JP2008050420A - Pigment dispersant, pigment composition, and pigment dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment dispersant effective for pigment dispersion when preparing an ink, a coating material or the like; to provide a pigment composition containing the pigment dispersant; and to provide a pigment dispersion obtained by improving fluidity characteristics at the dispersion of a pigment, and having various characteristics of low viscosity and good temporal stability of the viscosity. <P>SOLUTION: The pigment dispersant comprises a compound obtained by linking a quinophthalone skeleton with an alkylamine group through a divalent linking group (a sulfonamide bond, an ether bond, an ester bond, a sulfoxide bond, a sulfone bond or an amino group) and an arylene group or a heterocycle. <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. 2002-121457 discloses various quinophthalone derivatives in which the terminal of a substituent is substituted with a carboxyl group, an ester group, a hydroxyl group, a mercapto group, a sulfonic acid group, an unsubstituted group, and a 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 2002-121457 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 , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom or an alkyl group,
R ⁵ , R ⁶ , R ⁷ , R ⁸ and 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 , R ¹¹ , R ¹² and R ¹³ are each independently hydrogen atom, halogen atom, hydroxyl group, alkyl group, alkoxyl group, nitro group, amino group, sulfonic acid group, carboxylic acid group, or The group represented by the general formula (2) is shown, and one or two of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are groups represented by the following general formula (2). )

General formula (2)

(In the formula, X ¹ represents a sulfonamide bond, an ether bond, an ester bond, a sulfoxide bond, a sulfone bond, or an amino group;
X ² represents an arylene group having 20 or less carbon atoms, which may have a substituent, or a divalent heterocyclic group which may have a substituent and has 20 or less carbon atoms,
X ³ represents an amide bond, a sulfonamide bond, an ether bond, an ester bond, a sulfide bond, a sulfoxide bond, a sulfone bond, or an amino group.
m represents 0 or 1, and n represents an integer of 0 to 20. However, when m = 1, n = 0 is not satisfied.
X ⁴ represents —O— (CH ₂ ) _t —Y ¹ , —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 optionally substituted alkyl group having 20 or less carbon atoms.
t represents an integer of 1 to 20. )
The present invention also relates to a pigment composition containing the pigment and 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, C.I. I. Pigment Yellow 185, which is at least one pigment selected from the above pigment compositions.

  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. The present invention relates to the above pigment composition, which is at least one pigment selected from CI Pigment Green 36.

  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, 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 the quinophthalone skeleton and the alkylamine group are divalent linking groups (sulfonamide bond, ether bond, ester bond, sulfoxide bond, sulfone bond, or amino group). ) And an arylene group or a heterocyclic ring. By using this to disperse various pigments in a non-aqueous medium, it is possible to prepare compositions and dispersions having good physical properties.

General formula (1)

In the general formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom or an alkyl group. Among these, a halogen atom such as a chlorine atom or a bromine atom is particularly preferable.

R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxyl group, a phenyl group or a nitro group. Of these, a hydrogen atom is particularly preferable.

R ¹⁰ , R ¹¹ , R ¹² and 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, or the following general group Formula (2) is shown, and one or two of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are groups represented by the following general formula (2). Among these, it is particularly preferable that R ¹¹ or R ¹² is the following general formula (2), and the others are hydrogen atoms.

General formula (2)

In the general formula (2), X ¹ represents a group selected from a sulfonamide bond, an ether bond, an ester bond, a sulfoxide bond, a sulfone bond, or an amino group, and among these, a sulfonamide bond is particularly preferable. preferable.

X ² represents a group selected from an arylene group having 20 or less carbon atoms, which may have a substituent, or a divalent heterocyclic ring which may have a substituent and has 20 or less carbon atoms, A phenylene group is particularly preferred.

X ³ represents an amide bond, a sulfonamide bond, an ether bond, an ester bond, a sulfide bond, a sulfoxide bond, a sulfone bond, or a group selected from an amino group, and of these, an amide bond or a sulfonamide bond Is particularly preferred.

  m represents 0 or 1, and n represents an integer of 0 to 20. When m = 0, n = 0 is not satisfied.

X ⁴ represents —O— (CH ₂ ) _t —Y ¹ , —Y ² .

Y ¹ and Y ² each independently represent —NA ¹ A ² or a monovalent aliphatic heterocyclic group.

A ¹ and A ² each independently represent a hydrogen atom or an optionally substituted alkyl group having 20 or less carbon atoms.

  t represents an integer of 1 to 20.

  Examples of the halogen atom in the present invention include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  As the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, Examples include isohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and the like.

  Alkoxyl groups include methoxy, ethoxy, propoxy, butoxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, isopentyloxy, isohexyloxy Group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, An octadecyloxy group, a nonadecyloxy group, etc. are mentioned.

  Arylene groups include phenylene group, biphenylylene group, terphenylylene group, quarterphenylylene group, pentalenylene group, indenylene group, naphthylene group, binaphthalenylene group, turnaphthalenylene group, quarter naphthalenylene group, azurelenylene group, heptalenylene group, biphenylene group Renylene group, Indasenylene group, Furenolanthenylene group, Acephenanthrenelenylene group, Aceantrilenylene group, Phenalenylene group, Furenolenylene group, Anthrylene group, Bianthracenylene group, Teranthracenylene group, Quarteranthraceni Len group, anthraquinolylene group, phenanthrylene group, triphenylenylene group, pyrenylene group, chrysenylene group, naphthacenylene group, preadenylene group, picenylene group, peryleneylene group, pentaf Ylene group, a pentacenylene group, tetraphenylene Reni alkylene group, hexamethylene phenylene group, Hekisaseniren group, Renbiseniren group, Koroneniren group, tri naphthylene Leni alkylene group, hepta-phenylene group, Heputaseniren group, Pirantoreniren group, Obareniren group and the like.

  Examples of the divalent heterocyclic group include thienylene group, benzo [b] thienylene group, naphtho [2,3-b] thienylene group, thiantrelenylene group, furylene group, pyranylene group, isobenzofuranylene group, chromenylene group, Xanthenylene group, phenoxathiylene group, 2H-pyrrolylene group, pyrrolylene group, imidazolylene group, pyrazolylene group, pyridylene group, pyrazinylene group, pyrimidinylene group, pyridazinylene group, indolizinylene group, isoindolinylene group, 3H-indolinylene group, Indoleylene group, 1H-indazolylene group, plinylene group, 4H-quinolidinylene group, isoquinolylene group, quinolylene group, phthalazinylene group, naphthyridinylene group, quinoxalinylene group, quinazolinylene group, cinnolinylene group, pteridinylene group, 4aH-carlenbazolen group Group, carenbazolylene group, β-carenborinylene group, phenanthridinylene group, acridinylene group, perimidinylene group, phenanthrolinylene group, phenazinylene group, phenalenesasinylene group, isothiazolylene group, phenothiazinylene group, isoxazolylene group, flazanylene Group, phenoxazinylene group, isochrominylene group, chromanylene group, pyrrolidinylene group, pyrrolinylene group, imidazolidinylene group, imidazolinylene group, pyrazolidinylene group, pyrazolinylene group, piperidylene group, piperazinylene group, indolinylene group, isoindolinylene group, quinuclidinylene group Group, molen holinylene group, molen holino group and the like.

  As the monovalent aliphatic heterocyclic ring, an aliphatic heterocyclic ring represented by the following structural formula is preferable.

The alkyl groups for A ¹ and A ² are the same as those already shown.

  The arylene group and the divalent heterocyclic group may be further substituted with a substituent. In this case, the substituent includes a halogen atom, cyano group, nitro group, sulfonic acid group, carboxylic acid group, unsubstituted or substituted amino group, unsubstituted or substituted alkyl group, unsubstituted or substituted group Or an aryl group having an unsubstituted or substituted group, or a heterocyclic group having an unsubstituted or substituted group.

  Further, examples of the alkyl group to be substituted are the same as those already shown.

  Further, examples of the alkoxyl group to be substituted are the same as those already shown.

  Further examples of the aryl group to be substituted include an aryl group such as phenyl group, biphenylyl group, terphenylyl group, quarterphenylyl group, pentarenyl group, indenyl group, naphthyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, Azulenyl, heptaenyl, biphenylenyl, indacenyl, fluoranthenyl, acephenanthrenyl, aceanthrylenyl, phenalenyl, fluorenyl, anthryl, bianthracenyl, teranthracenyl, quarteranthracene Nyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetra Enireniru group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl groups, trinaphthylenyl groups, heptacenyl groups, pyranthrenyl groups, ovalenyl group and the like.

  Further examples of the substituted heterocyclic group include a thienyl group, a benzo [b] thienyl group, a naphtho [2,3-b] thienyl group, a thiantenyl group, a furyl group, a pyranyl group, and an isobenzofuran group. Nyl 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, Enanthridinyl group, acridinyl 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, pyrrolidinyl group, imidazolidinyl group Group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, morpholino group and the like.

  Representative examples of the compounds of the present invention are specifically illustrated in Table 1 below, but the present invention is not limited to the following representative examples.

Table 1

  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 yellow pigment used as the pigment composition of the present invention is not particularly specified, but 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 preferred. These pigments may be used alone or in combination of two or more.

  Examples of green pigments include C.I. I. Gment Green 7, C.I. I. Pigment green 10, C.I. I. Cement green 36, C.I. I. Mentment green 37 and the like. Among these, C.I. I. Pigment Green 7 and 36 are particularly preferable.

  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 207, C.I. I. Pigment Red 48: 1 and the like, and orange pigments include C.I. I. Pigment orange 71, C.I. I. And CI Pigment Orange 73.

  As the pigment used in the pigment composition of the present invention, the above-mentioned commercially available pigment may be used as it is, but it is used after the pigment particles are refined by a method such as solvent salt milling or dry milling as necessary. May be. 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.

  Method for synthesizing quinophthalone derivative (I)

  Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BSF, Inc.) (400 g, 0.57 mol), potassium hydroxide (400 g, 10.0 mol), and 3600 g of water were charged at 16 at 90 degrees. After reacting for hours, the mixture was cooled to room temperature, and 540 ml of 36% hydrochloric acid was added dropwise. After filtration, washing with water, and washing with acetone, vacuum drying was performed to obtain Compound (I) represented by the above formula.

  Method for synthesizing pigment derivative (A)

  4-Nitrophthalic anhydride (15 g, 0.08 mol) was mixed with 1000 g of water to form a slurry. To this was added sodium sulfide nonahydrate (193 g, 0.8 mol), and the mixture was stirred at 70 degrees for 24 hours, and then filtered to separate the product. The product separated by filtration was added to 3000 ml of 1N-hydrochloric acid to form a slurry, stirred at room temperature for 1 hour, filtered and washed with water. Subsequently, it was added to 2000 ml of 1N-sodium hydroxide aqueous solution to form a slurry, stirred at room temperature for 1 hour, filtered and washed with water. Slurry with water, filtration, and water washing were repeated until the filtrate became neutral, followed by drying to obtain 10 g (yield 80%) of compound (1-2).

  4-Chlorosulfonylbenzoic acid (22 g, 0.10 mol) was added to a 200 ml dichloromethane solution containing (compound (1-2) (20 g, 0.12 mol) and triethylamine (13 g, 0.12 mol) under ice-cooling and stirred. After the reaction, it was added to 1000 ml of acetone to form a slurry, and stirred at room temperature for 1 hour, followed by filtration to obtain 26 g (yield 73%) of compound (1-3).

  Compound (1-3) (26 g, 0.10 mol) 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, 0.40 mol), and the mixture was further reacted for 6 hours. Excess thionyl chloride was removed under reduced pressure, and the reaction proceeded directly to the next reaction.

  The acid chloride (1-4) obtained above was added to 200 ml of DMAc (dimethylacetamide) containing diethylaminopropylamine (52 g, 0.40 mol) and triethylamine (60 g, 0.60 mol) under ice cooling and stirred. After the reaction, 1500 ml of 5% aqueous potassium carbonate solution was added, and the mixture was extracted with ethyl acetate to obtain 27 g (yield 60%) of compound (1-5).

  Compound (I) (35 g, 0.084 mol), Compound (1-5) (50 g, 0.11 mol) and 200 g of benzoic acid 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 58 g (yield 81%) of yellow crystals of the pigment derivative (A).

  Method for synthesizing pigment derivative (B)

  Compound (I) (35 g, 0.084 mol), compound (2-1) (27 g, 0.11 mol) and 200 g of benzoic acid 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 compound (2-2).

  Compound (2-2) (63 g, 0.10 mol) 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, 0.40 mol), and the mixture was further reacted for 6 hours. Excess thionyl chloride was removed under reduced pressure, and the reaction proceeded directly to the next reaction.

  The acid chloride (2-3) obtained above was added to 200 ml of DMAc (dimethylacetamide) containing 4-aminobenzoic acid (54 g, 0.40 mol) and triethylamine (60 g, 0.60 mol) under ice cooling, and stirred. did. After the reaction, 1500 ml of a 5% aqueous potassium carbonate solution was added, and the mixture was extracted with ethyl acetate to obtain 47 g (yield 62%) of compound (2-4).

  Compound (2-4) (38 g, 0.05 mol) was added to 120 ml of dichlorobenzene, and 0.8 g of pyridine was added, followed by heating to 100 ° C. To this was added dropwise thionyl chloride (23 g, 0.20 mol), and the mixture was further reacted for 6 hours. Excess thionyl chloride was removed under reduced pressure, and the reaction proceeded directly to the next reaction.

  The acid chloride (2-5) obtained above was added to 100 ml of DMAc (dimethylacetamide) containing 3-dimethylamino-1-propanol (20 g, 0.20 mol) and triethylamine (30 g, 0.30 mol) under ice cooling. Added and stirred. After the reaction, 800 ml of a 5% aqueous potassium carbonate solution was added and the mixture was extracted with ethyl acetate to obtain 23 g (yield 55%) of the pigment derivative (B).

  Method for synthesizing pigment derivative (C)

  A dichloromethane 500 ml solution containing the compound (2-3) (261 g, 0.4 mol) was added to a dichloromethane 500 ml solution containing the compound (3-1) (100 g, 0.48 mol) and pyridine 63 g under ice cooling, followed by stirring. The solution 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 275 g (yield 81%) of yellow crystals of the pigment derivative (C).

  Method for synthesizing pigment derivative (D)

  A 500 ml dichloromethane solution containing trimellitic anhydride chloride (84 g, 0.4 mol) was added to a 500 ml dichloromethane solution containing compound (4-1) (78 g, 0.48 mol) and 63 g pyridine under ice cooling and stirred. After the reaction, the pale yellow solid was filtered to obtain 118 g (yield 87%) of compound (4-2).

  A dichloromethane 500 ml solution containing the compound (2-3) (260 g, 0.4 mol) was added to a dichloromethane 500 ml solution containing the compound (4-1) (78 g, 0.48 mol) and pyridine 60 g under ice cooling, followed by stirring. The solution 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 218 g (yield 76%) of yellow crystals of the pigment derivative (D).

  Method for synthesizing pigment derivative (E)

  8-amino-2-methylquinoline (14 g, 0.088 mol), compound (1-5) (50 g, 0.11 mol), and 84.6 g of benzoic acid are heated and heated, and stirred at 120 ° C. for 6 hours. Next, after cooling to room temperature, phthalic anhydride (14.3 g, 0.096 mol) was added, the temperature was raised again, and the mixture was stirred at 180 ° C. for 6 hours. After cooling to room temperature, the reaction product was poured into 421 ml of methanol and stirred at room temperature for 1 hour. The precipitated crystals were filtered, washed with water, and dried to obtain 51.3 g (yield 79%) of yellow crystals 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 1-7
Each pigment, the pigment dispersant obtained by the above synthesis method, the above acrylic resin solution and cyclohexanone as a solvent are blended in the amounts shown in the following Table 2, and a 140 ml screw cap bottle together with 150 g of zirconia beads having a diameter of 1.25 mm. The pigment dispersion was obtained by putting in 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 2.

Table 2

  As shown in Table 2, 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 , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom or an alkyl group,
R ⁵ , R ⁶ , R ⁷ , R ⁸ and 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 , R ¹¹ , R ¹² and R ¹³ are each independently hydrogen atom, halogen atom, hydroxyl group, alkyl group, alkoxyl group, nitro group, amino group, sulfonic acid group, carboxylic acid group, or The group represented by the general formula (2) is shown, and one or two of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are groups represented by the following general formula (2). )
General formula (2)

(In the formula, X ¹ represents a sulfonamide bond, an ether bond, an ester bond, a sulfoxide bond, a sulfone bond, or an amino group;
X ² represents an arylene group having 20 or less carbon atoms, which may have a substituent, or a divalent heterocyclic group which may have a substituent and has 20 or less carbon atoms,
X ³ represents an amide bond, a sulfonamide bond, an ether bond, an ester bond, a sulfide bond, a sulfoxide bond, a sulfone bond, or an amino group.
m represents 0 or 1, and n represents an integer of 0 to 20. However, when m = 1, n = 0 is not satisfied.
X ⁴ represents —O— (CH ₂ ) _t —Y ¹ , —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 optionally substituted alkyl group having 20 or less carbon atoms.
t represents an integer of 1 to 20. ) 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, 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. The pigment composition according to claim 5, wherein the pigment composition is at least one pigment selected from CI Pigment Green 36. 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, C.I. I. The pigment composition according to claim 7, wherein the pigment composition is at least one pigment selected from CI Pigment Orange 73. A pigment dispersion obtained by dispersing the pigment composition according to any one of claims 2 to 8 in a non-aqueous medium.