number 21108), or CI pigment yellow 188 (CI number 21094), CI pigment red 187 (CI number 12486), CI pigment red 170 ( CI No. 12475), CI Pigment Yellow 74 (CI No. 11714), CI Pigment Yellow 150 (CI No. 48545), CI Pigment Red 48 (CI No. 15865), CI Pigment Red 53 (CI No. 15585), CI Pigment Orange 64 ( Azo pigments such as CI No. 12760) or CI Pigment Red 247 (CI No. 15915), Indanthrone pigments such as CI Pigment Blue 60 (CI No. 69800), CI Pigment Green 7 (CI No. 74260), CI Pigment Green Phthalocyanine pigments, such as 36 (CI number 74265), pigment green 37 (CI number 74255), pigment blue 16 (CI number 74100), CI pigment blue 75 (CI number 74160: 2), or 15 (CI number 74160), Triarylcarbonium type | system | group, such as CI pigment blue 56 (CI number 42800) or CI pigment blue 61 (CI number 42765: 1). Dioxazine pigments such as CI pigment violet 23 (CI number 51319) or CI pigment violet 37 (CI number 51345), aminoanthraquinone pigments such as CI pigment red 177 (CI number 65300), CI pigment red 254 (CI) Diketopyrrolopyrrole pigments, CI pigments such as CI pigment red 255 (CI number 561050), CI pigment red 264, CI pigment red 272 (CI number 561150), CI pigment orange 71, or CI pigment orange 73 Thio indigo pigments, such as Red 88 (CI number 73312), CI pigment yellow 139 (CI number 56298), isoindolin chlorine series, such as CI pigment orange 66 (CI number 48210), CI pigment yellow 109 (CI number 56284) , Or CI Isoindolinone pigments such as pigment orange 61 (CI number 11295), pyrantron pigments such as CI pigment orange 40 (CI number 59700) or CI pigment red 216 (CI number 59710), or CI pigment violet 31 (60010) Isobioanthrone pigments such as

In the manufacturing method of the organic particle of this invention, you may use combining two or more types of organic pigments or solid solutions of organic pigments.

As an organic pigment | dye, an azo pigment | dye, a cyanine pigment | dye, a merocyanine pigment | dye, a coumarin pigment | dye, etc. are mentioned, for example. As a high molecular compound, polydiacetylene, a polyimide, etc. are mentioned, for example.

[Formation of Organic Particles]

Next, formation of organic particle | grains is demonstrated.

The organic particle | grains of this invention mix the base material solution which melt | dissolved the organic material in the good solvent, the poor solvent (henceforth simply called the "poor solvent of organic particle") with respect to the organic material, and the solution containing the polymer dispersing agent, Organic particles are obtained (hereinafter, this method is also referred to as "organic particle precipitation method", and the organic particle liquid thus obtained is called "organic particle precipitation liquid").

(Good solvent)

First, the good solvent which melt | dissolves an organic material is demonstrated.

The good solvent is not particularly limited as long as it can dissolve the organic material to be used and is compatible with or uniformly mixed with the poor solvent used in the production of the organic particles. It is preferable that the solubility of an organic material is 0.2 mass% or more, and, as for the solubility with respect to the good solvent of an organic material, it is more preferable that it is 0.5 mass% or more. This solubility may be solubility when melt | dissolved in presence of an acid or an alkali. It is preferable that the amount of melt | dissolution with respect to the poor solvent of a good solvent is 30 mass% or more, and, as for the preferable range of the compatibility of a poor solvent and a good solvent, it is more preferable that it is 50 mass% or more.

As a good solvent, For example, an aqueous solvent (for example, water or hydrochloric acid, a sodium hydroxide aqueous solution), an alcohol solvent, an amide solvent, a ketone solvent, an ether solvent, an aromatic solvent, carbon bisulfide, Aliphatic solvents, nitrile solvents, sulfoxide solvents, halogen solvents, ester solvents, ionic liquids, mixed solvents thereof, and the like, and aqueous solvents, alcohol solvents, ester solvents, and sulfoxide solvents. Or an amide solvent is preferable, Aqueous solvent, a sulfoxide solvent, or an amide solvent is more preferable, A sulfoxide solvent or an amide solvent is especially preferable.

As the amide solvent, for example, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrroli Dinon, ε-caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, and the like. .

Moreover, as a density | concentration of the organic material solution which melt | dissolved the organic material in the good solvent, the range of the saturation density | concentration with respect to the good solvent of the organic material in the conditions at the time of melt | dissolution to about 1/100 of this is preferable, and also in the organic material used Although it depends, for example, 0.5-12 mass% is preferable and when higher yield is calculated | required from an industrial production scale, it is preferable to set it as 2-12 mass%.

The preparation conditions of the organic material solution are not particularly limited to the preparation conditions of the organic material solution, and a range of subcritical and supercritical conditions can be selected from normal pressure. -10-150 degreeC is preferable, as for the temperature in normal pressure, -5-130 degreeC is more preferable, and 0-100 degreeC is especially preferable.

In this invention, although an organic material melt | dissolves uniformly in a good solvent, it is also preferable to melt | dissolve acidically or alkaline. In general, in the case of a pigment having an alkali dissociable group in a molecule, acidity is used when the alkalinity does not exist in the alkali dissociated group and has a large number of nitrogen atoms in the molecule to which protons are easily added. For example, quinacridone, diketopyrrolopyrrole, and disazo condensed pigments are alkaline, and phthalocyanine pigments are dissolved in acid.

The base used in the case of alkali dissolution is an inorganic base such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide, or trialkylamine, diazabicycloundecene (DBU), metal alkoxide or the like. Although it is an organic base, Preferably it is an inorganic base.

The amount of the base to be used is not particularly limited as long as it is an amount capable of dissolving the pigment uniformly, but in the case of the inorganic base, it is preferably 1.0 to 30 molar equivalents, more preferably 1.0 to 25 molar equivalents, more preferably relative to the organic material. Preferably it is 1.0-20 molar equivalent. In the case of an organic base, Preferably it is 1.0-100 molar equivalent with respect to an organic material, More preferably, it is 5.0-100 molar equivalent, More preferably, it is 20-100 molar equivalent.

The acid used in the case of acidic dissolution is an inorganic acid such as sulfuric acid, hydrochloric acid or phosphoric acid, or an organic acid such as acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, or trifluoromethanesulfonic acid, but is preferably an inorganic acid. Especially preferably, it is sulfuric acid.

The amount of the acid to be used is not particularly limited as long as it is an amount capable of dissolving the organic material uniformly, but it is often used in an excessive amount compared to the base. Regardless of the case of inorganic acid and organic acid, Preferably it is 3-500 molar equivalent with respect to an organic material, More preferably, it is 10-500 molar equivalent, More preferably, it is 30-200 molar equivalent.

When an alkali or an acid is mixed with an organic solvent and used as a good solvent for an organic material, in order to completely dissolve the alkali or the acid, a solvent having a high solubility in an alkali or an acid such as some water or a lower alcohol is organic. May be added to the solvent. 50 mass% or less is preferable with respect to the organic material solution whole quantity, and, as for the quantity of water and a lower alcohol, 30 mass% or less is more preferable. Specifically, water, methanol, ethanol, n-propanol, isopropanol, butyl alcohol, etc. can be used.

(Poor solvent)

Next, the poor solvent of an organic material is demonstrated.

The poor solvent of the organic material is not particularly limited as long as it is a poor solvent with respect to the organic material and is compatible with or uniformly mixed with a good solvent for dissolving the organic material. In the production method of the present invention, the poor solvent is compatible with the good solvent of the organic material solution in this way, thereby acting on the solubility of the organic material molecules in the liquid, and the organic material precipitates and forms. As a poor solvent of an organic material, it is preferable that the solubility of an organic material is 0.02 mass% or less, and it is more preferable that it is 0.01 mass% or less. This solubility may be solubility when melt | dissolved in presence of an acid or an alkali. In addition, the compatibility or uniform mixing property of a good solvent and a poor solvent is as having described in the term of a good solvent.

As the poor solvent, for example, an aqueous solvent (for example, water or hydrochloric acid, an aqueous sodium hydroxide solution), an alcohol solvent, a ketone solvent, an ether solvent, an aromatic solvent, carbon bisulfide, an aliphatic solvent, Nitrile solvents, halogen solvents, ester solvents, ionic liquids, mixed solvents thereof, and the like, with preference given to aqueous solvents, alcohol solvents or ester solvents. Especially in inkjet use, an aqueous solvent is very preferable.

Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol and the like. As a ketone solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone is mentioned, for example. As an ether solvent, dimethyl ether, diethyl ether, tetrahydrofuran, etc. are mentioned, for example. As an aromatic solvent, benzene, toluene, etc. are mentioned, for example. As an aliphatic solvent, hexane etc. are mentioned, for example. As a nitrile solvent, acetonitrile etc. are mentioned, for example. As a halogen type solvent, dichloromethane, trichloroethylene, etc. are mentioned, for example. As ester solvent, ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate, etc. are mentioned, for example. As the ionic liquid, for example, a 1-butyl-3-methyl imidazolium and PF ₆ ^-, and the like salts.

[Dispersant]

In the manufacturing method of the organic particle of this invention, a polymeric dispersing agent is mixed as a 3rd solution separately from the organic material solution and the poor solvent of an organic material. The molecular weight of the high molecular dispersant can be used without limitation as long as it can be dissolved homogeneously as a solution. Preferably, the molecular weight is 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, and 10,000 to 10,000 100,000 is particularly preferable (In the present invention, unless otherwise specified, the molecular weight means a mass average molecular weight. The high molecular compound is a polydispersion system and does not necessarily have the same molecular weight or particle weight. The value becomes the average molecular weight averaged in some form, The main three types are: (1) number average molecular weight Mn, (2) mass average molecular weight Mw, (3) Z average molecular weight Mz, and Mn < The relationship of Mw <Mz holds.).

In the method for producing organic particles of the present invention, the solvent for dissolving the polymer dispersant is not particularly limited as long as it can dissolve the polymer dispersant at a desired concentration. For example, an aqueous solvent (for example, water or hydrochloric acid, Sodium hydroxide aqueous solution), alcohol solvent, ketone solvent, ether solvent, aromatic solvent, carbon sulfide, aliphatic solvent, nitrile solvent, halogen solvent, ester solvent, ionic liquid, mixed solvent thereof, etc. Aqueous solvent, an alcoholic solvent, or an ester solvent is preferable.

Moreover, although the density | concentration in the solution of a polymeric dispersing agent is suitably determined by the solubility of a polymeric dispersing agent, etc., it is preferable that the quantity (the total amount when using together with other dispersing agents) is 1-90 mass% with respect to the total amount of a solution, It is more preferable that it is 10-80 mass%, and it is especially preferable that it is 30-80 mass%.

Specifically as the polymer dispersant, for example, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, polyethyleneimine, vinyl alcohol-vinyl acetate copolymer , Polyvinylalcohol-particulate, polyvinylalcohol-partial butyralide, vinylpyrrolidone-vinyl acetate copolymer, polyethylene oxide / propyleneoxide block copolymer, polyacrylate, polyvinyl sulfate, poly (4-vinyl Pyridine) salts, polyamides, polyallylamine salts, condensed naphthalenesulfonates, styrene-acrylate copolymers, styrene-methacrylate copolymers, acrylic ester-acrylate copolymers, acrylic ester-methacrylate copolymers, meta Methacrylic Acid Ester-Acrylate Copolymer, Methacrylic Acid Ester-Methacrylate Copolymer Compound, styrene-itaconate copolymer, itaconic acid ester itaconate copolymer, vinylnaphthalene-acrylate copolymer, vinylnaphthalene-methacrylate copolymer, vinylnaphthalene-itaconate copolymer, cellulose derivative, starch derivative Etc. can be mentioned. In addition, natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tragant rubber and lignin sulfonate can also be used. Especially, polyvinylpyrrolidone, polyacrylamide, and polyethyleneimine are preferable. These polymeric dispersants can be used individually or in combination of 2 or more types.

In the manufacturing method of this invention, the polymeric compound represented by following General formula (1) can be used as said polymer dispersing agent or in combination with it.

[Formula 1]

In General Formula (1), A ¹ represents an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, and an isocyanate. Monovalent organic group containing the monovalent organic group which has group selected from group and hydroxyl group, or the organic pigment | dye structure or heterocycle which may have a substituent is shown. n piece A <^1> may be the same and may differ.

Specifically, A ¹ is not particularly limited, and the as the "monovalent organic group having an acidic group", for example, a carboxylic acid group, a sulfonic acid group, a mono sulfuric acid ester group, a phosphate group, monophosphate ester group, boric acid group Monovalent organic group which has etc. are mentioned. Further, the above as the "monovalent organic group having a group having a basic nitrogen atom", for example, an amino group (-NH ₂₎ a monovalent organic group, an imino group ^{(-NHR 8, -NR 9 R 10} ) substituted with Monovalent organic group which has (R <^8> , R <^9> , and R <^10> respectively independently represents a C1-C20 alkyl group, a C6-C20 aryl group, and a C7-C30 aralkyl group. .), Monovalent organic group which has a guanidyl group represented by the following general formula (a1) [In general formula (a1), R <^a1> and R <^a2> are respectively independently C1-C20 alkyl groups, C6 or more An aryl group having 20 or less and an aralkyl group having 7 to 30 carbon atoms.], A monovalent organic group having an amidinyl group represented by the following General Formula (a2) [In Formula (a2), R ^a3 and R ^a4. Are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 30 carbon atoms. The following aralkyl groups are shown.] Etc. are mentioned.

[Formula 2]

As the "monovalent organic group having a urea", for example, -NHCONHR ¹⁵ (here, R ¹⁵ is a hydrogen atom or, an aryl group, the following group, having 6 to 20 or more carbon atoms of 1 to 20 carbon atoms 7 To 30 or more aralkyl groups.) And the like.

As said "monovalent organic group which has a urethane group", For example, -NHCOOR ¹⁶ , -OCONHR ¹⁷ (Here, R <^16> and R <^17> is respectively independently a C1-C20 alkyl group, C6-C20 or less An aryl group, an aralkyl group having 7 to 30 carbon atoms.), And the like.

As said "group which has a group which has a coordinating oxygen atom", the group which has an acetylacetonato group, the group which has a crown ether, etc. are mentioned, for example.

As said "group which has a C4 or more hydrocarbon group", a C4 or more alkyl group (for example, an octyl group, a dodecyl group, etc.), a C6 or more aryl group (for example, a phenyl group, a naphthyl group, etc.), C7 or more Aralkyl group (for example, benzyl group) etc. are mentioned. Although there is no upper limit in carbon number at this time, it is preferable that it is 30 or less. As said "group which has an alkoxy silyl group", group which has a trimethoxysilyl group, a triethoxysilyl group, etc. is mentioned, for example.

As said "group which has an epoxy group", group which has a glycidyl group etc. is mentioned, for example.

As said "group which has an isocyanate group", 3-isocyanatopropyl group etc. are mentioned, for example.

As said "group which has a hydroxyl group", 3-hydroxypropyl group etc. are mentioned, for example.

Wherein in is, as the A ¹ is preferably an acidic group, a group having a basic nitrogen atom, a urea group, and a monovalent organic group having 4 or more carbon atoms selected from hydrocarbon groups.

Moreover, it does not specifically limit as said organic pigment | dye structure or heterocycle, More specifically, as an organic pigment | dye structure, For example, a phthalocyanine compound, an insoluble azo compound, an azolake compound, an anthraquinone compound, a quinacridone compound, A dioxazine compound, a diketopyrrolopyrrole compound, an anthrapyridine compound, an anthrone compound, an indanthrone compound, a hula advanth compound, a perinone compound, a perylene compound, a thioindigo compound, etc. are mentioned. Moreover, as a heterocyclic ring, for example, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxa Diazoles, triazoles, thiadiazoles, pyrans, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindolin, isoindolinone, benzimi Dazolone, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridon, anthraquinone and the like.

Moreover, the said organic pigment | dye structure or heterocycle may have a substituent, As a substituent, For example, C6-C16 alkyl groups, such as a C1-C20 alkyl group, a phenyl group, a naphthyl group, such as a methyl group and an ethyl group, etc. An alkoxy group having 1 to 6 carbon atoms, such as an acyloxy group having 1 to 6 carbon atoms, such as an aryl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group, a methoxy group, or an ethoxy group And carbonic ester groups such as alkoxycarbonyl groups having 2 to 7 carbon atoms, cyano groups and t-butyl carbonates such as halogen atoms such as chlorine and bromine, methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group.

In addition, as the A ^1, preferably to a monovalent organic group represented by the general formula (4).

[Formula 3]

In the general formula (4), B ¹ is an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, The organic pigment | dye structure or heterocycle which may have a group selected from an isocyanate group, a hydroxyl group, or a substituent is shown, and R <^18> represents a single bond or a1-valent organic or inorganic coupling group. a1 represents 1-5, and a1 B <^1> may be the same and may differ.

B ¹ is the same meaning as said A ¹ in General formula (4), and although a preferable aspect is also the same, As said organic pigment | dye structure or heterocycle, it is a phthalocyanine compound, an insoluble azo compound, an azo lake compound, an anthra, for example. Organic pigments such as quinone compounds, quinacridone compounds, dioxazine compounds, diketopyrrolopyrrole compounds, anthrapyridine compounds, ananthrone compounds, indanthrone compounds, flavantron compounds, perinone compounds, perylene compounds, thioindigo compounds Structures such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole , Thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindolin, isoindolinone, benzimidazolone, succinate And heterocycles such as mead, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridon and anthraquinone.

Moreover, the said organic pigment | dye structure or heterocycle may have a substituent, As a substituent, For example, C6-C16 alkyl groups, such as a C1-C20 alkyl group, a phenyl group, a naphthyl group, such as a methyl group and an ethyl group, etc. An alkoxy group having 1 to 6 carbon atoms, such as an acyloxy group having 1 to 6 carbon atoms, such as an aryl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group, a methoxy group, or an ethoxy group And carbonic ester groups such as alkoxycarbonyl groups having 2 to 7 carbon atoms, cyano groups and t-butyl carbonates such as halogen atoms such as chlorine and bromine, methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group.

R <^18> represents a single bond or a1 + monovalent coupling group, and a1 represents 1-5. As the linking group R ¹⁸ , up to 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 atoms The group which consists of a sulfur atom up to is contained, and even if it is unsubstituted, it may have a substituent further. R ¹⁸ is preferably an organic linking group.

As a specific example of R <^18> , group comprised by combining the following structural unit or its structural unit is mentioned.

[Formula 4]

When R ¹⁸ has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms, such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms, such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, Halogen atoms such as alkoxy groups having 1 to 6 carbon atoms such as acyloxy groups such as sulfonamide groups, N-sulfonylamide groups, and acetoxy groups, methoxy groups and ethoxy groups, chlorine, and bromine, Carbonic acid ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, etc., such as a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group, are mentioned.

In said general formula (1), R <^1> represents a (m + n) valent coupling group. m + n satisfies 3-10.

Examples of the (m + n) valence group represented by R ¹ include up to 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200 carbon atoms. The group consisting of a hydrogen atom and 0 to 20 sulfur atoms is contained, and may be unsubstituted or may further have a substituent. R ¹ is preferably an organic linking group.

As a specific example of R <^1> , the group (you may form ring structure) comprised by combining the structural unit of said (t-1)-(t-34) or its structural unit is mentioned.

When R ¹ has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, Halogen atoms such as alkoxy groups having 1 to 6 carbon atoms such as acyloxy groups such as sulfonamide groups, N-sulfonylamide groups, and acetoxy groups, methoxy groups and ethoxy groups, chlorine, and bromine, Carbonic acid ester groups, such as a C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, etc., such as a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group, are mentioned.

R ² represents a single bond or a divalent linking group. As R ² , up to 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 The group which consists of a sulfur atom of is contained, and may be unsubstituted or may have a substituent further. R ² is preferably an organic linking group.

As a specific example of R <^2>, the group comprised by the said t-3, 4, 7-18, 22-26, 32, 34 structural unit or its structural unit is mentioned.

R ² When the substituent has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms, such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms, such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, and a sulfonamide. C1-C6 alkoxy groups, such as acyloxy groups, such as group, N-sulfonylamide group, and acetoxy group, a methoxy group, an ethoxy group, halogen atoms, such as chlorine and a bromine, and methoxy Carbonic acid ester groups, such as the C2-C7 alkoxycarbonyl group, a cyano group, t-butyl carbonate, such as a carbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group, etc. are mentioned.

M shows 1-8 in the said General formula (1). As m, 1-5 are preferable, 1-3 are more preferable, and 1-2 are especially preferable.

In addition, n represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In said general formula (1), P <^1> represents a polymer skeleton and can be selected from a conventional polymer etc. according to the objective.

Among the polymers, polymers or copolymers of vinyl monomers, ester-based polymers, ether-based polymers, urethane-based polymers, amide-based polymers, epoxy-based polymers, silicone-based polymers, modified substances thereof, or copolymers may be used to form a polymer skeleton. For example, a copolymer of a polyether / polyurethane copolymer, a polymer of a polyether / vinyl monomer, or the like (random copolymer, block copolymer, graft copolymer may be used), or the like. At least one species selected is preferred, and at least one species selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified or copolymers thereof is more preferred, and vinyl monomers. Polymers or copolymers of are particularly preferred.

Furthermore, it is preferable that the said polymer is soluble in an organic solvent. When affinity with an organic solvent is low, when used as a pigment dispersant, for example, affinity with a dispersion medium will become weak and it will become impossible to ensure the adsorption layer sufficient for dispersion stabilization.

Among the polymer compounds represented by the general formula (1), the polymer compounds represented by the following general formula (2) are more preferable.

[Formula 5]

In the said General formula (2), A <^2> is synonymous with A <^1> in the said General formula (1), Although the specific preferable aspect is also the same, As a specific example of an organic pigment | dye structure, a phthalocyanine compound, an azo lake compound, Anthraquinone compound, a dioxazine compound, a diketopyrrolopyrrole compound, etc. are more preferable, and as a heterocyclic ring, imidazole, a triazole, a pyridine, a piperidine, a morpholine, a triazine, isoindolin, isoindolinone, Benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridon, anthraquinone and the like are more preferable.

In addition, and may have the same substituents as A ^1, for the substituent, the same as in the case of the A ^1, it is also the same preferred embodiment.

Moreover, as A <^2> , the monovalent organic group represented by the said General formula (4) is preferable, and it is the same about the detail, a specific example, and a preferable aspect of this organic group.

In the said General formula (2), R <^3> represents a (x + y) valent coupling group. Examples of the (x + y) valence group represented by R ³ include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 100 carbon atoms. The group consisting of a hydrogen atom and 0 to 20 sulfur atoms is contained, and may be unsubstituted or may further have a substituent.

As (x + y) valence group represented by said R <^3> , it is synonymous with the (m + n) valence coupler in said R <^1> , and its preferable aspect is also the same. Moreover, the group comprised by combining the same structural unit or its structural unit as a specific example is mentioned.

Among these, it is preferable that the coupling group represented by R <^3> is an organic coupling group, and the preferable specific example of this organic coupling group is shown below. However, in this invention, it is not limited to these.

[Formula 6]

[Formula 7]

Among the above, from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents, (r-1), (r-2), (r-10), (r-11), and (r-16) ) and (r-17) are preferred.

Moreover, when said R <^3> has a substituent, As this substituent, C1-C20 alkyl groups, such as a methyl group and an ethyl group, C6-C16 aryl groups, such as a phenyl group and a naphthyl group, and a hydroxyl group are mentioned, for example. C1-C6 alkoxy groups, such as an acyloxy group, a methoxy group, an ethoxy group, such as an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, and an acetoxy group, a chlorine, bromine Carbonic ester groups, such as alkoxycarbonyl groups, a cyano group, t-butyl carbonate, etc. which are C2-C7, such as a halogen atom, such as a halogen atom, a methoxycarbonyl group, an ethoxycarbonyl group, and a cyclohexyloxycarbonyl group, are mentioned.

In the said General formula (2), R <^4> and R <^5> represents a single bond or a bivalent coupling group each independently.

As a "bivalent coupling group" represented by said R <^4> , R <^5> , it may be unsubstituted or may have a substituent, and is a linear, branched, or cyclic alkylene group, arylene group, aralkylene group, -O-, -S -, -C (= O)-, -N (R ¹⁹ )-, -SO-, -SO _2- , -CO _2- , -N (R ²⁰ ) SO _2- , or a combination of two or more groups thereof Preferred divalent groups are exemplified (the above R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Especially, it is preferable that it is an organic coupling group.

Examples of the R ^4, an aralkyl group, -O-, an alkylene group, a straight chain or branched -C (= O) -, -N (R 19) -, -SO 2 -, -CO 2 -, -N ( R ²⁰ ) SO ₂ -or a divalent group obtained by combining two or more of these groups is more preferable, and a linear or branched alkylene group, an aralkylene group, -O-, -C (= O)-, -N Especially preferred are (R ¹⁹ )-, -CO _2- , or a divalent group in which two or more groups thereof are combined.

As the R ^5, a single bond, a straight-chain or branched alkylene group, an aralkyl group, -O-, -C (= O) -, -N (R 19) -, -SO 2 -, -CO 2 -, -N (R ²⁰ ) SO ₂ -or a divalent group obtained by combining two or more of these groups is more preferable, and a linear or branched alkylene group, an aralkylene group, -O-, -C (= O)-, Particular preference is given to -N (R ¹⁹ )-, -CO _2- , or divalent groups in which two or more groups thereof are combined.

Moreover, when said R <^4> , R <^5> has a substituent, As this substituent, For example, C6-C16 aryl groups, such as a C1-C20 alkyl group, such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, C1-C6 alkoxy groups, such as an acyloxy group, a methoxy group, an ethoxy group, such as a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, and an acetoxy group, a chlorine, Carbonate ester groups such as alkoxycarbonyl groups having 2 to 7 carbon atoms, cyano groups, t-butyl carbonates, such as halogen atoms such as bromine, methoxycarbonyl groups, ethoxycarbonyl groups, and cyclohexyloxycarbonyl groups.

In said general formula (2), y represents 1-8, 1-5 are preferable, 1-3 are more preferable, and 1-2 are especially preferable. Moreover, x represents 2-9, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In addition, P <^2> in General formula (2) represents a polymer skeleton and can be selected with a normal polymer etc. according to the objective. About a preferable aspect of a polymer, it is the same meaning as P <^1> in the said General formula (1), and its preferable aspect is also the same.

Among the polymer compounds represented by the general formula (2), in particular, R ³ is the specific examples (r-1), (r-2), (r-10), (r-11), and (r-16). , Or (r-17), R ⁴ is a single bond, a linear or branched alkylene group, an aralkylene group, -O-, -C (= O)-, -N (R ¹⁹ )-, -CO _A divalent or organic divalent organic group in which two or more of these groups are combined, R ⁵ is a single bond, an ethylene group, a propylene group, or a linking group represented by the following general formula (sa) or (sb), wherein P ² is As the polymer or copolymer of the vinyl monomer, the ester polymer, the ether polymer, the urethane polymer, or a modified product thereof, y is 1 to 2, and a polymer compound having 3 to 6 is particularly preferable. In addition, in the following group, R <^21> represents a hydrogen atom or a methyl group, and l represents 1 or 2.

[Formula 8]

1000-500,000 are preferable, as for the mass mean molecular weight of the high molecular compound represented by General formula (1), 3000-100000 are more preferable, 5000-80000 are more preferable, 7000-60000 are especially preferable. When the weight average molecular weight is in the above range, the effect of the plurality of functional groups introduced to the terminal of the polymer is sufficiently exhibited, and the performance excellent in adsorption to the solid surface, micelle formation ability, and surface activity is exhibited. In particular, when such a polymer compound is used as the pigment dispersant, good dispersibility and dispersion stability can be achieved.

Although the polymer compound (including the thing represented by General formula (2)) represented by the said General formula (1) is not specifically limited, It can synthesize | combine by the following method etc .. Among the following synthesis methods, from the ease of synthesis, synthesis methods such as 2, 3, 4, and 5 are more preferable, and synthesis methods such as 3, 4 and 5 are particularly preferable.

1. carboxyl group, a hydroxyl group, and the introduction of a functional group at the terminal polymer selected from an amino group, a plurality of acid halide functional group, or a plurality of functional groups (the formula of A having a (A ¹ or A ² in the formula) alkyl halide, or a plurality of functional groups having ¹ or a ²⁾ (a method of reacting a polymer such as an isocyanate having a ¹ or a ²⁾ in the formula.

2. at the terminal carbon-carbon double bond functional group and the introduction of polymer, a plurality of methods of a mercaptan having a (A ¹ or A ² in the formula), the Michael addition reaction.

3. A method in which a polymer having a carbon-carbon double bond introduced at its terminal and a mercaptan having a plurality of functional groups (A ¹ or A ² in the general formula) are reacted in the presence of a radical generator.

4. A method in which a polymer having a plurality of mercaptans introduced at its terminal and a functional group (A ¹ or A ² in the above general formula) having introduced a carbon-carbon double bond are reacted in the presence of a radical generator.

5. A method for radical polymerization of a vinyl monomer with a mercaptan compound having a plurality of functional groups (A ¹ or A ² in the general formula) as a chain transfer agent.

Among the above, the high molecular compound (preferably the high molecular compound represented by General formula (2)) used by the manufacturing method of this invention can be synthesize | combined by the method of any of said 2, 3, 4, 5, for example. However, for ease of synthesis, it is more preferable to synthesize by the method of 5.

More specifically, it is preferable to radical-polymerize using the compound represented by following General formula (3) as a chain transfer agent.

[Formula 9]

In the general formula (3), R ⁶ , R ⁷ , A ³ , g, and h are the same meanings as R ³ , R ⁴ , A ² , x and y in the general formula (2), respectively. The preferable aspect is also the same.

Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid diester, (meth ) Acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable. As such an example, the following compounds are mentioned.

Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate and isomethacrylate (meth) acrylate. Butyl, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t- (meth) acrylate Octyl, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, (meth) Diethylene glycol monomethyl ether acrylic acid, diethylene glycol monoethyl ether (meth) acrylate , (Meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, (meth) acrylic acid β-phenoxy Ethoxyethyl, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoro (meth) acrylate Lopentyl, perfluorooctyl ethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, and the like.

Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.

Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, vinyl benzoate and the like.

Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, dibutyl maleate and the like.

Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

Examples of the itaconic acid diesters include dimethyl itaconic acid, ethyl itaconic acid, dibutyl itaconic acid, and the like.

As an example of the said (meth) acrylamide, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) Acrylamide, Nn-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N- Dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloyl morpholine, diacetone acrylamide Etc. can be mentioned.

Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene and bromine Styrene styrene, vinyl benzoate methyl, alpha -methyl styrene, etc. which were protected by the group which is deprotected by an acidic substance (for example, t-Boc etc.), etc. are mentioned.

As an example of the said vinyl ether, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxy ethyl vinyl ether, etc. are mentioned.

In addition to the above compounds, (meth) acrylonitrile, a heterocyclic group substituted with a vinyl group (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinyl caprolactone, etc. can also be used.

In addition to the above compounds, vinyl monomers having functional groups such as urethane groups, urea groups, sulfonamide groups, phenol groups and imide groups can also be used. As a monomer which has such a urethane group or a urea group, it can synthesize | combine suitably using the addition reaction of an isocyanate group, a hydroxyl group, or an amino group, for example. Specifically, addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or a primary or secondary amino group-containing monomer and a monoisocyanate It can synthesize | combine suitably by addition reaction or the like.

Said vinyl monomer may be superposed | polymerized only by 1 type, and may be copolymerized using 2 or more types together, Such a radical polymer is obtained by superposing | polymerizing a corresponding vinyl monomer according to a conventional method, respectively.

For example, these vinyl monomers and a chain transfer agent are dissolved in a suitable solvent, and a radical polymerization initiator is added to it, and it is obtained using the method (solution polymerization method) which superposes | polymerizes in solution at about 50 degreeC-220 degreeC. .

As an example of the suitable solvent used by the solution polymerization method, it can select arbitrarily according to the solubility of the monomer to be used and the copolymer to produce | generate. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, Ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform and toluene. You may use these solvent in mixture of 2 or more type.

Moreover, as a radical polymerization initiator, azo compounds, such as 2,2'- azobis (isobutylonitrile) (AIBN) and 2,2'- azobis- (2,4'- dimethylvaleronitrile), benzoyl perox Peroxides such as seeds, persulfates such as ammonium potassium persulfate, and the like.

Although the compound represented by the said General formula (3) can be synthesize | combined by the following method etc., from the ease of synthesis, the method of following 7 is more preferable.

6. A method of converting a halide compound having a plurality of functional groups (A ¹ or A ² in the general formula) to a mercaptan compound (reaction with thiourea, hydrolysis, direct reaction with NaSH, CH ₃ COSNa And a hydrolysis method).

7. Method for addition-reacting a compound having 3 to 10 mercapto groups in one molecule and a compound having a functional group (A ¹ or A ² in the general formula) and having a functional group capable of reacting with a mercapto group

As a "functional group which can react with a mercapto group" in the said method 7, an acid halide, an alkyl halide, an isocyanate, a carbon-carbon double bond, etc. are mentioned preferably.

It is especially preferable that "the functional group which can react with a mercapto group" is a carbon-carbon double bond, and an addition reaction synthesize | combines by a radical addition reaction. As a carbon-carbon double bond, a 1- or 2-substituted vinyl group is more preferable at the point of the reactivity with a mercapto group.

The following compounds are mentioned as a specific example of said "compound which has 3-10 mercapto groups in 1 molecule."

[Formula 10]

[Formula 11]

Among them, from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents, (u-1), (u-2), (u-10), (u-11), and (u-16) and (u-17) are preferable.

It has a functional group (A ¹ or A ² in the formula), and carbon-As the compound having a carbon double bond, may be mentioned, but not limited to, the following.

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

For example, the said "compound which has a 3-10 mercapto group in 1 molecule", the said "acidic group, the group which has a basic nitrogen atom, the urea group, a urethane group, the group which has coordinating oxygen atom, C4 The radical addition reaction product with the "compound which has at least 1 sort (s) of functional group chosen from a hydrocarbon group, an alkoxy silyl group, an epoxy group, an isocyanate group, and a hydroxyl group mentioned above, and has a carbon-carbon double bond, for example, Said "compound having 3-10 mercapto groups in one molecule" and "acid group, group having basic nitrogen atom, urea group, urethane group, group having coordinating oxygen atom, hydrocarbon group having 4 or more carbon atoms, A compound having at least one functional group selected from an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group, and further having a carbon-carbon double bond ”is dissolved in a suitable solvent, A radical generator is added here and it is obtained using the method (thiol-ene reaction method) to add at about 50 degreeC-100 degreeC.

As an example of the preferable solvent used by the said method, the "compound which has 3-10 mercapto groups in 1 molecule" used, an "acid group, the group which has a basic nitrogen atom, a urea group, a urethane group, and a coordinating oxygen atom Functional group which has at least 1 sort (s) of functional group chosen from the group which has, a C4 or more hydrocarbon group, an alkoxy silyl group, an epoxy group, an isocyanate group, and a hydroxyl group, and can react with a mercapto group (for example, carbon-carbon double bond) And a solubility of the radical addition reaction product to be produced. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, Ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform and toluene. You may use these solvent in mixture of 2 or more type.

Moreover, as a radical generator, azo compounds, such as 2,2'- azobis (isobutylonitrile) (AIBN) and 2,2'- azobis- (2,4'- dimethylvaleronitrile), benzoyl perox Peroxides such as seeds, persulfates such as potassium persulfate, ammonium persulfate, and the like.

The specific example of the compound represented by General formula (1) used preferably by the manufacturing method of this invention is shown below. However, the present invention is not limited to these specific examples at all.

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

Moreover, it is preferable that this high molecular compound is a high molecular compound which has an acidic group, It is more preferable that it is a high molecular compound which has a carboxyl group, At least 1 sort (s) of the repeating unit derived from the compound which has (A) carboxyl group, and (B) carboxylic acid Particularly preferred is a copolymer compound containing at least one type of repeating unit derived from a compound having an ester group.

As a repeating unit derived from the compound which has the said (A) carboxyl group, it is preferable that it is a repeating unit represented by the following general formula (I), It is more preferable that it is a repeating unit derived from acrylic acid or methacrylic acid, The said (B It is preferable that it is a repeating unit represented by the following general formula (II) as a repeating unit derived from the compound which has a carboxylic ester group, It is more preferable that it is a repeating unit represented by the following general formula (IV), Benzyl acrylate Particularly preferred is a repeating unit derived from benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate, 3-phenylpropyl acrylate, or 3-phenylpropyl methacrylate.

[Formula 35]

(R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

[Formula 36]

(R ₂ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ₃ represents a group represented by the following general formula (III).)

[Formula 37]

(R ₄ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxy group, a hydroxyalkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ₅ and R ₆ each represent a hydrogen atom. Or an alkyl group having 1 to 5 carbon atoms, i represents a number of 1 to 5.

[Formula 38]

(R ₇ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ₈ represents a group represented by the following General Formula (V).)

[Formula 39]

(R ₉ represents an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms. R ₁₀ and R ₁₁ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. J is 1 to 5 Indicates water.)

Moreover, when it is referred as polymerization ratio of the repeating unit derived from the compound which has the (A) carboxyl group, and the repeating unit derived from the compound which has the said (B) carboxylic acid ester group, to the total number of repeating units of the repeating unit (A) It is preferable that it is 3-40 with respect to the water content ratio with respect to, and it is more preferable that it is 5-35.

Although the molecular weight of a polymer in the manufacturing method of this invention says a mass mean molecular weight unless there is particular notice, as a measuring method of the molecular weight of a polymer, the chromatography method, a viscosity method, the light scattering method, the sedimentation rate method, etc. are mentioned. . In the present invention, unless otherwise specified, the mass average molecular weight measured by the chromatography method is used.

The polymer compound may be either water-soluble or oil-soluble, or may be water-soluble or oil-soluble.

The polymer dispersant may be added not only at the time of formation of the organic nanoparticles, but also at the time of extraction or concentration (or before or after), at the time of dispersion of the aggregated organic particles after concentration (or before or after), or after their processes are completed. Moreover, you may combine these. A polymeric dispersant may be contained in a composition as a binder mentioned later, for example, after concentrating an organic particle precipitation liquid, it is also preferable to add at the time of fine dispersion of aggregated organic particle | grains.

The amount (total amount when used in combination with other dispersants) of the polymer dispersant is in the range of 0.1 to 1000 parts by mass with respect to 100 parts by mass of the organic material in order to further improve the uniform dispersibility and storage stability of the organic particles. It is preferable, More preferably, it is the range of 1-500 mass parts, Especially preferably, it is the range of 10-250 mass parts. If it is less than 0.1 mass part, the improvement of the dispersion stability of organic material particle may not be seen.

In the manufacturing method of this invention, it is also preferable to use the following dispersing agents of <1>-<9>.

Pigment dispersant containing a <1> amino group:

Here, an amino group contains a primary amino group, a secondary amino group, and a tertiary amino group, and the number of amino groups may be one, or multiple may be sufficient as it. The pigment derivative compound which introduce | transduced the substituent which has an amino group in a pigment skeleton may be sufficient, and the polymer compound which made the monomer which has an amino group the polymerization component may be sufficient. Examples thereof include, for example, the compounds described in JP-A-2000-239554, 2003-96329, 2001-31885, and JP-A-10-339949 and JP-A 5-72943. Although these etc. are mentioned, It is not limited to these.

<2> anionic dispersing agent (anionic surfactant):

N-acyl-N-alkyltaurine salts, fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylnaphthalenesulfonates, dialkylsulfo succinate salts, alkylphosphate ester salts, naphthalenesulfonate formalin condensates, polyoxyethylene alkyl sulfates Ester salts; and the like. Especially, N-acyl-N-alkyl taurine salt is preferable. As N-acyl-N-alkyltaurine salt, it is preferable to describe in Unexamined-Japanese-Patent No. 3-273067 specification. These anionic dispersants can be used individually or in combination of 2 or more types.

<3> cationic dispersing agent (cationic surfactant):

Quaternary ammonium salts, alkoxylated polyamines, aliphatic aminepolyglycol ethers, aliphatic amines, diamines and polyamines derived from aliphatic amines and fatty alcohols, imidazolines derived from fatty acids and salts of their cationic substances. These cationic dispersants can be used individually or in combination of 2 or more types.

<4> cationic dispersant:

It is a dispersing agent which has the anion base part which the said anionic dispersing agent has in a molecule | numerator, and the cationic group part which a cationic dispersing agent has in a molecule | numerator together.

 <5> nonionic dispersing agent (nonionic surfactant):

Polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester and the like. Especially, polyoxyethylene alkyl aryl ether is preferable. These nonionic dispersants can be used individually or in combination of 2 or more types.

<6> pigment dispersant:

It is a dispersant derived from an organic pigment as a parent material and produced by chemically modifying a friend. For example, a sugar-containing pigment dispersant, a piperidyl-containing pigment dispersant, a naphthalene or perylene-derived pigment dispersant, a pigment dispersant having a functional group linked to a pigment friend group via a methylene group, a pigment friend group chemically modified with a polymer, and a sulfonic acid group Pigment dispersants, pigment dispersants having sulfonamide groups, pigment dispersants having ether groups, or pigment dispersants having carboxylic acid groups, carboxylic ester groups or carboxamide groups. When considering a color filter use, it is preferable to use alkali-soluble polymer dispersing agent. Moreover, the compound represented by general formula (I) of Unexamined-Japanese-Patent No. 2000-239554 is also used preferably.

<7> Dispersant represented by general formula (D1)

[Formula 40]

In general formula (D1), A represents the component which can form an azo pigment | dye with X-Y. The said A can be arbitrarily selected as long as it is a compound which can couple with a diazonium compound and form an azo pigment | dye. Although the specific example of said A is shown below, this invention is not limited at all by these.

[Formula 41]

[Formula 42]

In general formula (D1), X represents group selected from the bivalent coupling group represented by a single bond or the structural formula of following formula (i)-(v).

[Formula 43]

In general formula (D1), Y represents group represented by the following general formula (D2).

[Formula 44]

In General Formula (D2), Z represents a lower alkylene group. Z is, - (CH _{2) b} -, but represented by the b represents an integer of 1-5, preferably represents 2 or 3. In general formula (D2), -NR ₂₁ represents a lower alkylamino group or a 5-6 membered saturated heterocyclic group containing a nitrogen atom. When the -NR ₂₁ represents a lower alkylamino group, -N (C _r H _{2r + 1} ) ₂ is represented, r represents an integer of 1 to 4, and preferably 1 or 2. When -NR ₂₁ represents a 5-6 membered saturated heterocyclic group containing a nitrogen atom, either heterocyclic group represented by the following structural formula is preferable.

[Formula 45]

In General Formula (D2), Z and —NR ₂₁ may each have a lower alkyl group or an alkoxy group as a substituent. In General Formula (D2), A represents 1 or 2, preferably 2.

Although the specific example of a compound represented by the said general formula (D1) is shown below, this invention is not limited to these specific examples at all.

[Formula 46]

[Formula 47]

[Formula 48]

[Formula 49]

The compound represented by general formula (D1) can be synthesize | combined by the method of Unexamined-Japanese-Patent No. 2000-239554, for example.

Dispersant represented by <8> general formula (D3)

[Formula 50]

In general formula (D3),

Q is an anthraquinone compound pigment, an azo compound pigment, a phthalocyanine compound pigment, a quinacridone compound pigment, a dioxazine compound pigment, an anthrapyrimidine compound pigment, an anthrone compound pigment, an indanthrone compound pigment, a flavantron compound pigment, pyran An organic pigment residue selected from a tron compound dye, a perinone compound dye, a perylene compound dye, and a thioindigo compound dye is shown, and it is preferable that it is an azo compound dye or a dioxazine compound dye especially, and it is an azo compound dye. More preferred.

X ₁ represents -CO-, -CONH-Y _2- , -SO ₂ NH-Y _2- , or -CH ₂ NHCOCH ₂ NH-Y ₂ -and that is -CO-, -CONH-Y _2- desirable.

Y <_2> represents the alkylene group or arylene group which may have a substituent, Especially, it is preferable that it is phenylene, toluylene, or hexylene, and it is more preferable that it is phenylene.

R ₁₁ and R ₁₂ may each independently form a substituted or unsubstituted alkyl group or a heterocyclic group containing at least a nitrogen atom with R ₁₁ and R ₁₂ . Especially, it is preferable that it is a pyrrolidinyl group containing a methyl group, an ethyl group, a propyl group, or a nitrogen atom, and it is more preferable that it is an ethyl group.

Y ₁ represents -NH- or -O-.

Z ₁ may represent a hydroxyl group or a group represented by general formula (D3a), or may be -NH-X ₁ -Q when n1 is 1; m1 represents the integer of 1-6, and 2-3 are preferable. n1 represents the integer of 1-4, and 1-2 is preferable.

[Formula 51]

In General Formula (D3a), Y ₃ represents -NH- or -O-, and m1, R ₁₁ , and R ₁₂ have the same meaning as those in General Formula (D3).

The compound represented by general formula (D3) is more specifically represented by the following general formula, for example.

[Formula 52]

Further, with respect to Formula (D3-1) ~ (D3-6), Q, m1, n1, R 11, R 12 is the same meaning as those in formula (D3). Although the specific example of a compound represented by general formula (D3) below is given, this invention is not limited by these. In addition, Cu-Pc represents copper phthalocyanine in a formula.

 [Formula 53]

 [Formula 54]

The compound represented by the general formula (D3), for example, is reacted with R ₁₁ and R ₁₂ of the amine compound and the R ₁₁ and R ₁₂ to the alcohol compound halogenated triazine compound having having, by reacting a dye compound of the obtained intermediate You can get it. In addition, description of Unexamined-Japanese-Patent No. 5-72943 can also be referred to.

Pigment dispersant containing <9> graft copolymer

In the manufacturing method of this invention, it is also preferable to use the dispersing agent containing the graft copolymer which has an amino group and an ether group, and contains the other component suitably selected as needed.

The graft copolymer may have at least an amino group and an ether group, and may contain other monomers or the like as a copolymer unit.

As mass average molecular weight (Mw) of the said graft copolymer, 3000-100000 are preferable and 5000-50000 are more preferable. When the said mass average molecular weight (Mw) is less than 3000, aggregation of a pigment nanoparticle cannot be prevented, a viscosity may rise, and when it exceeds 100000, the solubility with respect to the organic solvent will be insufficient and a viscosity will rise. There is a case. In addition, the mass mean molecular weight is the polystyrene conversion mass mean molecular weight measured by gel permeation chromatography (carrier: tetrahydrofuran).

The graft copolymer is a copolymer of (i) a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal, (ii) a monomer having an amino group and an ethylenically unsaturated double bond, and (iii) a polymerizable monomer having an ether group. It is preferable to include at least as a unit and to contain (iv) another monomer as a copolymerization unit as needed.

As content in the said graft copolymer of these copolymer units, it is preferable that (i) the said polymeric oligomer is 15-98 mass%, It is more preferable that it is 25-90 mass%, (ii) An amino group It is preferable that it is 1-40 mass%, and it is more preferable that it is 5-30 mass%, (iii) It is preferable that the polymerizable monomer which has the said ether group is 1-70 mass%, and 5-60 mass% It is more preferable that is.

When the content of the polymerizable oligomer is less than 15% by mass, the steric repulsion effect as a dispersant may not be obtained, and aggregation of the pigment nanoparticles may not be prevented. When the content of the polymerizable oligomer exceeds 98% by mass, the ratio of the nitrogen-containing monomer is This decreases, the adsorption ability to the pigment particles is lowered, the dispersibility may not be sufficient. If the content of the nitrogen-containing monomer is less than 1% by mass, the adsorption capacity to organic particles may be lowered and dispersibility may not be sufficient. If the content of the nitrogen-containing monomer exceeds 40% by mass, the proportion of the polymerizable oligomer is reduced. In this regard, the steric repulsion effect as a dispersant may not be obtained, and aggregation of the pigment particles may not be sufficiently prevented. When content of the polymerizable monomer which has the said ether group is less than 1 mass%, the development suitability at the time of manufacture of color filters etc. may not be enough, and when it exceeds 70 mass%, the capability as a dispersing agent may fall. .

(i) polymerizable oligomers

The said polymerizable oligomer (henceforth a "macro monomer" may be called.) Is an oligomer which has the terminal which has an ethylenically unsaturated double bond at the terminal. In this invention, it is preferable to have a group which has the said ethylenically unsaturated double bond only in one of the both terminals of the said oligomer among the said polymerizable oligomers.

As said oligomer, generally, the homopolymer formed from at least 1 sort (s) of monomer chosen from alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, styrene, acrylonitrile, vinyl acetate, and butadiene, for example. Or a copolymer etc. are mentioned, Among these, the homopolymer or copolymer of alkyl (meth) acrylate, a polystyrene, etc. are preferable. In this invention, these oligomers may be substituted by the substituent and there is no restriction | limiting in particular as the substituent, For example, a halogen atom etc. are mentioned.

As group which has the said ethylenically unsaturated double bond, a (meth) acryloyl group, a vinyl group, etc. are mentioned preferably, for example, Among these, a (meth) acryloyl group is especially preferable.

In this invention, among the said polymerizable oligomers, the oligomer represented by the following general formula (E6) is preferable.

[Formula 55]

In General Formula (E6), R ⁶¹ and R ⁶³ represent a hydrogen atom or a methyl group. R <^62> represents the alkylene group which may be substituted by the C1-C8 alcoholic hydroxyl group, and a C2-C4 alkylene group is preferable. Y ⁶ is a phenyl group, a phenyl group having an alkyl group having 1 to 4 carbon atoms, or -COOR ⁶⁴ (wherein R ⁶⁴ is an alkyl group having 1 to 6 carbon atoms, an alkyl group which may be substituted with halogen, a phenyl group, or 7 to 10 carbon atoms). Is an aryl alkyl group.), And a phenyl group or -COOR ⁶⁴ (wherein R ⁶⁴ represents an alkyl group which may be substituted with an alcoholic hydroxyl group having 1 to 4 carbon atoms) is preferable. q represents 20-200.

Specific examples of the polymerizable oligomer include poly-2hydroxyethyl (meth) acrylate, polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and poly-i-butyl (meth). As an acrylate and its copolymer, the polymer in which the (meth) acryloyl group couple | bonded with one of the terminal of a molecule | numerator is preferable.

A commercial item may be sufficient as the said polymeric oligomer, and what was synthesize | combined suitably may be sufficient as this commercial item, for example, single-end methacryloylated polystyrene oligomer (Mn = 6000, brand name: AS-6, Toa synthetic chemical industry (Note) Co., Ltd.), single terminal methacryloylated polymethylmethacrylate oligomer (Mn = 6000, trade name: AA-6, manufactured by Toa Synthetic Chemical Industry Co., Ltd.), single terminal methacryloylated poly-n-butyl Acrylate oligomer (Mn = 6000, brand name: AB-6, Toa Synthetic Chemical Industry Co., Ltd.), single-ended methacryloylated polymethyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000 AA-714, Toa Synthetic Chemical Industry Co., Ltd.), single terminal methacryloylated polybutyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, brand name: 707S, Toa synthesis) Chemical Industry Co., Ltd.), Hen However, methacryloylated poly 2-ethylhexyl methacrylate / 2-hydroxyethyl methacrylate oligomer (Mn = 7000, trade name: AY-707S, AY-714S, manufactured by Toa Synthetic Chemical Co., Ltd.) Can be mentioned.

As a preferable specific example of the said polymerizable oligomer in this invention, it is an at least 1 sort (s) of oligomer chosen from the polymer of alkyl (meth) acrylate, and the copolymer of alkyl (meth) acrylate and polystyrene, and a number average molecular weight is 1000-. 20000 and the thing which has a (meth) acryloyl group at the terminal is mentioned.

(ii) amino group-containing monomers

As said amino-group containing monomer, at least 1 sort (s) chosen from the compound represented by the following general formula (E2) is mentioned preferably, for example.

[Formula 56]

In said general formula (E2), R <^21> represents a hydrogen atom or a methyl group. R <^22> represents a C1-C8 alkylene group, Among these, a C1-C6 alkylene group is preferable and a C2-C3 alkylene group is especially preferable.

X ² represents -N (R ²³ ) (R ²⁴ ) and -R ²⁵ N (R ²⁶ ) (R ²⁷ ). Here, R <^23> and R <^24> represents a hydrogen atom, a C1-C6 alkyl group, or a phenyl group. R <^25> represents a C1-C6 alkylene group and R <^26> and R <^27> represents a hydrogen atom, a C1-C6 alkyl group, or a phenyl group.

In the above, R ²³ and R ²⁴ of —N (R ²³ ) (R ²⁴ ) are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or a phenyl group, and are preferably selected from -R ²⁵ -N (R ²⁶ ) (R ²⁷ ). R ²⁵ is preferably an alkylene group having 2 to 6 carbon atoms, and R ²⁶ and R ²⁷ are preferably an alkyl group having 1 to 4 carbon atoms. m2 and n2 represent 1 or 0, and m2 = 1, n2 = 1, or m2 = 1 and n2 = 0 are preferable (that is, correspond to the monomer represented by the following general formula (E3) and (E4)). do).

In this invention, at least 1 sort (s) chosen from the monomer represented by either of the following general formula (E3) and (E4) among the monomer represented by the said General formula (E2) is preferable.

[Formula 57]

In said general formula (E3), R <^31> is synonymous with R <^21> . R ³² has the same meaning as R ²² . X ³ has the same meaning as X ² .

[Formula 58]

In General Formula (E4), R ⁴¹ has the same meaning as R ²¹ . X ⁴ has the same meaning as X ^2, and —N (R ⁴³ ) (R ⁴⁴ ) (where R ⁴³ and R ⁴⁴ have the same meaning as R ²³ and R ²⁴ ), or —R ⁴⁵ —N (R ⁴⁶ ) (R ⁴⁷ ), wherein R ⁴⁵ , R ⁴⁶ and R ⁴⁷ have the same meaning as R ²⁵ , R ²⁶ and R ²⁷ , respectively.

As a specific example of the monomer represented by the said general formula (E2), dimethyl (meth) acrylamide, diethyl (meth) acrylamide, diisopropyl (meth) acrylamide, di-n-butyl (meth) acrylamide, di -i-butyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-phyllolidyl (meth) acrylamide and N, N-methylphenyl ( Meth) acrylamide (ideal (meth) acrylamides); 2- (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3 -(N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethyl Methyl (meth) acrylamide, 6- (N, N-diethylamino) hexyl (meth) acrylamide (above aminoalkyl (meth) acrylamides), etc. are mentioned as a preferable thing.

(iii) a polymerizable monomer having an ether group

As a polymerizable monomer which has the said ether group, at least 1 sort (s) chosen from the monomer represented by following General formula (E1) is mentioned preferably, for example.

[Formula 59]

In said general formula (E1), R <^11> represents a hydrogen atom or a methyl group. R <^12> represents a C1-C8 alkylene group, Especially, a C1-C6 alkylene group is preferable and a C2-C3 alkylene group is more preferable. X ¹ represents -OR ¹³ or -OCOR ¹⁴ . R ¹³ represents a phenyl group substituted with a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or an alkyl group having 1 to 18 carbon atoms. R <^14> represents a C1-C18 alkyl group. Moreover, m3 represents 2-200, 5-100 are preferable and 10-100 are especially preferable.

The polymerizable monomer having an ether group is not particularly limited as long as it has an ether group and is polymerizable, and can be appropriately selected from conventional ones. For example, polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth Acrylate, polyethyleneglycol polypropylene glycol mono (meth) acrylate, polytetramethylene glycol monomethacrylate, etc. are mentioned, These may be a commercial item, and what synthesize | combined suitably may be sufficient. As the commercial item, methoxy polyethylene glycol methacrylate (trade name: NK ester M-40G, M-90G, M-230G (above, manufactured by Toa Synthetic Chemical Industry Co., Ltd.); trade name: Brenma PME-100, PME -200, PME-400, PME-1000, PME-2000, PME-4000 (above, manufactured by Nippon Oil Holding Co., Ltd.), polyethylene glycol monomethacrylate (trade name: Brenma PE-90, PE-200, PE-350, manufactured by Nippon Oil Co., Ltd.), polypropylene glycol monomethacrylate (brand name: Brenma PP-500, PP-800, PP-1000, manufactured by Nippon Oil Co., Ltd.), polyethylene glycol polypropylene Glycol Monomethacrylate (Brand Name: Brenma 70 PEP-370B, manufactured by Nippon Oil Holding Co., Ltd.), Polyethylene Glycol Polytetramethylene Glycol Monomethacrylate (Brand Name: Brenma 55 PET-800, Nippon Oil Co., Ltd.) The polypropylene glycol polytetramethylene glycol monomethacrylate (brand name) And the like do NHK-5050, manufactured by Nippon maintain Co., Ltd.).

(iv) other monomers

The graft copolymer may further contain the other monomer as a copolymer unit, and the other graft copolymer is not particularly limited and may be appropriately selected according to the purpose, for example, an aromatic vinyl compound (eg, styrene). , α-methylstyrene and vinyltoluene), (meth) acrylic acid alkyl esters (e.g. methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and i-butyl (meth) acrylate ), (Meth) acrylic acid alkylaryl esters (e.g. benzyl (meth) acrylate), glycidyl (meth) acrylates, carboxylic acid vinyl esters (e.g. vinyl acetate and vinyl propionate), vinyl cyanide (e.g. ( Meth) acrylonitrile and α-chloroacrylonitrile), aliphatic conjugated dienes (eg, 1,3-butadiene and isoprene), (meth) acrylic acid, and the like. Among these, unsaturated carboxylic acid, (meth) acrylic-acid alkylester, (meth) acrylic-acid alkylaryl ester, and carboxylic acid vinyl ester are preferable.

As content of the other monomer in the said graft copolymer, 5-70 mass% is preferable, for example. If the said content rate is less than 5 mass%, control of the physical property of a coating film may become impossible, and when it exceeds 70 mass%, the capability as a dispersing agent may not fully be exhibited.

As a preferable specific example of the said graft copolymer,

(11) 3- (N, N-dimethylamino) propylacrylamide / polyethyleneglycol mono (meth) acrylate / terminal methacryloylated polymethyl (meth) acrylate copolymer,

(12) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminal methacryloylated polystyrene copolymer,

(13) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / methyl (meth) acrylate terminal methacryloylated polystyrene copolymer,

(14) of the copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethyleneglycol mono (meth) acrylate / terminal methacryloylated methyl (meth) acrylate and 2-hydroxyethyl methacrylate Copolymer,

(15) Copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol mono (meth) acrylate / terminated methacryloylated methyl methacrylate and 2-hydroxyethyl methacrylate ,

(16) Copolymer of 3- (N, N-dimethylamino) propylacrylamide / polyethyleneglycol mono (meth) acrylate / terminated methacryloylated methylmethacrylate and 2-hydroxyethylmethacrylate ,

(17) 3- (N, N-dimethylamino) propylacrylamide / polypropylene glycol mono (meth) acrylate / terminal methacroylated polymethyl (meth) acrylate copolymer,

(18) 3- (N, N-dimethylamino) propylacrylamide / polyethyleneglycolpolypropyleneglycol mono (meth) acrylate / terminal methacroylated polymethyl (meth) acrylate copolymer,

(19) 3- (N, N-dimethylamino) propylacrylamide / polyethylene glycol polytetramethylene glycol mono (meth) acrylate / terminal methacroylated polymethyl (meth) acrylate copolymer,

(20) 3- (N, N-dimethylamino) propylacrylamide / polypropylene glycol polytetramethylene glycol mono (meth) acrylate / terminal methacroylated polymethyl (meth) acrylate copolymer, etc. may be mentioned. .

Especially, (11), (14) and (18) are preferable and the compound represented by following formula (D4) is more preferable. In formula (D4), Me represents a methyl group.

[Formula 60]

[Generation of Organic Particles]

There is no restriction | limiting in particular in the conditions of the poor solvent at the time of manufacturing organic particle, ie, precipitating and forming organic particle | grains, The range of subcritical and supercritical conditions can be selected from normal pressure. -30-100 degreeC is preferable, as for the temperature in normal pressure, -10-60 degreeC is more preferable, and 0-30 degreeC is especially preferable.

The mixing method of the organic material solution (a), the poor solvent (b) of the organic material, and the polymer dispersant solution (c) is not particularly limited, and may be mixed at the same time or mixed sequentially, but a sufficient amount of the poor solvent (b ), It is preferable to add the organic material solution (a) and the polymer dispersant solution (c) continuously, and more preferably add the organic material solution (a) and the polymer dispersant solution (c) at the same time.

When the organic material solution (a) and / or the polymer dispersant solution (c) is added to the poor solvent (b), it is preferable that the poor solvent (b) is in a stirred state. As for stirring speed, 100-10000 rpm is preferable, 150-8000 rpm is more preferable, 200-6000 rpm is especially preferable. A pump etc. can also be used for addition and it is not necessary to use it. Moreover, although addition in liquid may be sufficient as addition besides liquid, addition in liquid is more preferable.

As for the mixing ratio of the organic material solution (a), the poor solvent (b), and the polymer dispersant solution (c), 1 <b / a <20 and 1 <b / c <100 are preferable by volume ratio.

The concentration of the obtained organic particle precipitate is not particularly limited as long as it is a range in which organic particles can be produced, but the organic particles are preferably in the range of 10 to 40000 mg, more preferably in the range of 20 to 30000 mg, with respect to 1000 ml of the dispersion solvent. Especially preferably, it is the range of 50-25000 mg.

 [Particle Size, Monodispersity of Organic Particles]

Regarding the particle diameter of the organic particles, there is a method of quantifying by means of a measurement method and expressing the average size of the population, but is often used, the mode diameter indicating the maximum value of the distribution, the median diameter corresponding to the median of the integral distribution curve, and the like. Average diameter (number average, length average, area average, mass average, volume average, etc.), etc. In this invention, unless otherwise indicated, a number average diameter is used. In this invention, it is preferable that the average particle diameter of organic particle | grains (primary particle) is 500 micrometers or less, 100 micrometers or less are more preferable, 10 micrometers or less are especially preferable. Moreover, when manufacturing nanometer size nanoparticles, it is preferable that the average particle diameter is 1 nm-1 micrometer, It is more preferable that it is 1-200 nm, It is further more preferable that it is 2-100 nm, It is 5-80 nm Particularly preferred. In the production method of the present invention, the particles to be formed may be crystalline particles or amorphous particles, or a mixture thereof.

In addition, in this invention, the ratio (Mv / Mn) of volume average particle diameter (Mv) and number average particle diameter (Mn) is used as an index which shows the monodispersity of particle | grains, unless there is particular notice. It is preferable that the organic particle | grains (primary particle) obtained by the manufacturing method of this invention are monodispersion, It is preferable that Mv / Mn is 1.0-2.0, It is more preferable that it is 1.0-1.8, It is especially preferable that it is 1.0-1.5 Do.

As a measuring method of the particle diameter of organic particle | grains, a microscopy method, a mass method, a light scattering method, the light blocking method, an electrical resistance method, an acoustic method, and a dynamic light scattering method are mentioned, A microscope method and a dynamic light scattering method are especially preferable. As a microscope used by a microscopy method, a scanning electron microscope, a transmission electron microscope, etc. are mentioned, for example. As a particle measuring apparatus by the dynamic light scattering method, Nikkiso Corporation nano truck UPA-EX150 (brand name), the Otsuka Electronics company dynamic light scattering photometer DLS-7000 series (brand name), etc. are mentioned, for example.

 [Manufacturing device]

In the manufacturing method of the organic particle of this invention, although the preferable specific example is demonstrated about the manufacturing apparatus used for organic particle formation and the particle formation method using the same below, this invention is not limitedly interpreted by this illustration.

(Organic Particle Manufacturing Apparatus Example 1)

1A is a schematic diagram of a manufacturing apparatus used as one embodiment in the present invention. In FIG. 1A, the organic material solution is continuously supplied into the mixing chamber 13 formed in the container 11 by the supply pipe 14a and the polymer dispersant solution by the supply pipe 14b. The poor solvent 11a is accommodated in the container 11 here, The mixing chamber 13 is formed under the liquid level of the poor solvent, The inside is filled with the poor solvent. In addition, the bulk poor solvent in the reaction vessel 11 is always convection so as to traverse the inside of the mixing chamber 13 from below to upward (in the direction of the arrow in the drawing) by the action of stirring in the mixing chamber 13. It is supposed to be.

FIG. 1B is an enlarged partial cross-sectional view schematically showing an enlarged mixing chamber 13 as one embodiment of the manufacturing apparatus of FIG. 1A. The organic material solution is supplied from the supply pipe 14a and the polymer dispersant solution from the supply pipe 14b into the mixing chamber 13. The mixing chamber 13 is formed by a casing (mixing chamber) 17 formed of a rectangular cylinder having a constant cross-sectional area, an upper end of the casing 17 is an open end, and a circular hole 18 is formed at the lower end of the mixer ( The poor solvent in 13) is to be connected with the bulk poor solvent. Here, the organic material solution supply pipe 14a and the polymer dispersant solution supply pipe 14b are formed in the wall constituting the lower end of the casing 17 and open toward the circular hole. Moreover, the stirring blade 12 is formed in the said mixer 13, The stirring blade is attached to the shaft 15, and is made to rotate by the motor (16 in FIG. 1A). By the rotation of the stirring blade 12, the poor solvent passes through the circular hole 18 so as to circulate constantly in the mixer 13 from below to upward.

The stirring blade 12 formed in the said mixing chamber 13 should be what produces | generates the desired mixing force in a mixing chamber. The strength of this mixing is estimated to be an important operating factor for the size of the droplets (droplets) when the organic material solution and the polymer dispersant solution are mixed.

In addition, the stirring blades 12 are combined with other organic particles to form larger particles by the organic particles generated in the mixing space staying in the mixing chamber 13, or the organic material solution supplied to the mixing chamber 13. It is preferable to have a capability of quickly removing the produced organic particles and quickly discharging them out of the mixing chamber 13 so that they are exposed to become large particles and do not produce large particles.

As the stirring blade 12, if the said objective is achieved, what kind of thing may be sufficient and a turbine type, a fan turbine type, etc. can be used, for example.

Moreover, it is preferable that the casing 17 is comprised by the square cylinder as mentioned above. By doing in this way, the corner of the casing 17 disperse | distributes the flow created by the stirring blade 12, and a mixing effect can be heightened further without requiring an additive like a baffle plate.

FIG. 1C is an enlarged partial sectional view of a mixer in which the stirring blades in the mixing chamber are set to two sets (mixing stirring blades 19a and discharge stirring blades 19b) as another embodiment of the manufacturing apparatus of FIG. 1A. By forming two sets of stirring blades as described above, the ability to adjust the strength of the mixing and the ability to discharge the generated organic particles out of the mixer can be independently selected, and the strength and circulation amount of the mixing are independently set to desired values. It becomes possible to operate.

(Organic Particle Manufacturing Apparatus Example 2)

2 is a cross-sectional view schematically showing another embodiment of the manufacturing apparatus that can be used in the method for producing organic particles of the present invention. In FIG. 2, the organic material solution and the poor solvent are continuously supplied into the stirring vessel 21a by supply pipes 24a and 24b, respectively. At the same time, the polymer dispersant solution is continuously supplied from the other supply pipe 24c into the stirring vessel 21a. The organic particles produced in the stirring vessel 21a stay in the stirring vessel 21a to combine with other organic particles to become larger particles, or to be exposed to the supplied organic material solution to become large particles, thereby producing large particles. In order to prevent this, the produced organic particle precipitates are quickly withdrawn from the discharge pipe 23.

(Organic Particle Manufacturing Apparatus Example 3)

3 is a cross-sectional view schematically showing still another embodiment of the apparatus that can be used in the method for producing organic particles of the present invention. In the manufacturing apparatus of FIG. 3, the stirring apparatus 50 includes two liquid supply ports 32 and 33 for introducing an organic material solution and a poor solvent, and a supply port 31 for introducing a polymer material solution and stirring treatment. Stirring means for controlling the stirring state of the liquid in the stirring tank 38 by being rotationally driven in the stirring tank 38 and the cylindrical stirring tank 38 having a liquid discharge port 36 for discharging the mixed liquid which has been finished. It consists of a pair of stirring blades 41 and 42 which are phosphorus.

The stirring vessel 38 is comprised from the cylindrical tank main body 39 which faces the center axis in the up-down direction, and the seal plate 40 used as the tank wall which blocks the upper and lower opening ends of the tank main body 39. As shown in FIG. Moreover, the stirring vessel 38 and the tank main body 39 are formed with the nonmagnetic material excellent in permeability. The two liquid supply ports 32 and 33 are equipped at a position near the lower end of the bath main body 39, and the liquid discharge port 36 is equipped at a position near the upper end of the bath main body 39.

And the pair of stirring blades 41 and 42 is arrange | positioned apart from the upper and lower phases which mutually oppose in the stirring tank 38, and is rotationally driven mutually in the opposite direction. Each stirring blade 41 and 42 comprises the external magnet 46 and the magnetic coupling C arrange | positioned on the outer side of the rough wall (sealing plate 40) which each stirring blade 41 and 42 adjoins. That is, each of the stirring vanes 41 and 42 is connected to each of the external magnets 46 by magnetic force, and is rotated in the opposite direction by rotating each of the external magnets 46 by independent motors 48 and 49. Rotation is manipulated.

The pair of stirring blades 41 and 42 arranged in the tank 38 opposing the tank 38 with stirring flows different in direction so as to be indicated by a broken arrow X and a solid arrow Y in FIG. 3. In). And since the stirring flows which form each stirring blade 41 and 42 differ in a flow direction, they generate | occur | produce high speed turbulence in the tank 38 which collides with each other and promotes stirring in the tank 38, The flow in the tank 38 is prevented from being normalized, and even when the rotation of the stirring vanes 41 and 42 is accelerated, the cavity is prevented from being formed in the rotation of the rotating shafts of the stirring vanes 41 and 42, and the stirring action is performed. It is possible to prevent the occurrence of the problem that a steady flow flowing in the tank 38 is formed along the inner circumferential surface of the stirring tank 38 without being sufficiently received. Therefore, by speeding up the rotation of the stirring blades 41 and 42, the processing speed can be easily improved, and at that time, the flow of the liquid in the tank 38 is normalized, and the liquid with insufficient stirring mixing is discharged. This can be prevented and the deterioration of the processing quality can be prevented.

Moreover, since each stirring blade 41 and 42 in the stirring tank 38 is connected to the motors 48 and 49 arrange | positioned outside the stirring tank 38 by the magnetic coupling C, the stirring tank 38 Since it is not necessary to insert the rotary shaft through the rough wall of the crankcase, the stirring vessel 38 can be made into a sealed container structure without the insertion passage portion of the rotary shaft, thereby preventing leakage of the stirred and mixed liquid into the tank and It is possible to prevent the deterioration of the processing quality due to the mixing of the lubricating liquid (sealing liquid) and the like into the liquid in the bath 38 as impurities.

In the manufacturing method of the organic particle | grains of this invention, using the manufacturing apparatus which has these structures, organic particle | grains can be manufactured not only by a batch system but also by a continuous flow system, and can respond to mass production. In addition, by quickly discharging the produced organic particle precipitate, the ratio between the organic material solution and the poor solvent solution supplied into the stirring vessel can be made constant at all times. For this reason, the solubility of the organic material of a dispersion liquid can be made constant from the start of manufacture to the end of manufacture, and the monodisperse organic particle can be manufactured stably.

In addition, monodispersion is prevented by normalizing the flow of the liquid in the tank to prevent discharge of the mixed liquid with insufficient stirring and mixing, and by preventing the mixing of the lubricating liquid (sealing liquid) and the like for the rotary shaft into the liquid in the tank as impurities. Phosphorus organic particle | grains can be manufactured more stably.

 [Concentration of Organic Particle Precipitation Liquid]

According to the production method of the present invention, it is possible to obtain a preferable ink jet recording ink by concentrating the organic particle precipitation liquid, and therefore, the organic particle dispersion composition can be produced on an industrial scale.

Below, the method of concentrating a dispersion liquid is demonstrated.

The concentration method is not particularly limited as long as the organic particle liquid can be concentrated. For example, (i) a method of performing desalination concentration by an ultrafiltration method, and (ii) a filter extraction method as necessary by a concentration extraction method (filter filtration as necessary). And (iii) precipitation and concentration of organic particles by centrifugation, (iv) drying (sublimation of solvent by vacuum lyophilization and concentration, drying of solvent by heating to reduced pressure). And the like), and combinations thereof are also preferably used. The concentration of the organic particle liquid after concentration (hereinafter also referred to as "concentrated organic particle liquid") is appropriately determined according to the use, redispersion conditions, etc., but the concentration of the organic particles is 1 to 100 mass based on the total amount of the concentrated organic particle liquid. It is preferable that it is%, It is more preferable that it is 5-100 mass%, It is especially preferable that it is 10-100 mass%.

According to the manufacturing method of the organic-particle dispersion composition of this invention, it can be obtained in a dispersed state, without making the organic particle in a concentrated organic particle liquid aggregate, and it can be set as an organic particle-dispersion composition. That is, at the time of particle formation, re-agglomeration can be suppressed by mixing a polymer dispersant solution in a system different from the organic material solution and the poor solvent of the organic material. In addition, the thickening of the solution of the organic material is very effective when the concentration process is facilitated in view of the industrial production scale. However, even in such a case, the polymer dispersant is co-existed in the organic material solution to thicken the particle size. Undesirable changes can be suppressed. The change in particle size due to aggregation before and after concentration may vary depending on the organic materials used, etc., but when not aggregated, it is 20% when the particle diameter change rate is expressed by the particle diameter change rate (the particle size after concentration divided by the particle size before concentration is minus 1). It is preferable that it is the following, and it is more preferable that it is 10% or less.

(i) ultrafiltration

The ultrafiltration method is demonstrated.

Ultrafiltration can apply the method used for the desalination / concentration of a silver halide emulsion, for example. Research Disclosures No. 10208 (1972), No. 13 122 (1975) and No. 16 351 (1977) are known. The pressure difference and the flow rate which are important as the operating conditions can be selected by reference to the characteristic curve described in Oyaharuhiko, "Measurement for Use of Membrane Handbook" published by Saiwai Shobo Store (1978), p. 275. In order to suppress aggregation of particle | grains, it is necessary to find out the optimal conditions. In addition, in the method of replenishing the solvent lost from the membrane permeation, there is a regular formula for continuously adding a solvent and a batch formula for intermittently adding the solvent, but a basic formula having a relatively short desalting time is preferable. The pure water obtained by ion-exchange or distillation is used for the solvent to be supplemented in this way, The poor solvent of a dispersing agent and a dispersing agent may be mixed in pure water, or may be added directly to an organic particle dispersion composition.

4, the example of 1 structure of the apparatus for performing ultrafiltration is shown. As shown in FIG. 4, the apparatus includes a tank 81 for storing the organic particle precipitation liquid, a circulation pump 82 for circulating the organic particle precipitation liquid in the tank 81, and a circulation pump 82. It has an ultrafiltration module 83 which removes by-product inorganic salt in the dispersion introduced by this as permeate. The dispersion from which the permeate is separated is returned to the tank 81 again, and the same operation is repeated until the predetermined purpose of the removal of byproduct inorganic salt is achieved. In addition, the apparatus is provided with a supplementary pure water measurement flowmeter 84 used to replenish a constant amount of the solvent lost by the permeate as pure water, and a permeate measurement flow meter 85 used to determine the pure water replenishment amount. ) Is installed. Moreover, the reverse direction washing pump 86 for introducing the water for thinning the permeate is provided.

The ultrafiltration membranes are commercially available from Asahi Kasei Co., Ltd., Daicel Chemical Co., Ltd., Tore Co., Ltd., and Nitto Electric Co., Ltd., in which flat, spiral, cylindrical, hollow fiber, and hollow fiber types are already combined as modules. Although it is, from a viewpoint of total film area and washability, a spiral type or a hollow fiber type is preferable. Moreover, although the fractional molecular weight used as the index of the threshold of the component which can permeate a membrane needs to be determined from the molecular weight of the dispersing agent used, it is preferable that it is 5,000 or more and 50,000 or less, and it is more preferable that it is 5,000 or more and 15,000 or less.

(ii) concentrated extraction

Next, the method of concentrating by the concentrated extraction method is demonstrated.

In the concentrated extraction method, an extraction solvent is added to and mixed with the organic particle precipitate, and the organic particles are concentrated and extracted on the extraction solvent (the organic particle liquid after the concentrated extraction is also referred to as "concentrated extract", "organic particle concentrated extract", etc.). .), The concentrated extract is filtered through a filter or the like as necessary to concentrate.

The extraction solvent to be used is not particularly limited, but is not substantially mixed with the dispersing solvent (for example, the aqueous solvent) of the organic particle precipitation liquid (not substantially mixed with each other in the present invention). 50 mass% or less of melt | dissolution is preferable, and 30 mass% or less is more preferable), and after mixing, it is preferable that it is a solvent which forms an interface. In addition, the extraction solvent is preferably a solvent that causes weak aggregation (redispersion is possible even without applying a high shear force such as milling or high speed stirring) in which the organic particles can be redispersed in the extraction solvent. Such a state is preferable in that it is possible to remove the dispersing solvent such as water easily by filter filtration and the like while wetting the desired organic particles with the extraction solvent without causing firm aggregation to change the particle size.

The extraction solvent is preferably an ester solvent, an alcohol solvent, an aromatic solvent or an aliphatic solvent, more preferably an ester solvent, an aromatic solvent or an aliphatic solvent, and particularly preferably an ester solvent.

As ester solvent, 2- (1-methoxy) propyl acetate, ethyl acetate, ethyl lactate, etc. are mentioned, for example. As an alcoholic solvent, n-butanol, isobutanol, etc. are mentioned, for example. As an aromatic solvent, benzene, toluene, xylene, etc. are mentioned, for example. As an aliphatic solvent, n-hexane, cyclohexane, etc. are mentioned, for example. Moreover, the pure solvent by said preferable solvent may be sufficient as an extraction solvent, and the mixed solvent by a some solvent may be sufficient as it.

The amount of the extraction solvent is not particularly limited as long as the organic particles can be extracted. However, the amount of the extraction solvent is preferably smaller than that of the organic particle precipitate in consideration of concentration and extraction. When this is represented by a volume ratio, when the organic particle | grains precipitation liquid is 100, it is preferable that the extraction solvent added is in the range of 1-100, More preferably, it is the range of 10-90, and the range of 20-80 is especially preferable. Too large an amount requires a great time for concentration, and when too small, insufficient extraction leaves particles in the dispersing solvent.

After the extraction solvent is added, it is preferable to stir and mix so as to be in sufficient contact with the dispersion. Stirring mixing can use a well-known method. Although there is no restriction | limiting in particular in the temperature at the time of adding and mixing an extraction solvent, It is preferable that it is 1-100 degreeC, and it is more preferable that it is 5-60 degreeC. Although what kind of apparatus may be used as long as addition and mixing of an extraction solvent can perform each process preferably, it can carry out using a separatory lot type apparatus, for example.

According to the concentrated extraction method, the organic particles can be efficiently concentrated from the organic particle precipitation liquid. Regarding the concentration magnification, for example, the concentration in the organic particle liquid after concentration may preferably be concentrated to about 100 to 1000 times, more preferably about 500 to 1000 times. In addition, organic particles hardly remain in the dispersion solvent left after the extraction of the organic particles, and the extraction rate can be high.

In order to separate the dispersion solvent and the concentrated extract liquid of the organic particle | grains precipitation liquid, it is preferable to filter. As an apparatus for filter filtration, an apparatus such as pressure filtration can be used, for example. As a preferable filter, a nano filter, an ultra filter, etc. are mentioned. By filter filtration, it is preferable to remove the remaining dispersion solvent and to further concentrate the organic particles in the concentrated extract.

(iii) centrifugation

Next, the centrifugal separation method will be described.

The centrifugal separator used for the concentration of the organic particles by centrifugation may be used as long as it can settle the organic particles in the organic particle precipitation liquid (or the organic particle concentrated extract liquid). Examples of the centrifugal separator include a device having a skimming function (a function of sucking the supernatant layer during rotation and discharging it out of the system) in addition to the general-purpose apparatus, and a continuous centrifuge for continuously discharging solids.

As for centrifugal separation conditions, 50-10000 are preferable at centrifugal force (a value which shows how many times the acceleration of gravity takes up), 100-8000 are more preferable, 150-6000 are especially preferable. As for the temperature at the time of centrifugation, -10-80 degreeC is preferable with the solvent species of a dispersion liquid, -5-70 degreeC is more preferable, 0-60 degreeC is especially preferable.

(iv) drying method

Next, drying is demonstrated.

ㆍ vacuum drying

The apparatus used for concentrating the organic particles by drying under reduced pressure is not particularly limited as long as the solvent of the organic particle precipitation liquid (or the organic particle concentration extract liquid) can be evaporated. For example, a general purpose vacuum dryer and a rotary pump, the apparatus which can heat-dry under reduced pressure, stirring a liquid, the apparatus which can be made to continuously dry by letting a liquid pass through the heat-reduced pipe | tube, etc. are mentioned.

30-230 degreeC is preferable, 35-200 degreeC is more preferable, and 40-180 degreeC of heating under reduced pressure drying temperature is especially preferable. 100-100000 Pa is preferable, as for the pressure at the time of pressure reduction, 300-90000 Pa is more preferable, 500-80000 Pa is especially preferable.

When it concentrates by the vacuum drying method, organic particle | grains can be concentrated efficiently from an organic particle | grain precipitation liquid, and when it concentrates, for example, when the density of the organic particle | grains in the organic particle | grains precipitation liquid used as a raw material is set to 1, it concentrates. The density in the organic particle liquid is preferably about 100 to 3000 times, more preferably about 500 to 2000 times.

Freeze drying method

The method of freeze drying is not particularly limited, and examples thereof include a refrigerant straightening method, a double freezing method, a fruit circulation method, a triple heat exchange method, and an indirect heating freezing method, but preferably a refrigerant straightening method and an indirect heating method. It is preferable to use a freezing method, more preferably an indirect heating freezing method. In either method, it is preferable to perform freeze drying after preliminary freezing. Although the conditions of preliminary freezing are not specifically limited, It is necessary for the sample which performs freeze drying to be frozen freely.

Examples of the apparatus of the indirect heating freeze method include small freeze dryers, FTS freeze dryers, LYOVAC freeze dryers, laboratory freeze dryers, research freeze dryers, triple heat exchange vacuum freeze dryers, mono cooling freeze dryers, and HULL freeze dryers. Preferably, a small freeze dryer, a laboratory freeze dryer, a research freeze dryer, a mono cooling freeze dryer, more preferably a small freeze dryer, a mono cooling freeze dryer is preferable.

Although the temperature of freeze drying is not specifically limited, For example, it is -190--4 degreeC, Preferably it is -120--20 degreeC, More preferably, it is about -80-60 degreeC. The pressure of the lyophilization is not particularly limited and can be appropriately selected by those skilled in the art. For example, the pressure is preferably 0.1 to 35 Pa, preferably 1 to 15 Pa, more preferably about 5 to 10 Pa. The freeze drying time is, for example, 2 to 48 hours, preferably 6 to 36 hours, more preferably about 16 to 26 hours. However, these conditions can be suitably selected by those skilled in the art. About the freeze-drying method, for example, Formulation Machine Technology Handbook: Formulation Machine Technology Study Group, Chijing Hokan, p.120-129 (September 2000); Vacuum Handbook: Japan Vacuum Technology Co., Ltd., Omsa, p. 328-331 (1992); Freezing and Drying Research Society Journal: Ito Koji et al., No. 15, p. 82 (1965), and the like.

In the manufacturing method of the organic particle dispersion composition of this invention, it is preferable to set it as the composition which removed unnecessary ions. Although the ion removed is not specifically limited, It is preferable to remove the thing with small molecular weights, such as sodium (Na), potassium (K), calcium (Ca), and chlorine (Cl). For example, in a color filter application, when there are many ions which are easy to move because of a low molecular weight, it becomes an obstacle without being able to maintain required voltage DF. As for the total amount of the ion after removal, 1 mass% or less is preferable with respect to an organic material, Furthermore, 0.1 mass% or less is more preferable, 0.01 mass% or less is especially preferable. Removal of unnecessary ions can be performed, for example, using the above-described ultrafiltration device.

 [Redispersion of Concentrated Organic Particle Liquid]

In the present invention, the concentrated organic particles can be finely dispersed again in a suitable solvent in accordance with the use of a color filter, ink jet ink, or the like to obtain an organic particle dispersion composition. To increase the degree of dispersion by loosening agglomeration).

For example, in a color filter use, it can add and disperse | distribute to a vehicle. The vehicle refers to a portion of a medium in which organic particles are dispersed when the paint is in a liquid state, and refers to a portion (binder) that binds to the organic particles as a liquid to solidify the coating film and a component (organic solvent) that dissolves and dilutes the coating film. It contains.

As described in the above-described concentrated extraction method, in the organic particle-concentrated extract, it is possible to rapidly filter the organic matter, so that the organic particles may be aggregated together with the concentration. Moreover, also in the centrifugal separation method or the drying method, the same concentrated organic particle may generate | occur | produce aggregation.

As a method of dispersing such agglomerated particles (in the present invention, agglomerated particles refer to aggregates of particles such as agglomerates with a secondary force), for example, a dispersion method using ultrasonic waves or a method of applying physical energy can be used. Can be.

It is preferable that the ultrasonic irradiation apparatus used has a function which can apply the ultrasonic wave 10kHz or more, For example, an ultrasonic homogenizer, an ultrasonic washing machine, etc. are mentioned. When the liquid temperature rises during ultrasonic irradiation, thermal coagulation of the particles occurs (see the "Latest Pigment Dispersion Technology" Technical Information Association, 1995, p166, etc.), so that the liquid temperature is preferably 1 to 100 ° C, and 5 to 60 ° C More preferred. The control method of temperature can be performed by control of dispersion temperature, temperature control of the temperature adjusting layer which controls temperature of a dispersion liquid, etc.

There is no restriction | limiting in particular as a disperser used when disperse | distributing concentrated organic particle | grains by adding physical energy, For example, well-known dispersers, such as a kneader, a roll mill, an atrider, a super mill, a dissolva, a homomixer, a sand mill, etc. Can be mentioned.

It is also preferable to use what was shown by the term of [dispersing agent] as a dispersing agent used at the time of redispersion, at the time of organic particle formation.

According to the manufacturing method of the organic particle dispersion composition of this invention, the organic particle | grain (primary particle) after redispersion can be made into the finely disperse | distributed particle | grains, When obtaining as a nanoparticle, particle size can preferably be 1-200 nm. 2-100 nm are more preferable, and 5-50 nm are especially preferable. Moreover, it is preferable that Mv / Mn of the particle | grains after redispersion is 1.0-2.0, It is more preferable that it is 1.0-1.8, It is especially preferable that it is 1.0-1.5. Although the organic particle concentration of the organic-particle dispersion composition after redispersion is suitably determined by a use etc., for example, it is preferable that the quantity of organic particle | grains is 0.5-50 mass% with respect to the total amount of a composition, and it is 1-30 mass% It is more preferable that is.

[Ink for inkjet recording]

Next, the preferable aspect of the inkjet recording ink of this invention is demonstrated.

In the inkjet recording ink of the present invention, it is preferable to apply heat treatment to the organic particle dispersion composition. As a result, the crystallinity of the organic particles is improved, firm crystals are formed, and the weather resistance of the image obtained by the inkjet recording ink containing the organic particle dispersion composition can be remarkably improved. 40-100 degreeC is preferable, as for the temperature of the heat processing, 40-90 degreeC is more preferable, It is still more preferable that it is 50-90 degreeC. It is preferable to perform 10 minutes-3 days of the time of the heat processing, It is more preferable to carry out for 1 hour-3 days, It is further more preferable to carry out for 6 hours-2 days. During this time, the liquid may be left to stand or may be stirred.

An aqueous solvent and other additives are further added to the organic particle dispersion composition, and can be used as the inkjet recording ink of the present invention.

In 100 mass parts of inkjet recording ink of this invention, it is preferable to contain 0.2-10 mass parts of organic particle | grains, More preferably, it is 0.5-7.5 mass parts.

The ink for inkjet recording of the present invention includes a drying inhibitor for preventing clogging due to drying at the injection port of the ink, a penetration accelerator for better penetration of the ink into paper, an ultraviolet absorber, an antioxidant, a viscosity regulator, a surface tension regulator, Additives, such as a dispersing agent, a dispersion stabilizer, an antiseptic agent, a rust preventive agent, a pH adjuster, an antifoamer, a chelating agent, can be selected suitably and can be used suitably.

As the aqueous solvent, a water-soluble organic solvent having a lower vapor pressure than water is preferable. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin Polyhydric alcohols represented by trimethylolpropane; lower alkyl of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether Ethers; heterocyclics such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and N-ethylmorpholine; sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolene; polyfunctional compounds such as diacetone alcohol and diethanolamine; and other urea derivatives. Among these, polyhydric alcohols, such as glycerin and diethylene glycol, are more preferable. The aqueous solvent mentioned above also acts as a drying inhibitor in the ink for inkjet recording. A drying inhibitor may be used independently or may be used together 2 or more types. It is preferable that these drying inhibitors contain 10-50 mass% in ink.

As the penetration accelerator, alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, nonionic surfactants and the like can be used. If they contain 10-30 mass% in ink, it will have sufficient effect, and it is preferable to use in the range of the addition amount which does not produce printing bleeding and a paper punch (print through).

As the ultraviolet absorber used to improve the image storage ability, Japanese Patent Laid-Open Nos. 58-185677, 61-190537, and Japanese Patent Laid-Open Nos. 2-782, 5-197075 and 9-34057 Benzotriazole compounds described in Japanese Patent Application Laid-Open No. 46-2784, benzophenone compounds described in JP-A-5-194483, US Patent No. 3214463, and Japanese Patent Application Publication No. 48-30492. , Japanese Patent Application Laid-Open No. Hei 10-88106, etc., cinnamic acid-based compound, etc .: Japanese Patent Application Laid-Open Nos. 4-298503, 8-53427, 8-239368, and 10-182621. Triazine compounds described in Japanese Patent Application Laid-Open No. Hei 8-501291, etc., compounds that absorb and fluoresce ultraviolet rays represented by the compounds described in Research Disclosure No.24239, stilbene and benzoxazole compounds, and so-called fluorescence. Whitening agent can be used.

As the antioxidant used to improve the storage of images, various organic and metal complex discoloration inhibitors can be used. Examples of organic fading inhibitors include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, cromanns, alkoxyanilines, and hetero reflux. Nickel complexes and zinc complexes as metal complex fading inhibitors Etc. More specifically, paragraphs I to J of Research VII No. 17643, Sections VII to J, No. 15162, No.18716, page 650, column No.36544, page 527, and No.307105, page 872, The compound described in the patent cited in No. 15162 or the compound contained in the general formulas and compound examples of the typical compounds described in pages 127 to 137 of JP-A-62-215272 can be used.

Examples of the flavoring agent include sodium dehydroacetic acid, sodium benzoate, sodium pyridinthione 1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. It is preferable to use these 0.02-5.00 mass% in ink. In addition, these details are described in "Anti-microbial antimicrobial dictionary" (Japanese antimicrobial antimicrobial society dictionary editing committee edition). Moreover, as antirust agent, acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropyl ammonium nitrite, pentaerythritol tetranitrate, dicyclohexyl ammonium nitrite, benzotriazole, etc. are mentioned, for example. It is preferable to use 0.02-5.00 mass% of these in ink.

A pH adjuster can be used preferably from a viewpoint of pH adjustment, dispersion stability provision, etc. of an organic particle dispersion composition, It is preferable to add so that it may become pH 4.5-10.0, and it is more preferable to add so that it may become pH 6-10.0. As a pH adjuster, an organic base, an inorganic alkali, etc. are basic things, and an organic acid, an inorganic acid, etc. are mentioned as an acid thing. Triethanolamine, diethanolamine, N-methyl diethanolamine, dimethylethanolamine, etc. are mentioned as said organic base. Examples of the inorganic alkali include alkali metal hydroxides (for example, sodium hydroxide, lithium hydroxide, potassium hydroxide, and the like), carbonates (for example, sodium carbonate, sodium hydrogencarbonate, and the like), ammonia, and the like. Moreover, acetic acid, propionic acid, trifluoroacetic acid, alkylsulfonic acid, etc. are mentioned as said organic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid, and the like.

Examples of the surface tension modifier include nonionic, cationic or anionic surfactants. As these surfactants, SURFYNOLS (trade name, AirProducts & Chemicals Co., Ltd.), which is an acetylene-based polyoxyethylene oxide surfactant, is preferably used in addition to those described above. Moreover, the amine oxide type amphoteric surfactant, such as N, N- dimethyl-N-alkylamine oxide, etc. are also preferable. Moreover, what was mentioned as surfactant as described in (37)-(38) page of Unexamined-Japanese-Patent No. 59-157636, Research Disc Closure No.308119 (1989) can also be used. The surface tension of the ink of the present invention is preferably 20 to 60 mN / m with or without them. Moreover, 25-45 mN / m is preferable.

The viscosity of the ink for inkjet recording is preferably 30 mPa · s or less, more preferably 20 mPa · s or less, and a viscosity modifier can be used for the purpose of adjusting the viscosity.

As a viscosity modifier, water-soluble polymers, such as cellulose and polyvinyl alcohol, nonionic surfactant, etc. are mentioned, for example. More specifically, "Viscosity Preparation Technology" (Technical Information Society, 1999), Chapter 9, and "Chemicals for Inkjet Printers (98 Supplement)-Development Trends and Prospects of Materials-" (Sim Si, 1997) 162-174.

In the inkjet recording ink of the present invention, as the dispersant and the dispersion stabilizer, the above-mentioned various cationic, anionic and nonionic surfactants, and antifoaming agents, fluorine-based, silicone-based compounds and chelating agents typified by EDTA can be used as necessary.

Inkjet recording inks can be used not only for monochromatic image formation but also for full color image formation. Crimson hue ink, cyan hue ink, and yellow hue ink can be used to form a full color image, and black hue ink may be further used to prepare the hue. If at least one of these various color inks is the inkjet recording ink of the present invention, it is preferable because a good color can form a full color image. Moreover, since all of these inks of various colors are the inkjet recording ink of this invention, since a full color image excellent in color can be formed, it is more preferable.

Examples of the water phase material used in the inkjet recording method include plain paper, coated paper, and plastic film. When coated paper is used as the water-based material, it is preferable that image quality and image storage durability are improved.

As the recording material, plain paper, resin coated paper, for example: Japanese Patent Application Laid-Open No. Hei 8-169172, 8-27693, 2-276670, 7-276789, 9-323475, Inkjet paper, film described in Nos. 62-238783, 10-153989, 10-217473, 10-235995, 10-337947, 10-217597, 10-337947, etc. Electrophotographic paper, cloth, glass, metal, ceramics, etc. can be used for image formation.

Furthermore, the recording paper and the recording film will be described.

The support which can be a recording paper and a recording film is usually made of chemical pulp such as LBKP, NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP, CGP, recycled pulp such as DIP, and the like. According to the present invention, additives such as conventional pigments, binders, size agents, fixatives, cationic agents, and strength enhancers may be mixed, and those produced by various devices such as long paper paper machines and long paper paper machines may be used. In addition to these supports, any of synthetic paper and a plastic film sheet may be used, and the thickness of the support is preferably 10 to 250 µm and the basis weight thereof is preferably 10 to 250 g / m 2. The support body may be formed of an ink receiving layer and a backcoat layer as it is, or may be an aqueous phase material. After forming a size press or an anchor coat layer with starch, polyvinyl alcohol, or the like, an ink receiving layer and a backcoat layer may be formed as an aqueous phase material. The support may be planarized by calendar devices such as machine calendars, TG calendars, and soft calendars. In this invention, as a support body, the paper and plastic film which laminated both surfaces with polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene, and those copolymers) are used more preferable. In the polyolefin polyolefin, preference is given to adding white pigments (eg titanium oxide, zinc oxide) or color dyes (eg cobalt blue, ultramarine blue, neodium oxide).

The ink receiving layer formed on the support contains a pigment and an aqueous binder.

As the pigment, a white pigment is preferable, and as a white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, litpon, zeolite, barium sulfate, Inorganic pigments such as calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. As a white pigment contained in an ink receiving layer, a porous inorganic pigment is favorable and especially a synthetic amorphous silica with a large pore area is preferable. Although synthetic amorphous silica can use both the silicic acid anhydride obtained by a dry manufacturing method and the hydrous silicic acid obtained by a wet manufacturing method, it is preferable to use hydrous silicic acid especially. These pigments may use 2 or more types together.

As the aqueous binder contained in the ink receiving layer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationic starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polyalkylene oxide, Water-soluble polymers, such as a polyalkylene oxide derivative, water-dispersible polymers, such as styrene butadiene latex and an acryl emulsion, etc. are mentioned. These aqueous binders can be used individually or in combination of 2 or more types. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in view of adhesion to pigments and peeling resistance of the ink receiving layer.

In addition to the pigment and the aqueous binder (aqueous binder), the ink-receiving layer can contain water additives, light resistance enhancers, surfactants, film additives and other additives.

The mordant added in the ink receiving layer is preferably immobilized. To that end, a polymer mordant is preferably used. About the polymer mordant: JP-A-48-28325, 54-74430, 54-124726, 55-22766, 55-142339, 60-23850, 60-23851 60-23852, 60-23853, 60-57836, 60-60643, 60-118834, 60-122940, 60-122941, 60-122942, 60-235134, Japanese Unexamined Patent Publication No. Hei 1-61236, each of US Patents 2484430, 2548564, 3148061, 3309690, 4115124, 4124386, 4193800, and 4273853. It is described in each specification of Unexamined-Japanese-Patent No. 442305 and 4450224. : Particularly preferred is an aqueous phase material containing the polymer mordant described in pages 212 to 215 of JP-A-H11-161236. By using the polymer mordant disclosed in the publication, an image of excellent image quality can be obtained and the light resistance of the image is improved.

The water resistant agent is effective for water resistance of an image, and as these water resistant agents, cationic resin is especially preferable. As such cation resin, polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyl diallyl ammonium chloride polymer, cationic polyacrylamide, colloidal silica, etc. are mentioned, Especially among these cationic resin, polyamide polyamine Epichlorohydrin is preferred. 1-15 mass% is preferable with respect to the total solid of an ink receiving layer, and, as for content of these cationic resin, it is preferable that it is 3-10 mass% especially.

The surfactant functions as a coating aid, a peelability improver, a slippery improver, or an antistatic agent. Regarding surfactants, there are described in JP-A-62-173463 and 62-183457. You may use an organic fluoro compound instead of surfactant. It is preferable that an organic fluoro compound is hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oil-like fluorine-based compound (eg fluorine oil), and a solid fluorine compound resin (eg, tetrafluoroethylene resin). About an organic fluoro compound, it describes in each of Unexamined-Japanese-Patent No. 57-9053 (8-17 columns), Unexamined-Japanese-Patent No. 61-20994, and 62-135826.

As a film-forming agent: The material described on page 222 of Unexamined-Japanese-Patent No. 1-61236 can be used.

Examples of the additive added to the other ink receiving layer include a pigment dispersant, a thickener, an antifoaming agent, a dye, a fluorescent brightener, a preservative, a pH adjuster, a mat agent and a film-forming agent. In addition, one layer or two layers may be sufficient as an ink receiving layer.

A backcoat layer can also be formed in a recording paper and a recording film, As a component which can be added to this layer, a white pigment, an aqueous binder (aqueous binder), and other components are mentioned. Examples of the white pigment contained in the back coat layer include hard calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate and diatomaceous earth. White inorganic pigments such as calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, ibite, aluminum hydroxide, alumina, littphone, zeolite, hydrolyzate, magnesium carbonate and magnesium hydroxide, styrene And organic pigments such as plastic pigments, acrylic plastic pigments, polyethylene, microcapsules, urea resins, and melamine resins.

Examples of the aqueous binder contained in the backcoat layer include styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationic starch, casein, gelatin, carboxymethyl cellulose and hydroxy. Water-soluble polymers such as ethyl cellulose and polyvinylpyrrolidone, and water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion. As other components contained in a backcoat layer, an antifoamer, an inhibitor, a dye, a fluorescent brightener, a preservative, a water resistant agent, etc. are mentioned.

Polymer latex is added to the constituent layers (including the white layer) of the inkjet recording paper and the recording film. Polymer latex is used for the purpose of improving film properties such as stabilization of dimensions, prevention of curling, prevention of adhesion, and prevention of cracking of the film. About polymer latex, each is disclosed by Unexamined-Japanese-Patent No. 62-245258, 62-1316648, and 62-110066. When the latex polymer latex (40 degrees C or less) of low glass transition temperature is added to the layer containing a mordant, the crack and curl of a layer can be prevented. Moreover, curling can be prevented even if the polymer latex with high glass transition temperature is added to a back layer.

When the ink for inkjet recording of the present invention is used, there is no limitation on the inkjet recording method, for example, a charge control method for ejecting ink using electrostatic attraction and a drop-on demand method using vibration pressure of a piezo element (pressure pulse Method), an acoustic inkjet method in which an electrical signal is converted into an acoustic beam and irradiated with ink to eject ink by using radial pressure, and a thermal inkjet (bubble jet (registered trademark)) that uses a pressure generated by heating ink to form bubbles. ) Is used for the method. In the inkjet recording method, a plurality of low-density inks, called photo inks, are ejected into a small volume, a method of improving image quality by using a plurality of inks having different densities with substantially the same color, or using a colorless transparent ink. This includes.

According to the method for producing organic particles of the present invention, the organic particle dispersion prepared by the organic particle precipitation method can be concentrated by suppressing the aggregation of particles, and can be easily redispersed even when the particles are aggregated by concentration. Moreover, according to the manufacturing method of the organic particle of this invention, even when the raw material solution is made high concentration, the organic particle which has the said outstanding characteristic can be obtained, and manufacture of organic particle | grains of high efficiency is possible.

According to the manufacturing method of the organic-particle dispersion composition of this invention, the preferable inkjet ink or its raw material microparticles | fine-particles which organic particle | grains are sufficiently fine, is excellent in monodispersity, and excellent in discharge stability can be obtained.

Although an Example demonstrates this invention further more concretely below, this invention is not limited by these.

(Example 1)

6 g of pigment (pigment red 254) was dissolved in a solution in which dimethyl sulfoxide and an 8 mol / l potassium hydroxide aqueous solution were mixed at 6: 1, and a dissolved pigment solution A1 was prepared so that the pigment concentration was 150 mmol / L.

Methacrylic acid / methacrylic acid benzyl copolymer (molar ratio 28/72, mass average molecular weight: 30,000, 40% 1-methoxy-2-propylacetate solution) 2.0 g, pigment dispersant A 0.6 g, and dispersant polyvinyl 18 g of pyrrolidone (made by Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000) was melt | dissolved in the 1-methoxy- 2-propyl acetate solution, and 50 ml of polymer dispersant solution B1 was prepared. Apart from this, water was prepared as a poor solvent.

[Formula 61]

Here, pigment solution A1 was added to 1000 ml of poor solvent waters which were heated at 1 degreeC and stirred at 500 rpm by GK-0222-10 type | mold Ramond stirrer manufactured by Fuji Corporation and the chemical industry NP-KX-500 by Nippon Fine Chemicals, Inc. A 200ml injection was performed at a flow rate of 50ml / min using a large-capacity, non-flowing pump. At the same time, the polymer dispersant solution B1 was mixed by injecting 100 ml of the polymer dispersant solution B1 at a flow rate of 25 ml / min using a Nippon Fine Chemicals NP-KX-500 large-capacity no-flow pump, and pigment particles were formed to prepare a pigment particle precipitate.

Unnecessary ions and an organic solvent were removed by using the prepared pigment particle precipitation liquid (pigment particle concentration about 0.5 mass%) by the ultrafilter, and 400 ml of pigment particle dispersion compositions (pigment particle concentration about 10.0 mass%) were obtained.

(Example 2)

6 g of pigments (pigment red 254) were dissolved in a solution in which dimethyl sulfoxide and an 8 mol / l potassium hydroxide aqueous solution were mixed at 6: 1 to prepare a dissolved pigment solution A1 so that the pigment concentration was 150 mmol / L. Moreover, 0.6 g of pigment dispersants A and 18 g of dispersant polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000) were dissolved in a 1-methoxy-2-propyl acetate solution to obtain a polymer dispersant solution B2. 50 ml was prepared. Separately, water was prepared as a poor solvent.

Here, pigment solution A1 was added to 1000 ml of poor solvents which temperature-controlled at 1 degreeC, and was stirred at 500 rpm by GK-0222-10 type | mold Ramond stirrer manufactured by Fuji Corporation and the chemical industry NP-KX- 200 ml was injected at a flow rate of 50 ml / min using a 500 type large-capacity no-flow pump. At the same time, the polymer dispersant solution B2 was mixed by injecting 100 ml of the polymer dispersant solution B2 at a flow rate of 25 ml / min using a Nippon Fine Chemicals NP-KX-500 large-capacity no-flow pump, to form pigment particles to prepare a pigment particle precipitate.

The prepared pigment particle precipitation liquid (pigment particle concentration about 0.5% by mass) was removed by using an ultrafilter to remove unnecessary ions and organic solvents, and concentrated to about 3 times to obtain 400 ml of pigment particle dispersion composition (pigment particle concentration about 10.0). Mass%) was obtained.

(Example 3)

In the same manner as in Example 2, using 18 g of polyacrylamide instead of 18 g of the dispersant polyvinylpyrrolidone, 400 ml of a pigment particle dispersion composition (pigment particle concentration of about 10.0% by mass) was obtained.

(Example 4)

In the same manner as in Example 2, using 18 g of polyethyleneimine instead of 18 g of the dispersant polyvinylpyrrolidone, 400 ml of a pigment particle dispersion composition (pigment particle concentration of about 10.0% by mass) was obtained.

(Comparative Example 1)

0.6 g of a pigment (pigment red 254) was dissolved in a solution in which dimethyl sulfoxide and 8 mol / l potassium hydroxide aqueous solution was mixed at 6: 1, so that the pigment concentration was 150 mmol / L, and 0.3 g of pigment dispersant A was dissolved. To prepare pigment solution A2. Apart from this, water was prepared as a poor solvent.

Here, pigment solution A2 was added to Nippon Fine Chemicals NP-KX- by 1000 ml of poor solvents which temperature-controlled at 1 degreeC, and stirred at 500 rpm by GK-0222-10 type | mold Ramond stirrer by Fuji Corporation and the chemical industry. Pigment particles were formed by injecting 200 ml at a flow rate of 50 ml / min using a 500 type large-capacity no-flow pump to prepare a pigment particle precipitate.

The prepared pigment particle precipitation liquid (pigment particle concentration about 0.05% by mass) was removed by using an ultrafilter to remove unnecessary ions and organic solvents, and further concentrated to about three times, and 400 ml of pigment particle dispersion composition (pigment particle concentration about 1.0 mass%) was obtained.

(Comparative Example 2)

Pigment solution A4 which melt | dissolved 0.6 g of pigments (pigment red 254) in the solution which mixed dimethyl sulfoxide and 8 mol / l potassium hydroxide aqueous solution at 6: 1 so that a pigment concentration might be 150 mmol / L was prepared. Separately from this, 0.3 g of the pigment dispersant A and 0.6 g of the polymer dispersant polyvinylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000) were dissolved in water to prepare a poor solvent.

Here, the pigment solution A4 is made into Nippon Fine Chemicals-made NP-KX-500 type | mold to 1000 ml of poor solvents which temperature-controlled at 1 degreeC, and stirred at 500 rpm by GK-0222-10 type | mold Ramond stirrer manufactured by Fuji Corporation and the chemical industry. Pigment particles were formed by injecting 200 ml at a flow rate of 50 ml / min using a large-capacity no-flow pump to prepare a pigment particle precipitate.

Unnecessary ions and an organic solvent were removed by using the ultrafiltration filter of the prepared pigment particle precipitation liquid (pigment particle concentration about 0.05 mass%), and 400 ml of pigment particle dispersion compositions (pigment particle concentration about 1.0 mass%) were obtained.

(Comparative Example 3)

6 g of pigments (pigment red 254) were dissolved in a solution in which dimethyl sulfoxide and 8 mol / l potassium hydroxide aqueous solution was mixed at 6: 1, so that the pigment concentration was 150 mmol / L, and the pigment dispersant A 3 g, dispersant poly 6 g of vinylpyrrolidone (K30, Wako Pure Chemical Co., Ltd. product, molecular weight 40,000) was dissolved, and the pigment solution A5 was prepared. Apart from this, water was prepared as a poor solvent.

Here, pigment solution A5 was added to Nippon Fine Chemicals Corporation NP-KX- in 1000 ml of water of the poor solvent which temperature-controlled at 30 degreeC, and stirred at 500 rpm by GK-0222-10 type | mold Ramond stirrer manufactured by Fuji Corporation and the chemical industry. 200 ml was injected at the flow rate of 50 ml / min using the 500 type large capacity | capacitance pump, and the pigment particle was formed and the pigment particle precipitation liquid was prepared.

The prepared pigment particle precipitation liquid (pigment particle concentration about 0.5% by mass) is removed by using an ultrafilter to remove unnecessary ions and organic solvents, and concentrated to about three times, and 400 ml of pigment particle dispersion composition (pigment particle concentration about 10.0). Mass%) was obtained.

The particle size ratio of the pigment particle precipitation liquid (before concentration) prepared by each Example and the comparative example, the pigment particle dispersion composition (after concentration), and the particle number ratio of 100 nm or more after concentration were made using the Nikkiso company nano truck UPA-EX150. Each was measured. The results are summarized in Table 1.

As can be seen from the results in Table 1, in Comparative Example 2, even if the polymer dispersant was contained in water as a poor solvent, the particle size fluctuations before and after concentration were not improved.

On the other hand, even when a polymer dispersing agent was contained in a pigment solution, when the pigment solution was made high (comparative example 3), the ratio of the coarse particle after concentration became large.

By separately adding the polymer dispersant solution as in the present invention (Examples 1, 2, 3, and 4), even when the pigment solution was concentrated at a high concentration, the proportion of the coarse particles was small and the effect of the present invention was realized.

(Example 5)

The particle size after preserving the pigment particle dispersion composition obtained in Example 1 at 60 ° C. for 2 weeks showed no change, and no precipitate was seen. Next, the ink for inkjet recording of the following composition was manufactured using this pigment particle dispersion composition.

12.5 g of the dispersion

Ethylene glycol 1.3g

Glycerin 1.3g

25g of water as a whole

An image was recorded on photo glossy paper EX (manufactured by Fuji Photo Film Co., Ltd.) by inkjet printer PM770C (trade name, manufactured by Seiko Epson Co., Ltd.) using the obtained ink. The obtained image was a clear red image without granularity and excellent in color development. In addition, clogging of the nozzle did not occur even after printing for one week at room temperature.

In addition, the detail of the used reagent is as follows.

According to the manufacturing method of this invention, since organic particle | grains which are fine enough and excellent in monodispersity, and its concentrated dispersion composition can be manufactured, it is high in industrial utility, and is used suitably for manufacture of the organic particle dispersion composition contained in inkjet ink etc. .

While the present invention has been described together with the embodiments thereof, we do not intend to limit our invention to any detail of the description unless specifically indicated, and are broadly interpreted without departing from the spirit and scope of the invention as set forth in the appended claims. I think it should be.

Claims (9)

At least three kinds of a solution of an organic material dissolved in a good solvent, a solvent which is compatible with the good solvent and becomes a poor solvent for the organic material, and a solution containing a polymer dispersant And mixing, and producing the said organic material as particle | grains in the liquid mixture. The manufacturing method of the organic particle | grains characterized by the above-mentioned. The method of claim 1, The said organic material is an organic pigment, The manufacturing method of the organic particle | grains characterized by the above-mentioned. The method according to claim 1 or 2, The poor solvent is an aqueous solvent, characterized in that the method for producing organic particles. The method according to any one of claims 1 to 3, The polymer dispersant is a polymer dispersant having a mass average molecular weight of 1000 or more. The method according to any one of claims 1 to 4, The organic material was produced as monodisperse nanoparticles of nanometer size in the presence of the polymer dispersant. The method according to any one of claims 1 to 5, The polymer dispersing agent is polyvinylpyrrolidone, polyacrylamide or polyethyleneimine. The organic particle dispersion liquid is manufactured by the manufacturing method in any one of Claims 1-6, and this is concentrated to predetermined concentration, The manufacturing method of the organic particle dispersion composition characterized by the above-mentioned. An inkjet recording ink, comprising an organic particle dispersion composition produced by the manufacturing method according to claim 7. The method of claim 8 The average particle diameter of the organic particle | grains contained in the said organic particle dispersion composition is 1-100 nm, The inkjet recording ink characterized by the above-mentioned.

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