JP2008081566A - Pigment dispersant, pigment composition and pigment dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment dispersant effective for pigment dispersion in preparing an ink, a coating, etc., and a pigment dispersion containing the same. <P>SOLUTION: This pigment dispersant has a phthaloyl nucleus, quinaldine nucleus and phthalic imide nucleus. The dispersant has a structure in which the amino group of a compound expressed by formula (I) constitutes the phthalic imide nucleus. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a pigment dispersant used for dispersing a pigment, a pigment composition containing the pigment dispersant, and a pigment dispersion. More particularly, the present invention relates to a pigment dispersant effective for the preparation of inks and paints, a pigment composition containing the same, and a pigment dispersion in which the pigment composition is dispersed in a non-aqueous vehicle.

  In general, the coloring power and sharpness of pigments used in various ink compositions and paints are closely related to the properties of pigment particles. Usually, pigment particles form an aggregate of primary particles, and it is known that the finer the primary particles, the higher the coloring power of the pigment and the higher the sharpness. Therefore, in order to improve the coloring power and sharpness of the pigment, it is necessary to make the aggregation state of the primary particles finer. On the other hand, as the pigment particles become finer, aggregation between particles tends to occur. For this reason, it is necessary to stably disperse the pigment particles in the vehicle in a fine state. Various printing inks and paints are obtained by finely and stably suspending a solid pigment powder in a liquid vehicle. The dispersion process essentially includes a three-step process of wetting, miniaturization, and stabilization. However, in an actual distributed system, each process occurs in parallel, and it is often difficult to strictly separate these processes.

  Although the above is known regarding the pigment particles and the dispersion process, it is often difficult to prepare a stable dispersion by suspending fine pigment particles in a non-aqueous vehicle. Therefore, the quality of the dispersion stability of the pigment in the non-aqueous vehicle has a significant effect on the production process of printing inks and paints such as offset inks and gravure inks and the quality of products, and may cause various problems. It is known to cause.

  Dispersions containing fine pigment particles often exhibit high viscosity, which can make it difficult to remove from the preparation container or transfer between containers, possibly resulting in changes in state such as gelation. Quality may be lost. In addition, when pigments with different chemical structures are used in a mixed state, a phenomenon called color separation or sedimentation caused by aggregation of pigment particles occurs, resulting in a state such as a decrease in gloss or poor leveling on the surface of the developed paint film. May cause defects. Further, when the dispersion stability of the pigment in the ink and the paint is low, the state of the pigment crystal may change due to the energy instability in the non-aqueous vehicle of the pigment particles. That is, the pigment crystal changes its aggregated state and shifts to a more stable state, thereby causing phenomena such as a change in hue, a decrease in coloring power and sharpness, and formation of agglomerated particles. May change and significantly impair commercial value.

  As described above, in the field where pigments are used in a dispersed state, various problems associated with dispersion are assumed, and various types of dispersants have been developed for this purpose. As such a dispersant, it is known that it is effective to use a derivative having a skeleton of a pigment to be dispersed or a chemical structure similar thereto. To date, pigment derivatives in which specific functional groups such as acidic groups or basic groups have been introduced into the pigment skeleton, resin-type pigment dispersants in which these functional groups have been introduced into acrylic resins, polyester resins, etc., as part of the resin Resin-type pigment derivatives incorporating a pigment skeleton have been developed. These dispersants are used alone or in combination, and the effect is exhibited by any of the usage methods.

  Examples of the derivatives having an acidic group introduced into the skeleton as a pigment include phthalocyanine pigments, quinacridone pigments, azo pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, isoindolinone pigments, sulfonic acid groups and carboxyl groups that are acidic groups. Derivatives having a structure in which is introduced are disclosed. These pigment derivatives are widely used as dispersants, crystal growth inhibitors or inhibitors. Furthermore, in recent years, such a technique has been widely developed as a color filter ink.

As examples of the above pigment derivatives, JP-A-8-3122 discloses a derivative having an acidic group introduced into the pigment skeleton, and examples of the acidic group include a sulfonic acid group and a terephthalic acid monoamidomethyl group. Japanese translations of PCT publication No. 2004-501911 disclose various quinophthalone derivatives into which a sulfonic acid group or a carboxyl group is introduced. JP 2002-179979 discloses a sulfonated derivative of PY138 as a yellow pigment, and JP 2004-67715 discloses PY138, a derivative obtained by introducing a basic group into a quinophthalone derivative having a polar group, and a sulfonated derivative. JP-A-2004-292785 discloses a sulfonic acid divalent metal salt of a quinophthalone pigment. Japanese Patent Application Laid-Open No. 2001-335711 discloses basic quinophthalone derivatives containing an alkylamino group or a nitrogen-containing heterocyclic group, and Japanese Patent Application Laid-Open No. 2002-121418 is a wide range of quinoline derivatives substituted with unsubstituted and substituted amino groups. Is disclosed. JP-A No. 2002-121456 discloses various pigment derivatives in which the terminal of the substituent is substituted with a carboxyl group, ester group, hydroxyl group, mercapto group, sulfonic acid group, unsubstituted or substituted amino group.
All currently used pigment derivatives have the effect of improving the dispersion state, but pointed out that the properties are not yet satisfactory in terms of viscosity, flow characteristics and stability over time. Has been. Therefore, it is desired to develop pigment derivatives having excellent properties that do not have these problems.

JP-A-8-3122 Special table 2004-501911 gazette JP 2002-179799 A JP 2004-67715 A JP 2004-292785 A JP 2001-335711 A JP 2002-121418 A JP 2002-121456 A

  The problem to be solved by the present invention is to provide a pigment dispersant effective for pigment dispersion during the preparation of inks, paints and the like, and a pigment composition containing the same. It is another object of the present invention to provide a pigment dispersion having various properties such as improved flow characteristics at the time of pigment dispersion, low viscosity, and good viscosity stability over time.

As a result of intensive studies by the present inventors, it has been found that the compound represented by the general formula (1) has the above-mentioned properties, and has led to the present invention. That is, this invention relates to the pigment dispersant which consists of following General formula (1).

General formula (1)

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom, a halogen atom, or an alkyl group,
R ^{5 to} R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxyl group, a phenyl group, or a nitro group,
R ^{10 to} R ¹³ are each independently a hydrogen atom, halogen atom, hydroxyl group, alkyl group, alkoxyl group, nitro group, amino group, sulfonic acid group, carboxylic acid group, the following general formula (2), or the following general formula The group represented by the formula (3) is shown, and at least one of R ^{10 to} R ¹³ is a group represented by the following general formula (2) or the following general formula (3).
R ¹¹ and R ¹² may be integrated. )

General formula (2)

(In the formula, X ¹ represents a sulfone bond or a carbonyl bond,
X ² is a monovalent heterocyclic group which may have a substituent. However, the monovalent heterocyclic group has at least one nitrogen atom. )

General formula (3)

(In the formula, X ³ represents a group selected from a sulfonamide bond, an ether bond, an ester bond, a sulfoxide bond, a sulfone bond, an amino bond, and an amide bond.
X ⁴ represents a direct bond or a divalent aliphatic heterocyclic ring.
m represents an integer of 1 to 20.
X ⁵ represents —O— (CH ₂ ) _t —Y ¹ or —Y ² .
Y ¹ and Y ² each independently represent —NA ¹ A ² or a monovalent aliphatic heterocyclic group which may have a substituent.
A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 20 or less carbon atoms which may have a substituent.
t represents an integer of 1 to 20.
R ¹¹ and R ¹² may be integrated into the following general formula (4). )

General formula (4)

  The present invention also relates to a pigment and a pigment composition containing the pigment dispersant.

  Moreover, this invention relates to the said pigment composition whose pigment is a yellow pigment.

  In the present invention, the yellow pigment is C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, and C.I. I. The present invention relates to the pigment composition, which is at least one pigment selected from CI Pigment Yellow 185.

  Moreover, this invention relates to the said pigment composition whose pigment is a green pigment.

  In the present invention, the green pigment is C.I. I. Pigment green 7, C.I. I. Pigment green 10, C.I. I. Pigment green 36 or C.I. I. The present invention relates to the above pigment composition, which is at least one pigment selected from CI Pigment Green 37.

  The present invention also relates to the above pigment composition, wherein the pigment is a red pigment or an orange pigment.

  In the present invention, the red pigment or the orange pigment is C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 177, C.I. I. Pigment red 179, C.I. I. Pigment red 207, C.I. I. Pigment red 48: 1, C.I. I. Pigment orange 71, and C.I. I. The pigment composition is at least one pigment selected from CI Pigment Orange 73.

  The present invention also relates to a pigment dispersion obtained by dispersing the above pigment composition in a non-aqueous medium.

  By using the pigment dispersant of the present invention, a higher effect is obtained with respect to fine and low viscosity dispersion of the pigment as compared with the conventional pigment dispersant, transparency, coloring power is high, and storage stability is improved. It becomes possible to prepare a good dispersion. In addition, by using the pigment composition or pigment dispersion containing the pigment dispersant of the present invention, it is possible to easily prepare products such as high-quality and highly stable inks and paints.

  The pigment dispersant of the present invention is represented by the general formula (1) and has a structure in which the quinophthalone skeleton is substituted with a phthalimide group having a substituent. A substituent is a compound in which a skeleton and an alkylamine group are bonded to a divalent linking group (sulfonamide bond, ether bond, ester bond, sulfoxide bond, sulfone bond, or amino group) via an alkylene group. is there. By using this to disperse various pigments in a non-aqueous medium, it is possible to prepare compositions and dispersions having good physical properties.

  The structure will be specifically described below. First, general formula (1) will be described.

Examples of the halogen atom in R ^{1 to} R ¹³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group in R ^{1 to} R ⁴ and R ^{10 to} R ¹³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and an isopentyl group. , Neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl And nonadecyl group.
Examples of the alkoxyl group in R ^{5 to} R ¹³ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, and isopentyl. Oxy group, isohexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group , Heptadecyloxy group, octadecyloxy group, nonadecyloxy group and the like.

  Next, general formula (2) will be described.

Examples of the aliphatic heterocyclic ring of the monovalent aliphatic heterocyclic group which may have a substituent for X ² include piperidine, piperazine, pyrrolidine, 1-methylpyrrolidine, morpholine, thiomorpholine and the like.

Examples of the substituent that the monovalent heterocyclic group for X ² may have include an alkyl group.
Here, the alkyl group is the same meaning as the alkyl group for R ¹ to R ⁴ and R ¹⁰ to R ^13.

As the monovalent aliphatic heterocyclic ring which may have a substituent for X ² , an aliphatic heterocyclic ring represented by the following structural formula is preferable.

Next, general formula (3) will be described.

The sulfonamide bond and the amide bond in X ³ have the structures shown below.

R ¹⁴ and R ¹⁵ are each independently an alkyl group.

Here, the alkyl group is the same meaning as the alkyl group for R ¹ to R ⁴ and R ¹⁰ to R ^13.

Examples of the aliphatic heterocyclic ring of the divalent aliphatic heterocyclic group for X ⁴ include piperidine, piperazine, pyrrolidine, 1-methylpyrrolidine, morpholine, thiomorpholine and the like.

  The divalent aliphatic heterocyclic group preferably has the following structure.

The monovalent aliphatic heterocyclic group which may have a substituent in Y ¹ and Y ² is an aliphatic heterocyclic group having at least one nitrogen atom.

Examples of the substituent that the monovalent aliphatic heterocyclic group for Y ¹ and Y ² may have include an alkyl group.
Here, the alkyl group is the same meaning as the alkyl group for R ¹ to R ⁴ and R ¹⁰ to R ^13.

As the monovalent aliphatic heterocyclic group which may have a substituent in Y ¹ and Y ^2, an aliphatic heterocyclic group represented by the following structural formula is preferable.

Examples of the alkyl group which may have a substituent in A ¹ and A ² and has 20 or less carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert -Butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl , Hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and the like.

Examples of the substituent that the alkyl group in A ¹ and A ² may have include an unsubstituted or substituted amino group amino group, halogen atom, and heterocyclic group.

  Here, examples of the amino group having a substituent include methylamino group, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, di (sec-butyl) amino group, di (tert-butyl). ) Amino group, dipentylamino group, diisopentylamino group, dineopentylamino group, di (tert-pentyl) amino group, dihexylamino group, diisohexylamino group, diheptylamino group, dioctylamino group, dinonylamino group , Didecylamino group, diundecylamino group, didodecylamino group, ditridecyl group, ditetradecylamino group, dipentadecylamino group, dihexadecylamino group, diheptadecylamino group, dioctadecylamino group, dinonadecylamino group Group, diphenylamino group, dibiphenylylamino group, bis (t (Phenylyl) amino group, bis (quarterphenylyl) amino group, di (o-tolyl) amino group, di (m-tolyl) amino group, di (p-tolyl) amino group, dixylylamino group, di (o- Cumenyl) amino group, di (m-tolyl) amino group, di (p-cumenyl) amino group, dimesitylamino group, dipentalenylamino group, diindenylamino group, dinaphthylamino group, bis (binaphthalenyl) amino group Bis (tarnaphthalenyl) amino group, bis (quarternaphthalenyl) amino group, diazurenylamino group, diheptarenylamino group, bis (biphenylenyl) amino group, diindacenylamino group, difluoranthenylamino group, Diacenaphthylenyl group, bis (aceanthrylenyl) amino group, diphenalenylamino group, difluorenylamino group, dianthrylamino group, bis (bi Ntracenyl) amino group, bis (teranthracenyl) amino group, bis (quarteranthracenyl) amino group, bis (anthraquinolyl) amino group, diphenanthrylamino group, ditriphenylenylamino group, dipyrenylamino group, Lysenylamino group, dinaphthacenylamino group, diplyadenylamino group, dipicenylamino group, diperylenylamino group, bis (pentaphenyl) amino group, dipentacenylamino group, bis (tetraphenylenyl) Amino group, bis (hexaphenyl) amino group, dihexacenylamino group, dirubicenylamino group, dicoronenylamino group, bis (trinaphthylenyl) amino group, bis (heptaphenyl) amino group, diheptacenylamino Group, dipyranthrenylamino group, diovalenylamino group, methylethylamino group, methylpropyl Amino group, methylbutyl group, methylpentylamino group, methylhexylamino group, ethylpropylamino group, ethylbutylamino group, ethylpentylamino group, ethylhexylamino group, propylbutylamino group, propylpentylamino group, propylhexylamino group, Butylpentylamino group, butylhexylamino group, pentylhexylamino group, phenylbiphenylylamino group, phenylterphenylylamino group, phenylnaphthylamino group, phenylanthrylamino group, phenylphenanthrylamino group, biphenylylnaphthylamino Group, biphenylylanthrylamino group, biphenylylphenanthrylamino group, biphenylylterphenylylamino group, naphthylanthrylamino group, naphthylphenanthrylamino group, naphthyl Luterphenylylamino group, anthrylphenanthrylamino group, anthrylterphenylylamino group, methylphenylamino group, methylbiphenylylamino group, methylnaphthylamino group, methylanthrylamino group, methylphenanthrylamino group , Methylterphenylylamino group, ethylphenylamino group, ethylbiphenylylamino group, ethylnaphthylamino group, ethylanthrylamino group, ethylphenanthrylamino group, ethylterphenylylamino group, propylphenylamino group, propyl Biphenylylamino group, propylnaphthylamino group, propylanthrylamino group, propylphenanthrylamino group, propylterphenylylamino group, butylphenylamino group, butylbiphenylylamino group, butylnaphthylamino group , Butylanthrylamino group, butylphenanthrylamino group, butylterphenylylamino group, pentylphenylamino group, pentylbiphenylylamino group, pentylnaphthylamino group, pentylanthrylamino group, pentylphenanthrylamino group, Pentylterphenylylamino group, hexylphenylamino group, hexylbiphenylylamino group, hexylnaphthylamino group, hexylanthrylamino group, hexylphenanthrylamino group, hexylterphenylylamino group, heptylphenylamino group, heptylbiphenyl Rylamino group, heptylnaphthylamino group, heptylanthrylamino group, heptylphenanthrylamino group, heptylterphenylylamino group, octylphenylamino group, octylbiphenylylamino group, Chi Luna border Le amino group, octyl anthryl group, octyl phenanthryl group, octyl terpolymers phenylene Lil amino group, bis [4- (α, α'- dimethylbenzyl) phenyl] amino group, and the like.

  Here, the halogen atom is the same as that already shown.

  Here, as the heterocyclic group, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group Phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl Group, purinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group Le group, Acry Nyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group Group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, morpholino group and the like.

In the general formula (1), R ^{1 to} R ⁴ are particularly preferably halogen atoms such as chlorine atom and bromine atom.

In the general formula (1), R ^{5 to} R ⁹ are particularly preferably hydrogen atoms.

In the general formula (1), R ^{10 to} R ¹³ are groups in which R ¹¹ and R ¹² are each independently represented by the following general formula (2) or the following general formula (3); Particularly preferred is an atom.

In the general formula (3), X ³ is particularly preferably a sulfonamide bond, an ester bond, or an amide group.

In the general formula (3), Y ¹ and Y ² are particularly preferably —NA ¹ A ² .

  Specific examples of the compound of the present invention are specifically illustrated below, but the present invention is not limited to the following representative examples.

  The pigment composition of this invention contains the pigment and the pigment dispersant of this invention represented by General formula (1).

  Commercially available pigments such as azo, anthanthrone, anthrapyrimidine, anthraquinone, isoindolinone, isoindoline, indanthrone, quinacridone, quinophthalone, dioxazine, diketopyrrolopyrrole , Organic pigments such as thioindigo, pyranthrone, phthalocyanine, flavanthrone, perinone, perylene, benzimidazolone, carbon black, titanium oxide, yellow lead, cadmium yellow, cadmium red, petal, zinc oxide, Inorganic pigments such as bitumen and ultramarine can be used. Two or more of these pigments may be used in combination. Among the above pigments, an organic pigment is preferably used when the pigment dispersant of the present invention is used.

  The pigment used as the pigment composition of the present invention is not particularly specified, but is preferably the following.

  Examples of the yellow pigment include pigments classified as yellow according to a color index.

  Examples of the green pigment include pigments classified as green according to a color index (Color Index).

  Examples of the red pigment include pigments classified as red or orange according to a color index.

  The yellow pigment used is preferably the following.

  Examples of yellow pigments include C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment Yellow 185 and the like. Among these, C.I. I. Pigment Yellow 138 is particularly preferable. These pigments may be used alone or in combination of two or more.

  As the green pigment to be used, the following are preferable.

  Examples of green pigments include C.I. I. Pigment green 7, C.I. I. Pigment green 10, C.I. I. Pigment green 36, C.I. I. Pigment Green 37 and the like. Among these, C.I. I. Pigment green 7, C.I. I. Pigment Green 36 is particularly preferable. These pigments may be used alone or in combination of two or more.

  The red pigment used is preferably the following.

  Examples of red pigments include C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 177, C.I. I. Pigment red 179, C.I. I. Pigment red 207, C.I. I. Pigment Red 48: 1 and the like, and orange pigments include C.I. I. Pigment orange 71, C.I. I. Pigment Orange 73 is particularly preferable. These pigments may be used alone or in combination of two or more.

    As the pigment used in the pigment composition of the present invention, the above pigment may be used as it is, but may be used after subjecting the pigment particles to refinement by a method such as solvent salt milling or dry milling as necessary. . For example, when the organic pigment is refined by solvent salt milling, a mixture of the organic pigment, the water-soluble inorganic salt and the water-soluble solvent is strongly kneaded using a kneader such as a kneader. Next, the kneaded mixture is poured into water and stirred with various stirrers to form a slurry. The inorganic salt and the solvent are removed by filtering this. Through the above steps, a refined organic pigment can be obtained. In this pigment refinement method, the pigment may be either a single pigment or a mixture of two or more.

  Sodium chloride, potassium chloride, etc. can be used as a water-soluble inorganic salt in said refinement | miniaturization process. These inorganic salts are used in the range of 1 to 20 times the weight of the organic pigment. When the inorganic salt to be used is small, sufficient refinement is not performed, and when there is a large amount of inorganic salt, labor is required to remove the inorganic salt, and the processing efficiency is lowered, which is not preferable in terms of productivity. As the water-soluble solvent, it is preferable to use a solvent having a boiling point in the range of 120 to 250 ° C. from the viewpoint of safety. Examples of solvents having such properties include 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, di Examples include propylene glycol monoethyl ether.

  In the pigment composition of the present invention, the addition amount of the pigment dispersant represented by the general formula (1) is preferably 0.5 to 30 parts by weight with respect to 100 parts by weight of the pigment. When the amount added is less than 0.5 parts by weight, the effect of dispersing the pigment is reduced, which is not preferable. Moreover, even if it uses more than 30 weight part, the dispersion effect according to the addition amount is not acquired, and the fall of a characteristic may be caused depending on the case.

  As a method for preparing the pigment composition of the present invention, a sufficient dispersion effect can be obtained only by mixing the pigment powder and the pigment dispersant represented by the general formula (1). However, a dissolver, a high-speed mixer, a homomixer, A mechanical mixing method using various pulverizers such as a kneader, a roll mill, an attritor, a sand mill, a pigment dispersant solution or a suspension represented by the general formula (1) in a pigment water or organic solvent suspension. A higher dispersion effect is obtained by adding a turbid liquid, dissolving an organic pigment and a pigment dispersant in a good solvent such as sulfuric acid, and injecting the solution into a poor solvent such as water and coprecipitation. be able to.

  The pigment dispersion of the present invention is obtained by dispersing the pigment composition of the present invention in a non-aqueous medium. The pigment dispersion of the present invention can be prepared by dispersing a mixture of a pigment, the pigment dispersant of the present invention, an organic solvent, and a resin with various dispersers. Further, if necessary, in addition to the above raw materials, various additives, a resin-type dispersant, and the like may be added and then dispersed. In the preparation, the pigment and the pigment dispersant may be added as a pigment composition obtained by mixing in advance, or may be dispersed after being added separately. There is no particular limitation on the order of addition and the method of adding each raw material.

  Examples of the resin used to prepare the pigment dispersion of the present invention include petroleum resin, casein, back rack, rosin modified maleic resin, rosin modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber , Chlorinated rubber, oxidized rubber, hydrochloric acid rubber, phenol resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, acrylic resin, methacrylic resin, polyurethane resin, silicone resin, fluorine resin, drying oil Synthetic drying oil, styrene-modified maleic acid resin, pyramide resin, polyimide resin, benzoguanamine resin, melamine resin, urea resin, chlorinated polypropylene, butyral resin, vinylidene chloride resin and the like.

  Moreover, you may use photosensitive resin as resin. As an example of photosensitive resin. A polymer having a reactive functional group such as a hydroxyl group, a carboxyl group, or an amino group is reacted with an acrylic compound or cinnamic acid having a reactive substituent such as an isocyanato group, a formyl group, or an epoxy group to produce an acryloyl group or styryl group. Hydroxyalkyl is a linear polymer containing a resin in which a photocrosslinkable group such as a group is introduced, or an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer. Examples thereof include those obtained by half-esterification with an acrylic compound having a hydroxyl group such as acrylate.

  The resin can be used in an amount of 10 to 400 parts by weight with respect to 100 parts by weight of the pigment.

  The organic solvent used for preparing the pigment dispersion of the present invention is not particularly limited. Any of those generally used as a solvent can be used. For example, cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, toluene, xylene, ethyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, propylene glycol monomethyl ether, acetic acid Examples include ethyl, butyl acetate, hexane, methanol, ethanol, isopropyl alcohol, butanol, dioxane, dimethylformamide, and petroleum solvents. These solvents can be used either alone or in combination.

  The disperser used for preparing the pigment dispersion of the present invention is not particularly specified. For example, horizontal sand mill, vertical sand mill, annular bead mill, attritor, microfluidizer, high speed mixer, homomixer, ball mill, roll mill , Stone mill, ultrasonic disperser, paint conditioner, etc. Usually, any disperser or mixer used in preparing various dispersions can be used. In addition, before dispersion by various dispersers, predispersion by a kneader mixer such as a kneader, three roll mill, or solid dispersion by a two roll mill may be performed. In addition, after being dispersed with various dispersers, post-processing for about several hours to one week in a heated state at 30 to 80 ° C., processing using an ultrasonic disperser or a collision type beadless disperser, etc. It is effective for imparting dispersion stability to the pigment dispersion.

  Examples will be specifically shown below, but the present invention is not limited thereto.

Synthesis example 1
Synthesis method of compound (I) (intermediate) C.I. I. Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BSF, Inc.) (400 g), potassium hydroxide (400 g), and 3600 g of water were charged and reacted at 90 ° C. for 16 hours. After cooling, 540 ml of 36% hydrochloric acid was added dropwise. After filtration, washing with water, and washing with acetone, vacuum drying was performed to obtain a compound (I) represented by the following formula.

Synthesis example 2
Method for synthesizing pigment derivative (A) (compound (1))

  Compound (I) (35 g), compound (1-1) (27 g) and benzoic acid 200 g were heated and heated, and stirred at 180 ° C. for 6 hours. After cooling to room temperature, the reaction product was poured into 1000 ml of methanol and stirred at room temperature for 1 hour. The precipitated crystals were filtered, washed with water and dried to obtain 45 g (yield 85%) of yellow crystals of the compound. Compound (1-2) (63 g) was added to 240 ml of dichlorobenzene, and 1.5 g of pyridine was added, followed by heating to 100 ° C. To this was added dropwise thionyl chloride (46 g), and the mixture was further reacted for 6 hours. Excess thionyl chloride was removed under reduced pressure, and the reaction proceeded as it was. The obtained (1-3) was added to 200 ml of acetonitrile containing N, N-diethylaminopropylamine (15 g) and triethylamine (10 g) under ice cooling and stirred. After the reaction, the reaction mixture was cooled to room temperature, poured into 1000 ml of methanol, and stirred at room temperature for 1 hour. The precipitated crystals were filtered, washed with methanol and dried to obtain 62 g (yield 83%) of yellow pigment crystals (A). The mass analysis result of this crystal by TOF-MS was consistent with the molecular weight of the pigment derivative (A).

Synthesis example 3
Method for synthesizing pigment derivative (B) (compound (2))

  (1-3) obtained above was added to 200 ml of acetonitrile containing N, N, N′-trimethylpropylenediamine (14 g) and triethylamine (10 g) under ice cooling and stirred. After the reaction, the reaction mixture was cooled to room temperature, poured into 1000 ml of methanol, and stirred at room temperature for 1 hour. The precipitated crystals were filtered, washed with methanol and dried to obtain 60 g (yield 79%) of yellow pigment crystals (B). The mass analysis result of this crystal by TOF-MS was consistent with the molecular weight of the pigment derivative (B).

Synthesis example 4
Method for synthesizing pigment derivative (C) (compound (3))

Compound (I) (35 g), compound (2-1) (20 g) and benzoic acid 200 g were heated and heated, and stirred at 180 ° C. for 7 hours. After cooling to room temperature, the reaction product was poured into 1000 ml of methanol and stirred at room temperature for 1 hour. The precipitated crystals were filtered, washed with water and dried to obtain 42 g (yield 87%) of yellow crystals of the compound. Compound (2-2) (60 g) was added to 240 ml of dichlorobenzene, and 1.5 g of pyridine was added, followed by heating to 100 ° C. To this was added dropwise thionyl chloride (46 g), and the mixture was further reacted for 6 hours. Excess thionyl chloride was removed under reduced pressure, and the reaction proceeded as it was. The obtained (2-3) was added to 200 ml of acetonitrile containing N, N-diethylaminopropylamine (15 g) and triethylamine (10 g) under ice cooling and stirred. After the reaction, the reaction mixture was cooled to room temperature, poured into 1000 ml of methanol, and stirred at room temperature for 1 hour. The precipitated crystals were filtered, washed with methanol and dried to obtain 63 g (yield 89%) of yellow crystals of the pigment derivative (C). The mass analysis result of this crystal by TOF-MS was consistent with the molecular weight of the pigment derivative (C).

Synthesis example 5
Method for synthesizing pigment derivative (D) (compound (4))

  By the above method, the obtained (2-3) was added to 200 ml of acetonitrile containing 1-methylpiperazine (12 g) and triethylamine (10 g) under ice cooling and stirred. After the reaction, the reaction mixture was cooled to room temperature, poured into 1000 ml of methanol, and stirred at room temperature for 1 hour. The precipitated crystals were filtered, washed with methanol and dried to obtain 54 g (yield 79%) of yellow crystals of the pigment derivative (D). The mass analysis result of this crystal by TOF-MS was consistent with the molecular weight of the pigment derivative (D).

Synthesis Example 6
Method for synthesizing pigment derivative (E) (compound (5))

  The obtained (2-3) was added to 200 ml of acetonitrile containing 3-dimethylamino-1-propanol (14 g) and triethylamine (10 g) under ice cooling and stirred. After the reaction, the reaction mixture was cooled to room temperature, poured into 1000 ml of methanol, and stirred at room temperature for 1 hour. The precipitated crystals were filtered, washed with methanol and dried to obtain 63 g (yield 92%) of yellow crystals of the pigment derivative (E). The mass analysis result of this crystal by TOF-MS was consistent with the molecular weight of the pigment derivative (E).

Preparation of Acrylic Resin Solution 800 g of cyclohexanone was added to a four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, and heated to 100 ° C. under nitrogen gas injection. At this temperature, a mixture of 60 g of methacrylic acid, 65 g of methyl methacrylate, 65 g of butyl methacrylate, 60 g of 2-hydroxyethyl methacrylate, 10 g of 2,2′-azobisisobutyronitrile is dropped over about 1 hour, and the polymerization reaction is carried out. went. After completion of the dropwise addition, the mixture was further stirred for 3 hours, a solution in which 2 g of 2,2′-azobisisobutyronitrile was dissolved in 50 g of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour, and the weight average molecular weight was about A 40,000 acrylic resin solution was obtained.

  After cooling to room temperature, about 2 g of the resin solution was sampled and heated to dryness at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexane was added to the previously synthesized resin solution so that the nonvolatile content was 20%. An acrylic resin solution was prepared.

Preparation of yellow treated pigment Quinophthalone yellow pigment C.I. I. A mixture of 200 g of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BSF, Inc.), 800 g of sodium chloride and 100 g of diethylene glycol was used using a 1 gallon kneader (manufactured by Inoue Seisakusho) made of stainless steel. Kneading was performed at 120 ° C. for 2 hours. Next, this kneaded material was put into 3 liters of warm water and stirred at 70 ° C. for 1 hour. Thereafter, filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 80 ° C. for 24 hours to obtain 192 g of a yellow-treated pigment.

Preparation of Green Treated Pigment Phthalocyanine Green Pigment C.I. I. Pigment Green 36 (200 ml of “Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.), 800 g of sodium chloride and 100 g of diethylene glycol were kneaded at 120 ° C. for 2 hours using a 1 gallon kneader (manufactured by Inoue Seisakusho). Next, the kneaded product was poured into 3 liters of warm water and stirred for 1 hour at 70 ° C. Thereafter, filtration and washing were repeated, and after removing sodium chloride and diethylene glycol, the mixture was removed at 80 ° C. for 24 hours. Dried to obtain 194 g of green treated pigment.

Examples 1-10 and Comparative Examples 1-8
Each pigment, the pigment dispersant obtained by the above synthesis method as a pigment dispersant, or the pigment dispersant (F) described in JP-A-2003-346926, the acrylic resin solution, and cyclohexanone as a solvent in the amounts shown in Table 1. The pigment dispersion was obtained by blending, putting together with 150 g of zirconia beads having a diameter of 1.25 mm in a 140 ml screw-mouth bottle, and dispersing for 15 hours with a paint conditioner.

The viscosity and thixotropic index (TI value) of the pigment dispersion thus obtained were measured with a B-type viscometer. Further, after the pigment dispersion was stored at 40 ° C. for one week, the viscosity was measured again, and the result of the viscosity increase rate was evaluated in four stages A to D according to the following criteria.
A: Almost no thickening is observed B: Some thickening is observed, but it is in a usable range C: Some thickening is observed and it cannot be used D: Thickening is remarkably unusable

  The evaluation results are collectively shown in Table 1.

Table 1

As shown in Table 1, it is understood that those using the pigment dispersant of the present invention have a low viscosity, a small TI value, and excellent fluidity. Furthermore, the viscosity stability over time showed good results.

  By using the pigment dispersant, pigment composition and pigment dispersion of the present invention, it is possible to obtain inks, paints, etc. that are non-aggregating, non-crystalline, low viscosity, low thixotropic and have good viscosity stability over time. The product can be easily obtained. The pigment dispersant, pigment composition and pigment dispersion of the present invention are gravure ink, general paint for automobiles, wood and metal, magnetic tape back coat paint, radiation cure ink, ink jet printer ink, color filter ink It can be applied to other uses.

Claims (9)

A pigment dispersant comprising the following general formula (1).
General formula (1)

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom, a halogen atom, or an alkyl group,
R ^{5 to} R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxyl group, a phenyl group, or a nitro group,
R ^{10 to} R ¹³ are each independently a hydrogen atom, halogen atom, hydroxyl group, alkyl group, alkoxyl group, nitro group, amino group, sulfonic acid group, carboxylic acid group, the following general formula (2), or the following general formula The group represented by the formula (3) is shown, and at least one of R ^{10 to} R ¹³ is a group represented by the following general formula (2) or the following general formula (3).
R ¹¹ and R ¹² may be integrated. )

General formula (2)

(In the formula, X ¹ represents a sulfone bond or a carbonyl bond,
X ² is a monovalent aliphatic heterocyclic group which may have a substituent. However, the monovalent aliphatic heterocyclic group has at least one nitrogen atom. )

General formula (3)

(In the formula, X ³ represents a group selected from a sulfonamide bond, an ether bond, an ester bond, a sulfoxide bond, a sulfone bond, an amino bond, and an amide bond.
X ⁴ represents a direct bond or a divalent aliphatic heterocyclic ring.
m represents an integer of 1 to 20.
X ⁵ represents —O— (CH ₂ ) _t —Y ¹ or —Y ² .
Y ¹ and Y ² each independently represent —NA ¹ A ² or a monovalent aliphatic heterocyclic group which may have a substituent.
A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 20 or less carbon atoms which may have a substituent.
t represents an integer of 1 to 20.
R ¹¹ and R ¹² may be integrated into the following general formula (4). )
General formula (4)

A pigment composition comprising a pigment and the pigment dispersant according to claim 1. The pigment composition according to claim 2, wherein the pigment is a yellow pigment. The yellow pigment is C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, and C.I. I. The pigment composition according to claim 3, which is at least one pigment selected from CI Pigment Yellow 185. The pigment composition according to any one of claims 2 to 4, wherein the pigment is a green pigment. The green pigment is C.I. I. Pigment green 7, C.I. I. Pigment green 10, C.I. I. Pigment green 36 or C.I. I. The pigment composition according to claim 5, which is CI Pigment Green 37. The pigment composition according to any one of claims 2 to 4, wherein the pigment is a red pigment or an orange pigment. Red or orange pigments are C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 177, C.I. I. Pigment red 179, C.I. I. Pigment red 207, C.I. I. Pigment red 48: 1, C.I. I. Pigment orange 71, and C.I. I. The pigment composition according to claim 7, which is at least one pigment selected from CI Pigment Orange 73. The pigment dispersion formed by disperse | distributing the pigment composition in any one of Claims 2-8 to a non-aqueous medium.