KR20110063333A - Pigment fine particle dispersion, photocurable composition and color filter using the same, and pigment derivative compound for use in the same and preparation method thereof - Google Patents

Abstract

PURPOSE: A pigment fine particle dispersion is provided to ensure small particle diameter of fine particle and sharp particle size distribution peak, to improve contrast when a pixel of a color filter is formed, and to exhibit high heat resistance and light resistance. CONSTITUTION: A pigment fine particle dispersion includes pigment derivative compounds and pigment fine particles. The pigment derivative compound is obtained by reacting pigment, a compound represented by chemical formula (1) and a compound represented by chemical formula (2) in an acidic solvent. In chemical formula (1), Q is an aromatic hydrocarbon group which may have a substituent and n is an integer of 1~4. In chemical formula (2), R^1 and R^2 are respectively hydrogen atom or alkyl group.

Description

Pigment fine particle dispersion, the photocurable composition and color filter using the same, and the pigment derivative compound used for the same, and its manufacturing method TECHNICAL FIELD PREPARATION METHOD THEREOF}

The present invention relates to a pigment fine particle dispersion particularly suitable for use as a color material such as a color filter, a color filter using the same, a pigment derivative compound used in the same, and a method for producing the same.

High performance and high quality are demanded about a color filter, and improvement of the organic pigment used for the manufacture is tried. Specifically, what is excellent in storage stability in preparation of a pigment dispersion, what is excellent in the contrast of the coating film of the color filter colored pixel part using this, etc. is calculated | required. In order to meet these requirements, the research which small sized and disperse | distributes a pigment particle to the range of 10-100 nm, for example, is vigorously progressing. As a result, the nanometer size makes it possible to make effective use of the effect that is expressed for the first time and to effectively extract new characteristics that were not previously expected. In addition to the color filter applications described above, research and development are also being carried out in paints, printing inks, electrophotographic toners, inkjet inks, and the like. In particular, the above-mentioned color filters and inkjet inks are coped with for high performance using fine chemical technology, and the results are expected.

Here, when speaking about the dispersion method of an organic pigment, there exist various milling methods (breakdown method), such as a bead mill method and a salt milling method, a liquid phase method, etc. Patent Literature 1, Patent Literature 2, and the like have been disclosed in which the pigment fine particles prepared by the breakdown method are utilized for an ink or the like. Patent Literature 1 discloses a pigment derivative in which a group having a triazine moiety is introduced into a pigment molecule, and proposes to apply this to a dispersion of breakdown pigment particles to improve a decrease in viscosity and gloss of ink. Patent document 2 proposes to improve the brightness of a red ink using the pigment derivative which introduce | transduced the sulfonic acid group into the pigment molecule.

On the other hand, the liquid phase method is also suitable for obtaining fine pigment particles, and specifically, there is a reprecipitation method in which a pigment solution in which a pigment is dissolved in a good solvent (first solvent) and a poor solvent (second solvent) are mixed to precipitate nanoparticles. In recent years, it is proposed to add a predetermined polymer compound or the like as a dispersant to the dispersion liquid obtained by this reprecipitation method (see Patent Documents 3 to 6).

Japanese Patent Publication No. 2007-186681 Japanese Patent Publication No. 2000-160084 International Publication WO 2006/12116 Brochure Japanese Patent Publication No. 2004-43776 Japanese Patent Publication No. 2007-119586 Japanese Patent Publication No. 2007-23169

The present invention is particularly suitable as a color material for color filters because the particle size of the pigment fine particles is small, the particle size distribution peak is sharp, and the dispersibility is good, and when the pixels of the color filter are formed using this, the contrast can be improved. A pigment fine particle dispersion and a photocurable composition which can be said to exhibit high heat resistance and light resistance, a color filter using the same, and the pigment derivative compound used for it, and its manufacturing method are provided.

The problem has been solved by the following means.

(1) A pigment fine particle dispersion containing a pigment derivative compound and pigment fine particles, wherein the pigment derivative compound contains a pigment, a compound represented by the following general formula (1) and a compound represented by the following general formula (2) in an acidic solvent It is a compound obtained by making it react, The pigment fine particle dispersion characterized by the above-mentioned.

(In General Formula (1), Q represents an aromatic hydrocarbon group which may have a substituent. N represents an integer of 1 to 4. In General Formula (2), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group. .)

(2) The pigment fine particle dispersion according to (1), wherein the pigment derivative compound is a compound obtained by reacting a compound represented by the following General Formula (3).

(In General Formula (3), T represents a monovalent organic group. K represents an integer of 0 to 4. R ³ represents a hydrogen atom or a hydroxymethyl group.)

(3) The pigment fine particle dispersion according to (1), wherein the pigment serving as a substrate of the pigment derivative compound is a diketopyrrolopyrrole pigment compound.

(4) The pigment fine particles according to (1), wherein the pigment fine particles are produced by mixing a dissolving solution in which a pigment is dissolved in a good solvent and a medium compatible with the good solvent to form a poor solvent for the pigment. Dispersion.

(5) The pigment fine particle dispersion as described in (1) whose pigment which comprises the said pigment fine particle is at least 1 sort (s) chosen from the group which consists of a diketopyrrolopyrrole pigment, a quinacridone pigment, an anthraquinone pigment, and an azo pigment. sieve.

(6) The pigment fine particle dispersion according to (1), further comprising a dispersant having a polycaprolactone structure.

(7) The polymer compound according to (1), further comprising at least one repeating unit selected from repeating units represented by any one of the following general formulas (I) and (II). Pigment particulate dispersion.

(In General Formula (I) and General Formula (II), R ²¹ to R ²⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ²¹ and X ²² each independently represent —CO—, —C (═O). O-, -CONH-, -OC (=)-or a phenylene group, L ²¹ and L ²² each independently represent a single bond or a divalent organic linking group, and A ²¹ and A ²² each independently represent a monovalent organic group. Group, ma and na each independently represent an integer of 2 to 8, and p and q each independently represent an integer of 1 to 100.)

(8) The pigment fine particle dispersion according to (1), which is a color material for color filters.

(9) The photocurable composition containing the pigment fine particle dispersion in any one of (1)-(8), a polymeric compound, and a photoinitiator.

(10) A color filter comprising a pixel formed by curing the photocurable composition according to (9).

(11) A pigment derivative compound comprising the residues of the respective substrates obtained by reacting a pigment, a compound represented by the following general formula (1), and a compound represented by the following general formula (2) in an acidic solvent.

(In General Formula (1), Q represents an aromatic hydrocarbon group which may have a substituent. N represents an integer of 1 to 4. In General Formula (2), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group. .)

(12) The pigment derivative compound as described in (11) which further has the residue obtained by making the compound represented by following General formula (3) react.

(In General Formula (3), T represents a monovalent organic group. K represents an integer of 0 to 4. R ³ represents a hydrogen atom or a hydroxymethyl group.)

(13) A method for producing the pigment derivative compound according to (11), wherein the pigment and the compound represented by the general formula (1) and the compound represented by the general formula (2) are reacted in an acidic solvent. A method for producing a pigment derivative compound.

Effect of the Invention

Since the pigment fine particle dispersion of this invention and the photocurable composition using the same have a small particle diameter, the particle size distribution peak is sharp, and it shows favorable dispersibility (the property which is hard to secondary aggregate), It is especially suitable as a color material, and when the pixel of a color filter is formed using this, the contrast is improved, and the outstanding effect of showing high heat resistance and light resistance is shown.

Moreover, the pigment derivative compound of this invention is useful as a dispersion support agent in the crystal growth inhibitor or pigment dispersion at the time of pigment fine particle formation.

The pigment fine particle dispersion of this invention is characterized by containing the fine particle of a pigment, and the pigment derivative compound produced by the specific manufacturing method.

[Pigment derivative compound]

(A) pigment

The pigment to react in an acidic solvent is an organic pigment, specifically, a perylene pigment, a perinone pigment, a quinacridone pigment, a quinacridonequinone pigment, an anthraquinone pigment, an anthrone pigment, a benzimazolone pigment, a disazo pigment , Azo pigment, indanthrone pigment, phthalocyanine pigment, triarylcarbonium pigment, dioxazine pigment, aminoanthraquinone pigment, diketopyrrolopyrrole pigment, indigo pigment, thioindigo pigment, isoindolin pigment, isoindolinone pigment, Pyrantrone pigment or isobiolanthrone pigment. Among these, Preferably it is a quinacridone pigment, an anthraquinone pigment, a diketopyrrolopyrrole pigment, a benzimidazolone pigment, a phthalocyanine pigment, an azo pigment, a dioxazine pigment, an isoindolin pigment, More preferably, a quinacridone pigment , Anthraquinone pigments and diketopyrrolopyrrole pigments, and particularly preferably diketopyrrolopyrrole pigments. In addition, the pigment used here may be called "a pigment substrate", distinguishing it from the pigment which comprises the pigment fine particle mentioned later.

(B) the compound represented by General formula (1)

In the formula, Q represents an aromatic hydrocarbon group which may have a substituent. At this time, examples of the optional substituent include halogen (-F, -Br, -Cl, -I), an alkyl group, a hydroxyl group, an alkoxy group, a nitro group, and the like. Among these, Preferably, they are an alkyl group, a hydroxyl group, and unsubstituted (hydrogen). The alkyl group represents a linear or branched hydrocarbon group, and preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. Specific examples of the aromatic hydrocarbon group include benzene, naphthalene, anthracene, pyrene, azulene, chrysene, kekrene and coronene. Among these, Preferably it is benzene, naphthalene, anthracene, More preferably, it is benzene, naphthalene, Especially preferably, it is benzene.

n represents the integer in any one of 1-4, Preferably it is an integer in any one of 1-2, Most preferably, it is 1.

(C) the compound represented by General formula (2)

In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group. R ¹ and R ² may be the same or different. The alkyl group represents a linear or branched hydrocarbon group, and preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. Among these, R ¹ and R ² are more preferably a hydrogen atom and a methyl group, and particularly preferably both R ¹ and R ² are hydrogen atoms.

(D) the compound represented by General formula (3)

Examples of the monovalent organic group represented by T include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, a cyano group, a nitro group, an amide group, a sulfonamide group, an alkylthio group, an arylthio group, and an alkyldithio group. , Aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group , N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group , Alkyl sulfoxy group, aryl sulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, urethane group, ureido group, N'-alkylureido group, N ', N'-dialkyl urea Pottery, N'-aryl ureido group, N ', N'- diaryl ureido group, N'-alkyl-N'- aryl ureido group, N-alkyl ureido group, N-aryl ureido , N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-aryl Ureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N ', N'- diaryl-N-alkylureido group, N', N'- diaryl-N -Aryl ureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-aryl ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N- Alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, Carboxyl group and its conjugated base group (hereinafter referred to as carboxylate), ester group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcar Bamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-a Arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-SO ₃ H) and its conjugated base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryl jade Sysulfonyl group, sulfinamoyl group, N-alkyl sulfinamoyl group, N, N-dialkyl sulfinamoyl group, N-aryl sulfinamoyl group, N, N- diaryl sulfinamoyl group, N-alkyl-N-arylsulphi Namoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group , N-acylsulfamoyl group and its conjugated base group, N-alkylsulfonylsulfamoyl group (-SO ₂ NHSO ₂ (alkyl)) and its conjugated base group, N-arylsulfonylsulfamoyl group (-SO ₂ NHSO ₂ ( Allyl)) and its conjugated base group, N-alkylsulfonylcarbamoyl group (-CONHSO ₂ (alkyl)) and its conjugated base group, N-arylsulfonylcarbamoyl group (-CONHSO ₂ (allyl)) and its conjugate salt unit, an alkoxysilyl group (-Si (O-alkyl) _3), aryl Group-Sicily (-Si (O-allyl) _3), hydroxy silyl group (-Si (OH) ₃₎ and its conjugated salts device, a phosphono group (-PO ₃ H ₂₎ and its conjugated salts device (hereinafter referred to as phosphonate Dialkylphosphono group (-PO ₃ (alkyl) ₂ ), diaryl phosphono group (-PO ₃ (aryl) ₂ ), alkylaryl phosphono group (-PO ₃ (alkyl) (aryl) )), Monoalkylphosphono group (-PO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (-PO ₃ H (aryl)) and its A conjugated base group (hereinafter referred to as an arylphosphonate group), a phosphonooxy group (-OPO ₃ H ₂ ), and a conjugated base group (hereinafter referred to as a phosphonateoxy group), a dialkylphosphonooxy group ( -OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (-OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (-OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group ( -OPO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonateoxy group), monoarylfo Phosphonooxy groups (-OPO ₃ H (aryl)) and conjugated base groups thereof (hereinafter referred to as arylphosphonateoxy groups) are listed. As a particularly preferable substituent, halogen, alkyl, alkoxy, amino group, carboxyl group, cyano group, nitro group, amide group, sulfonamide group, ester group, urethane group, ureido group, sulfo group, phosphono group are mentioned. From the viewpoint of carbon number, the substituent T is preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.

k represents the integer of 0-4, Preferably it is an integer of 0-2, More preferably, it is 0 or 1.

R ³ represents a hydrogen atom or a hydroxymethyl group.

(Acid solvent)

Acidic solvents used in the production of the pigment derivatives include inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid and trifluoromethanesulfonic acid. Among these, sulfuric acid, hydrochloric acid, phosphoric acid, trifluoroacetic acid, polyphosphoric acid, methanesulfonic acid and trifluoromethanesulfonic acid are preferable, and sulfuric acid, methanesulfonic acid, and trifluoromethanesulfonic acid are more preferable from the viewpoint of pigment solubility. Sulfuric acid is particularly preferable because a pigment derivative can be obtained in good yield by reaction with sulfuric acid.

(Reaction conditions)

Preferred reaction conditions of each said substrate for synthesizing the pigment derivative compound of the present invention are shown here. First, the pigment substrate (A) is added to an acidic solvent such as sulfuric acid. At this time, even if the pigment substrate (A) is melt | dissolved completely, it is not necessary to melt | dissolve. At this time, it is preferable that reaction temperature is 0 degreeC-100 degreeC, It is more preferable that it is 0 degreeC-60, It is especially preferable that it is 0 degreeC-40 degreeC. Then, the compound represented by (B) General formula (1) and the compound represented by (C) General formula (2) are added. At this time, you may add the compound represented by (D) General formula (3) further. In addition, the order of adding a substrate compound (B), (C), and (D) may be simultaneous or any order may be sufficient. Moreover, you may add whole quantity at once or may add separately. After completion of the addition, the pigment derivative is synthesized by stirring at the reaction temperature for 30 minutes to 10 hours.

Although the quantity in the system of a reaction substrate is not specifically limited, Considering a heterogeneous condition, it is enumerated that a pigment substrate (A) is 1-50 mass% in reaction conditions. About compound (B) represented by General formula (1), it is enumerated that it is 0.1-10 equivalent with respect to 1 equivalent of pigment substrate (A). About compound (C) represented by General formula (2), it is enumerated that it is 0.1-30 equivalent with respect to 1 equivalent of pigment substrate (A). About compound (D) represented by General formula (3), it is enumerated that it is 0.1-10 equivalent with respect to 1 equivalent of pigment substrate (A).

Here, although the example of the substrate and reaction solvent of the said synthetic reaction is listed, this invention is not limited to this and is not interpreted.

(A) pigment (B) general formula (1) (C) general formula (2) (D) general formula (3) Acid solvent
Example 1
PR-254 Paratoluenesulfonic acid
Monohydrate
Paraformaldehyde
none
Sulfuric acid Example 2 PR-254 Benzenesulfonic Acid Monohydrate Paraformaldehyde none Sulfuric acid Example 3 PR-254 Benzenesulfonic Acid Paraformaldehyde none Sulfuric acid
Example 4
PR-254 Paratoluenesulfonic acid
Monohydrate
Paraformaldehyde
Phthalimide
Sulfuric acid Example 5 PR-254 Benzenesulfonic Acid Monohydrate Paraformaldehyde Phthalimide Sulfuric acid Example 6 PR-254 Benzenesulfonic Acid Paraformaldehyde Phthalimide Sulfuric acid
Example 7
PR-254 Paratoluenesulfonic acid
Monohydrate
Paraformaldehyde 4-methyl
Phthalimide
Sulfuric acid
Example 8
PR-254
Benzenesulfonic Acid Monohydrate
Paraformaldehyde 4-methyl
Phthalimide
Sulfuric acid
Example 9
PR-254 Paratoluenesulfonic acid
Monohydrate
Paraformaldehyde 4-carboxy
Phthalimide
Sulfuric acid
Example 10
PR-122 Paratoluenesulfonic acid
Monohydrate
Paraformaldehyde
Phthalimide
Sulfuric acid
Example 11
PR-177 Paratoluenesulfonic acid
Monohydrate
Paraformaldehyde
Phthalimide
Sulfuric acid

The pigment derivative compound of this invention which passed through the said synthesis reaction consists of the residue of each said substrate. That is, the said pigment derivative compound is a residue of the pigment substrate (A), the residue of the compound (B) represented by the said General formula (1), and the residue of the compound (C) represented by the said General formula (2), as needed. It has a molecular structure which the residue of the compound (D) represented by the said General formula (3) couple | bonded.

As an example of the compound obtained by the said reaction, the thing of the structure in which the pigment (Pig) like following A-1 and the aromatic hydrocarbon group (Q) represented by General formula (1) are couple | bonded through the methylene group.

n is an integer of 0-4, n1, m1 represents the integer of 1-4 each independently.

In addition, when using the pigment derivative compound represented by the said General formula (3) as a raw material, if it is described corresponding to said Formula A-1, the thing of the structure of following formula A-2 is enumerated. N, n1, m1 in a formula are the same as that of Formula A-1, and l1 represents the integer of 1-4.

In the pigment fine particle dispersion of this invention, content of the pigment derivative produced by the said manufacturing method is not specifically limited, It is preferable that it is 1-100 mass parts with respect to 100 mass parts of pigments, and it is more preferable that it is 10-50 mass parts. Do. By setting it as the said lower limit or more, the pigment microparticles | fine-particles refine | miniaturized and the surface area increased can be disperse | distributed stably, and below the said upper limit can prevent the fall of the color value by the addition of a pigment derivative.

The pigment derivative phase produced by the above production method may be added at any stage in the dispersion of the pigment fine particles, but may be added to a good solvent or a poor solvent in the later reprecipitation method, or after precipitation of the pigment fine particles or the You may add after concentration or redispersion later. In the present invention, in consideration of using as a non-aqueous dispersion for color filters, it is preferable to add the dispersion as a dispersion aid together with a dispersant suitable as a photocurable composition for color filters when the dispersion is concentrated or powdered and redispersed. .

According to one embodiment of the present invention, since the pigment derivative compound has a pigment mother-nucleus structure, the mother-nucleus is strongly adsorbed to the pigment molecule by strong interaction. At this time, since an acidic group (sulfonic acid group) is introduce | transduced through a specific coupling group, it is thought to suppress aggregation of a pigment particle. As a result, although the detailed reason is not clear, when the color filter is used using the dispersion, for example, very high contrast and high light resistance can be made compatible. In addition, although it is not clear about the mechanism of action, the surface state peculiar to the build-up fine particles obtained by the reprecipitation method which cannot be obtained by crushing acts particularly preferably with the pigment derivative compound, and the above effects are combined. It is displayed at a higher level.

In addition, in description of group in this specification, the description which is not describing substitution and unsubstitution means including what has a substituent with the thing which does not have a substituent. For example, the expression "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

[Organic Pigment]

The pigment fine particle dispersion of the present invention contains fine particles of a pigment (hereinafter may be referred to as "pigment E") together with the pigment derivative compound.

Pigment E is an organic pigment and is not limited in color, for example, perylene pigment, perinone pigment, quinacridone pigment, quinacridonequinone pigment, anthraquinone pigment, anthrone molecule, benzimidazolone Pigments, disazo condensation pigments, disazo pigments, azo pigments, indanthrone pigments, phthalocyanine pigments, triarylcarbonium pigments, dioxazine pigments, aminoanthraquinone pigments, diketopyrrolopyrrole pigments, thioindigo pigments, isoindolin pigments , Isoindolinone pigments, pyrantrone pigments or isobiol anthrone pigments or mixtures thereof. Especially, it is a quinacridone pigment, an anthraquinone pigment, a benzimidazolone pigment, a phthalocyanine pigment, an azo pigment, a dioxazine pigment, an isoindolin pigment, More preferably, a quinacridone pigment, an anthraquinone pigment, and diketopyrrolo. It is a pyrrole pigment and an azo pigment, Especially preferably, it is a diketopyrrolopyrrole pigment.

In this invention, you may use combining the solid solution of said organic pigment or organic pigment. Moreover, it is good also as a composite material combined with other compounds.

In addition, the pigment E may be the same kind as the pigment substrate (A) used when producing a pigment derivative, or may be another species, and it is preferable that it is structurally similar among these. Examples of structurally similar pigment compounds include those having the same structure as chromophores. Even when the pigment E and the pigment substrate (A) are different, the pigment fine particle dispersion of the present invention can achieve desired color purity and high contrast as a color material for a color filter. It is preferable because it is easy to adjust.

In the pigment fine particle dispersion of the present invention, the content of the pigment fine particles is not particularly limited, but when considering the color material for the color filter, it is preferable that the concentration contained in the pigment fine particle dispersion is 1 to 40% by mass. It is more preferable that it is 5-20 mass%.

[Pulverization method]

The pigment fine particles used in the present invention may be pigment fine particles prepared by a breakdown method such as a grinding method. In this case, various solvents, resins, varnishes, and the like may be mixed and dispersed in a horizontal sand mill, a vertical sand mill, a round bead mill, an atomizer, or the like as necessary. Although the specific polymeric compound (specific polymer) mentioned later and other pigment dispersants may be disperse | distributed after mixing all components, initially, only a pigment or a pigment and a pigment dispersant, such as a pigment and a specific polymeric compound (specific polymer), are disperse | distributed, Subsequently, you may add another component and disperse again.

In addition, before dispersing with a horizontal sand mill, a vertical sand mill, an annular bead mill, an atomizer, and the like, a solid dispersion or a basic group to a pigment by pre-dispersion using a meat mixer such as a kneader or three roll mills, two roll mills, or the like You may perform the process of the synergy and / or dispersing agent which have. Moreover, dispersers and mixers, such as a high speed mixer, a homo mixer, a ball mill, a roll mill, a mill mill, an ultrasonic disperser, can be used.

[Reprecipitation method]

In the pigment fine particle dispersion of this invention, the organic pigment particle contained in it is compatible with the solution of the organic pigment which melt | dissolved the organic material in the good solvent (Hereinafter, this may be called a 1st medium), and the said good solvent. It is preferable to produce | generate by mixing the medium which has a property and becomes a poor solvent (Hereinafter, this may be called a 2nd medium) with respect to an organic pigment. Hereinafter, this method may be called "reprecipitation method", and the dispersion liquid containing the organic pigment particle obtained at this time may be called "pigment reprecipitation liquid." Moreover, what dissolves the said pigment derivative compound and dispersing agent together in the solution of the said organic pigment, and performs reprecipitation may be distinguished among reprecipitation methods, and it may be especially called "coprecipitation method."

1. Poor solvent (second medium)

First, the poor solvent of an organic pigment is demonstrated. The poor solvent is not particularly limited as long as it is compatible with the good solvent for dissolving the organic pigment or mixed uniformly. It is preferable that the solubility of an organic pigment is 0.02 mass% or less, and, as a poor solvent, it is more preferable that it is 0.01 mass% or less. There is no particular lower limit to the solubility of the organic pigment in the poor solvent, but considering the organic pigments that are usually used, 0.000001 mass% or more is practical. This solubility may be solubility in the presence of an acid or an alkali, and particularly in the case of pigment species whose solubility is significantly changed by the hydrogen ion concentration (pH), it is preferable to mix an acid or an alkali with a poor solvent as appropriate.

It is preferable that it is 30 mass% or more, and, as for the melt | dissolution amount with respect to the poor solvent of a good solvent, it is more preferable that it is 50 mass% or more. Although there is no upper limit in particular in the amount of melt | dissolution with respect to the poor solvent of a good solvent, it is practical to mix in arbitrary ratios.

As a poor solvent, an aqueous solvent (for example, water or hydrochloric acid, sodium hydroxide aqueous solution), an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, an aliphatic compound solvent, a nitrile compound solvent, a halogen compound Solvents, ester compound solvents, ionic liquids, mixed solvents thereof, and the like, and an aqueous solvent, an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an ester compound solvent or a mixture thereof is preferable, and an aqueous solvent, an alcohol compound More preferred are solvents or ester compound solvents.

Examples of the alcohol compound solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol and the like. As a ketone compound solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are mentioned, for example. As an ether compound solvent, dimethyl ether, diethyl ether, tetrahydrofuran, etc. are mentioned, for example. As an aromatic compound solvent, benzene, toluene, etc. are mentioned, for example. Examples of the aliphatic compound solvents include hexane and the like. As a nitrile compound solvent, acetonitrile etc. are mentioned, for example. Dichloromethane, trichloroethylene, etc. are mentioned as a halogen compound solvent, for example. Examples of the ester compound solvent include ethyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate (MMPGAc), and the like. Examples of the ionic liquid include salts of 1-butyl-3-methylimidazolium and PF ₆ ^{− and} the like.

The poor solvent may be used by mixing a plurality of solvents, and depending on the system, it is also possible to mix and use a good solvent. However, in this case, it is necessary to mix in the range which does not prevent precipitation, refinement | miniaturization, and crystallization of a pigment particle.

2. Good solvent (first medium)

Next, the good solvent which melt | dissolves an organic pigment is demonstrated. A good solvent can melt | dissolve the pigment to be used, and if it is a thing compatible with the said poor solvent or mixed uniformly, it will not specifically limit. It is preferable that it is 0.2 mass% or more, and, as for the solubility to the good solvent of an organic pigment, it is more preferable that it is 0.5 mass% or more. Although there is no upper limit in particular in solubility, when it considers the organic pigment used normally, it is practically 50 mass% or less. This solubility may be solubility when melt | dissolved in presence of an acid or an alkali. The preferable range of solubility or compatibility of the poor solvent and the good solvent is as described above.

As a good solvent, for example, an aqueous solvent (for example, water or hydrochloric acid, an aqueous sodium hydroxide solution), an alcohol compound solvent, an amide compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, an aliphatic compound solvent , Nitrile compound solvents, sulfoxide compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, mixed solvents thereof, and the like, and aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, sulfoxide compound solvents, and the like. , Ester compound solvents, amide compound solvents or mixtures thereof are preferred, and aqueous solvents, alcohol compound solvents, ester compound solvents, sulfoxide compound solvents or amide compound solvents are preferred, and aqueous solvents, sulfoxide compound solvents or amide compound solvents. More preferably, the sulfoxide compound solvent or Especially preferred is an amide compound solvent.

Examples of the sulfoxide compound solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like. As the amide compound solvent, for example, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, 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 pigment solution which melt | dissolved the organic pigment in the good solvent, the saturated concentration with respect to the good solvent of the organic pigment in the conditions at the time of melt | dissolution, or about 1/100 of this range is preferable. There is no restriction | limiting in particular in the preparation conditions of an organic pigment solution, The 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 the present invention, the organic pigment can also be dissolved in a good solvent in an acidic or alkaline manner. In general, in the case of a pigment having an alkaline dissociable group in a molecule, acidity is used when the alkalinity does not have a group dissociated in alkali and has many nitrogen atoms in the molecule to which protons are easily added. For example, quinacridone, diketopyrrolopyrrole, and disazo condensation compound pigments are alkaline, and phthalocyanine compound pigments are dissolved in acid.

The base used for alkali dissolution is an inorganic base such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide or barium hydroxide, or an organic base such as trialkylamine, diazabicycloundecene (DBU), metal alkoxide, And preferably an organic base. The amount of the base to be used is an amount capable of dissolving the pigment uniformly and is not particularly limited. In the case of the inorganic base, the amount is preferably 1.0 to 30 molar equivalents, more preferably 1.0 to 25 molar equivalents, more preferably relative to the organic pigment. 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 pigment, More preferably, it is 1.0-50 molar equivalent, More preferably, it is 1.0-20 molar equivalent.

The acid used when dissolved in acid 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 acid to be used is an amount capable of uniformly dissolving the organic pigment, and is not particularly limited, but is often used in an excessive amount compared to the base. Regardless of the case of the inorganic acid and the organic acid, the amount is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, and more preferably 30 to 200 molar equivalents based on the organic pigment.

When alkali or acid is mixed with an organic solvent and used as a good solvent for organic pigments, a solvent having high solubility in alkali or acid such as some water or lower alcohol may be added to the organic solvent in order to completely dissolve the alkali or acid. Can be. 50 mass% or less is preferable with respect to organic pigment 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.

3. Mixing condition

There is no restriction | limiting in particular in the usage conditions of the poor solvent at the time of organic particle preparation, 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.

As for the mixing ratio (good solvent / poor solvent ratio in reprecipitation liquid) of a pigment solution and a poor solvent, 1 / 50-1 / 1 is preferable by volume ratio, 1 / 40-1 / 1 is more preferable, 1 / 10-1 // 1 is particularly preferred. This may be the same as or different from the volume flow rate ratio of the pigment solution and the poor solvent in the flow path of the flow reactor. For example, when making a mixing ratio 1/2, the following method can be taken as a specific example.

(i) The volume flow rate ratio of the good solvent and the poor solvent is 1/2.

(ii) The volume flow rate ratio of the pigment solution and the solvent A is made 1/5 using the solvent A which mixed the good solvent with the poor solvent in the ratio of (volume ratio of good solvent / poor solvent) = (1/4) previously. . In this case, the amount of the good solvent in the pigment solution plus the good solvent in the solvent A is 1 + 1 = 2. On the other hand, since the amount of the poor solvent in the solvent A is 4, the final mixing ratio of the good solvent and the poor solvent is 1/2. do.

The pigment concentration in the pigment reprecipitation liquid is not particularly limited as long as it can produce pigment particles, but the pigment 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 reprecipitation liquid. Preferably it is the range of 40-25000 mg.

In the present invention, it is preferable to quickly mix the pigment solution and the poor solvent, and in this part, a means for promoting the mixing is particularly preferable. In one of the methods, for example, a method of promoting mixing by turbulent mixing field, for example, flowing a high-speed fluid in a counter-flow state to collide in a narrow space is considered. However, the mixing mode is not limited to turbulent control. For example, as shown in Japanese Patent Laid-Open No. 2006-104448, the mixing is performed by molecular diffusion by bringing fluids into laminar flow at the intersections of the Y-shaped flow paths. The method of planning is also considered.

In the present invention, the determination of whether the fluid state is turbulent or laminar is performed with the tube Reynolds number. That is, the pipe representative length (referred to as the representative diameter in the present invention) is D [m], the line flow velocity of the liquid to be distributed is u [m / s] (defined later), and the density and viscosity of the liquid are respectively ρ [kg. / M 3], η [Pa · s], the tube Reynolds number Re [-]

Re = Duρ / η

Is defined by In the present invention, a state in which Re is 1000 or more is turbulent, and a state in which 100 or more is less than 1000 is a transition region, and a state in which the state is less than 100 is laminar flow.

The representative length D of the above formula is the physical property of the tube as it most affects the flow in the tube. In the case of the cylindrical tube, the diameter thereof is defined by the following formula.

D = 4A / p

Here, A [m 2] is the cross-sectional area of the flow path, and p [m] is the length (the needle length) of the portion where the fluid is in contact with the wall in the flow path.

The line flow rate u described above using this D is defined as follows.

u = Q / {(D / 2) 2 × π}

Here, Q is the volume flow rate [m 3] of the fluid flowing through the flow path defining the line flow rate.

The representative diameter in the case of changing the diameter or the cross-sectional shape in the middle of the flow path is calculated according to the changed cross-sectional shape, and the line flow velocity and the Reynolds number may be determined according to the representative diameter.

In addition, although the flow state of a mixing field is important in this invention, since it is difficult to measure the state of a mixing field appropriately, when the following two conditions are satisfied, it is estimated that the state of a mixing field is turbulent dominance.

(i) The flow state in one flow path connecting at least the mixing field from the tube Reynolds number Re immediately before mixing of each of the fluids to be mixed is considered turbulent.

(ii) From the tube Reynolds number Re immediately after mixing of the fluid after mixing, the flow state immediately after mixing is considered turbulent.

In the said particle formation process, it is preferable to adjust the representative diameter, flow volume, etc. of a reactor so that the average particle diameter of the precipitated pigment particle may become a desired range. In the reactor used in this embodiment, the flow volume of each flow path can be made relatively large, and it is thought that the mixed state of the mixing field produced at this time is suitable for pigment particle formation. It is preferable that the line flow velocity of the pigment solution and the poor solvent in each raw material supply flow path of a reactor is 1-30 m / s.

[Dispersant used for reprecipitation method]

In this invention, when dissolving a pigment in a good solvent, you may melt | dissolve a pigment dispersant and a pigment derivative together. In the organic solvent, a polymer dispersant is preferably used as the dispersant from the viewpoint of securing dispersibility by the repulsive action using the entropy repulsion of the molecular chain. The use of the pigment derivative can also modify the surface of the particles, and in particular, it is possible to improve the interaction force with other dispersants or to control the solubility of the particles, the crystalline form, and the like.

As a dispersant which can be used, for example, a low molecular or polymer dispersant of anionic, cationic, zwitterionic, nonionic or pigment derivative can be used. Further, the molecular weight of the polymer dispersant can be used without limitation as long as it can be dissolved in a solution uniformly, but preferably has a molecular weight of 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, even more preferably 10,000 to 500,000, 10,000 to 100,000 This is particularly preferred. Examples of the polymer dispersant include those exemplified in the dispersants A and B described later.

As anionic dispersants (anionic surfactants), N-acyl-N-alkyltaurine salts, fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinate salts, alkyl phosphate ester salts, naphthalene Sulfonic acid formalin condensates, polyoxyethylene alkyl sulfate ester salts and the like. These anionic dispersants can be used individually or in combination of 2 or more types.

Cationic dispersants (cationic surfactants) include quaternary ammonium salts, alkoxylated polyamines, aliphatic aminepolyglycol ethers, aliphatic amines, diamines and polyamines derived from aliphatic amines and aliphatic alcohols, imidazolines derived from fatty acids and their cations Salts of sexual substances are included. These cationic dispersants can be used individually or in combination of 2 or more types.

The zwitterionic dispersant is a dispersant having an anionic group portion of the anionic dispersant in the molecule and a cationic group portion of the cationic dispersant in the molecule together. As the nonionic dispersant (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 Esters and the like. These nonionic dispersants can be used individually or in combination of 2 or more types.

The pigment derivative-type dispersant is defined as a pigment derivative-type dispersant derived from an organic pigment as a parent material and produced by chemical modification of its friend, or a pigment derivative-type dispersant obtained by the pigmentation reaction of a chemically modified pigment precursor. For example, sugar-containing pigment derivative type dispersant, piperidyl-containing pigment derivative type dispersant, naphthalene or perylene derived pigment derivative type dispersant, pigment derivative type dispersant having a functional group linked to the pigment friend via methylene group, chemically modified with polymer Pigment derivative-like dispersants having a sulfide acid group, pigment derivative-type dispersants having a sulfonamide group, pigment derivative-type dispersants having an ether group, or pigment derivative-type dispersants having a carboxylic acid group, a carboxylic acid ester group or a carboxamide group, etc. There is this.

In this invention, it is also preferable to use the compound represented by following General formula (1).

In General Formula (1), X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group. R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. Provided that at least one of R ¹ and R ² represents a substituted or unsubstituted alkyl group.

In X ¹ and X ² , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable.

In X ¹ and X ² , the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and may be any of linear, branched and cyclic. As a specific group, a methyl group, a butyl group, t-butyl group is mentioned, for example, and a methyl group is preferable.

When an alkyl group has a substituent, a hydroxyl group, an alkoxy, alkylcarbonyl, an alkylcarbonyloxy, and an aromatic group are mentioned as a substituent.

In X ¹ and X ² , examples of the aromatic group include a phenyl group, a naphthyl group and a biphenyl group, and a phenyl group is preferable.

When an aromatic group has a substituent, a hydroxyl group, an alkoxy, alkylcarbonyl, alkylcarbonyloxy, and an aromatic group are mentioned as a substituent.

X ¹ and X ² are preferably a hydrogen atom, a chlorine atom, a methyl group, a t-butyl group or a phenyl group, and more preferably a hydrogen atom or a chlorine atom. Although X <^1> and X <^2> may be same or different, it is preferable that it is the same group.

In R ¹ and R ² , the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and may be any of linear, branched and cyclic. Specific examples of the group include methylene, ethylene, propylene, butylene, pentene, hexene, isopropylene and isobutylene, and methylene, ethylene, propylene and pentene are preferable.

When the alkyl group has a substituent, the substituent includes a halogen atom, an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, and an aryl Oxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including an alino group), acylamino group, aminocarbonylamino group, Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulphi Neyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, po Pinyloxy group, phosphinylamino group, silyl group are mentioned, Preferably a halogen atom, an aryl group, heterocyclic group, cyano group, carboxyl group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyl jade Period, aryloxycarbonyloxy, amino group (including an alinino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, alkylthio group , Arylthio group, heterocyclic thi group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group or these Is a combination.

It is preferable that R <^1> and R <^2> are the following structures.

Q ₁ is alkyl, aromatic (including aryl). Q ₂ is cyclic aliphatic, aromatic (including aryl). Q ₃ is alkyl, aromatic (including aryl), and Q ₄ is aromatic (including aryl). Alkyl and aromatic are the same as those mentioned above. Specific examples of R ¹ and R ² are listed below.

Although the specific example of a compound represented by General formula (1) is listed below, this invention is limited to this and is not interpreted.

Although content of the compound represented by the said General formula (1) in the pigment fine particle dispersion of this invention is not specifically limited, It is preferable that it is 0.1-100 mass parts with respect to 100 mass parts of pigments, and it is more preferable that it is 1-50 mass parts desirable. By setting it as the said lower limit or more, crystal growth of a pigment molecule can be suppressed effectively, and by using below the said upper limit, the color taste of an effective pigment | dye pigment can be maintained.

In addition, in description of group in this specification, the description which is not describing substitution and unsubstitution means including what has a substituent with the thing which does not have a substituent. For example, the expression "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

Pigment Fine Particles

The particle size of the fine particles can be quantified by a measurement method to express the average size of the population. However, the particle diameter of the fine particles is well used, and a mode diameter representing the maximum value of the distribution, a median diameter corresponding to the median of the integral distribution curve, and various average diameters ( Horizontal ball, length average, area average, mass average, volume average, etc.), and in the present invention, the average particle diameter refers to the number average diameter unless otherwise specified. 100 nm or less is preferable, as for the average particle diameter of the microparticles | fine-particles (primary particle) in the dispersion of this invention, 75 nm or less is more preferable, It is especially preferable that they are 5 nm or more and 50 nm or less. It is preferable that the microparticles | fine-particles in the dispersion of this invention are a monocrystal, polycrystal, and an aggregate of the size.

As an indicator of the uniformity (monodispersibility) of the particles, in the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) and the number average particle diameter (Mn) is used unless otherwise specified. Monodispersibility of the organic nanoparticles (primary particles) of the present invention (in the present invention, monodispersity refers to the degree of coincidence of particle diameter), that is, Mv / Mn is preferably 1.0 to 2.0, and 1.0 to 1.8. It is more preferable that it is, and it is especially preferable that it is 1.0-1.5.

As a measuring method of the particle diameter of organic particle | grains, a microscopic method, a mass method, the light scattering method, the light blocking method, an electrical resistance method, an acoustic method, the dynamic light scattering method are mentioned, A microscope method and the dynamic light scattering method are especially preferable. As a microscope used for a microscopic method, a scanning electron microscope, a transmission electron microscope, etc. are mentioned, for example. As a particle measuring device by a dynamic light scattering method, for example, NIKKISO CO., LTD. Nanotrac UPA-EX150, OHTSUKA ELECTRONICS CO., LTD. The dynamic light scattering photometer DLS-7000 series (all are brand names) etc. which are products are mentioned. In this invention, the value regarding a particle diameter means what was measured by the method employ | adopted in the Example unless there is particular notice.

It is preferable that the crystallinity degree of the microparticles | fine-particles in a dispersion medium of the microparticles | fine-particles in this invention is 65% or more, but it is preferable that this crystallinity is 80 to 100%, and it is more preferable that it is 90 to 100%. Although the crystallite diameter of microparticles | fine-particles in the dispersion liquid of this invention is not specifically limited, It is preferable that it is 20-500 angstroms, and it is more preferable that it is 20-200 angstroms. In the present invention, the crystallinity and the crystallite diameter refer to values measured as follows unless otherwise specified.

(Evaluation of Crystallinity)

As a representative index of the degree of crystallinity, the method for obtaining the degree of crystallinity, the peak intensity I _α of 28 ± 0.5 °, which is the characteristic Bragg angle (2θ) of the _α- type crystals, and 27 °, which is the characteristic Bragg angle (2θ) of the I _β- type crystals The peak intensity I _β is calculated by the following equation.

(α degree of crystallization) = (I _α ) / (I _α + I _β )

the α-form crystal characteristic of the Bragg angle (2θ) of 28 ± 0.5 ° of the peak intensity I _α of the 27 ° characteristic of the Bragg angle (2θ) of the peak intensity I I _β-form crystal _β is determined as follows. The background is removed from the diffraction pattern obtained by the X-ray diffraction measurement as follows. A straight line in contact with the bottom 23 ° vicinity of the low angle side of the Bragg angle of the α-type crystal and near 30 ° below the high angle side was drawn, and this straight line was removed as the background. The peak intensities I _α and I _β are obtained from the rotation pattern from which the background is removed, and α crystallinity is calculated by the above formula.

(Measurement of crystalline diameter)

X-ray diffraction analysis using Cu-K alpha 1 ray is performed. Then, the full width at half maximum of the peak showing the maximum intensity in the range of 2θ = 4 deg to 70 deg or the peak showing the sufficiently large intensity separable from the adjacent peak is measured, and the crystallite diameter is calculated by the following Sherrer equation:

D = K × λ / (β × cosθ)... Scherrer's Expression

[D: crystallite diameter (Å, size of crystallite), λ: measured X-ray wavelength (Å), β: width of diffraction line (in radians) by the size of crystal, θ: Bragg angle of radiant line (in radians), K: integer (different from integers of β and D)]

In general, it is known that K = 0.9 when the full width at half maximum β1 / 2 is used for β. In addition, since the wavelength of Cu-K (alpha) 1 line is 1.54050 Hz, the crystallite diameter D in this invention is computed based on following Formula:

D = 0.9 × 1.54050 / (β1 / 2 × cosθ)

Here, when the peak of the spectrum obtained by the measurement cannot determine the half width of the peak broadly, it is estimated that the crystallite diameter is in an amorphous state (amorphous) with a diameter of less than 20 Hz.

[Concentration and redispersion]

1. Concentration of Dispersion

Although it does not specifically limit as a removal process of the solvent powder from the mixed liquid after precipitation of organic pigment microparticles | fine-particles, For example, the method of filtering by a filter etc., the method of sedimenting and concentrating organic pigment microparticles | fine-particles by centrifugation, etc. are mentioned. The device for filter filtration can use, for example, a device such as reduced pressure or pressure filtration. As a preferable filter, a filter paper, a nano filter, an ultra filter, etc. can be mentioned. The centrifugal separator may be any device as long as it can settle the water insoluble compound fine particles. For example, in addition to the general-purpose apparatus, what has a skimming function (the function which draws a supernatant layer during rotation, and discharges it out of a system), the continuous centrifugal separator etc. which discharge | emit a solid material continuously are mentioned. The centrifugal conditions are preferably 50-10000, more preferably 100-8000, particularly preferably 150-6000 in terms of centrifugal force (a value indicating how many times the acceleration of gravity takes centrifugal acceleration). Although the temperature at the time of centrifugation depends on the solvent species of a dispersion liquid, -10-80 degreeC is preferable, -5-70 degreeC is more preferable, and 0-60 degreeC is especially preferable. Moreover, the method of subliming a solvent by vacuum freeze-drying and concentrating as a solvent powder removal process, the method of drying and concentrating a solvent by heating or reduced pressure, the method of combining them, etc. can also be used.

2. Redispersion

Microparticles | fine-particles of an organic pigment can be used, for example in the state disperse | distributed in the vehicle. The vehicle refers to a part of a medium in which an organic pigment is dispersed when in a liquid state, and refers to a part (binder) which binds to the water-insoluble compound and solidifies the coating film in a liquid phase, and a component that dissolves and dilutes it (organic solvent). ). In addition, in this invention, the polymeric compound used at the time of microparticle formation and / or the organic pigment dispersant used for redispersion are collectively called a binder.

Although the fine particle density | concentration of the dispersion of microparticles | fine-particles after redispersion is suitably determined according to the objective, Preferably it is preferable that it is 2-30 mass% with respect to the whole dispersion amount, It is more preferable that it is 4-20 mass%, It is especially preferable that it is 5-15 mass%. In the case of dispersing in the vehicle as described above, the amount of the binder and the dissolved dilution component is appropriately determined by the kind of the water-insoluble compound, etc., but the binder is preferably 1-30% by mass, and 3-20% by mass, based on the total amount of the dispersion. It is more preferable that it is, and it is especially preferable that it is 5-15 mass%. It is preferable that it is 5-80 mass%, and, as for a melt | dissolution dilution component, it is more preferable that it is 10-70 mass%.

The fine particles of the organic pigment can be redispersed in the same organic solvent as that used in the poor solvent solution, and the aggregated state of the organic pigment fine particles spontaneously dissolves and is dispersed in the medium in the same organic solvent as the poor solvent without the addition of a separate dispersant or the like. It is preferable to have a property, and what has this property is said to be "self-dispersible" or "it has self-dispersibility." However, in order to further improve redispersibility in this invention, you may add a pigment dispersing agent etc. at the time of redispersion of microparticles | fine-particles. From this point of view, there are cases in which agglomerates that are difficult to redistribute are distinguished from agglomerates or loose flocculates that are capable of redispersion. For the agglomeration form of such fine particles, etc., refer to the Japanese Imaging Society "Minification and Dispersion Technology of Organic Pigments" Deno Takashi, Vol. 45, No. 5, 2006, pages 12-21.

As a method of redispersing fine particles in such agglomerates, for example, a dispersion method using ultrasonic waves or a method of applying physical energy can be used. 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 cleaner, etc. are mentioned. When liquid temperature rises during ultrasonic irradiation, since thermal coagulation of a nanoparticle arises, it is preferable to make liquid temperature 1-100 degreeC, and 5-60 degreeC is more preferable. 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 a pigment nanoparticle by physical energy, For example, dispersers, such as a kneader, a roll mill, an ato rider, a super mill, a dissolver, a homo mixer, and a sand mill, are mentioned. Moreover, the high pressure dispersion method and the dispersion method by use of a microparticle bead are also listed as a preferable thing.

[Polymer dispersant]

In the present invention, it is preferable to remove the aqueous solvent component of the dispersion prepared by the reprecipitation method as described above. It is preferable not to have a drying process after the process of removing said water phase. At this time, in order to improve the dispersibility of a pigment further, dispersing agents, such as a specific pigment dispersing agent and surfactant, can also be added unless the effect of this invention is impaired. In addition, you may use the dispersing agent used here in the reprecipitation method mentioned above and coexist at the time of precipitation of a pigment fine particle, for example. In addition, although a high molecular compound is mainly illustrated as a following dispersing agent, when it mentions molecular weight in this invention, unless otherwise indicated, a mass mean molecular weight means the molecular weight and a dispersion degree mean the value measured by the following measuring method.

[Measurement method of molecular weight and dispersion]

Molecular weight and dispersion degree are measured using GPC (gel filtration chromatography) method unless otherwise stated. The gel packed in the column used in the GPC method is preferably a gel having an aromatic compound in a repeating unit. Examples thereof include gels composed of styrene-divinylbenzene copolymers. It is preferable to use two to six columns. Examples of the solvent used include ether solvents such as tetrahydrofuran and amide solvents such as N-methylpyrrolidinone, but ether solvents such as tetrahydrofuran are preferable. It is preferable to perform a measurement in the range whose solvent flow rate is 0.1-2 mL / min, and it is most preferable to carry out in the range which is 0.5-1.5 mL / min. By carrying out the measurement within this range, it is possible to measure efficiently without the load on the apparatus. It is preferable to perform measurement temperature at 10-50 degreeC, and it is most preferable to carry out at 20-40 degreeC.

Specific conditions of molecular weight measurement are shown below.

Device: HLC-8220GPC (manufactured by TOSOH CORPORATION)

Detector: Differential Refractometer (RI Detector)

Precolumn: TSKGUARD COLUMN MP (XL) 6mm × 40mm (manufactured by TOSOH CORPORATION)

Sample column: Connect the following two directly (all from TOSOH CORPORATION)

ㆍ TSK-GEL Multipore-HXL-M 7.8mm × 300mm

Reference side column: same as sample side column

Bath temperature: 40 ℃

Mobile layer: tetrahydrofuran

Sample-side mobile bed flow rate: 1.0 mL / min

Moving bed reference flow rate: 0.3 mL / min

Sample concentration: 0.1% by weight

Sample injection volume: 100 μl

Data collection time: 16 to 46 minutes after sample injection

Sampling Pitch: 300m / sec

1.Dispersant A

You may add dispersing agents, such as a pigment dispersing agent and surfactant, to the pigment dispersion of this invention in order to improve the dispersibility of a process pigment further. As a dispersant (pigment dispersant), a polymeric dispersant (for example, polyamideamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, ( Meta) acrylic copolymers, naphthalenesulfonic acid formalin condensates) and polyoxyethylene alkyl phosphate esters, polyoxyethylene alkylamines, alkanolamines, pigment derivatives, and the like. Polymeric dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers from the structure.

The polymeric dispersant adsorbs on the surface of the pigment and acts to prevent reagglomeration. Therefore, terminal modified polymers, graft polymers, and block polymers having anchor sites on the pigment surface can be listed as preferred structures. On the other hand, the pigment derivative has the effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface. The polymer dispersant is adsorbed on the surface of the pigment in the dispersing process and acts to prevent reagglomeration. Therefore, block type polymers, graft type polymers, and terminal modified polymers having anchor sites on the pigment surface can be enumerated as preferable structures. On the other hand, the pigment derivative has the effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface. By using the pigment derivative of this invention in combination with the polymer dispersing agent which has the following specific structure, the interaction of the above-mentioned surface modification effect and dispersibility improvement effect is further improved, and it is preferable.

(Grafted polymer)

Although it does not restrict | limit especially about a graft type polymer, The compound which made the polyalkylene imine and the polyester compound react as described in Unexamined-Japanese-Patent No. 54-37082, 61-174939, etc., Unexamined-Japanese-Patent No. 9 The compound which modified the amino group of the side chain of polyallylamine of Unexamined-Japanese-Patent No. 169821 with polyester, the polyester polyol addition polyurethane of Unexamined-Japanese-Patent No. 60-166318, etc. are mentioned preferably, Furthermore, Unexamined-Japanese-Patent No. As described in Japanese Patent Application Laid-Open No. 9-171253 and the Chemistry and Industry of Macromonomers (IPC Publishing, 1989) and the like, graft polymers having a polymerizable oligomer (hereinafter referred to as a macromonomer) as a copolymerization component can also be preferably listed. Moreover, the graft type polymer which has the organic pigment | dye part of Unexamined-Japanese-Patent No. 2003-238837 is preferable at the point which adsorb | sucks into a pigment and gives favorable dispersibility. The branched portion of the graft polymer is preferably polystyrene, polyethylene oxide, polypropylene oxide, poly (meth) acrylic acid ester, polycaprolactone, or the like, but a graft polymer having a polycaprolactone chain is more preferable. Commercially available products of the graft polymer include Solsperse 24000, Solsperse 28000, Solsperse 32000, Solsperse 38500, Solsperse 39000, Solsperse 55000 (above, manufactured by Lubrizol Corporation), Disperbyk-161, Disperbyk-171, Disperbyk-174 (above, BYK Chemie Japan KK Products) and the like (all trade names).

(Terminal modified polymer)

As the terminal-modified polymer, for example, the polymers described in Japanese Patent Application Laid-Open No. 9-77994, Japanese Patent Application Laid-Open No. 2002-273191, Japanese Patent Application Laid-Open No. 2007-277514, Japanese Patent Application Laid-Open No. 2007-140487, and the like. The polymer which has a functional group at the terminal can be mentioned.

(Block type polymer)

Although it does not specifically limit as a block type polymer, The block type polymer which consists of a pigment adsorption block and the block which does not adsorb | suck to a pigment is mentioned. Although it does not specifically limit as a monomer which comprises a pigment adsorption block, For example, the monomer which has a functional group which can adsorb | suck to a pigment is mentioned. Specifically, the monomer which has an organic pigment | dye structure or heterocyclic structure, the monomer which has an acidic group, the monomer which has a basic nitrogen atom, etc. can be mentioned. As a monomer which has an organic pigment | dye structure or a heterocyclic structure, the organic pigment | dye skeleton, maleimide derivative, etc. which were described, for example in Unexamined-Japanese-Patent No. 2003-238837 are mentioned. It is also possible to use a commercial item as a block polymer. As a specific example, Disperbyk-2000, Disperbyk-2001 (above, BYK Chemie Japan K.K.), EFKA4330, EFKA4340 (above, EFKA), etc. [all brand names] are mentioned.

Although the usage-amount of the dispersing agent A in a dispersion is not specifically limited, When using as a color material with a color filter, for example, it is preferable that it is 10-400 mass parts with respect to 100 mass parts of pigments, and it is more preferable that it is 20-200 mass parts. Do.

2. Dispersant B

In this invention, the high molecular compound containing the at least 1 sort (s) of repeating unit chosen from the repeating unit represented by either of the following general formula (I) and general formula (II) (henceforth "dispersant B"). It is preferable to contain.

In Formulas (I) and (II), R ²¹ to R ²⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ²¹ and X ²² each independently represent —CO—, —C (═O) O—. , -CONH-, -OC (= O)-or a phenylene group, L ²¹ and L ²² each independently represent a single bond or a divalent organic linking group, and A ²¹ and A ²² each independently represent a monovalent organic group. Ma and na each independently represent an integer of 2 to 8, and p and q each independently represent an integer of 1 to 100.

R ²¹ to R ²⁶ each independently represent a hydrogen atom or a monovalent organic group. As monovalent organic group, a substituted or unsubstituted alkyl group is preferable. As an alkyl group, a C1-C12 alkyl group is preferable, A C1-C8 alkyl group is more preferable, A C1-C4 alkyl group is especially preferable. When the alkyl group has a substituent, for example, as the substituent, a hydroxy group, an alkoxy group (preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), methoxy group, ethoxy group, cyclohex And siloxy groups. Specifically as a preferable alkyl group, For example, a methyl group, an ethyl group, a propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, a cyclohexyl group, 2-hydroxyethyl group, 3-hydroxy A hydroxypropyl group, 2-hydroxypropyl group, and 2-methoxyethyl group are mentioned. As R <^21> , R <^22> , R <^24> and R <^{25>, a} hydrogen atom is preferable and R <^23> and R <^26> are the most preferable also at the point of the adsorption efficiency on a pigment surface as a hydrogen atom or a methyl group.

X ²¹ and X ²² each independently represent a —CO—, —C (═O) O—, —CONH—, —OC (═O) — or a phenylene group. Especially, -C (= O) O-, -CONH-, and a phenylene group are preferable from a viewpoint of adsorption to a pigment, and -C (= O) O- is the most preferable.

L ²¹ and L ²² each independently represent a single bond or a divalent organic linking group. As a divalent organic coupling group, a substituted or unsubstituted alkylene group and the bivalent organic coupling group which consists of a partial structure containing the said alkylene group and a hetero atom or a hetero atom are preferable. Here, as an alkylene group, a C1-C12 alkylene group is preferable, A C1-C8 alkylene group is more preferable, A C1-C4 alkylene group is especially preferable. Moreover, as a hetero atom in the partial structure containing a hetero atom, an oxygen atom, a nitrogen atom, and a sulfur atom are mentioned, for example, Especially, an oxygen atom and a nitrogen atom are preferable. As a preferable alkylene group, a methylene group, an ethylene group, a propylene group, trimethylene group, tetramethylene group is mentioned specifically ,. When an alkylene group has a substituent, the said hydroxyl group etc. are mentioned, for example. The divalent organic linking group has a partial structure containing a hetero atom or a hetero atom selected from -C (= 0)-, -OC (= 0)-, and -NHC (= 0)-at the terminal of the alkylene group. It is preferable in view of the adsorptivity to the pigment that it is connected to an adjacent oxygen atom through the hetero atom or the partial structure containing the hetero atom. Here, an adjacent oxygen atom means the oxygen atom couple | bonded with L <^21> in general formula (I) and L <^22> in general formula (II) by the side chain terminal side.

As A <^21> and A <^22> , the group chosen from the linear stability of 1-20 carbon atoms, the branched carbon atoms of 3-20 carbon atoms, and the cyclic alkyl group of 5-20 carbon atoms from a dispersion stability and developability, and carbon is preferable. Groups selected from a straight chain having 4 to 15 atoms, a branched carbon group having 4 to 15 carbon atoms, and a cyclic alkyl group having 6 to 10 carbon atoms are more preferable, and a straight chain having 6 to 10 carbon atoms and 6 carbon atoms More preferred are groups selected from ˜12 branched alkyl groups.

ma and na each independently represent the integer of 2-8. 4-6 are preferable and 5 is especially preferable at the point of dispersion stability and developability.

p and q respectively independently represent the integer of 1-100. Different p and different q may be mixed. 5-60 are preferable from a point of dispersion stability and developability, 5-40 are more preferable, and 5-20 are more preferable.

It is preferable that the dispersing agent B in this embodiment contains the repeating unit represented by the said General formula (I) from a point of dispersion stability.

Moreover, as a repeating unit represented by general formula (I), it is more preferable that it is a repeating unit represented with the following general formula (I) -2.

In General Formula (I) -2, R ²¹ to R ²³ each independently represent a hydrogen atom or a monovalent organic group, La represents a C2-C10 alkylene group, and Lb is -C (= 0)-or- NHC (= O)-is represented, A <^21> represents monovalent organic group, ma represents the integer of 2-8, p represents the integer of 1-100. The preferable ranges of ma and p are the same as that of general formula (I).

The repeating unit represented by general formula (I), general formula (II), or general formula (I) -2 is a monomer represented by the following general formula (i), general formula (ii) or general formula (i) -2, respectively. It is introduced as a repeating unit of a high molecular compound by superposing | polymerizing or copolymerizing.

In the general formulas (i), (ii) and (i) -2, R ²¹ to R ²⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ²¹ and X ²² each independently represent -CO. -, -C (= O) O-, -CONH-, -OC (= O)-or a phenylene group, L ²¹ and L ²² each independently represent a single bond or a divalent organic linking group, and La is a carbon number 2-10 alkylene groups, Lb represents -C (= 0)-or -NHC (= 0)-, A ²¹ and A ²² each independently represent a monovalent organic group, and ma and na each independently The integer of 2-8 is represented, and p and q respectively independently represent the integer of 1-100. The preferred ranges of ma.na and p.q are the same as in general formula (I) or general formula (II).

Although the preferable specific example [monomer (A-1)-(A-23)] of the monomer represented by general formula (i), general formula (ii), or general formula (i) -2 is listed below, The present invention is not limited to these.

Dispersant B in this embodiment should just contain at least 1 sort (s) of repeating units chosen from the repeating unit represented by either of General formula (I) and (II), and may contain only 1 sort. Or two or more kinds.

In addition, although content of the repeating unit represented by either of general formula (I) and general formula (II) in dispersing agent B does not have a restriction | limiting in particular, General formula when the total repeating unit contained in a polymer is 100 mass% It is preferable to contain 5 mass% or more of repeating units represented by either of (I) and general formula (II), It is more preferable to contain 50 mass%, It is still more preferable to contain 50 mass%-80 mass%. .

Dispersant B in the present embodiment is a monomer having a functional group capable of adsorbing to the pigment in order to increase the adsorption to the pigment and the general formula (i), general formula (ii), general formula (i) -2 It is preferable that it is a high molecular compound copolymerized with the monomer shown. As a monomer which has a functional group which can adsorb | suck to a pigment, specifically, the monomer which has an organic pigment | dye structure or a heterocyclic structure, the monomer which has an acidic group, the monomer which has a basic nitrogen atom, the monomer which has an ionic group, etc. can be mentioned. Especially, the monomer which has an organic pigment | dye structure or a heterocyclic structure is preferable at the point of the adsorption power to a pigment.

As a monomer which has an organic pigment | dye structure or a heterocyclic structure, it is preferable that it is 1 type chosen from the group which consists of a monomer represented by following General formula (11), a maleimide, and a maleimide derivative. Especially, it is especially preferable that it is a monomer represented by following General formula (11).

R <^11> in the said General formula (11) represents a hydrogen atom or an alkyl group. R ¹² represents a single bond or a divalent linking group. Y represents -CO-, -C (= 0) O-, -CONH-, -OC (= 0)-or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic group.

As an alkyl group represented by R <^11> in General formula (11), a C1-C12 alkyl group is preferable, A C1-C8 alkyl group is more preferable, A C1-C4 alkyl group is especially preferable. When the alkyl group represented by R ¹¹ has a substituent, an alkoxy group such as a hydroxy group, a methoxy group, an ethoxy group or a cyclohexyloxy group is preferable as the substituent. As said alkoxy group, a C1-C5 thing is preferable, and a C1-C3 thing is preferable.

As a preferable alkyl group represented by R <^11> in General formula (11), Specifically, a methyl group, an ethyl group, a propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, Cyclohexyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group are mentioned. Especially, as R <^1> , a hydrogen atom or a methyl group is the most preferable.

As a bivalent coupling group represented by R <^12> in General formula (11), a bivalent group containing an alkylene group or an alkylene group is preferable. As said alkylene group, a C1-C12 alkylene group is preferable, A C1-C12 alkylene group is more preferable, A C1-C8 alkylene group is more preferable, A C1-C4 alkylene group is especially preferable. . In addition, when this alkylene group has a substituent, a hydroxyl group etc. are mentioned as said substituent, for example. As a preferable alkylene group represented by R <^12> , a methylene group, an ethylene group, a propylene group, trimethylene group, tetramethylene group is mentioned specifically ,.

As a bivalent group containing the alkylene group represented by R <^12> in General formula (11), even if the said alkylene group is connected 2 or more through a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom), good. Moreover, as a bivalent group containing the alkylene group represented by R <^12> , -O-, -S-, -C (= O) O-, -CONH- is the terminal of the side couple | bonded with Z in the said alkylene group. , -C (= O) S-, -NHCONH-, -NHC (= O) O-, -NHC (= O) S-, -OC (= O)-, -OCONH- and -NHCO- The hetero atom or the partial structure containing a hetero atom may be combined.

As a nitrogen-containing heterocyclic structure which comprises the nitrogen-containing heterocyclic group represented by Z in General formula (11), For example, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrrole ring, an imidazole ring, a tria Sol ring, tetrazole ring, indole ring, quinoline ring, acridine ring, phenothiazine ring, phenoxazine ring, acridon ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, Listed are those having a cyclic urea structure and a cyclic imide structure. These nitrogen-containing heterocyclic structures may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group and an alkoxycarbonyl group.

The nitrogen-containing heterocyclic group represented by Z is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and particularly preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms. As the nitrogen-containing heterocyclic structure having 6 or more carbon atoms, specifically, phenothiazine ring, phenoxazine ring, acridon ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, A cyclic urea structure and a cyclic imide structure are preferable, and it is especially preferable that it is a structure represented by following General formula (12), general formula (13), or general formula (14).

In formula (12), X is a single bond, an alkylene group (for example, methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, etc.), -O-, -S-, -NR ^A -and Any one selected from the group consisting of -C (= 0)-. Here, R ^A represents a hydrogen atom or an alkyl group. The alkyl group in the case where R ^A represents an alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, for example, a methyl group, ethyl group, n-propyl group, i-propyl group, n -Butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group, etc. are mentioned. Among the above, as X in General formula (12), a single bond, a methylene group, -O-, or -C (= O)-is preferable, and -C (= O)-is especially preferable.

Y and Z of the formula (14) are each independently -N =, -NH-, -N (R B) - represents the, -S- or -O-. R ^B represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n -Butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group, etc. are mentioned. Among the above, examples of Y and Z in the formula (14) -N =, -NH- and -N (R ^B) - is particularly preferred. As a combination of Y and Z, the combination (imidazolyl group) in which either Y and Z is -N = and the other -NH- is listed as a preferable thing.

In general formula (12), general formula (13), or general formula (14), ring A, ring B, ring C, and ring D each independently represent an aromatic ring. Examples of the aromatic ring include benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring and ah Cridine ring, phenothiazine ring, phenoxazine ring, acridon ring, anthraquinone ring, etc. are mentioned, Among these, a benzene ring, a naphthalene ring, anthracene ring, a pyridine ring, a phenoxazine ring, an acridine ring, a phenothiazine ring, a phenoxazine ring Noxazine ring, acridon ring and anthraquinone ring are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are especially preferable.

Specifically as ring A and ring B in General formula (12), a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, etc. are mentioned, for example. As ring C in General formula (13), a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, etc. are mentioned, for example. As ring C in General formula (14), a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, etc. are mentioned, for example. Also in the structure represented by General formula (12), General formula (13), or General formula (14), a benzene ring and a naphthalene ring are more preferable at the point of dispersibility and the time-lapse stability of a dispersion liquid, General formula (12) or a general formula In (14), a benzene ring is more preferable, and a naphthalene ring is more preferable in General formula (13).

In addition, the maleimide derivative in this invention means the maleimide whose N position is substituted by substituents, such as an alkyl group and an aryl group.

Hereinafter, although the specific example (monomer M-1-M-33) of the monomer, maleimide, and maleimide derivative represented by General formula (11) is enumerated below, this invention is not limited to these.

The dispersing agent B in this embodiment may contain only 1 type of repeating units derived from 1 type of monomer chosen from the group which consists of a monomer represented by General formula (11), a maleimide, and a maleimide derivative, and 2 You may include a species or more.

Content of the repeating unit derived from 1 type of monomers chosen from the group which consists of a monomer represented by General formula (11), maleimide, and a maleimide derivative among the dispersing agents B in this embodiment shows the total repeating unit contained in a polymer. When it is 100 mass%, it is preferable to contain 5 mass% or more, and it is more preferable to contain 10 mass%-50 mass%. That is, in order to effectively suppress the production of secondary aggregates, which are aggregates of primary particles of pigments, or to effectively weaken the cohesion of secondary aggregates, they are selected from the group consisting of monomers, maleimide and maleimide derivatives represented by the general formula (11). It is preferable that content of the polymerization unit derived from 1 type of monomer used becomes 5 mass% or more. In addition, from the developability viewpoint at the time of manufacturing a color filter with the coloring photosensitive composition containing a pigment dispersion, 1 type of monomer chosen from the group which consists of a monomer represented by General formula (1), a maleimide, and a maleimide derivative is mentioned. It is preferable that content of the polymerization unit derived from is 50 mass% or less.

As an example of the monomer which has an acidic group, the vinyl monomer which has a carboxyl group, and the vinyl monomer which has a sulfonic acid group are mentioned. Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimers and the like. Furthermore, the addition reaction product of the monomer which has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, and cyclic anhydrides, such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, (omega)-carboxy- polycaprolactone Mono (meth) acrylate etc. can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, a citraconic acid anhydride, as a precursor of a carboxyl group. Moreover, in these, (meth) acrylic acid is especially preferable from a viewpoint of copolymerizability, cost, and solubility.

Moreover, 2-acrylamide-2-methylpropanesulfonic acid etc. are mentioned as a vinyl monomer which has a sulfonic acid group, and monophosphate (2-acryloyloxyethyl ester) and monophosphate (1-methyl-2) are mentioned as a vinyl monomer which has a phosphoric acid group. -Acryloyloxyethyl ester), etc. are mentioned.

It is preferable that the dispersing agent B in this embodiment contains the repeating unit derived from the monomer which has an acidic group as mentioned above. By including such a repeating unit, when the pigment dispersion of this invention is applied to a coloring photosensitive composition, the image development removal property of an unexposed part is excellent.

The dispersant B in this embodiment may include only 1 type of repeating units derived from the monomer which has an acidic group, and may contain 2 or more types. In dispersant B, content of the repeating unit derived from the monomer which has an acidic group becomes like this. Preferably it is 50 mgKOH / g or more, Especially preferably, it is 50 mgKOH / g-200 mgKOH / g. That is, it is preferable that content of the repeating unit derived from the monomer which has an acidic group is 50 mgKOH / g or more from the point of suppressing generation | occurrence | production of the precipitate in a developing solution. In order to effectively suppress the formation of secondary aggregates, which are aggregates of pigment primary particles, or to effectively weaken the cohesion of secondary aggregates, the content of the repeating unit derived from the monomer having an acid group is preferably 50 mgKOH / g to 200 mgKOH / g. .

As a monomer which has a basic nitrogen atom, it is (meth) acrylic acid ester as (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl, (meth) acrylic acid 1- (N, N-dimethylamino ) -1,1-dimethylmethyl, (meth) acrylic acid N, N-dimethylaminohexyl, (meth) acrylic acid N, N-diethylaminoethyl, (meth) acrylic acid N, N-diisopropylaminoethyl, (meth N, N-di-n-butylaminoethyl acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholine ethyl (meth) acrylate, piperidinoethyl (meth) acrylate, (meth) Acrylic acid 1-pyrrolidinoethyl, (meth) acrylic acid N, N-methyl-2-pyrrolidylaminoethyl, (meth) acrylic acid N, N-methylphenylaminoethyl, etc. are mentioned, As (meth) acrylamide, -(N ', N'-dimethylaminoethyl) acrylamide, N- (N', N'-dimethylaminoethyl) methacrylamide, N- (N ', N'-diethylaminoethyl) acrylic Mead, N- (N ', N'-diethylaminoethyl) methacrylamide, N- (N', N'-dimethylaminopropyl) acrylamide, N- (N ', N'-dimethylaminopropyl) meta Krillamide, N- (N ', N'-diethylaminopropyl) acrylamide, N- (N', N'-diethylaminopropyl) methacrylamide, 2- (N, N-dimethylamino) ethyl ( Meta) 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-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide, mor Polyno (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide, and the like. Examples of the styrene include N, N-dimethylaminostyrene, N, N -Dimethylaminomethylstyrene and the like.

It is also possible to use a monomer having a urea group, a urethane group, a hydrocarbon group having 4 or more carbon atoms having a coordinating oxygen atom, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group. Specifically, the monomer of the following structure can be enumerated, for example.

As a monomer which has an ionic group, the vinyl monomer (anionic vinyl monomer, cationic vinyl monomer) which has an ionic group is mentioned. Examples of such anionic vinyl monomers include salts with alkali metal salts of organic monomers having an acidic group and organic amines (eg, tertiary amines such as triethylamine and dimethylaminoethanol), and the like as cationic vinyl monomers. Alkyl halides (alkyl groups: C1-18, halogen atoms: chlorine atoms, bromine atoms or iodine atoms); Benzyl halides such as benzyl chloride and benzyl bromide; Alkyl sulfonates (alkyl groups: C1-18), such as methanesulfonic acid; Aryl sulfonic acid alkyl esters (alkyl group: C1-18), such as benzene sulfonic acid and toluene sulfonic acid; The quaternized by dialkyl sulfate (alkyl group: C1-4) etc., a dialkyl diallyl ammonium salt, etc. are mentioned.

The monomer which has a functional group which can adsorb | suck to a pigment can be suitably selected according to the kind of pigment to be disperse | distributed, These may be used independently and may use 2 or more types together.

The dispersing agent B in this embodiment may further contain the repeating unit derived from the vinyl monomer which can be copolymerized in the range which does not impair the effect.

Although it does not specifically limit as a vinyl monomer which can be used here, 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 a specific example of such a vinyl monomer, the following compounds are mentioned, for example. In addition, in this specification, when showing one or both of "acryl and methacryl", it may describe as "(meth) acryl."

A preferred embodiment of the dispersant B in the present embodiment is a copolymer of at least a monomer represented by the general formula (i), the general formula (ii) or the general formula (i) -2 with a monomer having an organic dye structure or a heterocyclic structure. More preferably, at least the monomer represented by general formula (i) -2 mentioned above and the monomer represented by general formula (11) mentioned above and the monomer which has an acidic radical are copolymerized. Thereby, the pigment dispersion which is excellent in pigment adsorption and excellent in developability can be manufactured.

It is preferable that the preferable molecular weight of the dispersing agent B in this embodiment is the range of 400-100,000 in the range of 1,000-100,000 and the number average molecular weight (Mn) by mass average molecular weight (Mw). As for mass mean molecular weight (Mw), it is more preferable that it is the range of 2,000-30,000 in the range of 5,000-50,000, and number average molecular weight (Mn). In particular, it is most preferable that it is the range of 8,000-30,000 in mass average molecular weight (Mw), and the range of 4,000-12,000 in number average molecular weight (Mn). It is preferable that the mass mean molecular weight (Mw) of the dispersing agent B is 1000 or more from a viewpoint of effectively loosening the secondary aggregate which is an aggregate of the primary particle of a pigment, or effectively weakening reaggregation. Moreover, it is preferable that the mass mean molecular weight (Mw) of the dispersing agent B is 30000 or less from a developable viewpoint at the time of manufacturing a color filter with the coloring photosensitive composition containing a pigment dispersion.

The dispersant B in this embodiment is a radically polymerizable compound different from the monomer and copolymerization component represented by following General formula (i), General formula (ii), or General formula (i) -2 (as mentioned above), for example. Various monomers), and can be produced by a general radical polymerization method. Generally, suspension polymerization or solution polymerization is used. Examples of the solvent used when synthesizing such a dispersant B include ethylene chloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2- Methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propylacetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, lactic acid Methyl, ethyl lactate, and the like. These solvents may be used alone or in combination of two or more thereof. In addition, a radical polymerization initiator may be used in the radical polymerization, and a chain transfer agent (for example, 2-mercaptoethanol and dodecyl mercaptan) may be further used.

As content of the dispersing agent B in the pigment dispersion of this embodiment, pigment: dispersant B = 1: 0.1-1: 2 are preferable by mass ratio, More preferably, it is 1: 0.2-1: 1, More preferably, 1: 0.4-1: 0.7.

In addition, in the range which does not impair the effect of this embodiment, you may use another high molecular compound simultaneously other than the specific copolymer mentioned above as needed. As another high molecular compound, a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, etc. are used. Rosin is typical as a natural resin, and rosin derivative, a cellulose derivative, a rubber derivative, a protein derivative, and those oligomers are mentioned as a modified natural resin. Examples of the synthetic resins include epoxy resins, acrylic resins, maleic acid resins, butyral resins, polyester resins, melamine resins, phenol resins and polyurethane resins. Examples of the synthetic resin modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins. Examples of the synthetic resin include polyamideamine and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, polyurethanes, polyesters, poly (meth) acrylates, (meth) acrylic copolymers, and naphthalenesulfonic acid formalin condensates. do.

[Photocurable Composition]

The photocurable composition contains the dispersion of the pigment fine particles, a photopolymerizable compound, and a photopolymerization initiator, and preferably further contains an alkali-soluble resin. The method of manufacturing organic pigment microparticles | fine-particles and its dispersion was already demonstrated in detail. As for content of the microparticles | fine-particles in a photocurable composition, 3-90 mass% is preferable with respect to total solid ((in this invention, total solid means the composition total except an organic solvent.), 20-80 mass% is more preferable, 25-60 mass% is more preferable. When this amount is too large, the viscosity of a dispersion liquid may rise and it may become a problem in manufacture aptitude. When too small, the coloring power is not enough. Moreover, you may use it in combination with a normal pigment for coloring. The pigment can use what was described above.

It is preferable that it is a polyfunctional monomer which has two or more ethylenically unsaturated double bonds and add-polymerizes by irradiation of light as a photopolymerizable compound (henceforth a polymerizable monomer or a polymerizable oligomer). As such a photopolymerizable compound, the compound which has an ethylenically unsaturated group which can carry out at least 1 addition polymerization in a molecule | numerator, and whose boiling point is 100 degreeC or more at normal pressure is mentioned. Examples thereof include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropanediacrylate, neopentyl glycol di (meth) Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; Polyfunctional acrylates and polyfunctional methacrylates, such as those obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimethylolpropane and glycerin and then (meth) acrylated, can be enumerated. Moreover, the compound which (meth) acrylated after adding ethylene oxide or a propylene oxide to polyfunctional alcohol as described in Unexamined-Japanese-Patent No. 10-62986 to general formula (1) and (2) also has Listed as preferred.

Urethane acrylates described in Japanese Patent Application Laid-Open No. 48-41708, Japanese Patent Publication No. 50-6034, and Japanese Patent Application Laid-open No. 51-37193; Polyester acrylates described in JP-A-48-64183, JP-A-49-43191 and JP-A-52-30490; Polyfunctional acrylates and methacrylates, such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, can be mentioned.

Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable.

In addition, "polymerizable compound B" described in Unexamined-Japanese-Patent No. 11-133600 can also be enumerated as a preferable thing.

You may use a photopolymerizable compound individually or in mixture of 2 or more types, As for content with respect to the total solid of a photocurable composition, 5-50 mass% is common, and 10-40 mass% is preferable. When this amount is too large, control of developability becomes difficult and becomes a problem in manufacture aptitude. When too small, the hardening force at the time of exposure will be insufficient.

As a photoinitiator or a photoinitiator type | system | group (in this invention, a photoinitiator system means the mixture which expresses the function of photoinitiation in combination of a some compound.) Bisinal polyketaldonyl currently disclosed by US patent 2367660 specification. Compound, the acyl phosphorus compound described in US Pat. No. 2448828, the aromatic acyl phosphor substituted with α-hydrocarbon as described in US Pat. No. 2722512, US Pat. No. 3046127, and US Pat. No. 2951758 Multinuclear quinone compound described in the specification, a combination of triarylimidazole dimer and p-aminoketone described in US Pat. No. 3549367, benzothiazole compound and trihalomethyl described in Japanese Patent Publication No. 51-48516 -s-triazine compound, trihalomethyl-triazine compound described in US Pat. No. 4,239,850, Patent can be exemplified such as methyl trihalomethyl oxadiazole compounds as disclosed in the No. 4212976 specification. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole and triarylimidazole dimers are preferred.

In addition, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime and O-benzoyl are mentioned as "polymerization initiator C" and oxime system described in Unexamined-Japanese-Patent No. 11-133600. -4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophosphoro-trialkylphenylphosphonium salt, etc. are also listed as preferable. Can be.

Although a photoinitiator or a photoinitiator system may be used individually or in mixture of 2 or more types, it is preferable to use 2 or more types especially. The use of at least two photopolymerization initiators can result in less display characteristics, in particular, unevenness of the display. As for content of a photoinitiator or a photoinitiator system with respect to the total solid of a photocurable composition, 0.5-20 mass% is common, and 1-15 mass% is preferable. If this amount is too large, the sensitivity becomes too high and control becomes difficult. When too small, exposure sensitivity will become low too much.

As alkali-soluble resin, although it can add at the time of preparation of the photocurable composition or the inkjet ink for color filters, it is also preferable to add at the time of manufacturing the dispersion of the said microparticles, or at the time of microparticle formation. Alkali-soluble resin may be added to both or one of the poor solvents for adding the solution of the water-insoluble compound and the solution of the water-insoluble compound to produce fine particles of the water-insoluble compound. Or it is also preferable to add alkali-soluble resin solution at the time of microparticle formation of a water-insoluble compound in another system.

As alkali-soluble resin, the binder which has an acidic group is preferable, and the alkali-soluble polymer which has polar groups, such as a carboxylic acid group and a carboxylate group, in a side chain is preferable. Examples include Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 59-53836 Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like as described in Japanese Patent Application Laid-Open No. 59-71048 Can be enumerated. Moreover, the cellulose derivative which has a carboxylic acid group, a carboxylate, etc. in a side chain can also be enumerated, In addition, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. As particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid or polyunsaturated copolymers of benzyl (meth) acrylate with (meth) acrylic acid and other monomers described in US Pat. No. 4,139,391 may be listed. Can be.

Alkali-soluble resin may be used independently, or may be used in the state of the composition used together with a normal film-forming polymer, The addition amount with respect to 100 mass parts of microparticles | fine-particles of a water-insoluble compound is generally 10-200 mass parts, and 25- 100 mass parts is preferable.

In addition, in order to improve crosslinking efficiency, you may have a polymeric group in the side chain of alkali-soluble resin, UV curable resin, a thermosetting resin, etc. are also useful. Moreover, resin which has a water-soluble atomic group in a part of side chain can also be used as alkali-soluble resin. As for content of an organic solvent, 10-95 mass% is preferable with respect to the photocurable composition whole quantity. Moreover, a suitable surfactant, a thermal polymerization inhibitor, a ultraviolet absorber, an adhesion | attachment adjuvant, other additives, etc. can be contained in a photocurable composition.

The photocurable composition can be suitably adjusted to the inkjet ink. As inkjet ink, although it is good also as normal inkjet ink, such as printing, besides for a color filter, it is preferable to set it as the inkjet ink for color filters especially.

The inkjet ink may be any one containing the above water insoluble compound fine particles, and preferably contains the above water insoluble compound fine particles in a medium containing a polymerizable monomer and / or a polymerizable oligomer. Here, as the polymerizable monomer and / or the polymerizable oligomer, those described in the photocurable composition can be used.

At this time, the ink characteristics at the time of injection, the ink ejection method, the shape of the inkjet head, the pattern of the color filter, and the formation method thereof are the same as those disclosed in Japanese Patent Laid-Open No. 2008-138194.

About the containing component in the coating film using the photocurable composition, it is as having already described. In addition, about the property of the coating film using a photocurable composition, and the coating method to a base material, it is the same about what is disclosed by Unexamined-Japanese-Patent No. 2008-138194, and a preferable range.

[Color filter]

It is preferable that the pixel of the color filter of this invention was formed using the pigment fine particle dispersion mentioned above or the redispersant which switched the solvent, and it is preferable that it is excellent in contrast. In the present invention, the contrast refers to the ratio of the amount of transmitted light when the polarization axes are parallel and perpendicular between the two polarizing plates ("The Seventh Color Optical Conference of 1990, 512 Color Display 10.4" Size for TFT-LCD Color filter, Ueki, Ozeki, Fukunaga, Yamanaka, etc ..] The high contrast of the color filter means that the contrast of the contrast when combined with the liquid crystal can be increased, and the liquid crystal display is CRT. In order to be replaced by a very important performance.

When the color filter is used for television use, the values of the chromaticities of all the single colors of red (R), green (G), and blue (B) by the F10 light source are shown in the following table (hereinafter referred to as "target chromaticity" in the present invention). It is preferable that it is within a range of 5 or less, more preferably within 3, and particularly preferably within 2, as a difference (ΔE)).

In the present invention, chromaticity is measured by a microscopic spectrophotometer (OLYMPUS CORPORATION; OSP100 or 200), calculated as a result of 2 degrees F10 light source field of view, and represented by the xyY value of the xyz colorimeter. The difference from the target chromaticity is represented by the color difference of the La ^* b ^* color system.

It is preferable that the liquid crystal display device provided with a color filter has high contrast, is excellent in descriptive power, such as black clarity, and is especially a VA system. It can be used suitably also as a liquid crystal display device of big screens, such as a display for note PCs, and a television monitor. Moreover, the said color filter can be used for a CCD device, and exhibits the outstanding performance.

Example

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited and interpreted by this. In addition, in this Example, "part" and "%" are mass references | standards unless there is particular notice.

(Manufacture example) Example according to invention of pigment derivative compound

Preparation Example 1 Synthesis of Pigment Derivative a

30 parts by mass of PR255 (Cromophtal DPP Coral Red C [trade name], manufactured by Ciba Specialty Chemicals K. K.) was dissolved in 450 parts by mass of sulfuric acid, and stirred at 20 ° C. for 30 minutes. Subsequently, 19.8 parts by mass of paratoluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto with care not to exceed an internal temperature of 35 ° C. After the addition, the mixture was stirred at an internal temperature of 20 ° C. for 10 minutes, and then 3.82 parts by mass of paraformaldehyde (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) Was added thereto, followed by heating and stirring at 30 ° C. for 4 hours. 39.18 mass parts of pigment derivatives were obtained by filtering and wash | cleaning the precipitate obtained by inject | pouring, stirring stirring a reaction liquid after 1800 mass parts of ice water after heat stirring.

Preparation Example 2 Synthesis of Pigment Derivative b

30 parts by mass of PR255 (Cromophtal DPP Coral Red C [trade name], manufactured by Ciba Specialty Chemicals K. K.) was dissolved in 450 parts by mass of sulfuric acid, and stirred at 20 ° C. for 30 minutes. Subsequently, 19.8 mass parts of paratoluene sulfonic acid monohydrate (made by Wako Pure Chemical Industries, Ltd.) was added to this, and it stirred at internal temperature of 20 degreeC for 10 minutes. Subsequently, 3.82 parts by mass of paraformaldehyde (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) Was added, followed by heating and stirring at 30 ° C for 2 hours. Subsequently, 18.43 parts by mass of hydroxymethylphthalimide (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and heating and stirring were performed at 30 ° C for 2 hours. 27.5 mass parts of pigment derivatives b were obtained by filtering and wash | cleaning the precipitate obtained by inject | pouring, stirring the reaction liquid after stirring with 1800 mass parts of ice water after heat stirring.

Preparation Example 3 Synthesis of Pigment Derivative c

30 parts by mass of PR255 (Cromophtal DPP Coral Red C [trade name], manufactured by Ciba Specialty Chemicals K. K.) was dissolved in 450 parts by mass of sulfuric acid, and stirred at 20 ° C. for 30 minutes. Subsequently, 19.8 mass parts of paratoluene sulfonic acid monohydrate (made by Wako Pure Chemical Industries, Ltd.) was added to this, and it stirred at internal temperature of 20 degreeC for 10 minutes. Subsequently, 3.82 parts by mass of paraformaldehyde (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) Was added, followed by heating and stirring at 30 ° C for 2 hours. Subsequently, 15.31 parts by mass of phthalimide (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and after 10 minutes, 3.82 parts by mass of paraformaldehyde (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) Was added, and at 2O &lt; 0 &gt; C for 2 hours. Heat stirring was performed. 26.8 mass parts of pigment derivatives c were obtained by filtering and wash | cleaning the precipitate obtained by inject | pouring, stirring the reaction liquid after stirring with 1800 mass parts of ice water after heat stirring.

Preparation Example 4 Synthesis of Pigment Derivative d

30 parts by mass of PR255 (Cromophtal DPP Coral Red C [trade name], manufactured by Ciba Specialty Chemicals K. K.) was dissolved in 450 parts by mass of sulfuric acid, and stirred at 20 ° C. for 30 minutes. Subsequently, 18.43 mass parts of hydroxymethyl phthalimide (made by Wako Pure Chemical Industries, Ltd.) was added, and it stirred at 30 degreeC for 2 hours. Subsequently, 19.8 parts by mass of paratoluene sulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, and after 10 minutes, 3.82 parts by mass of paraformaldehyde (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) Was added, 30 Heating and stirring were performed at 2 ° C. for 2 hours. 29.4 mass parts of pigment derivatives d were obtained by filtering and wash | cleaning the precipitate obtained by inject | pouring, stirring stirring a reaction liquid after 1800 mass parts of ice water after heat stirring.

Preparation Example 5 Synthesis of Pigment Derivative e

30 parts by mass of PR255 (Cromophtal DPP Coral Red C [trade name], manufactured by Ciba Specialty Chemicals K. K.) was dissolved in 450 parts by mass of sulfuric acid, and stirred at 20 ° C. for 30 minutes. Subsequently, 18.32 parts by mass of benzenesulfonic acid monohydrate (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) Was added with care not to exceed the internal temperature of 35 ° C. After the addition, the mixture was stirred at an internal temperature of 20 ° C. for 10 minutes, and then 3.82 parts by mass of paraformaldehyde (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) Was added thereto, followed by heating and stirring at 30 ° C. for 4 hours. 37.1 mass parts of pigment derivatives e were obtained by filtering and wash | cleaning the precipitate obtained by inject | pouring, stirring stirring a reaction liquid after 1800 mass parts of ice water after heat stirring.

Preparation Example 6 Synthesis of Pigment Derivative f

30 parts by mass of PR255 (Cromophtal DPP Coral Red C [trade name], manufactured by Ciba Specialty Chemicals K. K.) was dissolved in 450 parts by mass of sulfuric acid, and stirred at 20 ° C. for 30 minutes. Subsequently, 19.8 mass parts of paratoluene sulfonic acid monohydrate (made by Wako Pure Chemical Industries, Ltd.) was added to this, and it stirred at internal temperature of 20 degreeC for 10 minutes. Subsequently, 3.82 parts by mass of paraformaldehyde (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) Was added, followed by heating and stirring at 30 ° C for 2 hours. Subsequently, 19.98 parts by mass of 4-nitrophthalimide were added, and 3.82 parts by mass of paraformaldehyde (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) Was added after 10 minutes, and heated and stirred at 30 ° C. for 2 hours. 29.2 mass parts of pigment derivatives f were obtained by filtering and wash | cleaning the precipitate obtained by inject | pouring, stirring a reaction liquid after stirring with 1800 mass parts of ice water after heat stirring.

Preparation Example 7 Synthesis of Pigment Derivative g

30 parts by mass of PR255 (Cromophtal DPP Coral Red C [trade name], manufactured by Ciba Specialty Chemicals K. K.) was dissolved in 450 parts by mass of sulfuric acid, and stirred at 20 ° C. for 30 minutes. Subsequently, 19.8 mass parts of paratoluene sulfonic acid monohydrate (made by Wako Pure Chemical Industries, Ltd.) was added to this, and it stirred at internal temperature of 20 degreeC for 10 minutes. Subsequently, 3.82 parts by mass of paraformaldehyde (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) Was added, followed by heating and stirring at 30 ° C for 2 hours. Subsequently, 16.76 mass parts of 4-methylphthalimide were added, 3.82 mass parts of paraformaldehyde (made by TOKYO CHEMICAL INDUSTRY CO., LTD.) Was added after 10 minutes, and it heated and stirred at 30 degreeC for 2 hours. 27.6 mass parts of pigment derivatives were obtained by filtering and washing the precipitate obtained by inject | pouring, stirring stirring a reaction liquid after 1800 mass parts of ice water after heat stirring.

Preparation Example 8 Synthesis of Pigment Derivative h

30 parts by mass of PR255 (Cromophtal DPP Coral Red C [trade name], manufactured by Ciba Specialty Chemicals K. K.) was dissolved in 450 parts by mass of sulfuric acid, and stirred at 20 ° C. for 30 minutes. Subsequently, 19.8 mass parts of paratoluene sulfonic acid monohydrate (made by Wako Pure Chemical Industries, Ltd.) was added to this, and it stirred at internal temperature of 20 degreeC for 10 minutes. Subsequently, 3.82 parts by mass of paraformaldehyde (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) Was added, followed by heating and stirring at 30 ° C for 2 hours. Subsequently, 23.51 parts by mass of 4-bromophthalimide was added, and 3.82 parts by mass of paraformaldehyde (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) Was added after 10 minutes, and the mixture was heated and stirred at 30 ° C. for 2 hours. 31.2 mass parts of pigment derivative h was obtained by filtering and washing the precipitate obtained by inject | pouring, stirring stirring a reaction liquid after 1800 mass parts of ice water after heat stirring.

Preparation Example 9 Synthesis of Pigment Derivative i

30 parts by mass of PR255 (Cromophtal DPP Coral Red C [trade name], manufactured by Ciba Specialty Chemicals K. K.) was dissolved in 450 parts by mass of sulfuric acid, and stirred at 20 ° C. for 30 minutes. Subsequently, 19.8 mass parts of paratoluene sulfonic acid monohydrate (made by Wako Pure Chemical Industries, Ltd.) was added to this, and it stirred at internal temperature of 20 degreeC for 10 minutes. Subsequently, 3.82 parts by mass of paraformaldehyde (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) Was added, followed by heating and stirring at 30 ° C for 2 hours. Subsequently, 19.88 parts by mass of 4-carboxyphthalimide was added, and 3.82 parts by mass of paraformaldehyde (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) Was added after 10 minutes, and the mixture was heated and stirred at 30 ° C. for 2 hours. 28.6 parts by mass of pigment derivative i were obtained by filtering and washing the precipitate obtained by inject | pouring, stirring the reaction liquid after stirring with 1800 mass parts of ice water after heat stirring.

Preparation Example 10 Synthesis of Pigment Derivative j

35.4 parts by mass of PR122 (Cromophtal Pink PT [trade name], manufactured by Ciba Specialty Chemicals K. K.) (Cromophtal DPP Coral Red C [trade name], manufactured by Ciba Specialty Chemicals K. K.) was dissolved in 220 parts by mass of sulfuric acid, and stirred at 60 ° C. for 30 minutes. Subsequently, 19.8 mass parts of paratoluene sulfonic acid monohydrate (made by Wako Pure Chemical Industries, Ltd.) was added to this, and it stirred at internal temperature of 60 degreeC for 10 minutes. Subsequently, 3.82 parts by mass of paraformaldehyde (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) Was added, followed by heating and stirring at 60 ° C for 2 hours. Subsequently, 18.43 parts by mass of hydroxymethylphthalimide (manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by heating and stirring at 60 ° C. for 2 hours. 38.7 mass parts of pigment derivatives j were obtained by filtering and wash | cleaning the precipitate obtained by inject | pouring, stirring stirring a reaction liquid after 1100 mass parts of ice water after heat stirring.

(Example I, Comparative Example I)

(Example 1)

<Preparation of Organic Pigment Nanoparticle Dispersion>

4000 g of dimethyl sulfoxide (manufacturer: Wako Pure Chemical Industries, Ltd.) was charged into a 10 L-made SUS304 pot (210 mm in diameter), and propeller agitation was performed at 600 rpm with three 30-blade propellers to obtain a PR254 IRGAZIN powder. (Manufacturer: Ciba Specialty Chemicals KK) Slowly add 300 g of a slurry of pigment. Subsequently, in order to dissolve the pigment in the slurry to the molecular level, a solution obtained by diluting 310 g of 25% aqueous tetramethylammonium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) in 950 g of known dimethyl sulfoxide was prepared. IWAKI CO., LTD. The product is a chemical gear pump, which is introduced into the slurry at a flow rate of 2 L / min. At this time, stirring of the slurry performed 600 rpm of propeller stirring as mentioned above. Immediately after the addition, the absorbance was measured with a spectrophotometer (manufacturer: Agilent Technologies, model number: 8453), and it was confirmed that the absorbance Abs at 750 nm and 800 nm was 0.005 or less. Subsequently, slurry creation of a pigment derivative is performed again separately from the said pigment crude liquid. 1300 g of known dimethyl sulfoxide is introduced into a 3 L volume port of SUS304 in advance, and 60 g of a pigment derivative is gradually introduced while stirring at a low speed at 600 rpm using a high-speed stirring disperser (power consumption of 1 Kw) having a turbine blade of Φ 18. At this time, since the slurry is not uniformly suspended, the rotation speed of the same dissolver blade is raised to 6000 rpm, and stirred at high speed for 2 minutes to form a uniform slurry. Subsequently, the said slurry is thrown in at once into the IRGAZIN melt | dissolution liquid produced. Subsequently, the solution was stirred at a low speed of 600 rpm, and a solution obtained by diluting 95 g of a known 25% tetramethylammonium hydroxide aqueous solution to 300 g of known dimethyl sulfoxide was added to IWAKI CO., LTD. The product is supplied at a flow rate of 0.2 L / min with the chemical gear pump. The crude liquid work ends here. Again, absorbance was measured to confirm that Abs at 750 nm and 800 nm was 0.005 or less. In addition, the liquid immediately before using for reactor mixing is used after confirming that Abs is 0.005 or less.

As a result of measuring the viscosity of this pigment solution using Viscometer VM-10A-L (brand name, the product of CBC Materials), the viscosity when the liquid temperature of the pigment solution was 24.5 degreeC was 14.3 mPa * s. Separately from this, 2000 ml of ion-exchanged water containing 38 g of 1 mol / L aqueous hydrochloric acid solution (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as a poor solvent.

Here, NP-KX-500 large capacity of the pigment solution in 1000 ml of the poor solvent which temperature-controlled at 10 degreeC and stirred at 500 rpm by GK-0222-10 type Ramond Stirrer (brand name, the product made by Fujisawa Pharmaceutical Co., Ltd.) An organic pigment particle having an average particle diameter of Table 2 was formed by injecting 200 ml at a flow rate of 400 ml / min from a liquid feeding pipe having a flow path diameter of 1.1 mm using a no-flow pump (trade name, manufactured by Nihon Seimitsu Kagaku Co., Ltd.).

<Adjustment of Organic Pigment Powder>

The paste containing the pigment | dye material of particulate form was obtained by filtering under reduced pressure the pigment dispersion liquid prepared by the above procedure by the aspirator using the 9-cm-diameter nut body and filter paper (Advantec, No. 2 (brand name)). The paste thus obtained was again dispersed in ion-exchanged water and filtered again to repeat the procedure of washing the paste to remove the good solvent and the water-soluble ions. The water washing of the paste was repeated until the conductivity when the paste was dispersed so that the pigment concentration was 5% became 1 ms / m or less.

189 parts by mass of propylene glycol monomethyl ether acetate was added to 30 parts by mass of the above water paste and 3 hours using GK-0222-10 type Ramond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.) at a temperature of 25 ° C. Crystal conversion was performed by stirring. Subsequently, the mixture was concentrated by soap filtration, washed with addition of ion-exchanged water, and filtered again to stop the excessive progress of crystallization by substituting the solvent twice with water, followed by concentration by quenching again. The water paste of 30% of solid content concentration containing the dichloro diketopyrrolopyrrole pigment which passed the conversion was obtained. The obtained water paste was frozen at -20 ° C for 2 hours and dried in a freeze dryer to obtain organic pigment powder 1.

<Preparation of organic pigment dispersion composition>

After the said organic pigment powder 1 was ground to 180 micrometers or less with a mortar, it was uniformly stirred and mixed as the organic pigment dispersion composition 1 of the following composition.

9.7 g of the organic pigment powder 1

Pigment derivative 1 2.0g

Pigment Derivative 2 2.3g

12.1 g of dispersion resin described in the table

Propylene glycol monomethyl ether acetate 112.7 g

The pigment derivative a 3.5g

The organic pigment dispersion composition 1 of the above composition was sand grinder mill BSG-01 (trade name, manufactured by AIMEX) at 1500 rpm using 0.5 mm zirconium oxide beads, and then 2500 rpm using zirconium oxide beads 0.05 mm in diameter. It disperse | distributed for 2 hours and obtained pigment dispersion composition 1.

(Example 2-Example 10, Comparative Example 1-Comparative Example 2)

The organic pigment dispersion compositions 2-10 (pigment dispersion compositions 2-10, except that the compound added to the organic pigment dispersion composition 1 was replaced with the pigment derivative a, and it changed as shown in following Table 2 in Example 1) c1 to c2) were prepared. In addition, the dispersion c2 in Table 2 means prepared without using the pigment derivative a. In addition, it means that the following compound was used instead of the pigment derivative a about dispersion c1.

(Example 11)

<Preparation of Organic Pigment Nanoparticle Dispersion>

4000 g of dimethyl sulfoxide (manufacturer: Wako Pure Chemical Industries, Ltd.) was charged into a 10 L-made SUS304 pot (210 mm in diameter), and propeller agitation was performed at 600 rpm with three 30-blade propellers to obtain a PR254 IRGAZIN powder. (Manufacturer: Ciba Specialty Chemicals KK) 300 g, 15 g of pigment derivatives 2 and 45 g of pigment derivatives 3 were gradually added to prepare a slurry of pigments. Subsequently, in order to dissolve the pigment in the slurry to the molecular level, a solution obtained by diluting 372 g of 25% aqueous tetramethylammonium hydroxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) with 950 g of known dimethyl sulfoxide was prepared. IWAKI CO., LTD. The product is a chemical gear pump, which is introduced into the slurry at a flow rate of 2 L / min. At this time, stirring of the slurry performed 600 rpm of propeller stirring as mentioned above. Immediately after the addition, the absorbance was measured with a spectrophotometer (manufacturer: Agilent Technologies, model number: 8453), and it was confirmed that the absorbance Abs at 750 nm and 800 nm was 0.005 or less. Subsequently, slurry creation of a pigment derivative is performed again separately from the said pigment crude liquid. 1300 g of known dimethyl sulfoxide is introduced into a 3 L volume port of SUS304 in advance, and 60 g of a pigment derivative is gradually introduced while stirring at a low speed at 600 rpm using a high-speed stirring disperser (power consumption of 1 Kw) having a turbine blade of Φ 18. At this time, since the slurry is not uniformly suspended, the rotation speed of the same dissolver blade is raised to 6000 rpm, and stirred at high speed for 2 minutes to form a uniform slurry. Subsequently, the said slurry is thrown in at once into the IRGAZIN melt | dissolution liquid produced. Subsequently, the solution was stirred at a low speed of 600 rpm, and a solution obtained by diluting 95 g of a known 25% tetramethylammonium hydroxide aqueous solution to 300 g of known dimethyl sulfoxide was added to IWAKI CO., LTD. The product is supplied at a flow rate of 0.2 L / min with the chemical gear pump. The crude liquid work ends here. Again, absorbance was measured to confirm that Abs at 750 nm and 800 nm was 0.005 or less. In addition, the liquid immediately before using for reactor mixing is used after confirming that Abs is 0.005 or less.

The viscosity of the pigment solution was measured using Viscometer VM-10A-L (brand name, the product of CBC Materials), and the viscosity when the liquid temperature of the pigment solution was 24.5 degreeC was 16.1 mPa * s. Separately from this, 2000 ml of ion-exchanged water containing 57 g of 1 mol / L aqueous hydrochloric acid solution (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as a poor solvent.

Here, NP-KX-500 large capacity of the pigment solution in 1000 ml of the poor solvent which temperature-controlled at 10 degreeC and stirred at 500 rpm by GK-0222-10 type Ramond Stirrer (brand name, the product made by Fujisawa Pharmaceutical Co., Ltd.) A pigment dispersion was prepared by injecting 200 ml at a flow rate of 400 ml / minute from a liquid feeding pipe having a flow path diameter of 1.1 mm using a no-flow pump (trade name, manufactured by Nihon Seimitsu Kagaku Co., Ltd.).

The paste containing the pigment | dye material of particulate form was obtained by filtering under reduced pressure the pigment dispersion liquid prepared by the above procedure by the aspirator using the 9-cm-diameter nut body and filter paper (Advantec, No. 2 (brand name)). The paste thus obtained was again dispersed in ion-exchanged water and filtered again to repeat the procedure of washing the paste to remove the good solvent and the water-soluble ions. The water washing of the paste was repeated until the conductivity when the paste was dispersed so that the pigment concentration was 5% became 1 ms / m or less.

189 parts by mass of propylene glycol monomethyl ether acetate was added to 30 parts by mass of the above water paste and 3 hours using GK-0222-10 type Ramond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.) at a temperature of 25 ° C. Crystal conversion was performed by stirring. Subsequently, the mixture was concentrated by soap filtration, washed with addition of ion-exchanged water, and filtered again to stop the excessive progress of crystallization by substituting the solvent twice with water, followed by concentration by quenching again. The water paste of 30% of solid content concentration containing the dichloro diketopyrrolopyrrole pigment which passed the conversion was obtained. The obtained water paste was frozen at -20 ° C for 2 hours and dried in a freeze dryer to obtain organic pigment powder 2.

<Preparation of organic pigment dispersion composition>

After grind | pulverizing the said organic pigment powder 2 to 180 micrometers or less with a mortar, it was uniformly stirred and mixed as the organic pigment dispersion composition 11 of the following composition.

9.7 g of the organic pigment powder 2

8.55 g of dispersion resin of the table | surface description

Propylene Glycol Monomethyl Ether Acetate 79.9g

2.7 g of the pigment derivative

The organic pigment dispersion composition 11 of the above composition was subjected to sand grinder mill BSG-01 (trade name, manufactured by AIMEX) at 1500 rpm using 0.5 mm zirconium oxide beads for 1 hour, followed by 2500 rpm using zirconium oxide beads of 0.05 mm diameter. It disperse | distributed for 2 hours and obtained pigment dispersion composition 11.

(Example 12-Example 20, Comparative Example 3-Comparative Example 4)

The organic pigment dispersion compositions 12-20 (pigment dispersion compositions 12-20, etc.) were carried out similarly to Example 11 except having changed the compound added to the organic pigment dispersion composition 11 into pigment derivative a, as shown in Table 2 below. c3 to c4) were prepared.

(Example 21)

C.I. 9.7 g of Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals KK) (average particle diameter 60 nm), 2 g of pigment derivative 1, 2.3 g of pigment derivative 2, dispersant resin 11.3 g, propylene glycol monomethyl 24.7 g of ether acetate and 3.5 g of a pigment derivative a were mixed, and the mixture was mixed with sand grinder mill BSG-01 (trade name, manufactured by AIMEX) for 1 hour at 1500 rpm using a zirconium oxide bead of 0.5 mm in diameter, followed by 0.05 mm in diameter. It was dispersed for 2 hours at 2500 rpm using zirconium oxide beads to obtain a pigment dispersion composition 21.

<Evaluation of Pigment Dispersion Composition>

The following evaluation was performed about each sample of the obtained pigment dispersion composition. The results are summarized in Table 2.

○ Measurement of particle diameter distribution of pigment fine particles and number average primary particle size (Dp)

The particle diameter distribution of the pigment particle contained in a dispersion liquid was measured on condition of the following, and the ratio P and the number average primary particle diameter Dp of the particle number of 20 nm-30 nm of particle diameters were computed.

<TEM shooting>

Device: Hitachi, Ltd. Product, H-7650 electron microscope

Acceleration voltage: 110 kV

(The graphography observation was performed to extract the surface with little overlap between particles from the 3D reconstruction data to obtain the projection area of the particles.)

<Image measurement>

Device: Carl Zeiss, KS-400

(The TEM images of 5000 pigment particles selected randomly were measured to calculate the circle equivalent diameter from the projected area, and the above ratios P and Dp were calculated.)

○ Measurement and evaluation of viscosity

About the obtained pigment dispersion composition, using the E-type clay system (TOKI SANGYO CO., LTD. Product, RE-85L [brand name], measurement temperature 25 degreeC), the viscosity of the pigment dispersion composition immediately after dispersion is carried out at room temperature after dispersion and dispersion. The viscosity (eta) 2 of the pigment dispersion composition after 1 week passed was measured, and the grade of thickening was evaluated. Here, the thing with a low viscosity shows that the raise of the viscosity resulting from a dispersing agent is suppressed, and the dispersibility and dispersion stability of a pigment are favorable.

○ Measurement and evaluation of contrast

The obtained pigment dispersion composition was apply | coated on a glass substrate, and the sample was produced so that the thickness of the coating film after drying might be set to 1 micrometer. The samples were placed on two polarizing plates, and the amount of transmitted light when the polarization axes were parallel and perpendicular was measured, and the ratio was called contrast (this evaluation method is `` 1990's 7th Color Optical Conference, 512 Color Display 10.4 ''). (See color filter for size TFT-LCD, Ueki, Ozeki, Fukunaga, Yamanaka.). Here, the high contrast means that the pigment is uniformly dispersed in a highly refined state, so that the transmittance, that is, the coloring power This is high.

Although the sample name was represented by the number of a dispersion, what was used for the measurement object is as having described in the text, respectively.

Resin 1: Disperbyk-161

Resin 2: Copolymer of the repeating unit (M-11) / (A-5) / methacrylic acid (Mw 20,000, composition ratio (wt%) 10/60/30)

Resin 3: Graft resin (backbone Mn: 600, graft amount 9.3 mol% (vs. total amine) having the following structure, acid value 10 mgKOH / g, Mw: 10000

Ra: -CO-nC ₇ H ₁₅ or a hydrogen atom, v: 40, w: 5, x: 10, y + z: 45)

As a result shown in the above table, the pigment dispersion composition to which the pigment derivative compound of the present invention was added at the time of dispersion shows better dispersion characteristics with respect to the comparative example. In addition, it was found that the pigment dispersion composition using the pigment derivative in the reprecipitation method was very small in average particle diameter and had favorable properties as compared with that of the comparative example.

(Example II, Comparative Example II)

<Preparation of a colored photosensitive composition>

The following colored photosensitive composition was prepared using said pigment dispersion composition (1A-11A, c1A-c2A), respectively.

ㆍ 2000 parts of pigment dispersion composition

ㆍ 100 parts of dipentaerythritol hexaacrylate (photopolymerizable compound)

30 parts of 4- [o-bromo-p-N, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine (photopolymerization initiator)

400 parts of propylene glycol monomethyl ether acetate solution (30% of solid content) (alkali-soluble resin) of the methacrylic acid benzyl / methacrylic acid (= 75/25 [mass ratio]) copolymer (weight average molecular weight: 12,000)

ㆍ 390 parts of 1-methoxy-2-propyl acetate (solvent)

<Production of Color Filters Using Colored Photosensitive Composition>

The prepared colored photosensitive composition (color resist liquid) was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the x value, which is an index of color density, was 0.650, and dried in an oven at 90 ° C. for 60 seconds ( Prebaking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm 2 (roughness 20 mW / cm 2), and the coated film after exposure was coated with a 1% aqueous solution of alkaline developer CDK-1 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) for 60 seconds. Stopped. After stopping, the pure water was spread out in the shower, and the developer was washed away. Then, the coating film subjected to exposure and development as described above was heat-treated in an oven at 220 ° C. for 1 hour (post-baking), and a colored pattern (colored area) for a color filter was formed on the glass substrate to form a colored filter substrate (colored). Filter).

<Evaluation of Colored Photosensitive Composition and Color Filter>

The produced colored photosensitive composition and the colored filter substrate (color filter) were evaluated as follows. The results are collectively shown in the table above.

○ Contrast of color filter (CF)

The polarizing plate is arrange | positioned on the coloring pattern of a color filter, a coloring pattern is inserted, and the luminance when it is orthogonal to the luminance when a polarizing plate is parallel is measured using BM-5 (brand name) made from TOPCON CORPORATION, and the luminance at parallel Is a value obtained by dividing by the luminance at orthogonality (= luminance at parallel / luminance at orthogonal angle) as an index for evaluating contrast. Larger values indicate higher contrast.

○ Measurement of light resistance

The sample used for the measurement of the contrast was irradiated with a high-pressure mercury lamp of 90 mW / cm 2 for 24 hours, and the color difference before and after irradiation was measured to be an index of light resistance. In addition, chromaticity is measured with a microscopic spectrophotometer (OLYMPUS CORPORATION; OSP100 or 200), is calculated as a result of the F10 light source field of view 2 degrees, and is represented by the xyY value of the xyz colorimeter. In addition, the difference of chromaticity is shown by the color difference of La ^* b ^* color system. The smaller the color difference, the higher the light resistance.

○ evaluation of light resistance

The produced color filter was forcibly heated in an oven at 250 ° C. for 1 hour, and the contrast retention rate before and after the treatment was evaluated.

As a result shown in the table, the pixel of the color filter produced using the dispersion using the pigment derivative compound of the present invention has very high contrast and exhibits high light resistance, and the pixel of the color filter of the present invention has black sharpness. Was excellent and the color taste was very good.

Claims (13)

As pigment particulate dispersions containing pigment derivative compounds and pigment particulates:
A pigment fine particle dispersion wherein said pigment derivative compound is a compound obtained by reacting a pigment, a compound represented by the following general formula (1), and a compound represented by the following general formula (2) in an acidic solvent.

[Q in general formula (1) represents the aromatic hydrocarbon group which may have a substituent. n represents the integer of 1-4. In General Formula (2), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group.] The method of claim 1,
The pigment derivative compound is a compound obtained by reacting a compound represented by the following general formula (3).

[T in general formula (3) represents a monovalent organic group. k represents the integer of 0-4. R ³ represents a hydrogen atom or a hydroxymethyl group.] The method of claim 1,
Pigment as a substrate of the pigment derivative compound is a pigment fine particle dispersion, characterized in that diketopyrrolopyrrole pigment compound. The method of claim 1,
The pigment fine particle dispersion which produced | generated the said pigment fine particle by mixing the melt | dissolution liquid which melt | dissolved the pigment in the good solvent, and the medium used as a poor solvent about the said pigment by making it compatible with the said good solvent. The method of claim 1,
The pigment fine particle dispersion characterized in that the pigment which comprises the said pigment fine particle is 1 or more types chosen from the group which consists of a diketopyrrolopyrrole pigment, a quinacridone pigment, an anthraquinone pigment, and an azo pigment. The method of claim 1,
The pigment fine particle dispersion further containing the dispersing agent which has a polycaprolactone structure. The method of claim 1,
The pigment fine particle dispersion further containing the high molecular compound containing 1 or more types of repeating units chosen from the repeating unit represented by either of following General formula (I) and General formula (II).

[In Formula (I) and Formula (II), R ²¹ to R ²⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ²¹ and X ²² each independently represent -CO- and -C (= O). O-, -CONH-, -OC (=)-or a phenylene group, L ²¹ and L ²² each independently represent a single bond or a divalent organic linking group, and A ²¹ and A ²² each independently represent a monovalent organic group. Group, ma and na each independently represent an integer of 2 to 8, and p and q each independently represent an integer of 1 to 100.] The method of claim 1,
It is a coloring material for color filters, The pigment fine particle dispersion characterized by the above-mentioned. The photocurable composition containing the pigment fine particle dispersion of any one of Claims 1-8, a polymeric compound, and a photoinitiator. It has the pixel formed by hardening | curing the photocurable composition of Claim 9, The color filter characterized by the above-mentioned. A pigment derivative compound comprising a residue of each of said substrates obtained by reacting a pigment, a compound represented by the following general formula (1), and a compound represented by the following general formula (2) in an acidic solvent.

[Q in general formula (1) represents the aromatic hydrocarbon group which may have a substituent. n represents the integer of 1-4. In General Formula (2), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group.] The method of claim 11,
The pigment derivative compound which further has this residue obtained by making the compound represented by following General formula (3) react.

[T in general formula (3) represents a monovalent organic group. k represents the integer of 0-4. R ³ represents a hydrogen atom or a hydroxymethyl group.] As a method for preparing the pigment derivative compound according to claim 11:
The pigment, the compound represented by the said General formula (1), and the compound represented by the said General formula (2) are made to react in an acidic solvent, The manufacturing method of the pigment derivative compound characterized by the above-mentioned.