JP2007254556A - Pigment composition and pigment dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stable pigment composition and a pigment dispersion in which a carboxyl-containing acidic urethane resin is used for pigment dispersion to enhance the interaction between acidic groups thought to be pigment adsorption sites in the urethane resin and a pigment derivative and which is excellent in dispersedness, non-aggregation properties, and fluidity and is suited for, e.g., offset inks, gravure inks, inkjet inks, coating materials, and colored urethane resin compositions. <P>SOLUTION: The pigment composition is one containing a carboxyl-containing acidic urethane resin and a pigment, wherein the urethane resin is a carboxyl-containing acidic urethane resin prepared by reacting a carboxyl-containing polyol (a) prepared by reacting a polycarboxylic acid anhydride (a1) with a polyol compound (a2) with a polyisocyanate compound (b). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a pigment composition, and more particularly to a stable pigment composition excellent in non-aggregability and fluidity, which is suitable for fields such as inks, paints and colored resin compositions.

  In general, when fine pigment particles are dispersed in vehicles such as offset inks, gravure inks and paints, it is difficult to obtain a stable dispersion, which can cause various problems in manufacturing operations and the properties of the resulting products. Are known. For example, dispersions containing pigments composed of fine particles often exhibit high viscosity, making the product difficult to remove and transport from the disperser, and in worse cases, gelation during storage. It may be difficult to use.

  Moreover, regarding the coating film surface of the color-extended product, a state defect such as a decrease in gloss and a leveling defect may occur. In particular, when different types of pigments are mixed and used, color unevenness due to aggregation and phenomena such as sedimentation may cause uneven color and a marked decrease in coloring power.

  In order to solve the various problems as described above, a method has been proposed in which a pigment derivative having a matrix as a base skeleton and a pigment derivative having an acidic group or a basic group as a substituent in a side chain is mixed with various varnishes. (Patent Document 1, Patent Document 2, Patent Document 3) However, this alone does not necessarily provide a satisfactory effect, and has a counter ion for a substituent having an acidic group or a basic group as described above. It has been proposed to use a resin. (Patent Documents 4 and 5) As the structure of the resin, a structure of an ionic site adsorbing to a pigment derivative having an acidic group or a basic group as a substituent and a site having a high affinity for a solvent as a dispersion medium The resin performance is determined by the balance between these two parts.

  Patent Document 4 exemplifies a pigment composition containing a pigment derivative having a basic group as a substituent and a resin having a phosphate ester. A resin having a phosphate ester is used in combination with a pigment derivative having a basic group as a substituent, and has a certain degree of pigment dispersion ability, but has poor storage stability or has defects due to phosphoric acid, such as low heat resistance. However, there are cases where problems arise due to low chemical resistance and poor compatibility. The same applies to the dispersant having sulfonic acid. Resins having such phosphate esters and sulfonic acids are poor in developability to applied inks and paints, etc., while resins using carboxylic acids are in terms of heat resistance, chemical resistance and compatibility. Although there is no problem, there are many cases where the ability as a dispersion resin is inferior, such as high viscosity, poor stability, poor pigment fine dispersion and the like.

  In recent years, with the increasing needs for the dispersion stability of pigments as described above, attention has been focused on urethane-based dispersion resins having locally introduced acidic groups. A method is disclosed in which an organic pigment is used as a base skeleton, and a pigment derivative having an acidic group or basic group as a substituent in the side chain is mixed with a urethane resin as a dispersant (see Patent Document 6).

However, none of the inventions are satisfactory in dispersibility with respect to organic pigments. Moreover, since there are a large number of varnish systems in paints and inks, a satisfactory effect is not obtained except for some varnish systems even if these inventions are used.
JP-A 63-305137 JP-A-1-247468 Japanese Laid-Open Patent Publication No. 3-26767 JP-A-63-248864 JP 9-176511 A JP-A-62-295966

  The present invention is suitable for offset inks, gravure inks, resist inks and ink jet inks for color filters, paints, colored resin compositions, etc., and has dispersibility and stability excellent in non-aggregability and fluidity, and contains acid groups It aims at providing the pigment composition containing a urethane resin.

The present invention is a pigment composition containing a carboxyl group-containing acidic urethane resin and a pigment,
A carboxyl group-containing polyol (a) obtained by reacting the polyhydric carboxylic acid anhydride (a1) and the polyol compound (a2) with the urethane resin;
Furthermore, it is related with the pigment composition characterized by being the carboxyl group-containing acidic urethane resin formed by reacting with a polyisocyanate compound (b).

Furthermore, the present invention is a pigment composition containing a carboxyl group-containing acidic urethane resin and a pigment,
A carboxyl group-containing polyol (a) obtained by reacting the polyhydric carboxylic acid anhydride (a1) and the polyol compound (a2) with the urethane resin;
Furthermore, the present invention relates to a pigment composition characterized by being a carboxyl group-containing acidic urethane resin obtained by reacting a polyisocyanate compound (b) with a polyol compound (c) other than the polyol (a).

  Furthermore, this invention relates to the said pigment composition whose said polyhydric carboxylic acid anhydride (a1) is tetracarboxylic dianhydride.

  Furthermore, this invention relates to the said pigment composition whose weight average molecular weights of the said carboxyl group-containing polyol (a) are 300-25000.

  Furthermore, this invention relates to the said pigment composition whose acid value of the said carboxyl group-containing polyol (a) is 10-400, and whose hydroxyl value is 20-300.

  Furthermore, in the present invention, the carboxyl group-containing polyol (a) comprises a molar ratio (a1) / () between the acid anhydride group in the polyvalent carboxylic acid anhydride (a1) and the hydroxyl group in the polyol compound (a2). a2) It is related with the said pigment composition which reacts on the conditions of 0.3-0.8.

  Furthermore, this invention relates to the said pigment composition whose acid value of carboxyl group-containing acidic urethane resin is 10-200.

  Furthermore, the present invention provides at least one basic derivative selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group. It contains the said pigment composition containing.

  Furthermore, the present invention relates to a pigment dispersion obtained by dispersing the above-described pigment composition in a varnish.

  According to the present invention, it is suitable for offset ink, gravure ink, color filter resist ink and ink jet ink, paint, colored resin composition, etc., and has excellent dispersibility and stability with excellent non-aggregability and fluidity, and high storage stability. It was possible to provide a pigment composition that has good properties and high stability over time, and does not show an increase in viscosity over time. By dispersing the pigment composition of the present invention, particularly a pigment composition containing an organic pigment, in various varnishes, the pigment dispersibility was dramatically improved, and a stable pigment dispersion could be provided. Therefore, when the pigment composition of the present invention is used, a stable pigment dispersion can be always produced even when the pigment dispersibility of the resin contained in the varnish is poor.

  The present invention is a pigment composition containing a carboxyl group-containing acidic urethane resin and a pigment, and the urethane resin is obtained by reacting a polyvalent carboxylic acid anhydride (a1) with a polyol compound (a2). A pigment composition comprising a carboxyl group-containing polyol (a), a polyisocyanate compound (b), and optionally a polyol compound (c). Here, it is possible to use a urethane resin using a carboxyl group-containing polyol (a) obtained by reacting the polyvalent carboxylic acid anhydride (a1) and the polyol compound (a2) as a raw material. It leads to stability.

  The polyvalent carboxylic acid anhydride (a1) used in the present invention is not particularly limited as long as it is a compound containing two or more acid anhydride groups. The acid anhydride group can react with a hydroxyl group to form an ester bond and leave a pendant carboxyl group on the polymer polyol main chain.

  For example, tetracarboxylic dianhydride, hexacarboxylic dianhydride, hexacarboxylic dianhydride, maleic anhydride copolymer resin and the like can be used. In the present invention, tetracarboxylic dianhydride is preferably used.

Specifically, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4- Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,5,6-tricarboxynornorbornane-2-acetic acid dianhydride, 2,3,4,5 -Tetrahydrofuran tetracarboxylic dianhydride, 5- (2,5-dioxotetrakilofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -Aliphatic tetracarboxylic dianhydrides such as oct-7-2,3,5,6-tetracarboxylic dianhydride,
Pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3,4,4-benzophenone tetracarboxylic dianhydride, 3,3,4,4-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3 , 3,4,4-biphenyltetracarboxylic dianhydride, 3,3,4,4-biphenyl ether tetracarboxylic dianhydride, 3,3,4,4-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3,4,4-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarbo Acid dianhydride, 4,4-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3,4,4-perfluoroisopropylidene diphthalic dianhydride, 3,3,4, 4-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride Bis (triphenylphthalic acid) -4,4-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4-diphenylmethane dianhydride, 9,9-bis (dicarboxyphenyl) fluorene dianhydride 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 3,4-dicarboxy-1,2,3,4 Aromatic tetracarboxylic dianhydrides such as tetrahydro-1-naphthalene succinic dianhydride and 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride Is mentioned.

As the polyol compound (a2) used in the present invention, known compounds can be used. Among them, there are those belonging to the following groups (1) to (7) as long as only typical ones are exemplified.
(1) ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1, 4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin, or Polyhydric alcohols such as hexanetriol;
(2) Various polyethers such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol Glycols;
(3) Various polyhydric alcohols described above and various (cyclic) ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether or allyl glycidyl ether. Modified polyether polyols obtained by ring-opening polymerization with
(4) Polyester polyols obtained by co-condensation with one or more of the various polyhydric alcohols described above and polycarboxylic acids, wherein the polycarboxylic acids are succinic acid, adipic acid, sebacic acid, Azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehycarboxylic acid, 1 , 2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid Polyols that can be used;
(5) A lactone system obtained by a polycondensation reaction between one or more of the various polyhydric alcohols described above and various lactones such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone. Polyester polyols, or
Lactone-modified polyester polyols obtained by polycondensation reaction of the various polyhydric alcohols, polycarboxylic acids, and various lactones;
(6) Various epoxy compounds such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and / or polyhydric alcohols, or glycidyl esters of monobasic acids and / or polybasic acids , Epoxy-modified polyester polyols obtained by combining one or more polyester polyols during synthesis;
(7) Polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative, hydroxyl group-containing acrylic copolymer, hydroxyl group-containing fluorine-containing compound or hydroxyl group-containing silicon resin Is mentioned.

  These polyol compounds (a2) shown in (1) to (7) may of course be used alone or in combination of two or more, but the number average molecular weight is in the range of 200 to 10,000. The inside is preferably in the range of 300 to 7,000, more preferably in the range of 500 to 3,000.

  Next, examples of the polyisocyanate compound (b) include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and the like.

  Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, and 4,4′-diphenylmethane diester. Isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1 , 3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, etc. it can.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, and 1,2-propylene diisocyanate. 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. Can do.

  Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate. -1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, and 1,3-cyclohexane diisocyanate. 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) G), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane and the like.

  In consideration of the viscosity after pigment dispersion, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates are preferable, and alicyclic polyisocyanates are more preferable.

  Further, for the purpose of increasing the molecular weight of the urethane resin, a polyisocyanate having three or more isocyanate groups in one molecule may be used in combination, and an aromatic polyisocyanate, an aliphatic polyisocyanate, an araliphatic polyisocyanate. And dimers and trimers such as alicyclic polyisocyanate.

  For example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2, 3-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimer and dimer of diisocyanate of 4,4′-toluidine diisocyanate, and three or more isocyanate groups 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', Examples thereof include 4 "-triphenylmethane triisocyanate. In addition, some of the above-mentioned polyisocyanate trimethylolpropane adducts. Biuret body reacts with water, isocyanurate - can be used trimer or the like having the door ring.

  As the polyol compound (c) other than the carboxyl group-containing polyol (a) used in the present invention, known compounds can be used. Examples of the polyol compound (c) include low molecular weight polyols, polyester polyols, polyether polyols, polyether ester polyols, polybutadiene polyols, polycarbonate polyols, polyacrylic polyols and hydroxy-terminated polyolefins. a2) can be used.

  The polyol compound (c) may be used alone or in combination of two or more, but the number average molecular weight thereof is in the range of 200 to 10,000, preferably 300 to 7,000. The range is more preferably within the range of 500 to 3,000. The polyol (c) can be used for adjusting the viscosity of the obtained urethane resin solution or adjusting the hardness and strength of the urethane resin.

  Further, in order to obtain a tough urethane resin, it is desirable to use a polyester polyol, for example, by polycondensation reaction of various lactones such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone. Use of the resulting lactone polyester polyol is desirable.

  As the catalyst used for producing the urethane resin of the present invention, a known catalyst can be used. Examples thereof include tertiary amine compounds and organometallic compounds.

  Examples of tertiary amine compounds include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo. -[4.3.0] -5-Nonene etc. are mentioned.

  Examples of organometallic compounds include tin compounds and non-tin compounds. Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, Examples include tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like. Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, and lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate. Iron, such as iron 2-ethylhexanoate and iron acetylacetonate, cobalt-based such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc-based such as zinc naphthenate and zinc 2-ethylhexanoate, naphthene Examples thereof include zirconium acid. These can be used alone or in combination.

  The urethane resin of the present invention can be produced using only the raw materials listed above, but it is preferable to use a solvent in order to avoid problems such as high viscosity and non-uniform reaction. As the solvent to be used, known solvents can be used. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile and the like can be mentioned.

  The method for producing the carboxyl group-containing polyol (a) of the present invention can be obtained by reacting the polyvalent carboxylic acid anhydride (a1) with the polyol compound (a2). The molar ratio of the acid anhydride group in the polyvalent carboxylic acid anhydride (a1) and the hydroxyl group in the polyol compound (a2) is preferably (a1) / (a2) = 0.3 to 0.8, If it is less than 0.3, the amount of the carboxyl group-containing polyol (a) produced may be reduced, and the acid value of the resin may be lowered. On the other hand, if it exceeds 0.8, the carboxylic acid group-containing polyol (a) will have a high molecular weight, and when used as a pigment composition, the interaction between the resins will be strong and the viscosity may increase. The reaction temperature is preferably 50 ° C to 200 ° C, more preferably 80 ° C to 150 ° C. If the reaction temperature is lower than 50 ° C, the reaction rate may be slow. If the reaction temperature is higher than 200 ° C, the carboxyl group reacts with the polyol compound (a2), and the acid value is reduced or urethanized. May cause gelation. Ideally, the reaction is stopped until the absorption of the acid anhydride disappears by infrared absorption, but when the acid value of the carboxyl group-containing polyol (a) falls within the range of 10 to 400, or a hydroxyl group The reaction may be stopped when the value falls within the range of 20 to 300.

  The weight average molecular weight of the obtained carboxyl group-containing polyol (a) is preferably 300 to 25000. If the weight average molecular weight is less than 300, there may be a problem with the urethane group density. Moreover, the acid value of the obtained carboxyl group-containing polyol (a) is preferably 10 to 400, and the hydroxyl value is preferably 20 to 300. When the acid value is less than 10, the pigment adsorption may be too weak and the pigment composition may have a high viscosity, and when it exceeds 400, the pigment adsorption may be too strong and may have a high viscosity. Furthermore, if the hydroxyl value is less than 20, the reactivity may decrease during urethanization, and if it exceeds 300, the reactivity may be difficult to control.

  Next, the method for producing a carboxyl group-containing acidic urethane resin by urethanizing the carboxyl group-containing polyol (a) includes the above-obtained carboxyl group-containing polyol (a), the polyisocyanate compound (b), and if necessary. If it is the method of making it react with the polyol compound (c) added in this way, it will not specifically limit, It can manufacture by a well-known method. For example, a method of reacting by mixing all raw materials at once, reacting a carboxyl group-containing polyol (a) with a polyisocyanate compound (b) to produce a urethane isocyanate prepolymer containing one or more isocyanate groups per molecule Examples thereof include a method of reacting the prepolymer with the polyol compound (c) after the formation. In particular, a method in which all raw materials are mixed and reacted is preferred. The temperature of the urethanization reaction for obtaining the carboxyl group-containing acidic group-containing urethane resin of the present invention is preferably 40 to 120 ° C. More preferably, it is 50-100 degreeC.

  The acid value of the carboxyl group-containing acidic urethane resin of the present invention is preferably 10 to 200, more preferably 20 to 80, and particularly preferably 30 to 70. If the acid value is less than 10, the pigment adsorbing ability may be lowered and there may be a problem in pigment dispersibility. If the acid value exceeds 200, the interaction between the resins may be strong and the viscosity of the pigment dispersion composition may be increased. .

  Moreover, it is preferable that the polymerization average molecular weight (polystyrene conversion value by GPC measurement) of the carboxyl group-containing acidic urethane resin of the present invention is 1000 to 100,000, more preferably 1000 to 50000, and 1000 to 30000. Is particularly preferred.

  As the pigment used in the present invention, various pigments used in inks and the like can be used. Such pigments include soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments. , Anthanthrone pigment, indanthrone pigment, flavanthrone pigment, pyranthrone pigment, diketopyrrolopyrrole pigment, and the like. More specific examples are indicated by generic names of the color index: pigment black 7, pigment blue 6,15 15: 1, 15: 3, 15: 4, 15: 6, 60, Pigment Green 7, 36, Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 144, 146, 149, 166 , 168, 177, 178, 1 9, 185, 206, 207, 209, 220, 221, 238, 242, 254, 255, pigment violet 19, 23, 29, 30, 37, 40, 50, pigment yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, Pigment Orange 13, 36, 37, 38, 43, 51, 55, 59, 61, 64, 71, 74, and the like. However, it is not limited to illustration.

  Also used are metal oxides such as titanium dioxide, iron oxide, antimony pentoxide, zinc oxide, silica, and inorganic pigments such as cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, talc, yellow lead, and carbon black. be able to. As the carbon black, any carbon black such as neutral, acidic and basic can be used.

  The pigment composition of the present invention is not limited to the above-described pigment, and for example, solid fine particles containing metal fine particles such as gold, silver, copper, platinum, iron, cobalt, nickel, and / or alloys thereof can be used. .

  The pigment composition of the present invention further includes at least one base selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group. It is preferable that a sex derivative is included.

  Here, the pigment derivative is obtained by introducing a specific substituent into the organic pigment residue described in the color index. In the present invention, a pigment derivative having a basic group is used.

  By including a basic derivative, a pigment that is difficult to disperse without a basic derivative (particularly, in the case of an organic pigment) is preferable because a pigment composition excellent in dispersibility, fluidity, and storage stability can be obtained.

  The basic derivatives that can be used in the pigment composition of the present invention are selected from the group of pigment derivatives having a basic group, anthraquinone derivatives having a basic group, acridone derivatives having a basic group, and triazine derivatives having a basic group. It will be chosen.

  The basic group of the basic derivative that can be used in the pigment composition of the present invention is at least one selected from the group consisting of groups represented by the following general formulas (1), (2), (3) and (4). One group.

General formula (1)

General formula (2)

General formula (3)

前記一般式（１）〜（４）において、
Ｘ：−ＳＯ₂−、−ＣＯ−、−ＣＨ₂ＮＨＣＯＣＨ₂−、−ＣＨ₂−または直接結合を表す。
ｍ：１〜１０の整数を表す。
Ｒ₁ 、Ｒ₂ ：それぞれ独立に、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいフェニル基、またはＲ₁とＲ₂とで一体となってさらなる窒素、酸素または硫黄原子を含む置換されていてもよい複素環残基を表す。
Ｒ₃ ：置換されていてもよいアルキル基、置換されていてもよいアルケニル基または置
換されていてもよいフェニル基を表す。
Ｒ₄ 、Ｒ₅ 、Ｒ₆、Ｒ₇：それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基または置換されていてもよいフェニル基を表す。
Ｙ：−ＮＲ₈−Ｚ−ＮＲ₉−または直接結合を表す。
Ｒ₈、Ｒ₉：それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基または置換されていてもよいフェニル基を表す。
Ｚ：置換されていてもよいアルキレン基、置換されていてもよいアルケニレン基または置換されていてもよいフェニレン基を表す。
Ｐ：式（５）で示される置換基または式（６）で示される置換基を表す。
Ｑ：水酸基、アルコキシル基、式（５）で示される置換基または式（６）で示される置換基を表す。 General formula (4)

In the general formulas (1) to (4),
X: represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
m represents an integer of 1 to 10.
R ₁ and R ₂ : each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ₁ and R ₂ together Represents an optionally substituted heterocyclic residue containing a nitrogen, oxygen or sulfur atom.
R _{3 represents} an alkyl group which may be substituted, an alkenyl group which may be substituted or a phenyl group which may be substituted.
R ₄ , R ₅ , R ₆ , R ₇ : each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group.
Y: represents —NR ₈ —Z—NR ₉ — or a direct bond.
R ₈ and R ₉ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group.
Z: represents an alkylene group that may be substituted, an alkenylene group that may be substituted, or a phenylene group that may be substituted.
P: The substituent shown by Formula (5) or the substituent shown by Formula (6) is represented.
Q: A hydroxyl group, an alkoxyl group, a substituent represented by the formula (5) or a substituent represented by the formula (6).

General formula (5)

式（１）〜式（４）で示される置換基を形成するために使用されるアミン成分としては、例えば、ジメチルアミン、ジエチルアミン、Ｎ，Ｎ−エチルイソプロピルアミン、Ｎ，Ｎ−エチルプロピルアミン、Ｎ，Ｎ−メチルブチルアミン、Ｎ，Ｎ−メチルイソブチルアミン、Ｎ，Ｎ−ブチルエチルアミン、Ｎ，Ｎ−ｔｅｒｔ−ブチルエチルアミン、ジイソプロピルアミン、ジプロピルアミン、Ｎ，Ｎ−ｓｅｃ−ブチルプロピルアミン、ジブチルアミン、ジ−ｓｅｃ−ブチルアミン、ジイソブチルアミン、Ｎ，Ｎ−イソブチル−ｓｅｃ−ブチルアミン、ジアミルアミン、ジイソアミルアミン、ジヘキシルアミン、ジ（２−エチルへキシル）アミン、ジオクチルアミン、Ｎ，Ｎ−メチルオクタデシルアミン、ジデシルアミン、ジアリルアミン、Ｎ，Ｎ−エチル−１，２−ジメチルプロピルアミン、Ｎ，Ｎ−メチルヘキシルアミン、ジオレイルアミン、ジステアリルアミン、Ｎ，Ｎ−ジメチルアミノメチルアミン、Ｎ，Ｎ−ジメチルアミノエチルアミン、Ｎ，Ｎ−ジメチルアミノアミルアミン、Ｎ，Ｎ−ジメチルアミノブチルアミン、Ｎ，Ｎ−ジエチルアミノエチルアミン、Ｎ，Ｎ−ジエチルアミノプロピルアミン、Ｎ，Ｎ−ジエチルアミノヘキシルアミン、Ｎ，Ｎ−ジエチルアミノブチルアミン、Ｎ，Ｎ−ジエチルアミノペンチルアミン、Ｎ，Ｎ−ジプロピルアミノブチルアミン、Ｎ，Ｎ−ジブチルアミノプロピルアミン、Ｎ，Ｎ−ジブチルアミノエチルアミン、Ｎ，Ｎ−ジブチルアミノブチルアミン、Ｎ，Ｎ−ジイソブチルアミノペンチルアミン、Ｎ，Ｎ−メチルーラウリルアミノプロピルアミン、Ｎ，Ｎ−エチルーヘキシルアミノエチルアミン、Ｎ，Ｎ−ジステアリルアミノエチルアミン、Ｎ，Ｎ−ジオレイルアミノエチルアミン、Ｎ，Ｎ−ジステアリルアミノブチルアミン、ピペリジン、２−ピペコリン、３−ピペコリン、４−ピペコリン、２，４−ルペチジン、２，６−ルペチジン、３，５−ルペチジン、３−ピペリジンメタノール、ピペコリン酸、イソニペコチン酸、イソニコペチン酸メチル、イソニコペチン酸エチル、２−ピペリジンエタノール、ピロリジン、３−ヒドロキシピロリジン、Ｎ−アミノエチルピペリジン、Ｎ−アミノエチル−４−ピペコリン、Ｎ−アミノエチルモルホリン、Ｎ−アミノプロピルピペリジン、Ｎ−アミノプロピル−２−ピペコリン、Ｎ−アミノプロピル−４−ピペコリン、Ｎ−アミノプロピルモルホリン、Ｎ−メチルピペラジン、Ｎ−ブチルピペラジン、Ｎ−メチルホモピペラジン、１−シクロペンチルピペラジン、１−アミノ−４−メチルピペラジン、１−シクロペンチルピペラジン等が挙げられる。 General formula (6)

Examples of the amine component used for forming the substituents represented by the formulas (1) to (4) include dimethylamine, diethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine , Di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, Didecylamine, diallylamine, N, -Ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamyl Amine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopro Ruamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecholine, 3-pipecholine, 4 -Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isnicopetinate, Ethyl isonicopetic acid, 2-Piperidinethanol, Pyrrolidine, 3-hydroxy Pyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecholine, N-aminopropyl Examples include propylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

  Organic dyes constituting pigment derivatives having basic groups include, for example, diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, anthanthrones Anthraquinone dyes such as indanthrone, pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, sulene dyes It is a dye such as a dye or a metal complex dye. In addition, anthraquinone derivatives having a basic group and acridone derivatives having a basic group include alkyl groups such as methyl and ethyl groups, amino groups, nitro groups, hydroxyl groups or methoxy groups, alkoxy groups such as ethoxy groups, chlorine, etc. It may have a substituent such as halogen.

  Triazines constituting triazine derivatives having basic groups are alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro Group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) And may have a substituent such as a phenylamino group (which may be substituted with an alkyl group, an amino group, an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, a halogen, or the like). It is also a good 1,3,5-triazine.

The pigment derivative, anthraquinone derivative and acridone derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, after introducing a substituent represented by formula (7) to formula (10) into an organic dye, anthraquinone or acridone, the substituent represented by formula (1) to formula (4) is reacted with the above substituent. Amine component to be formed, for example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5-triazine It can be obtained by reacting 2-ylamino] aniline or the like.
Formula (7) —SO ₂ Cl
Formula (8) -COCl
Formula (9) —CH ₂ NHCOCH ₂ Cl
Equation (10) -CH ₂ Cl
During the reaction between the substituents represented by the general formulas (7) to (10) and the amine component, a part of the substituents represented by the general formulas (7) to (10) are hydrolyzed to form chlorine atoms. May be mixed with those substituted with a hydroxyl group. In that case, the substituent represented by the general formula (7) or the general formula (8) is a sulfonic acid group or a carboxylic acid group, respectively. Or the salt with said monoamine may be sufficient.

  Further, when the organic dye is an azo dye, the substituent represented by the formula (1) to the formula (4) is previously introduced into the diazo component or the coupling component, and then the coupling reaction is performed, thereby performing the azo pigment. Derivatives can also be produced.

  The triazine derivative having a basic group can be synthesized by various synthetic routes. For example, an amine component starting from cyanuric chloride and forming a substituent represented by formula (1) to formula (4) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N- It can be obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  In the pigment composition of the present invention, the blending amount of the basic derivative is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and most preferably 5 to 25 parts by weight with respect to 100 parts by weight of the pigment. The compounding amount of the carboxyl group-containing acidic urethane resin is preferably 1 to 200 parts by weight, more preferably 2 to 175 parts by weight, and most preferably 5 to 150 parts by weight with respect to 100 parts by weight of the pigment.

  The pigment composition of the present invention is dispersed in a varnish by mixing various solvents, resins, additives, etc. as necessary, and dispersing with a horizontal sand mill, vertical sand mill, annular bead mill, attritor or the like. A pigment dispersion can be prepared. Pigments, basic derivatives, carboxyl group-containing acidic urethane resins, other resins, and additives may be dispersed after mixing all the components, but initially only the pigment and basic derivative or basic Only the derivative and the carboxyl group-containing acidic urethane resin, or only the pigment, the basic derivative, and the carboxyl group-containing acidic urethane resin may be dispersed, and then another component may be added and dispersed again.

  Also, before dispersing with a horizontal sand mill, vertical sand mill, annular bead mill, attritor, etc., pre-dispersion using a kneader mixer such as a kneader, 3-roll mill, etc., solid dispersion with 2-roll mill, etc., or pigment A basic derivative and / or a carboxyl group-containing acidic urethane resin may be treated. In addition, any disperser or mixer such as a high speed mixer, a homomixer, a ball mill, a roll mill, a stone mill, or an ultrasonic disperser can be used for producing the pigment dispersion. Examples of various solvents that can be used in the pigment dispersion include organic solvents and water. Moreover, when using for an active energy ray hardening-type composition, you may use an active energy ray-curable liquid monomer and liquid oligomer as a medium instead of a solvent.

  Examples of resins that can be used in the pigment dispersion of the present invention include petroleum resin, casein, shellac, rosin-modified maleic resin, rosin-modified phenol resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, Rubber, Oxidized rubber, Hydrochloric acid rubber, Phenol resin, Alkyd resin, Polyester resin, Unsaturated polyester resin, Amino resin, Epoxy resin, Vinyl resin, Vinyl chloride, Vinyl chloride-Vinyl acetate Acid group urethane resin, Acrylic resin, Methacrylic resin , Polyurethane resin, silicone resin, fluorine resin, drying oil, synthetic drying oil, styrene-modified maleic acid, polyamide resin, chlorinated polypropylene, butyral resin, vinylidene chloride resin and the like.

  The pigment dispersion of the present invention can be used for non-aqueous, aqueous or solvent-free paints, gravure ink, offset ink, ink jet ink, color filter ink, digital paper ink, plastic coloring, and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not specifically limited to an Example. In the examples, “parts” represents “parts by weight” and “%” represents “% by weight”. The number average molecular weight is a polystyrene equivalent molecular weight when using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector and using THF as a developing solvent.
(Production Example 1)
In a four-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel, 3,3,4,4-biphenyltetracarboxylic dianhydride (hereinafter referred to as BPDA) (manufactured by Mitsubishi Chemical Corporation) 16.4 parts, 10.5 parts of neopentyl glycol (manufactured by Wako Pure Chemical Industries, Ltd.) and 27.1 parts of cyclohexanone were charged, reacted at 100 ° C. for 4 hours, and cooled to obtain a carboxyl group-containing polyol (a). It was. Next, 51.8 parts of isophorone diisocyanate (manufactured by Degussa Japan Co., Ltd.), 21.4 parts of neopentyl glycol, and 73.2 parts of cyclohexanone were charged, gradually heated, and reacted at 90 ° C. After confirming the disappearance of the peak at 2270 cm ⁻¹ based on the isocyanate group by IR, it was cooled to 40 ° C. to obtain a carboxyl group-containing acidic urethane resin.
(Production Examples 2-3)
Synthesis was carried out in the same manner as in Production Example 1 except that the raw materials and preparation amounts shown in Table 1 were used to obtain a carboxyl group-containing acidic urethane resin.
(Production Example 4)
In a 4-neck flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel, 53.5 parts of a lactone-based polyester polyol containing a carboxyl group (PCL205BA, manufactured by Mw500 Daicel Chemical Industries, Ltd.), neopentyl 8.6 parts of glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 37.9 parts of isophorone diisocyanate (manufactured by Degussa Japan Co., Ltd.), 100.0 parts of cyclohexanone, reacted at 90 ° C., and based on isocyanate group by IR After confirming the disappearance of the peak at 2270 cm ⁻¹ , it was cooled to 40 ° C. to obtain a carboxyl group-containing acidic urethane resin.

ＢＰＤＡ：３，３，４，４−ビフェニルテトラカルボン酸二無水物（三菱化学株式会社製）
ＰＭＡ：ピロメリット酸二無水物（和光純薬株式会社製）
ＮＰＧ：ネオペンチルグリコール（和光純薬株式会社製）
ＩＰＤＩ：イソホロンジイソシアネート（デグサジャパン株式会社製）
ＰＣＬ２０５ＢＡ：カルボキシル基を有するカプロラクトンジオール（ダイセル化学工業株式会社製）
（実施例１〜３）＜分散体の製造＞
表２に示すように、顔料（C.I. Pigment Blue 15：3）、製造例１〜３にて合成したカルボキシル基含有酸性ウレタン樹脂、下記構造式（１１）で表される塩基性基を有する顔料誘導体、およびシクロヘキサノンを配合し、２ｍｍφジルコニアビーズ１００部を加えペイントコンディショナーで３時間分散し、塗料を作成した。
（比較例１）＜分散体の製造＞
製造例４にて合成したカルボキシル基含有酸性ウレタン樹脂を用いた以外は、実施例１〜３と同様に塗料を作成した。

BPDA: 3,3,4,4-biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation)
PMA: pyromellitic dianhydride (Wako Pure Chemical Industries, Ltd.)
NPG: Neopentyl glycol (manufactured by Wako Pure Chemical Industries, Ltd.)
IPDI: Isophorone diisocyanate (Degussa Japan Co., Ltd.)
PCL205BA: Caprolactone diol having a carboxyl group (manufactured by Daicel Chemical Industries, Ltd.)
Examples 1 to 3 <Production of Dispersion>
As shown in Table 2, a pigment (CI Pigment Blue 15: 3), a carboxyl group-containing acidic urethane resin synthesized in Production Examples 1 to 3, and a pigment derivative having a basic group represented by the following structural formula (11) , And cyclohexanone were added, 100 parts of 2 mmφ zirconia beads were added and dispersed for 3 hours with a paint conditioner to prepare a paint.
(Comparative Example 1) <Production of dispersion>
A paint was prepared in the same manner as in Examples 1 to 3, except that the carboxyl group-containing acidic urethane resin synthesized in Production Example 4 was used.

ＣｕＰｃは、銅フタロシアニン残基を表す。
（分散体の評価）
本発明の顔料分散体の性能を評価するために、得られた塗料の粘度をＢ型粘度計（２５℃、回転速度１００ｒｐｍ）で、ヘイズをヘイズメーター（ 光透過率２０％）で測定し、初期粘度およびヘイズで分散体の性能を評価した（粘度は低いほど良好。ヘイズは小さいほど良好）。初期粘度およびヘイズは分散後１日室温で放置後に測定、経時粘度は１週間４０℃に放置後に測定を行った。結果を表２に示す。
本発明の分散体は、比較例に比べ、良好な粘度およびヘイズを示した。 Structural formula (11)

CuPc represents a copper phthalocyanine residue.
(Evaluation of dispersion)
In order to evaluate the performance of the pigment dispersion of the present invention, the viscosity of the obtained paint was measured with a B-type viscometer (25 ° C., rotation speed 100 rpm), and the haze was measured with a haze meter (light transmittance 20%), The performance of the dispersion was evaluated based on the initial viscosity and haze (the lower the viscosity, the better. The smaller the haze, the better). The initial viscosity and haze were measured after standing at room temperature for 1 day after dispersion, and the time-lapse viscosity was measured after standing at 40 ° C. for 1 week. The results are shown in Table 2.
The dispersion of the present invention showed better viscosity and haze than the comparative example.

以上の評価結果から明らかなように、実施例１〜３は、低い初期粘度で、かつ経時粘度の増加がほとんどなく良好な安定性を示している。さらにヘイズも低い。これに対して、比較例１では、粘度とヘイズともに高く、分散性に問題があることがわかった。

As is clear from the above evaluation results, Examples 1 to 3 have a low initial viscosity and a good stability with little increase in viscosity over time. Furthermore, the haze is low. On the other hand, in Comparative Example 1, it was found that both the viscosity and haze were high, and there was a problem in dispersibility.

Claims (9)

A pigment composition containing a carboxyl group-containing acidic urethane resin and a pigment,
A carboxyl group-containing polyol (a) obtained by reacting the polyhydric carboxylic acid anhydride (a1) and the polyol compound (a2) with the urethane resin;
Furthermore, it is a carboxyl group-containing acidic urethane resin obtained by reacting with the polyisocyanate compound (b). A pigment composition containing a carboxyl group-containing acidic urethane resin and a pigment,
A carboxyl group-containing polyol (a) obtained by reacting the polyhydric carboxylic acid anhydride (a1) and the polyol compound (a2) with the urethane resin;
Furthermore, it is a carboxyl group-containing acidic urethane resin obtained by reacting a polyisocyanate compound (b) with a polyol compound (c) other than the polyol (a).   The pigment composition according to claim 1 or 2, wherein the polyvalent carboxylic acid anhydride (a1) is a tetracarboxylic dianhydride.   The pigment composition according to any one of claims 1 to 3, wherein the carboxyl group-containing polyol (a) has a weight average molecular weight of 300 to 25000.   The pigment composition according to any one of claims 1 to 4, wherein the carboxyl group-containing polyol (a) has an acid value of 10 to 400 and a hydroxyl value of 20 to 300.   The carboxyl group-containing polyol (a) has a molar ratio (a1) / (a2) = 0.3 between the acid anhydride group in the polyvalent carboxylic acid anhydride (a1) and the hydroxyl group in the polyol compound (a2). The pigment composition according to any one of claims 1 to 5, wherein the pigment composition is reacted under a condition of ~ 0.8.   The pigment composition according to any one of claims 1 to 6, wherein the carboxyl group-containing acidic urethane resin has an acid value of 10 to 200.   Furthermore, it includes at least one basic derivative selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group. The pigment composition in any one of 1-8. A pigment dispersion obtained by dispersing the pigment composition according to claim 1 in a varnish.