JP2011157416A - Curable dispersant, pigment composition using the same, and pigment dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce a dispersion excellent in non-aggregation property, fluidity and storage stability and suitable for fields such as coatings and colored resin compositions, and to produce a dispersion excellent also in chemical resistance, solvent resistance and heat resistance of a colored article therewith. <P>SOLUTION: This curable dispersant comprises a polyester moiety A having carboxy groups obtained by reacting acid anhydride groups in one or more acid anhydrides selected from tetracarboxylic acid anhydrides (a) and tricarboxylic acid anhydrides (b) with hydroxy groups in a hydroxy group-containing compound (c), and a vinyl polymer moiety B obtained by radically polymerizing one or more ethylenically unsaturated monomers selected from ethylenically unsaturated monomers (e) having no hydroxy group and ethylenically unsaturated monomers (f) having a hydroxy group, wherein the vinyl polymer moiety B has (meth)acryloyl groups. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a dispersant, and more particularly, can produce a dispersion excellent in non-aggregation property, fluidity, and storage stability, which is suitable for fields such as paints and colored resin compositions, and at the same time, is resistant to chemicals in color developed products The present invention relates to a curable dispersant capable of producing a dispersion having excellent properties, solvent resistance, and heat resistance, and a pigment composition and pigment dispersion using the same.

  Generally, when manufacturing ink etc., it is known that it is difficult to disperse | distribute a pigment stably at high concentration, and it is known that it causes various problems with respect to a manufacturing process or the product itself. For example, dispersions containing pigments composed of fine particles often exhibit high viscosity, making it difficult to remove and transport the product from the disperser, and if bad, cause gelation during storage and use It can even be difficult. Furthermore, regarding the surface of the color-extended product, a state failure such as a decrease in gloss and a leveling failure occurs. In addition, when different types of pigments are used in combination, color unevenness due to aggregation and phenomena such as sedimentation may cause uneven color and a marked reduction in coloring power.

  Therefore, in general, a dispersant is used in order to maintain a good dispersion state. The dispersant has a structure of a site that adsorbs to the pigment and a site that has a high affinity for the solvent that is the dispersion medium, and the performance of the dispersant is determined by the balance of these two functional sites. Various dispersants are used in accordance with the surface state of the pigment to be dispersed, but acidic pigments are generally used for pigments having a surface that is biased toward basicity. . In this case, the acidic functional group becomes the adsorption site of the pigment.

  Dispersants having a phosphoric acid group or a sulfonic acid group as an acidic functional group are known (for example, Patent Document 1 or Patent Document 2). These have high dispersibility and can produce a pigment dispersion having a low viscosity with a small amount of use. However, when storage stability is poor, defects due to phosphoric acid groups or sulfonic acid groups, such as poor compatibility (problems during production), low heat resistance, or low chemical resistance. Problems sometimes arise, and such a dispersant having a phosphoric acid group or a sulfonic acid group is poor in developability to applied inks or paints.

  A dispersant having a carboxylic acid group as an acidic functional group has no problem with a dispersant having a phosphoric acid group or a sulfonic acid group, but tends to be inferior in dispersion ability, and even if the amount used is increased, phosphoric acid It has been difficult to reduce the viscosity as in the case of using a dispersant having a group or a sulfonic acid group.

  In recent years, a dispersant using a carboxylic acid group and having improved ability as a dispersant has been proposed. Examples include block copolymerization of an acrylic resin having a carboxylic acid group, and examples in which polyester, polyether, polyurethane, or the like is grafted to an acrylic resin having a carboxylic acid group (for example, Patent Document 3 or Patent Document 4). .

  Although these have a high dispersion ability compared with a dispersant having a conventional carboxylic acid group, they have a low dispersion ability and a low viscosity compared to a dispersant having a phosphate group or a sulfonate group. In order to make a stable dispersion, it was necessary to use a certain amount.

  On the other hand, Patent Document 5, Patent Document 6, and Patent Document 7 propose a method of mixing a pigment composition with a synergist having an acidic group or a basic group as a substituent in a side chain using a pigment as a base skeleton. . However, this alone does not always provide a satisfactory effect, and it has been proposed to use a dispersant having a counter ion for synergists having the acidic group or basic group as a substituent as described above. (For example, patent document 8 or patent document 9). Here, the synergist has a structure similar to the chemical structure of the dye that forms the pigment, and is strongly adsorbed to the pigment by π-π interaction, and the surface of the pigment by the ionic functional group contained in the synergist Is made acidic or basic to increase the effect of the dispersing agent or pigment carrier having a counter ion.

  Patent Document 8 exemplifies a pigment composition containing a synergist having a basic group as a substituent and a dispersant having a phosphate group. A dispersant having a phosphoric acid group has a certain degree of pigment dispersion ability when used in combination with a synergist having a basic group as a substituent, 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. Pigment compositions using such dispersants having phosphoric acid groups or sulfonic acid groups are poor in expandability to applied inks and paints, etc., while conventional dispersants using carboxylic acids are basic. The pigment composition combined with a synergist having a substituent as a substituent has improved heat resistance, chemical resistance and compatibility compared to a dispersant having a phosphate group or a sulfonate group, but the viscosity is improved. There are problems such as high stability, poor stability, and poor microdispersion of the pigment, and it is necessary to increase the amount of dispersant added. As a result, low heat resistance and chemical resistance were exposed, and it was difficult to achieve both heat resistance, chemical resistance and pigment dispersion ability.

Japanese Patent No. 2633075 Japanese Patent No. 2747769 JP 2005-194487 A Japanese Patent No. 3049407 JP-A-63-305173 JP-A-1-247468 JP-A-3-26767 JP-A 63-248864 JP-A-9-176511

  An object of the present invention is to provide a curable dispersant that is excellent in dispersibility and at the same time exhibits excellent chemical resistance and solvent resistance after curing a color-extended product.

The present inventor has been earnestly researching the development of a carboxylic acid group-containing dispersant having a high dispersion ability, and comprising a carboxyl group-containing portion having a specific structure and a polymer portion having a curable functional group, It has been found that it is possible to obtain a curable dispersant that is excellent in dispersibility and at the same time exhibits excellent chemical resistance and solvent resistance after the color-extended product is cured.
That is, the first invention relates to an acid anhydride group in one or more acid anhydrides selected from tetracarboxylic acid anhydride (a) and tricarboxylic acid anhydride (b), and a hydroxyl group in the hydroxyl group-containing compound (c). At least one selected from the group consisting of a polyester part A having a carboxyl group, an ethylenically unsaturated monomer having no hydroxyl group (e), and an ethylenically unsaturated monomer having a hydroxyl group (f). The present invention relates to a dispersant comprising a vinyl polymer portion B formed by radical polymerization of an ethylenically unsaturated monomer, and a curable dispersant having a (meth) acryloyl group in the vinyl polymer portion B.

  In the second invention, the hydroxyl group in the compound (g) having two hydroxyl groups and one thiol group in the molecule is reacted with the acid anhydride group in the tetracarboxylic acid anhydride (a). In the presence of the compound (h1) produced in this manner, a hydroxyl group containing radically polymerized ethylenically unsaturated monomer (e) having no hydroxyl group and ethylenically unsaturated monomer (f) having a hydroxyl group A curable dispersion having a (meth) acryloyl group obtained by reacting a hydroxyl group in the compound (k1) with an isocyanate group in the compound (i) having one isocyanate group and one or more (meth) acryloyl groups. It relates to the agent.

In addition, the third invention relates to a hydroxyl group in a compound (g) having two hydroxyl groups and one thiol group in the molecule and a hydroxyl group-containing compound (j) having no thiol group, a tetracarboxylic acid anhydride ( a) an ethylenically unsaturated monomer having no hydroxyl group and an ethylenically unsaturated monomer having a hydroxyl group in the presence of the compound (h2) produced by reacting the acid anhydride group in a) with A hydroxyl group in the hydroxyl group-containing compound (k2) obtained by radical polymerization of the monomer (f);
The present invention relates to a curable dispersant having a (meth) acryloyl group obtained by reacting one isocyanate group with an isocyanate group in a compound (i) having one or more (meth) acryloyl groups.

Moreover, 4th invention makes the hydroxyl group in the compound (g) which has two hydroxyl groups and one thiol group in a molecule | numerator, and the acid anhydride group in a tricarboxylic acid anhydride (b) react. Hydroxyl-containing compound obtained by radical polymerization of ethylenically unsaturated monomer (e) having no hydroxyl group and ethylenically unsaturated monomer (f) having a hydroxyl group in the presence of the compound (h3) to be produced A curable dispersant having a (meth) acryloyl group obtained by reacting the hydroxyl group in (k3) with an isocyanate group in the compound (i) having one isocyanate group and one or more (meth) acryloyl groups. About.
The fifth invention relates to the curable dispersant according to any one of the first to fourth inventions, wherein the unsaturated double bond equivalent is 300 to 3,500.
The sixth invention relates to the curable dispersant according to any one of the first to fifth inventions having a weight average molecular weight of 2,000 to 100,000 and an acid value of 5 to 200 mgKOH / g.

The seventh invention is the curability of any one of the first to sixth inventions, wherein the tetracarboxylic acid anhydride (a) is represented by the following general formula (1) or general formula (2): It relates to a dispersant.
General formula (1)

［一般式（１）中、ｋは１又は２である。］
一般式（２）

[In General Formula (1), k is 1 or 2. ]
General formula (2)

［一般式（２）中、Ｒ¹は、直接結合、−Ｏ−、−ＣＯ−、−ＣＯＯＣＨ₂ＣＨ₂ＯＣＯ−、−ＳＯ₂−、−Ｃ（ＣＦ₃）₂−、式：

[In General Formula (2), R ¹ is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, a formula:

で表される基、又は式：

Or a group represented by the formula:

で表される基である。］

又、第８の発明は、トリカルボン酸無水物（ｂ）が、下記一般式（３）で表されることを特徴とする第１〜６いずれかの発明の硬化性分散剤に関する。
一般式（３）

It is group represented by these. ]

The eighth invention relates to the curable dispersant according to any one of the first to sixth inventions, wherein the tricarboxylic acid anhydride (b) is represented by the following general formula (3).
General formula (3)

［一般式（３）中、ｋは１又は２である。］

[In General Formula (3), k is 1 or 2. ]

  The ninth invention relates to the weight of the vinyl polymer portion B obtained by radical polymerization of an ethylenically unsaturated monomer (e) having no hydroxyl group and an ethylenically unsaturated monomer (f) having a hydroxyl group. The present invention relates to the curable dispersant according to any one of the first to eighth inventions having an average molecular weight of 1,000 to 50,000.

The tenth aspect of the invention is any one of the first to ninth aspects, wherein the ethylenically unsaturated monomer (e) having no hydroxyl group includes a monomer represented by the following general formula (4): The present invention relates to a curable dispersant according to the invention.
General formula (4)

［一般式（４）において、Ｒ²は、炭素原子数１〜４の直鎖状もしくは分岐状のアルキル基、又は炭素数６〜１５の脂環式のアルキル基である。］

[In General Formula (4), R ² is a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic alkyl group having 6 to 15 carbon atoms. ]

  The eleventh invention is a compound in which the compound (i) having one isocyanate group and one or more (meth) acryloyl groups has one isocyanate group and one or two (meth) acryloyl groups. The invention relates to the curable dispersant according to any one of the first to tenth inventions.

  In a twelfth aspect of the invention, the compound (i) having one isocyanate group and one or more (meth) acryloyl groups is substituted with 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, or 1,1-bis. The present invention relates to the curable dispersant according to any one of the first to eleventh aspects, which is any one of (acryloyloxymethyl) ethyl isocyanate.

  The thirteenth invention relates to a pigment composition containing the curable dispersant of any of the first to twelfth inventions and a pigment.

Further, the fourteenth invention is further characterized by a basicity 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 present invention relates to the pigment composition of the thirteenth invention containing at least one derivative.
The fifteenth invention relates to a pigment dispersion obtained by dispersing the pigment composition of the thirteenth or fourteenth invention in a varnish.

  By using the curable dispersant of the present invention, it is possible to obtain a pigment composition having dispersibility, fluidity and storage stability at a low use amount, and further, offset ink, gravure ink, color filter resist. Suitable for inks and ink jet inks, paints, colored resin compositions, etc. Has excellent dispersibility and stability in non-aggregation and fluidity, and at the same time has excellent chemical resistance and solvent resistance after curing the developed color. A pigment dispersion having

  In general, a pigment dispersant has a structure of a part that adsorbs to a pigment and a part that has a high affinity for a solvent as a dispersion medium, and the performance of the dispersant is determined by the balance between these two parts. That is, in order to develop dispersibility, both the ability of the dispersant to adsorb to the pigment and the affinity to the solvent as the dispersion medium are very important.

  The tetracarboxylic anhydride (a) used in the present invention reacts with a hydroxyl group to form an ester bond, and can leave a pendant carboxyl group on the resulting polyester main chain. The vinyl copolymer moiety can be introduced by radical polymerization of the ethylenically unsaturated monomer using the remaining thiol group as a chain transfer agent. Compound (g) having two hydroxyl groups and one thiol group:

と、コア部分Ｘ₁を有するテトラカルボン酸無水物を水酸基過剰の条件下で反応を行い、続いてエチレン性不飽和単量体を導入する場合の反応式を下記反応工程式（５）に示す。下記反応工程式（５）において、ｎは繰り返し単位数であり、Ｂはビニル共重合体部分である。

And a reaction formula in the case where the tetracarboxylic anhydride having the core portion X ₁ is reacted under an excess of hydroxyl groups and then introducing an ethylenically unsaturated monomer is shown in the following reaction process formula (5). . In the following reaction process formula (5), n is the number of repeating units, and B is a vinyl copolymer portion.

  Reaction process formula (5)

  Similarly, when the tricarboxylic acid anhydride (b) is used, it can react with a hydroxyl group to form an ester bond and leave a carboxyl group. The reaction formula at this time is shown in the following reaction process formula (6). In the following reaction process formula (6), B is a vinyl copolymer portion.

  Reaction process formula (6)

However, in the dispersant of the present invention, when only one carboxyl group is bonded to the core portions X ₁ and X ₂ (outside the scope of the present invention), high dispersibility, fluidity, and storage stability. Is not preferable.

In the dispersant of the present invention, the core part X ₁ is a reaction residue after the tetracarboxylic acid anhydride (a) has reacted with a hydroxyl group, and the core part X ₂ has a tricarboxylic acid anhydride (b) with a hydroxyl group. It is a reaction residue after the reaction, A is a trivalent residue, for example, a linear or branched trivalent having 1 to 10 carbon atoms (preferably 1 to 8 carbon atoms). Two hydroxyl groups that are aliphatic hydrocarbon groups and are bonded to A may be bonded to the same carbon atom or may be bonded to different carbon atoms. B is a vinyl copolymer part. A preferred form of the core portion X ₁ is a reaction residue after the tetracarboxylic acid anhydride (a) represented by the following general formula (1) or general formula (2) has reacted with the polyol compound.

  General formula (1)

［一般式（１）中、ｋは１、又は２である。］
一般式（２）

[In General Formula (1), k is 1 or 2. ]
General formula (2)

［一般式（２）中、Ｒ¹は、直接結合、−Ｏ−、−ＣＯ−、−ＣＯＯＣＨ₂ＣＨ₂ＯＣＯ−、−ＳＯ₂−、−Ｃ（ＣＦ₃）₂−、式：

[In General Formula (2), R ¹ is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, a formula:

で表される基、又は式：

Or a group represented by the formula:

で表される基である。］
好ましいコア部分Ｘ₂の形態は、下記一般式（３）で示されるトリカルボン酸無水物（ｂ）が、ポリオール化合物と反応した後の反応残基である。
一般式（３）

It is group represented by these. ]
A preferred form of the core portion X ₂ is a reaction residue after the tricarboxylic acid anhydride (b) represented by the following general formula (3) has reacted with the polyol compound.
General formula (3)

［一般式（３）中、ｋは１又は２である。］

[In General Formula (3), k is 1 or 2. ]

  The dispersant of the present invention does not have a compound (g) having two hydroxyl groups and one thiol group, a tetracarboxylic acid anhydride (a) or a tricarboxylic acid anhydride (b), and an optionally added thiol group. A first step of first producing compounds (h1) to (h3) having pendant carboxyl groups by reacting with the hydroxyl group-containing compound (j), followed by the remaining of the compounds (h1) to (h3) Polymer having a hydroxyl group by radical polymerization of an ethylenically unsaturated monomer (e) having no hydroxyl group and a ethylenically unsaturated monomer having a hydroxyl group (f) having a thiol group as a chain transfer agent A second step of producing the hydroxyl group-containing compounds (k1) to (k3) into which the moiety B has been introduced, and a compound (i) having one isocyanate group and one or more (meth) acryloyl groups; Is obtained by passing through the third step is a reaction. A plurality of carboxyl group portions in the dispersant of the present invention function as a pigment adsorbing portion, and a vinyl polymer portion functions as a solvent affinity portion.

  In this specification, “vinyl polymer part B formed by radical polymerization of ethylenically unsaturated monomer (e) having no hydroxyl group and ethylenically unsaturated monomer (f) having a hydroxyl group” means 2 A compound (g) having one hydroxyl group and one thiol group, a tetracarboxylic acid anhydride (a) or a tricarboxylic acid anhydride (b), and a hydroxyl group-containing compound (j) having no thiol group to be optionally added. It is a continuous part that does not contain the polyester part A having a reacted pendant carboxyl group, and usually one or more vinyl polymer parts B are contained in one molecule constituting the dispersant of the present invention.

The weight average molecular weight of the vinyl polymer portion B obtained by radical polymerization of the ethylenically unsaturated monomer (e) having no hydroxyl group and the ethylenically unsaturated monomer (f) having a hydroxyl group is 1,000 to It is preferably 50,000, more preferably 2,000 to 30,000, still more preferably 2,000 to 20,000, and particularly preferably 2,500 to 10,000. This part B becomes an affinity part to the solvent which is a dispersion medium. When the weight average molecular weight of the vinyl polymer part B is less than 1,000, the effect of steric repulsion by the solvent affinity part is reduced, and it is difficult to prevent the aggregation of the pigment, and the dispersion stability may be insufficient. . On the other hand, if it exceeds 50,000, the absolute amount of the solvent-affinity part increases, and the dispersibility effect itself may decrease. Further, the viscosity of the dispersion may increase. The vinyl polymer portion B can be easily adjusted in molecular weight within the above range, and has good affinity for the solvent.
First, a compound (g) having two hydroxyl groups and one thiol group in the molecule, a tetracarboxylic acid anhydride (a) or a tricarboxylic acid anhydride (b), and a hydroxyl group containing no thiol group to be optionally added The first step of producing compounds (h1) to (h3) having pendant carboxyl groups by reacting with compound (j) will be described.

  Examples of the compound (g) having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, and 3-mercapto-1. , 2-propanediol (alias: 1-thioglycerol), 2-mercapto-1,3-propanediol, 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2- And ethyl-1,3-propanediol.

Examples of the tetracarboxylic acid anhydride (a) used in the present invention include 1,2,3,4-butanetetracarboxylic acid anhydride, 1,2,3,4-cyclobutanetetracarboxylic acid anhydride, 1,3 -Dimethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-cyclopentanetetracarboxylic anhydride, 2,3,5-tricarboxycyclopentylacetic anhydride, 3,5 , 6-Tricarboxynorbornane-2-acetic anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic anhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1 , 2-dicarboxylic acid anhydrides, aliphatic tetracarboxylic acid anhydrides such as bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic acid anhydrides;
Pyromellitic anhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 3, 3 ', 4,4'-biphenyl ether tetracarboxylic acid anhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic acid anhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic acid Acid anhydride, 1,2,3,4-furantetracarboxylic acid anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diph Nyl sulfide anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane anhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride, bis (phthalic acid) phenylphosphine oxide anhydride, p-phenylene-bis (tri Phenylphthalic acid anhydride, m-phenylene-bis (triphenylphthalic acid) anhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether anhydride, bis (triphenylphthalic acid) -4,4 ′ -Diphenylmethane anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluoric anhydride, 9,9-bis [4- (3,4-dicarboxyl) Ciphenoxy) phenyl] fluorenic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic anhydride, 3,4-dicarboxy-1,2,3,4 And aromatic tetracarboxylic acid anhydrides such as tetrahydro-6-methyl-1-naphthalene succinic acid anhydride.

The tetracarboxylic acid anhydride (a) used in the present invention is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic acid anhydride groups. These may be used alone or in combination. What is preferably used in the present invention is an aromatic tetracarboxylic dianhydride from the viewpoint of reducing the viscosity of the pigment dispersion or various inks. Furthermore, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, ethylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′-biphenyl ether tetra Carboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 2,3,6 , 7-Naphthalenetetracarboxylic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are preferred.
The use of tricarboxylic acid anhydride (b) is also a preferred form of the dispersant of the present invention. Examples of the tricarboxylic acid anhydride (b) include aliphatic tricarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides.

  Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid- 1,2-anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride, etc. are mentioned.

  Examples of the aromatic tricarboxylic acid include benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzenetricarboxylic acid anhydride], etc.), naphthalenetricarboxylic acid, and the like. Acid anhydride (1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 1,2,8-naphthalenetricarboxylic acid anhydride Products), 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid anhydride, 2,3,2 ′ -Biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, 3,4,4'-biphenyl Sulfonic tricarboxylic acid anhydrides. When tricarboxylic acid anhydride is used, aromatic tricarboxylic acid anhydride is particularly preferable among the above, and trimellitic acid anhydride is more preferable.

  Moreover, in this invention, it is possible to use together the compound (g) which has two hydroxyl groups and one thiol group in a molecule | numerator, and the hydroxyl-containing compound (j) which does not have a thiol group in arbitrary ratios. is there. By using the hydroxyl group-containing compound (j) having no thiol group, the ratio of the pigment adsorbing part and the solvent dissolving part can be easily adjusted.

  As the hydroxyl group-containing compound (j) having no thiol group, a known compound can be used. For example, a compound having no thiol group and 2 to 4 hydroxyl groups in one molecule is used. Can do. 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 or polyether glycols described above and various (cyclic) 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 an ether bond-containing compound;

(4) Polyester polyols obtained by co-condensation of one or more of the various polyhydric alcohols or polyether glycols described above with polycarboxylic acids, wherein the polycarboxylic acids are succinic acid, adipine 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-cyclohexane Particularly represented by hycarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid. Polyester polyols obtained using

(5) Polycondensation reaction of one or more of the various polyhydric alcohols or polyether glycols described above with various lactones such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone. Or lactone-modified polyester polyols obtained by polycondensation reaction of the above-mentioned various polyhydric alcohols or polyether glycols, 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.

  The hydroxyl group-containing compound (j) having no thiol group added arbitrarily shown in (1) to (7) may be used alone or in combination of two or more, but its weight As an average molecular weight, 100-10,000 are preferable, More preferably, it is 100-2,000, More preferably, it is 100-1,000.

  A compound having only one hydroxyl group may be used in combination. There is no particular limitation as long as it has only one hydroxyl group. For example, aliphatic alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol, aliphatic aromatic alcohols such as benzyl alcohol and phenethyl alcohol, 2 Examples include alcohols having a photocurable site such as -hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.

  Here, the “photocurable site” in the present invention refers to a functional group that is polymerized by irradiation with active energy rays such as ultraviolet rays and electron beams, and specific examples thereof include a vinyl group, an acryloyl group, and a methacryloyl group. Group and the like.

  As the catalyst used for reacting the acid anhydride group and the hydroxyl group of the present invention, a known catalyst can be used. For example, triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene, monobutyltin oxide and the like.

  Compounds (h1) to (h3) having pendant carboxyl groups obtained in the first step are compounds (g) having two hydroxyl groups and one thiol group in the molecule, tetracarboxylic acid anhydride (a), and It can be obtained by reacting optionally added tricarboxylic acid anhydride (b) and a hydroxyl group-containing compound (j) having no thiol group. Compound (g) having an acid anhydride group in tetracarboxylic anhydride (a) and tricarboxylic anhydride (b), two hydroxyl groups and one thiol group in the molecule, and a hydroxyl group not having a thiol group The molar ratio with the hydroxyl group in the contained compound (j) is preferably 0.3 <[(a) + (b)] / [(g) + (j)] <1.0, more preferably 0. .5 <[(a) + (b)] / [(g) + (j)] <1.0, most preferably 0.6 <[(a) + (b)] / [(g) + ( j)] <0.8. If it is 0.3 or less, there may be fewer acid anhydride residues as the pigment adsorbing part, and the acid value of the resin may also be lower. If it is 1.0 or more, unreacted acid anhydride groups May remain, resulting in poor storage stability.

  The reaction temperature is 80 ° C to 180 ° C, preferably 90 ° C to 160 ° C. When the reaction temperature is less than 80 ° C., the reaction rate is slow. When the reaction temperature exceeds 180 ° C. or more, the carboxyl group undergoes an esterification reaction, which may cause a decrease in acid value or gelation. Ideally, the reaction is stopped until the absorption of the acid anhydride is eliminated by infrared absorption, but when the acid value falls within the range of 5 to 200 mgKOH / g, or the hydroxyl value is 20 to 200 mgKOH / g. The reaction may be stopped when entering the range of g.

  Next, the ethylenically unsaturated monomer (e) having no hydroxyl group and the ethylenically unsaturated monomer having a hydroxyl group using the remaining thiol groups of the compounds (h1) to (h3) as chain transfer agents The second step of producing the hydroxyl group-containing compounds (k1) to (k3) in which the vinyl polymer portion B having a hydroxyl group is introduced by radical polymerization of (f) will be described. By copolymerizing the ethylenically unsaturated monomer (f) having a hydroxyl group in the second step, a hydroxyl group can be introduced into the vinyl polymer portion B of the dispersant, and one isocyanate is obtained in the third step. It can be reacted with a compound (i) having a group and one or more (meth) acryloyl groups.

Examples of the ethylenically unsaturated monomer (e) having no hydroxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2,2,4-trimethylcyclohexyl (meth) acrylate, stearyl (meth) acrylate Alkyl (meth) acrylates such as lauryl (meth) acrylate and isobornyl (meth) acrylate;
Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate;
Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate;
(N-substituted) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine ( (Meth) acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate;
Nitriles such as (meth) acrylonitrile are exemplified.

  Here, “(meth) acrylate” means “methacrylate” or “acrylate”, and “(meth) acrylamide” means “methacrylamide” or “acrylamide”.

  As monomers that can be used in combination with the above acrylic monomers, styrenes such as styrene, α-methylstyrene, and indene, and vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether And fatty acid vinyls such as vinyl acetate and vinyl propionate.

  Moreover, a carboxyl group-containing ethylenically unsaturated monomer can be used in combination. As the carboxyl group-containing ethylenically unsaturated monomer, one or more kinds can be selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like.

In the present invention, among the ethylenically unsaturated monomers (e) having no hydroxyl group as exemplified above, the monomer represented by the following general formula (4) is used in terms of dispersibility. preferable.
General formula (4)

［一般式（４）において、Ｒ²は、炭素原子数１〜４の直鎖状もしくは分岐状のアルキル基、又は炭素数６〜１５の脂環式のアルキル基である。］

[In General Formula (4), R ² is a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic alkyl group having 6 to 15 carbon atoms. ]

  As the ethylenically unsaturated monomer (f) having a hydroxyl group, any monomer having a hydroxyl group and having an ethylenically unsaturated double bond may be used. (Meth) acrylate monomers having a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate And hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate, and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate, or (meth) acrylamide monomers having a hydroxyl group, such as N- (2-hydroxyethyl) (meth) acrylamide, N N- (hydroxyalkyl) (meth) acrylamide such as (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) acrylamide, or vinyl ether monomers having a hydroxyl group, such as 2 -Hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, hydroxyalkyl vinyl ethers such as 2- (or 3- or 4-) hydroxybutyl vinyl ether, or allyl ether monomers having a hydroxyl group, such as 2- Examples include hydroxyalkyl allyl ethers such as hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, and 2- (or 3- or 4-) hydroxybutyl allyl ether.

  Also obtained by adding alkylene oxide and / or lactone to the above hydroxyalkyl (meth) acrylate, alkyl-α-hydroxyalkyl acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl vinyl ether or hydroxyalkylallyl ether. The ethylenically unsaturated monomer obtained can also be used as the ethylenically unsaturated monomer (f) having a hydroxyl group in the method of the present invention. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and a combination system of two or more thereof are used. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. As the lactone to be added, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these are used. What added both alkylene oxide and lactone may be used.

  In the second step of the present invention, the compounds (h1) to (h3) are ethylenically unsaturated monomer (e) and an ethylenic group having a hydroxyl group in accordance with the molecular weight of the target vinyl polymer part B. It is possible to produce hydroxyl group-containing compounds (k1) to (k3) in which a vinyl polymer portion B having a hydroxyl group is introduced by mixing an unsaturated monomer (f) and a polymerization initiator and heating them. it can. Preferably, 10 to 300 parts by weight of the compounds (h1) to (h3) are added to 100 parts by weight of the ethylenically unsaturated monomer (e) and the ethylenically unsaturated monomer (f) having a hydroxyl group. Used for bulk polymerization or solution polymerization. The reaction temperature is 40 to 150 ° C., preferably 50 to 110 ° C., and the reaction time is 3 to 30 hours, preferably 5 to 20 hours.

  During polymerization, 0.001 to 5 parts by weight of a polymerization initiator is arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer (e) and the ethylenically unsaturated monomer (f) having a hydroxyl group. can do. As the polymerization initiator, azo compounds and organic peroxides can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

  In the case of solution polymerization, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, methoxypropyl acetate, etc. are used as the polymerization solvent, but are not particularly limited to these. Absent. These polymerization solvents may be used as a mixture of two or more.

  Next, the reaction between the hydroxyl group-containing compounds (k1) to (k3) and the compound (i) having one isocyanate group and one or more (meth) acryloyl groups in the third step will be described. The dispersant of the present invention reacts the hydroxyl group in the hydroxyl group-containing compounds (k1) to (k3) with the isocyanate group in the compound (i) having one isocyanate group and one or more (meth) acryloyl groups. Is obtained. Thereby, a (meth) acryloyl group can be arbitrarily introduced mainly into the vinyl polymer part B in the dispersant, and a curable dispersant having curability at the solvent affinity site can be obtained.

The compound (i) having one isocyanate group and one or more (meth) acryloyl groups used in the third step is a compound having one isocyanate group and one or two (meth) acryloyl groups. Specifically, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate are preferable.
The compound (i) having one isocyanate group and one or more (meth) acryloyl groups used in the present invention is not limited to the compounds exemplified above, and may have an isocyanate group and one or more (meth) acryloyl groups. Any structure is acceptable. These may be used alone or in combination.

The molar ratio of the hydroxyl group in the hydroxyl group-containing compounds (k1) to (k3) to the isocyanate group in the compound (i) having one isocyanate group and one or more (meth) acryloyl groups is determined by the hydroxyl group-containing compound (k1). ) To (k3) with respect to 1 mol of hydroxyl group, the isocyanate group in compound (i) having one isocyanate group and one or more (meth) acryloyl groups is 0.2 to 1.0 mol. Is more preferably 0.3 to 1.0 mol, and most preferably 0.5 to 1.0 mol. If the amount is less than 0.2 mol, the amount of (meth) acryloyl groups may be reduced, so that the curability may be insufficient. If the amount exceeds 1.0 mol, unreacted isocyanate groups are present in the resin. It may remain and storage stability may deteriorate.
The reaction temperature is 50 ° C to 150 ° C, preferably 70 ° C to 120 ° C. When the reaction temperature is less than 50 ° C., the reaction rate is slow, and when it exceeds 150 ° C., the urethane group produced by the reaction is decomposed.

The dispersant of the present invention can be produced using only the raw materials mentioned so far, 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 solvent used for the reaction can be removed by an operation such as distillation after the completion of the reaction, or can be used as a part of the product as it is.
The weight average molecular weight of the obtained dispersant is preferably 2,000 to 100,000. If the weight average molecular weight is less than 2,000, the stability of the pigment composition may decrease, and if it exceeds 100,000, the interaction between the resins may become strong and the viscosity of the pigment composition may increase. . Further, the acid value of the obtained dispersant is preferably 5 to 200 mgKOH / g. More preferably, it is 5-150 mgKOH / g, Most preferably, it is 5-100 mgKOH / g. When the acid value is less than 5 mgKOH / g, the pigment adsorbing ability may be lowered and there may be a problem in pigment dispersibility. There is a case.

  Examples of the pigment that can be dispersed with the dispersant of the present invention include various pigments used in inks and the like. 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, etc. More specific examples are shown by the generic names of Color Index: Pigment Black 7, Pigment Blue 6, 15 15: 1, 15: 6, 15: 4, 15: 6, 60, Pigment Green 7, 36, 58, Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 144, 146, 149 , 166, 168, 177, 17 , 179, 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-mentioned pigment, and for example, solid fine particles containing fine metal particles such as gold, silver, copper, platinum, iron, cobalt, nickel, and / or alloys thereof can be used. .

  The pigment composition using the dispersant of the present invention further includes 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 to contain at least one basic derivative selected from: 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 consisting 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.

A pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, or a triazine derivative having a basic group included in the present invention are represented by the following general formulas (5), (6), ( It has at least one substituent selected from the group represented by 7) and (8).
General formula (5)

General formula (6)

General formula (7)

General formula (8)

In the general formulas (5) to (8),
R ³ represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
m represents an integer of 1 to 10.
R ⁶ , R ⁷ Each independently represents an optionally substituted alkyl group, alkenyl group, phenyl group, or R ⁶ and R ⁷ formed together. However, the heterocycle may contain further nitrogen, oxygen or sulfur atoms. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ⁸ Represents an alkyl group, an alkenyl group or a phenyl group which may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group or a phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferred.
R ¹³ represents —NR ¹⁶ —R ¹⁸ —NR ¹⁷ — or a direct bond.
R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group or a phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferred.
R ¹⁸ represents an optionally substituted alkylene group, alkenylene group or phenylene group. As for carbon number of an alkyl group and an alkenyl group, 1-8 are preferable.
R ¹⁴ represents a substituent represented by the general formula (9) or a substituent represented by the general formula (10).
R ¹⁵ represents a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (9), or a substituent represented by the general formula (10).

General formula (9)

General formula (10)

In the general formulas (9) and (10),
R ⁴ and R ⁵ represent —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.

Examples of the alkyl group in R ^{6 to} R ¹² , R ¹⁶ and R ¹⁷ in the above general formula include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the alkenyl group include a vinyl group and a propenyl group.
Examples of the alkylene group for R ¹⁸ in the general formula include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of alkenylene groups include vinylene groups and propenylene groups.

Examples of the alkoxyl group for R ¹⁵ in the general formula include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
Examples of the functional group that may be substituted include a halogen group, a cyano group, an alkoxyl group, an amino group, a hydroxyl group, a nitro group, and an epoxy group.

  Examples of the amine component used to form the substituents represented by the general formulas (5) to (8) 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 N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylamino Amylamine, 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-laurylamino The Pyramine, 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-pipecholine, N-aminopropyl-4-pipecholine, N-amino Examples thereof include propylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

  Organic dyes contained in 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. 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, and chlorine. It may have a substituent such as halogen.

  Triazines constituting triazine derivatives having basic groups include 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 included in the present invention can be synthesized by various synthetic routes. For example, after introducing the substituents represented by the formulas (11) to (14) into an organic dye, anthraquinone or acridone, the substituents represented by the general formulas (5) to (8) are formed by reacting with the above substituents. Amine components such as 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 (11) -SO ₂ Cl
Formula (12) -COCl
Equation (13) -CH ₂ NHCOCH ₂ Cl
Equation (14) -CH ₂ Cl
Further, when the organic dye is an azo dye, the substituent represented by the general formulas (5) to (8) is introduced into the diazo component or the coupling component in advance, and then the coupling reaction is performed, thereby performing the azo pigment. Derivatives can also be produced.

The triazine derivative having a basic group included in the present invention can be synthesized by various synthetic routes. For example, starting from cyanuric chloride, an amine component that forms a substituent represented by general formulas (5) to (8) 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.
Specific examples of the derivative having a specific basic group are shown below, but are not limited thereto. These derivatives can be used alone or in admixture of two or more.

  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 amount of the dispersant 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 using the dispersant of the present invention is mixed with various solvents, resins, additives, etc. as necessary, and dispersed by a horizontal sand mill, vertical sand mill, annular bead mill, attritor, etc. A pigment dispersion obtained by dispersing the product in a varnish can be prepared. Pigments, basic derivatives, dispersants, other resins and additives may be dispersed after mixing all the components, but only the pigments and basic derivatives or the basic derivatives and dispersants may be mixed first. Or only the pigment, the basic derivative, and the dispersant 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, solid dispersion with 2-roll mill, etc., or pigment Treatment with a basic derivative and / or a dispersant may be performed. 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.

  The pigment composition of the present invention can be used as various printing inks and ink-jet inks, and can be used as a pigment dispersion by adding a varnish in order to impart fixability during color development. Resins that can be used as varnish include petroleum resin, casein, shellac, rosin modified maleic resin, rosin modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, hydrochloric acid rubber, phenolic resin, Alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate acidic group-containing urethane resin, acrylic resin, methacrylic resin, polyurethane resin, silicone resin, fluororesin, dryness Examples thereof include oil, synthetic drying oil, styrene-modified maleic acid, polyamide resin, chlorinated polypropylene, butyral resin, and vinylidene chloride resin.

  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.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “part” means “part by weight”.
Example 1
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc (methoxypropyl acetate), 0.2 part of monobutyltin oxide as a catalyst Was replaced with nitrogen gas and reacted at 120 ° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate Part, 50 parts of methacrylic acid and 663 parts of PGMAc, the inside of the reaction vessel was heated to 80 ° C., 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted for 12 hours. (Second step). It was confirmed that 95% had reacted by solid content measurement. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI) and 0.1 part of hydroquinone were charged, and 2270 cm based on isocyanate groups by IR. ^The reaction was continued until the disappearance of the ^-1 peak was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the solid content was adjusted with PGMAc to obtain a dispersant solution (1) having a solid content of 50%. The obtained dispersant had an acid value of 68, an unsaturated double bond equivalent of 1593, and a weight average molecular weight of 13,000.

(Example 2)
Synthesis was carried out in the same manner as in Example 1 except that 54.0 parts of 2-methacryloyloxyethyl isocyanate (MOI) was used in the third step to obtain a dispersant solution (2) having a solid content of 50%.
(Examples 3 to 10)
Synthesis was performed in the same manner as in Example 1 except that the raw materials and preparation amounts described in Table 1 and Table 2 were used, and dispersant solutions (3) to (10) having a solid content of 50% were obtained.

1,6-HD: 1,6-hexanediol PMA: pyromellitic dianhydride BTA: 1,2,3,4-butanetetracarboxylic dianhydride BPDA: 3,3 ′, 4,4′-biphenyl Tricarboxylic acid anhydride TMEG: Ethylene glycol ditrimellitic anhydride ester (manufactured by Shin Nippon Rika Co., Ltd .: Ricacid TMEG-100)
BTDA: 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride DSDA: 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride BPAF: 9,9-bis (3,4 -Dicarboxyphenyl) fluorene dianhydride TMA: trimellitic anhydride HEMA: 2-hydroxyethyl methacrylate 2HPMA: 2-hydroxypropyl methacrylate 2HBMA: 2-hydroxybutyl methacrylate FM-3: terminal hydroxyl group polycaprolactone modified methacrylate ( Daicel Chemical Industries: Plaxel FM-3)
EA: ethyl acrylate tBA: t-butyl acrylate 2MTA: 2-methoxyethyl acrylate MMA: methyl methacrylate BMA: n-butyl methacrylate BzMA: benzyl methacrylate St: styrene MAA: methacrylic acid MOI: 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko) : Karenz MOI)
AOI: 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko: Karenz AOI)
BEI: 1,1-bis (acryloyloxymethyl) ethyl isocyanate (manufactured by Showa Denko: Karenz BEI)
MOI-EG: 2-methacryloyloxyethoxyethyl isocyanate (manufactured by Showa Denko: Karenz MOI-EG)

(Comparative Example 1)
Synthesis was carried out in the same manner as in Example 4 except that 267 parts of phthalic anhydride was used in the first step to obtain a dispersant solution (11) having a solid content of 50%. The obtained dispersant had an acid value of 20, an unsaturated double bond equivalent of 898, and a weight average molecular weight of 9000.
(Comparative Example 2)
The process up to the second step of Example 1 was carried out, and the solid content was adjusted with PGMAc to obtain a dispersant solution (12) having a solid content of 50%. The obtained dispersant had an acid value of 75 and a weight average molecular weight of 12,000.
(Comparative Example 3)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 1374 parts of PGMAc were charged, and the reaction vessel was heated to 110 ° C. and replaced with nitrogen gas. A mixture of 400 parts of n-butyl methacrylate, 400 parts of benzyl methacrylate, 200 parts of 2-hydroxypropyl methacrylate, and 6 parts of 2,2′-azobisdiisobutyrate was dropped into the reaction vessel over 2 hours. Further, the reaction was carried out for 5 hours, and an intermediate having a weight average molecular weight of 8000, which was confirmed to be 95% by solid content measurement, was obtained. Next, 99 parts of pyromellitic anhydride, 113 parts of PGMAc, and 1.0 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. It was confirmed by the acid value measurement that 98% or more of the acid anhydride was half-esterified. Finally, 125 parts of 2-methacryloyloxyethyl isocyanate and 130 parts of PGMAc were charged, and the reaction was continued until the disappearance of the peak at 2270 cm ⁻¹ based on the isocyanate group was confirmed by IR. After confirming the disappearance of the peak, the reaction solution was cooled and the solid content was adjusted with PGMAc to obtain a dispersant solution (13) having a solid content of 50%. The obtained dispersant had an acid value of 43, an unsaturated double bond equivalent of 1593, and a weight average molecular weight of 25,000.

(Examples 11-20 and Comparative Examples 4-7)
Dispersant solution (1) obtained in Example 1, PB15: 6 (CI Pigment Blue 15: 6), basic derivative (1), solvent, glass beads (0.8 mm) as a pigment ) In a 140 mL glass bottle at a weight (g) ratio shown in Table 3 and Table 4, and placed in a shaker (Scandex SO400 manufactured by F & FM) (hereinafter referred to as Scandex) and dispersed for 3 hours. The glass beads were removed from the dispersion and left at 25 ° C. for 24 hours, and then subjected to the following test.
Further, the dispersant solutions (2) to (10) obtained in Examples 2 to 10, the dispersant solutions (11) to (13) obtained in Comparative Examples 1 to 3, and a commercially available dispersant (Comparative Example 7). Dispersant (14)), solvent, and glass beads (0.8 mm) were charged into a 140 mL glass bottle with a weight (g) ratio shown in Tables 3 and 4 and dispersed with a scandex for 3 hours. After standing at 25 ° C. for 24 hours, the following test was performed, and the results are shown in Tables 3 and 4.

(1) Viscosity measurement About the obtained dispersion, the viscosity at 25 degreeC was measured with the rotation speed of 10 rad / sec with the cone plate type | mold viscosity meter using the cone plate of diameter 60mm and angle 0 degree 59 minutes.
(2) Storage stability over time After the obtained dispersion was stored in a thermostat at 50 ° C. for 1 week and accelerated over time, the viscosity of the pigment dispersion after time elapsed was the same as in (1) “Viscosity measurement” in the previous section. The viscosity change rate before and after storage at 50 ° C. for 1 week was calculated and evaluated in two stages according to the following criteria.
○: When the viscosity change rate is within ± 10% and no sediment is formed.
X: When the viscosity change rate exceeds ± 10%, or when a precipitate is generated even when the viscosity change rate is within ± 10%.
(3) Solvent resistance The resulting dispersion was coated on an aluminum plate with a bar coater # 3 and baked in a 230 ° C. oven for 5 minutes. This was immersed in MEK for 15 minutes, and the appearance was visually determined.
○: When there is no particular change in appearance.
Δ: A slight change in appearance is observed.
X: When there is a significant change in the appearance, such as loss of surface gloss.
(4) Chemical resistance The colored film was immersed in a 5% strength saline solution for 24 hours to evaluate chemical resistance.
○: When there is no particular change in appearance.
Δ: A slight change in appearance is observed.
X: When the appearance is changed, for example, the surface is no longer glossy.

PB15: 6: C.I. I. Pigment Blue 15: 6 (copper phthalocyanine blue pigment)
PG36: C.I. I. Pigment Green 36 (copper halide phthalocyanine green pigment)
PY138: C.I. I. Pigment Yellow 138 (Kinophthalone Yellow Pigment)
PR254: C.I. I. Pigment Red 254 (diketopyrrolopyrrole red pigment)
PR177: C.I. I. Pigment Red 177 (anthraquinone red pigment)

Basic derivative (1):

（ＣｕＰｃは、銅フタロシアニン残基を表す）

塩基性誘導体（２）：

(CuPc represents a copper phthalocyanine residue)

Basic derivative (2):

（ＣｕＰｃは、銅フタロシアニン残基を表す）

塩基性誘導体（３）：

(CuPc represents a copper phthalocyanine residue)

Basic derivative (3):

塩基性誘導体（４）：

Basic derivative (4):

PGMAc: methoxypropyl acetate anone: cyclohexanone DEDG: diethylene glycol diethyl ether Commercial dispersant: BYK111 "BYK111"
As is clear from the above evaluation results, the pigment dispersions of Examples 11 to 20 dispersed using the dispersant of the present invention showed a good stability with a low initial viscosity and little increase in viscosity over time. It was also found that the coating film had good resistance. In contrast, the pigment dispersions of Comparative Examples 4 and 6 had high viscosity, poor stability over time, and had problems with dispersibility. Moreover, although the pigment dispersion of the comparative examples 5 and 7 can obtain a low-viscosity dispersion, it turned out that the tolerance of a coating film is bad.

Claims (15)

  A carboxyl group obtained by reacting an acid anhydride group in one or more acid anhydrides selected from tetracarboxylic acid anhydride (a) and tricarboxylic acid anhydride (b) with a hydroxyl group in the hydroxyl group-containing compound (c) One or more ethylenically unsaturated monomer radicals selected from a polyester portion A having a hydroxyl group, an ethylenically unsaturated monomer having no hydroxyl group (e), and an ethylenically unsaturated monomer having a hydroxyl group (f) A curable dispersant comprising a polymerized vinyl polymer portion B, wherein the vinyl polymer portion B has a (meth) acryloyl group. Compound (h1) produced by reacting a hydroxyl group in compound (g) having two hydroxyl groups and one thiol group in the molecule with an acid anhydride group in tetracarboxylic acid anhydride (a) In the presence of a hydroxyl group in a hydroxyl group-containing compound (k1) obtained by radical polymerization of an ethylenically unsaturated monomer having no hydroxyl group (e) and an ethylenically unsaturated monomer having a hydroxyl group (f). ,
A curable dispersant having a (meth) acryloyl group obtained by reacting one isocyanate group with an isocyanate group in the compound (i) having one or more (meth) acryloyl groups. Hydroxyl group in compound (g) having two hydroxyl groups and one thiol group in the molecule and hydroxyl group-containing compound (j) having no thiol group, and acid anhydride group in tetracarboxylic acid anhydride (a) Radical polymerization of an ethylenically unsaturated monomer (e) having no hydroxyl group and an ethylenically unsaturated monomer (f) having a hydroxyl group in the presence of the compound (h2) produced by the reaction of A hydroxyl group in the hydroxyl group-containing compound (k2),
A curable dispersant having a (meth) acryloyl group obtained by reacting one isocyanate group with an isocyanate group in the compound (i) having one or more (meth) acryloyl groups. Of the compound (h3) produced by reacting the hydroxyl group in the compound (g) having two hydroxyl groups and one thiol group in the molecule with the acid anhydride group in the tricarboxylic acid anhydride (b). In the presence, a hydroxyl group in a hydroxyl group-containing compound (k3) obtained by radical polymerization of an ethylenically unsaturated monomer having no hydroxyl group (e) and an ethylenically unsaturated monomer having a hydroxyl group (f);
A curable dispersant having a (meth) acryloyl group obtained by reacting one isocyanate group with an isocyanate group in the compound (i) having one or more (meth) acryloyl groups.   The curable dispersant according to any one of claims 1 to 4, wherein the unsaturated double bond equivalent is 300 to 3,500.   The curable dispersant according to any one of claims 1 to 5, having a weight average molecular weight of 2,000 to 100,000 and an acid value of 5 to 200 mgKOH / g. The curable dispersant according to any one of claims 1 to 6, wherein the tetracarboxylic anhydride (a) is represented by the following general formula (1) or general formula (2).
General formula (1)

[In General Formula (1), k is 1 or 2. ]
General formula (2)

[In General Formula (2), R ¹ is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, a formula:

Or a group represented by the formula:

It is group represented by these. ] The curable dispersant according to any one of claims 1 to 6, wherein the tricarboxylic acid anhydride (b) is represented by the following general formula (3).
General formula (3)

[In General Formula (3), k is 1 or 2. ]   The weight average molecular weight of the vinyl polymer part B formed by radical polymerization of the ethylenically unsaturated monomer (e) having no hydroxyl group and the ethylenically unsaturated monomer (f) having a hydroxyl group is 1,000 to It is 50,000, The curable dispersing agent in any one of Claims 1-8. The curable dispersant according to any one of claims 1 to 9, wherein the ethylenically unsaturated monomer (e) having no hydroxyl group contains a monomer represented by the following general formula (4).
General formula (4)

[In General Formula (4), R ² is a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic alkyl group having 6 to 15 carbon atoms. ]   The compound (i) having one isocyanate group and one or more (meth) acryloyl groups is a compound having one isocyanate group and one or two (meth) acryloyl groups. To 10. Any one of -10.   The compound (i) having one isocyanate group and one or more (meth) acryloyl groups is formed of 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, or 1,1-bis (acryloyloxymethyl) ethyl isocyanate. It is either, The curable dispersing agent in any one of Claims 1-11 characterized by the above-mentioned.   A pigment composition comprising the curable dispersant according to claim 1 and a pigment.   Further, it contains 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. Item 14. The pigment composition according to Item 13.   A pigment dispersion obtained by dispersing the pigment composition according to claim 13 or 14 in a varnish.