JP4396777B2 - Polyester dispersant, process for producing the same, and pigment composition using the same - Google Patents

Description

  The present invention relates to a polyester dispersant, and more specifically, a polyester dispersant capable of producing a dispersion excellent in non-aggregability, fluidity, and storage stability, which is suitable for fields such as paints and colored resin compositions. The production method and a pigment composition 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 will cause 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 or phenomena such as sedimentation may cause color unevenness or a significant 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 an acidic dispersant is 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 carboxylic acid as an acidic functional group are described in, for example, Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4.

However, these have some dispersibility, but it was necessary to increase the amount of use in order to produce a low viscosity and stable dispersion. However, increasing the amount used is not preferable in view of development in inks, paints, etc., because the resistance of the coating film may be reduced.
JP-A-61-61623 JP-A-1-141968 Japanese Patent Laid-Open No. 2-219866 JP 11-349842 A

  An object of this invention is to provide the dispersing agent for obtaining the pigment dispersion which is excellent in a dispersibility, fluidity | liquidity, and storage stability by the low usage-amount. Furthermore, the present invention is suitable for offset ink, gravure ink, color filter resist ink and ink jet ink, paint, colored resin composition, etc., and has dispersibility and stability excellent in non-aggregability and fluidity. An object of the present invention is to provide a polyester dispersant that can be used.

The present invention is produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (a1) having two hydroxyl groups and one thiol group in the molecule. A hydroxyl group in the vinyl polymer (a) having
An acid anhydride group in tetracarboxylic acid anhydride (b);
The present invention relates to a polyester dispersant produced by reaction of

In addition, the present invention is produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (a1) having two hydroxyl groups and one thiol group in the molecule. A hydroxyl group in the vinyl polymer (a) having a hydroxyl group, and a hydroxyl group in the polyol compound (c) other than the vinyl polymer (a);
An acid anhydride group in tetracarboxylic acid anhydride (b);
It also relates to a polyester dispersant produced by reacting.

Furthermore, the present invention is a product produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (a1) having two hydroxyl groups and one thiol group in the molecule, and has two hydroxyl groups in one terminal region. A hydroxyl group in the vinyl polymer (a) having
An acid anhydride group in tetracarboxylic acid anhydride (b) and an acid anhydride group in tricarboxylic acid anhydride (d);
The present invention relates to a polyester dispersant produced by reaction of

Furthermore, the present invention is a product produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (a1) having two hydroxyl groups and one thiol group in the molecule, and has two hydroxyl groups in one terminal region. A hydroxyl group in the vinyl polymer (a) having a hydroxyl group in the polyol compound (c) other than the vinyl polymer (a), and
An acid anhydride group of the tetracarboxylic acid anhydride (b) and an acid anhydride group in the tricarboxylic acid anhydride (d);
The present invention relates to a polyester dispersant produced by reaction of

  Furthermore, the present invention relates to a compound produced by reacting a hydroxyl group in compound (a1) having two hydroxyl groups and one thiol group in the molecule with an acid anhydride group in tetracarboxylic acid anhydride (b). The present invention relates to a polyester dispersant produced by radical polymerization of an ethylenically unsaturated monomer in the presence of (a2).

  Further, the present invention relates to a compound (a1) having two hydroxyl groups and one thiol group in the molecule and a hydroxyl group in a polyol compound (c ′) having no thiol group and a tetracarboxylic acid anhydride (b). The present invention relates to a polyester dispersant produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (a3) produced by reacting with an acid anhydride group.

  Furthermore, the present invention relates to a hydroxyl group in the compound (a1) having two hydroxyl groups and one thiol group in the molecule, an acid anhydride group in the tetracarboxylic acid anhydride (b), and a tricarboxylic acid anhydride (d). The present invention relates to a polyester dispersant produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (a4) produced by reacting with an acid anhydride group.

  Further, the present invention relates to a compound (a1) having two hydroxyl groups and one thiol group in the molecule and a hydroxyl group in a polyol compound (c ′) having no thiol group and a tetracarboxylic acid anhydride (b). It is formed by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound (a5) formed by reacting an acid anhydride group and an acid anhydride group in a tricarboxylic acid anhydride (d). It relates to a polyester dispersant.

  In a preferred embodiment of the polyester dispersant according to the present invention, the weight average molecular weight is 2000 to 35000, and the acid value is 5 to 200.

［一般式（１）中、ｋは１又は２である。］
一般式（２）

［一般式（２）中、Ｑ_１は、直接結合、−Ｏ−、−ＣＯ−、−ＣＯＯＣＨ_２ＣＨ_２ＯＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、式：

で表される基、又は式：

で表される基である。］In a preferred embodiment of the polyester dispersant according to the present invention, the tetracarboxylic acid anhydride (b) 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), Q ₁ represents 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. ]

  In a preferred embodiment of the polyester dispersant according to the present invention, the weight average molecular weight of the vinyl polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer is 1000 to 10,000.

  In a preferred embodiment of the polyester dispersant according to the present invention, the glass transition temperature of the vinyl polymer portion formed by radical polymerization of an ethylenically unsaturated monomer is -50 to 70 ° C.

  In a preferred embodiment of the polyester dispersant according to the present invention, the ethylenically unsaturated monomer contains 20% by weight to 70% by weight of benzyl (meth) acrylate.

  In a preferred embodiment of the polyester dispersant according to the present invention, the ethylenically unsaturated monomer includes a monomer represented by the following general formula (3).

  Furthermore, this invention relates to the pigment composition containing the said polyester dispersing agent and a pigment.

  Furthermore, the present invention 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. The above-mentioned pigment composition.

Furthermore, this invention relates to the pigment dispersion formed by disperse | distributing the said pigment composition to a varnish.

Furthermore, in the present invention, the ethylenically unsaturated monomer is radically polymerized in the presence of the compound (a1) having two hydroxyl groups and one thiol group in the molecule, so that it has two hydroxyl groups in one end region. Step A1 for producing the vinyl polymer (a),
A step B1 of reacting the vinyl polymer (a) with the tetracarboxylic acid anhydride (b);
The manufacturing method of the polyester dispersing agent containing this.

Furthermore, in the present invention, the ethylenically unsaturated monomer is radically polymerized in the presence of the compound (a1) having two hydroxyl groups and one thiol group in the molecule, so that it has two hydroxyl groups in one end region. Step A2 for producing the vinyl polymer (a),
A step B2 of reacting the vinyl polymer (a), the tetracarboxylic acid anhydride (b), and a polyol compound (c) other than the vinyl polymer (a);
The manufacturing method of the polyester dispersing agent containing this.

Furthermore, in the present invention, the ethylenically unsaturated monomer is radically polymerized in the presence of the compound (a1) having two hydroxyl groups and one thiol group in the molecule, so that it has two hydroxyl groups in one end region. Step A3 for producing the vinyl polymer (a),
A step B3 of reacting the vinyl polymer (a) with a tetracarboxylic acid anhydride (b) and a tricarboxylic acid anhydride (d);
The manufacturing method of the polyester dispersing agent containing this.

Furthermore, in the present invention, the ethylenically unsaturated monomer is radically polymerized in the presence of the compound (a1) having two hydroxyl groups and one thiol group in the molecule, so that it has two hydroxyl groups in one end region. Step A4 for producing a vinyl polymer (a),
A step B4 of reacting the vinyl polymer (a), the tetracarboxylic acid anhydride (b), the polyol compound (c) other than the vinyl polymer (a), and the tricarboxylic acid anhydride (d);
The manufacturing method of the polyester dispersing agent containing this.

The present invention further comprises reacting a hydroxyl group in the compound (a1) having two hydroxyl groups and one thiol group in the molecule with an acid anhydride group in the tetracarboxylic acid anhydride (b) to thereby react the compound (a2). Step B5 for manufacturing
A step A5 of radically polymerizing an ethylenically unsaturated monomer in the presence of the compound (a2);
The manufacturing method of the polyester dispersing agent containing this.

Furthermore, the present invention relates to a hydroxyl group in a compound (a1) having two hydroxyl groups and one thiol group in the molecule and a hydroxyl group in a polyol compound (c ′) having no thiol group and a tetracarboxylic acid anhydride (b Step B6 for producing a compound (a3) by reacting with an acid anhydride group in
A step A6 of radically polymerizing an ethylenically unsaturated monomer in the presence of the compound (a3);
The manufacturing method of the polyester dispersing agent containing this.

Furthermore, the present invention relates to a hydroxyl group in the compound (a1) having two hydroxyl groups and one thiol group in the molecule, an acid anhydride group in the tetracarboxylic acid anhydride (b), and a tricarboxylic acid anhydride (d). A step B7 of producing a compound (a4) by reacting an acid anhydride group therein,
A step A7 of radically polymerizing an ethylenically unsaturated monomer in the presence of the compound (a4);
The manufacturing method of the polyester dispersing agent containing this.

Furthermore, the present invention relates to a polyol compound having no hydroxyl group in the compound (a1) having two hydroxyl groups and one thiol group in the molecule, an acid anhydride group in the tetracarboxylic acid anhydride (b), and a thiol group. A step B8 of producing a compound (a5) by reacting a hydroxyl group in (c ′) with an acid anhydride group in a tricarboxylic acid anhydride (d);
A step A8 of radically polymerizing an ethylenically unsaturated monomer in the presence of the compound (a5);
The manufacturing method of the polyester dispersing agent containing this.

［一般式（１）中、ｋは１又は２である。］
一般式（２）

［一般式（２）中、Ｑ_１は、直接結合、−Ｏ−、−ＣＯ−、−ＣＯＯＣＨ_２ＣＨ_２ＯＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、式：

で表される基、又は式：

で表される基である。］In a preferred embodiment of the method of the present invention, the tetracarboxylic acid anhydride (b) 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), Q ₁ represents 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. ]

  In a preferred embodiment of the method of the present invention, the ethylenically unsaturated monomer contains benzyl (meth) acrylate in an amount of 20% to 70% by weight of the total monomer.

［一般式（３）中、Ｒは、炭素原子数１〜４の直鎖状若しくは分岐状のアルキル基である。］In a preferred embodiment of the method of the present invention, the ethylenically unsaturated monomer includes a monomer represented by the following general formula (3):
General formula (3)

[In General Formula (3), R is a linear or branched alkyl group having 1 to 4 carbon atoms. ]

  By using the polyester dispersant of the present invention, it is possible to provide a pigment composition having dispersibility, fluidity, and storage stability that has not been obtained conventionally. Furthermore, it is suitable for offset ink, gravure ink, color filter resist ink and ink jet ink, paint, colored resin composition, etc., has excellent dispersibility and stability with excellent non-aggregation and fluidity, and high storage stability. A pigment dispersion having high stability with time can be provided.

  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.

（式中、Ａは末端領域であり、Ｂはビニル重合体部分である）
のモル量「ａ」と、コア部分Ｘ_１を有するテトラカルボン酸無水物のモル量「ｂ」とについて、
（ｉ）ａ＞ｂ、（ii）ａ＝ｂ、又は（iii）ａ＜ｂ
としたときのテトラカルボン酸無水物とポリオール化合物との反応工程式を下記反応工程式（４）〜（６）に示す。下記反応工程式（４）〜（６）において、ｎは繰り返し単位数である。下記の反応工程式（６）において、生成物中に残っている酸無水物基を加水分解すれば、この反応工程による生成物は、構造式中のＸ_１部分にカルボキシル基を２個又は３個を有しており、この複数のカルボキシル基が顔料の吸着部位として有効である。The tetracarboxylic anhydride (b) used in the present invention reacts with a hydroxyl group to form an ester bond, and a pendant carboxyl group can be left on the resulting polyester main chain. Polyol compound having two hydroxyl groups in one terminal region (one terminal region):

(Where A is the terminal region and B is the vinyl polymer portion)
And the molar amount “b” of the tetracarboxylic anhydride having the core portion X ₁ ,
(I) a> b, (ii) a = b, or (iii) a <b
The reaction process formulas of the tetracarboxylic acid anhydride and the polyol compound are shown in the following reaction process formulas (4) to (6). In the following reaction process formulas (4) to (6), n is the number of repeating units. In the following reaction process formula (6), if the acid anhydride group remaining in the product is hydrolyzed, the product obtained by this reaction process has two or three carboxyl groups in the X ₁ portion in the structural formula. The plurality of carboxyl groups are effective as pigment adsorption sites.

Reaction process formula (4): (i) a> b

Reaction process formula (5): (ii) a = b

Reaction process formula (6): (iii) a <b

However, in the polyester dispersant of the present invention, when only one carboxyl group is bonded to the core portion X ₁ (outside the scope of the present invention), high dispersibility, fluidity and storage stability are exhibited. Not preferred.

In the polyester dispersant of the present invention, the core part X _1, the reaction residue after the reaction residue after tetracarboxylic anhydride is reacted with a hydroxyl group, = A-B is the polyol compound is reacted with an acid anhydride group It is. The terminal region of A is, for example, a linear or branched trivalent aliphatic hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 8 carbon atoms) (for vinyl polymer portion B). Will be described later). The two hydroxyl groups contained in this one terminal region may be bonded to the same carbon atom or may be bonded to different carbon atoms. Form preferred core portion X ₁ is a tetracarboxylic acid anhydride represented by the following general formula (1) or general formula (2) is the reaction residue after the reaction with a polyol compound.

［一般式（１）中、ｋは１、又は２である。］General formula (1)

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

［一般式（２）中、Ｑ_１は、直接結合、−Ｏ−、−ＣＯ−、−ＣＯＯＣＨ_２ＣＨ_２ＯＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、式：

で表される基、又は式：

で表される基である。］General formula (2)

[In General Formula (2), Q ₁ represents 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. ]

In the polyester dispersant of the present invention, by reacting the vinyl polymer (a) having two hydroxyl groups in one end region with the tetracarboxylic acid anhydride (b), the product in the above reaction process formula (4) a plurality of carboxyl groups moiety attached to the core portion X ₁ functions as a pigment adsorbing part, the vinyl polymer portion B functions as a solvent affinity part.

Furthermore, in the polyester dispersant of the present invention, the compound (a2) which does not contain the vinyl polymer portion B by reacting the compound (a1) having two hydroxyl groups and one thiol group with the tetracarboxylic acid anhydride (b). To (a5) is produced first, and then the vinyl polymer part B is introduced by radical polymerization using the remaining thiol groups of the compounds (a2) to (a5) as chain transfer agents. It is possible to obtain a resin having the following structure. A plurality of carboxyl groups moiety attached to the core moiety X ₁ in the product in the above reaction scheme (4) is formed in the first step B5~B8 a pigment adsorbing part, the vinyl introduced in the subsequent step A5~A8 It is possible to make the polymer part B function as a solvent affinity part.

As shown in the following reaction process formulas (7) to (10), in the first steps B5 to B8, a pendant carboxyl group can be left on the polyester main chain, and the vinyl is subsequently used in steps A5 to A8. Polymer part B can be introduced. In the following reaction process formulas (7) to (10), s and t are the number of repeating units, and HO—D—OH is a polyol compound (c ′) having no thiol group. This HO-D-OH may be the polyol compound B-A- (OH) ₂ .

Step B5 and Step A5 [when reacting compound (a1) having two hydroxyl groups and one thiol group with tetracarboxylic acid anhydride (b) and subsequently introducing an ethylenically unsaturated monomer]:
Reaction process formula (7)

Step B6 and Step A6 [compound (a1) having two hydroxyl groups and one thiol group, tetracarboxylic acid anhydride (b) and polyol compound (c ′) having no thiol group are reacted, followed by ethylene When introducing unsaturated unsaturated monomers]:
Reaction process formula (8)

Step B7 and Step A7 [compound (a1) having two hydroxyl groups and one thiol group, tetracarboxylic anhydride (b) and tricarboxylic anhydride (d) are reacted, followed by ethylenically unsaturated monomer When introducing the body]:
Reaction process formula (9)

Step B8 and Step A8 [compound (a1) having two hydroxyl groups and one thiol group, tetracarboxylic acid anhydride (b), polyol compound (c ′) having no thiol group, and tricarboxylic acid anhydride (d) And then introducing ethylenically unsaturated monomer]:
Reaction process formula (10)

  In this way, a plurality of pendant carboxyl groups can be formed and function as a pigment adsorbing part, and the vinyl polymer portion produced in the steps A5 to A8 that undergo radical polymerization as a chain transfer agent using the remaining thiol group is used as a solvent. It can function as an affinity part.

In the present specification, “a vinyl polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer” means a continuous portion that does not include a portion derived from tetracarboxylic anhydride (b) or tricarboxylic anhydride (d). It is a part, and usually a plurality of vinyl polymer parts B are contained in one molecule constituting the polyester dispersant of the present invention.
The weight average molecular weight of the vinyl polymer part B formed by radical polymerization of an ethylenically unsaturated monomer is preferably 1000 to 10,000, more preferably 2000 to 8000, still more preferably 2000 to 6000, and particularly preferably 3000 to 5000. It is. 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 1000, the effect of steric repulsion by the solvent affinity part is reduced, and it becomes difficult to prevent the aggregation of the pigment, and the dispersion stability may be insufficient. On the other hand, if it exceeds 10,000, the absolute amount of the solvent affinity part may increase, and the dispersibility effect itself may decrease. Further, the viscosity of the dispersion may increase. The vinyl polymer (a) can easily adjust the molecular weight to the above range, and also has good affinity for the solvent.

  The glass transition temperature of the vinyl polymer part B formed by radical polymerization of an ethylenically unsaturated monomer is preferably −50 to 70 ° C., and −50 to 40 ° C. from the viewpoint that the dispersibility of the pigment becomes higher. More preferred.

  In this specification, the Tg (glass transition temperature) of the vinyl polymer portion B formed by radical polymerization of an ethylenically unsaturated monomer uses a value calculated by the following Fox equation. A skeleton derived from a compound having two hydroxyl groups and one thiol group in the molecule is also present in the vinyl polymer (a), but is excluded from the following calculation for calculating the glass transition temperature.

1 / Tg = (W1 / Tg1) + (W2 / Tg2) + ... + (Wn / Tgn)
In the above formula, Tg is the glass transition temperature of the entire vinyl polymer portion B, W1 to Wn are the weight fractions of the monomers used, and Tg1 to Tgn are the glass transition temperatures of each homopolymer. (Unit is absolute temperature “K”).
The Tg of the main homopolymer used for the calculation is exemplified below.
n-butyl acrylate: -45 ° C (228K)
Methyl acrylate: 8 ° C (281K)
n-butyl methacrylate: 20 ° C. (293 K)
Benzyl methacrylate: 54 ° C (327K)
Lauryl methacrylate: -65 ° C (208K)
Methyl methacrylate: 105 ° C (378K)
Hydroxyethyl methacrylate: 55 ° C (328K)
2-hydroxypropyl methacrylate: 26 ° C (299K)
Acrylic acid: 105 ° C (378K)
Methacrylic acid: 130 ° C (403K)
Styrene: 100 ° C (373K)

  When calculated by the above method, the glass transition temperature of the vinyl polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer synthesized using 100 parts of n-butyl methacrylate and 100 parts of benzyl methacrylate is 36.1 ° C. It becomes.

  The vinyl polymer having two hydroxyl groups in one end region is not only a method of radically polymerizing an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule of the present invention. In addition, it can be obtained by the following method.

[1] Method of Michael addition of a resin having one (meth) acryl group in one end region and a compound having one amine and two hydroxyl groups [2] Having one carboxylic acid group in one end region Method of epoxy addition of resin and compound having one epoxy group and one hydroxyl group [3] Compound having one vinyl ether group in one end region, one carboxylic acid group and two hydroxyl groups [4] There is a method of performing radical polymerization or atom transfer radical polymerization (living radical polymerization) using a polymerization initiator having two hydroxyl groups as a polymerization initiator.
By using these methods, it is possible to synthesize a resin having two hydroxyl groups in one end region. However, it is often a multi-step reaction, and it is often difficult to control the molecular weight. From the viewpoint of properties, the method of radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group is most preferable.

  First, steps A1 to A4 for producing a vinyl polymer (a) having two hydroxyl groups in one end region will be described. The vinyl polymer (a) having two hydroxyl groups in one terminal region is obtained by radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule. Obtainable.

  Examples of the compound having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2- Propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1- Examples include mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.

  A compound having two hydroxyl groups and one thiol group in the molecule is mixed with an ethylenically unsaturated monomer and optionally a polymerization initiator in accordance with the molecular weight of the target vinyl polymer (a). The vinyl polymer (a) can be obtained by heating. The compound having two hydroxyl groups and one thiol group is preferably used for bulk polymerization or solution polymerization, more preferably 1 to 30 parts by weight, more preferably 100 parts by weight of ethylenically unsaturated monomer. 3 to 12 parts by weight, more preferably 4 to 12 parts by weight, particularly preferably 5 to 9 parts by weight. The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C.

  In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer. As the polymerization initiator, an azo compound and an organic peroxide 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 and the like are used as the polymerization solvent, but are not particularly limited thereto. These polymerization solvents may be used as a mixture of two or more.

  Examples of the ethylenically unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate , Phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, oxetane (meth) acrylate, etc. Alkoxypolyalkylene glycol (meth) acrylates such as polypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate, (meth) acrylamide, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) N-substituted (meth) acrylamides such as acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) ) Amino group-containing (meth) acrylates such as acrylate, and nitriles such as (meth) acrylonitrile.

  Examples of monomers that can be used in combination with the acrylic monomer include styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether, and acetic acid. And fatty acid vinyls such as vinyl 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 exemplified above, benzyl (meth) acrylate is preferably used in an amount of 20 to 70% by weight, more preferably 30 to 60% by weight. If the amount is less than 20% by weight, the solvent affinity becomes low, and a sufficient steric repulsion effect may not be obtained, and the pigment dispersibility may be lowered. As a result, the pigment dispersibility may decrease.

  Furthermore, in this invention, it is preferable to use the monomer represented by following General formula (3) among the ethylenically unsaturated monomers illustrated above. The amount of the monomer represented by the following general formula (3) is preferably 20% by weight to 100% by weight and more preferably 20% by weight to 70% by weight with respect to the whole monomer. When the monomer represented by the general formula (3) is used, the solvent affinity is improved and the pigment dispersibility is improved.

［一般式（３）中、Ｒは、炭素原子数１〜４の直鎖状若しくは分岐状のアルキル基である。］General formula (3)

[In General Formula (3), R is a linear or branched alkyl group having 1 to 4 carbon atoms. ]

  Next, steps B1 to B4 in which the vinyl polymer (a) having two hydroxyl groups in one terminal region and the tetracarboxylic anhydride (b) are reacted will be described. The polyester dispersant of the present invention comprises a hydroxyl group of a vinyl polymer (a) having two hydroxyl groups in one end region obtained in steps A1 to A4, and an acid anhydride group of a tetracarboxylic acid anhydride (b). It is obtained by making it react (process B1-B4).

Examples of the tetracarboxylic acid anhydride (b) 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) fluorenic anhydride, 9,9-bis [4- (3,4-dicarbo) 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 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. Furthermore, what is preferably used in the present invention is an aromatic tetracarboxylic acid anhydride from the viewpoint of reducing the viscosity of the pigment dispersion, and more preferably a tetracarboxylic acid anhydride having two or more aromatic rings. . A compound having one carboxylic anhydride group in the molecule or a compound having three or more can be used in combination.

It is preferable to use a compound having one carboxylic anhydride group in the molecule, and among the compounds having one carboxylic anhydride group in the molecule, tricarboxylic anhydride is more preferable. Carboxyl groups bound to the core moiety X ⁴ of the product shown in Scheme (11) the following is possible to two. Therefore the dispersion stabilizer. In the following reaction process formula (11), HO—Y′—OH is a polyol compound.

Reaction process formula (11)

  Examples of the tricarboxylic acid anhydride include an aliphatic tricarboxylic acid anhydride or an aromatic tricarboxylic acid anhydride.

  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.

  In this invention, it is possible to use polyol compounds (c) other than the said vinyl polymer (a) in arbitrary ratio in process B2 and process B4. By using the polyol compound (c) other than the vinyl polymer (a), it becomes easy to adjust the density of the carboxylic acid group and the ratio of the solvent-dissolving part.

  As the “polyol compound (c) other than the vinyl polymer (a)” used in the present invention, a known one can be used, for example, a polyol compound having 2 to 4 hydroxyl groups in one molecule. 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 as 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-hexane tricarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1 , 2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid or 2,5,7 obtained especially with those represented by naphthalene tricarboxylic 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.

  Of course, the polyol compound (c) other than the vinyl polymer (a) to be optionally added shown in (1) to (7) may be used alone or in combination of two or more. The weight average molecular weight is preferably 40 to 10000, more preferably 100 to 2000, and still more preferably 100 to 1000.

  As the catalyst used for the production of the polyester dispersant of the present invention, a known catalyst can be used. The catalyst is preferably a tertiary amine compound such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, 5-diazabicyclo- [4.3.0] -5-nonene and the like.

  The polyester dispersant of the present invention can be produced using only the raw materials listed 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 polyester dispersant of the present invention comprises a vinyl polymer (a) having two hydroxyl groups in one end region, a tetracarboxylic acid anhydride (b) and an optional polyol compound other than the vinyl polymer (a) ( c) ". The molar ratio between the acid anhydride group in the tetracarboxylic acid anhydride (b) and the hydroxyl group in the vinyl polymer (a) and the “polyol compound (c) other than the vinyl polymer (a)” is (b ) / [(A) + (c)] = 0.3 to 1.2, more preferably (b) / [(a) + (c)] = 0.4 to 1.1, more preferably (B) / [(a) + (c)] = 0.5 to 1.0, particularly preferably (b) / [(a) + (c)] = 0.6 to 0.8. . When (b) / [(a) + (c)]> 1, the remaining acid anhydride group may be hydrolyzed with a necessary amount of water and used. If it is less than 0.3, the acid anhydride residue as the pigment adsorbing portion may be decreased, and the acid value of the resin may be decreased. On the other hand, if it exceeds 1.2, an acid anhydride group remains in the polyester, which may cause a problem in the storage stability of the resin. In addition, the amount of water required to hydrolyze the remaining acid anhydride groups may increase, and solvent solubility may deteriorate.

  Furthermore, the polyester dispersant of the present invention is a vinyl polymer (a) having two hydroxyl groups in one end region, a tetracarboxylic anhydride (b), a polyol compound (c) other than (a) optionally added, and a tricarboxylic acid. It can be obtained by reacting the acid anhydride (d). The molar ratio of the acid anhydride group in the tetracarboxylic acid anhydride (b) and the tricarboxylic acid (d) to the hydroxyl group in the polyol compound (c) other than the vinyl polymers (a) and (a) is [[ b) + (d)] / [(a) + (c)] = 0.3 to 1.2, more preferably [(b) + (d)] / [(a) + (c)] = 0.4 to 1.1, more preferably [(b) + (d)] / [(a) + (c)] = 0.5 to 1.0, particularly preferably [(b) + (d ]] / [(A) + (c)] = 0.6 to 0.8.

  When the tetracarboxylic anhydride (b) and the tricarboxylic anhydride (d) are used in combination as the acid anhydride, the molar ratio of the tetracarboxylic anhydride (b) to the tricarboxylic anhydride (d) is (b) / [(D)] is preferably 0.1 to 10, more preferably (b) / [(d)] = 0.15 to 4, particularly preferably (b) / [(d)] = 0.3 to 2.

  The reaction temperature is 50 ° C to 180 ° C, preferably 80 ° C to 140 ° C. When the reaction temperature is 50 ° C. or less, the reaction rate is slow, and when the reaction temperature is 180 ° C. or more, the carboxyl group undergoes an esterification reaction, which may cause reduction of the acid value or gelation. Ideally, the reaction is stopped until the absorption of the acid anhydride is eliminated by infrared absorption, but after confirming that the acid anhydride is 95% or more half-esterified by acid value measurement, The reaction may be stopped.

  The weight average molecular weight of the obtained polyester dispersant is preferably 2000 to 35000, more preferably 4000 to 25000, still more preferably 6000 to 20000, and particularly preferably 7000 to 15000. If the weight average molecular weight is less than 2,000, the stability of the pigment composition may be lowered, and if it exceeds 35,000, the interaction between the resins becomes strong and the viscosity of the pigment composition may increase. The acid value of the obtained polyester dispersant is preferably 5 to 200. More preferably, it is 10-150, More preferably, it is 15-100, Most preferably, it is 20-80. If the acid value is less than 5, the pigment adsorbing ability may be reduced and the pigment dispersibility may be problematic, and if it exceeds 200, the interaction between the resins may become strong and the viscosity of the pigment dispersion composition may be increased.

Furthermore, in the present invention, a compound (a1) having two hydroxyl groups and one thiol group in the molecule, a tetracarboxylic acid anhydride (b), a polyol compound (c ′) having no thiol group, and a tricarboxylic acid anhydride. Steps B5 to B8 for producing compound (a2) by reacting with (d),
In the presence of the compound (a2), a dispersant having the same structure can be obtained by steps A5 to A8 in which radical polymerization is performed using the remaining thiol group of the compound (a2) as a chain transfer agent.

A compound (a1) having two hydroxyl groups and one thiol group in the molecule, a tetracarboxylic acid anhydride (b), a polyol compound (c ′) optionally having no thiol group, and further optionally a tricarboxylic acid Processes B5 to B8 for producing compounds (a2) to (a5) by reacting with the anhydride (d) will be described.
These compounds (a2) to (a5) are compounds other than the compound (a1) having two hydroxyl groups and one thiol group in the molecule, tetracarboxylic anhydride (b), and optionally added (a). It can be obtained in the same manner as in steps A1 to A4 in which the polyol compound (c) and the tricarboxylic acid anhydride (d) optionally added are reacted. Compound (a1) having an acid anhydride group in tetracarboxylic acid anhydride (b) and tricarboxylic acid anhydride (d), two hydroxyl groups and one thiol group in the molecule, and polyol having no thiol group The molar ratio with the hydroxyl group in the compound (c ′) is preferably [(b) + (d)] / [(a) + (c ′)] = 0.3 to 1.2, more preferably [( b) + (d)] / [(a) + (c ′)] = 0.4 to 1.1, more preferably [(b) + (d)] / [(a) + (c ′)] = 0.5 to 1.0, particularly preferably [(b) + (d)] / [(a) + (c ′)] = 0.6 to 0.8. When (b) / [(a) + (c ′)]> 1, the remaining acid anhydride group may be hydrolyzed with a necessary amount of water and used.

  Next, in the presence of the compounds (a2) to (a5), radical polymerization of ethylenically unsaturated monomers using the thiol groups in the remaining compounds (a2) to (a5) A5 to A5 A8 will be described. Obtained by the same method as in steps A1 to A4 for producing a vinyl polymer (a) having two hydroxyl groups in one terminal region, and using the remaining thiol group as a chain transfer agent, the molecular weight of the intended dispersant is adjusted. Then, the dispersant can be obtained by optionally mixing the ethylenically unsaturated monomer with a polymerization initiator and heating. Bulk polymerization using 3 to 100 parts by weight of ethylenically unsaturated monomer for 1 part by weight of compound (a1) having two hydroxyl groups and one thiol group in the molecule used in steps B5 to B8 Alternatively, solution polymerization is preferably performed. More preferably, it is 8-25 weight part, More preferably, it is 10-20 weight part. The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C.

  As the ethylenically unsaturated monomer to be used, since it is reacted with an acid anhydride group in steps B5 to B8, not only the unsaturated monomer shown above but also a site reactive with an acid anhydride group It is also possible to use one having For example, an ethylenically unsaturated monomer having a hydroxyl group can be mentioned.

  As the ethylenically unsaturated monomer having a hydroxyl group used in the above production method, any monomer having a hydroxyl group and having an ethylenically unsaturated double bond may be used. Specifically, a (meth) acrylate monomer having a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxy Hydroxyalkyl (meth) acrylates such as butyl (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate, or (meth) acrylamide monomers having a hydroxyl group, such as N- (2-hydroxyethyl) (meth) acrylamide N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxy N- (hydroxyalkyl) (meth) acrylamide such as (til) (meth) acrylamide or a vinyl ether monomer having a hydroxyl group, such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, 2 -(Or 3- or 4-) hydroxyalkyl vinyl ether such as hydroxybutyl vinyl ether, or an allyl ether monomer having a hydroxyl group, such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, Examples include hydroxyalkyl allyl ethers such as 2- (or 3- or 4-) hydroxybutyl allyl ether.

  In addition, an ethylenically unsaturated monomer obtained by adding alkylene oxide and / or lactone to the above hydroxyalkyl (meth) acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl vinyl ether or hydroxyalkyl allyl ether Can also be used as an ethylenically unsaturated monomer (h) having a hydroxyl group in the production method used in 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.

  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: 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-mentioned 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. .

  Further, 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 include at least one selected basic derivative. 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 (6), (7), (8) and (9). One group.

General formula (6)

General formula (7)

General formula (8)

General formula (9)

In the general formulas (6) to (9),
X, X ¹ and X ² represent —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 represents an optionally substituted alkyl group, alkenyl group, phenyl group, or a heterocyclic ring formed integrally with R ¹ and R ² . 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 ³ represents an optionally substituted alkyl group, alkenyl group or phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, 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, 1-5 are preferred.
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 alkenyl group or a phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferred.
Z 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.
P represents a substituent represented by the formula (10) or a substituent represented by the formula (11).
Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the formula (10) or a substituent represented by the formula (11).

General formula (10)

Formula (11)

Examples of the alkyl group in R ^{1 to} R ⁹ 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 in Z in the general formula include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the alkenylene group include a vinylene group and a propenylene group.

  Examples of the alkoxyl group for Q in the above 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 formulas (6) to (9) 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- dipropylamino-butyl amine, N, N- dibutyl aminopropyl amine, N, N- dibutyl aminoethyl amine, N, N- dibutyl-amino-butylamine, N, N- diisobutylamino pentyl amine, N, N- methyl - laurylaminopropionic Triethanolamine, N, N-ethyl - hexyl aminoethyl amine, N, N-distearyl-aminoethyl amine, N, N-dioleyl-aminoethyl amine, N, N-distearyl amino tributylamine, piperidine, 2-pipecoline, 3-pipecoline, 4 - pipecolic, 2,4- Rupechijin, lupetidine, 2,6-lupetidine, 3,5 Rupechijin, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, Lee Sun-hee pekoe Chin methyl, Lee Sun-hee pekoe Chin ethyl, 2-piperidine ethanol, pyrrolidine 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, N-aminopropyl-4-pipecoline N-aminop 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, an anthraquinone derivative having a basic group and an acridone derivative having a basic group are 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 the substituents represented by the general formulas (12) to (15) into the organic dye, anthraquinone or acridone, the substituents represented by the general formulas (6) to (9) are reacted with the above substituents. 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 (12) —SO ₂ Cl
Formula (13) -COCl
Formula (14) —CH ₂ NHCOCH ₂ Cl
Formula (15) —CH ₂ Cl

  During the reaction between the substituents represented by the general formulas (12) to (15) and the amine component, a part of the substituents represented by the general formulas (12) to (15) 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 (12) or the general formula (13) 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 general formulas (6) to (9) 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 can be synthesized by various synthetic routes. For example, starting from cyanuric chloride, an amine component that forms a substituent represented by formula (6) to formula (9) 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 blending amount of the polyester 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 polyester dispersant of the present invention is mixed with various solvents, resins, additives, etc. as necessary, and dispersed in a horizontal sand mill, vertical sand mill, annular bead mill, attritor, etc. A pigment dispersion obtained by dispersing the composition in a varnish can be prepared. Pigments, basic derivatives, polyester dispersants, other resins, and additives may be dispersed after mixing all the components, but only the pigment and the basic derivative or the basic derivative and the polyester at the beginning. Only the dispersant, or only the pigment, the basic derivative, and the polyester 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, three-roll mill, etc., solid dispersion with a two-roll mill, etc., or pigment A basic derivative and / or a carboxyl group-containing polyester may be treated. Or high- speed mixer, a homomixer, available a ball mill, a roll mill, a millstone type mill, for every disperser or mixer such as an ultrasonic dispersing machine to produce 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. Further, the polyester dispersant of the present invention can also be used as a binder resin for a pigment dispersion.

  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 weight average molecular weight is a polystyrene equivalent molecular weight when using TSKgel column (manufactured by Tosoh Corporation) and GPC (HLC-8120GPC, manufactured by Tosoh Corporation) equipped with an RI detector and using THF as a developing solvent.

Example 1
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 200 parts of n-butyl methacrylate was charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added and reacted for 12 hours. It was confirmed that 95% had reacted by solid content measurement. Next, 12 parts of pyromellitic anhydride, 224 parts of cyclohexanone, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. . By measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was completed to obtain a polyester dispersant having an acid value of 28 and a weight average molecular weight of 5800 (= dispersant 1; the same applies hereinafter). .

(Examples 2 to 6)
Synthesis was performed in the same manner as in Example 1 except that the raw materials and preparation amounts shown in Table 1 were used to obtain a polyester dispersant.

(Example 7)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 100 parts of n-butyl methacrylate and 100 parts of benzyl methacrylate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution in which 0.1 part of 2,2′-azobisisobutyronitrile was dissolved in 12 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 19 parts of pyromellitic anhydride, 231 parts of cyclohexanone, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated to obtain a polyester dispersant having an acid value of 43 and a weight average molecular weight of 8500.

(Example 8)
Synthesis was performed in the same manner as in Example 7 except that the raw materials and preparation amounts shown in Table 1 were used to obtain a polyester dispersant.

Example 9
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 100 parts of n-butyl methacrylate and 100 parts of benzyl methacrylate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution in which 0.1 part of 2,2′-azobisisobutyronitrile was dissolved in 12 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 37 parts of BPDA, 255 parts of cyclohexanone, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. Thereafter, 5 parts of neopentyl glycol was added, and it was confirmed that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. The reaction was terminated, and a polyester dispersant having an acid value of 56 and a weight average molecular weight of 9300 was obtained. Got.

(Examples 10 to 17)
Synthesis was performed in the same manner as in Example 7 except that the raw materials and preparation amounts shown in Table 1 were used to obtain a polyester dispersant.

(Examples 18 to 22)
Synthesis was performed in the same manner as in Example 9 except that the raw materials and preparation amounts shown in Table 1 were used, and a polyester dispersant was obtained.

(Examples 23 to 27)
Synthesis was performed in the same manner as in Example 7 except that the raw materials and preparation amounts shown in Table 1 were used to obtain a polyester dispersant.

(Example 28)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 100 parts of n-butyl methacrylate and 100 parts of n-butyl acrylate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution in which 0.1 part of 2,2′-azobisisobutyronitrile was dissolved in 12 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 4 parts of PMA, 26 parts of trimellitic anhydride, 242 parts of cyclohexanone, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. . By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated to obtain a polyester dispersant having an acid value of 71 and a weight average molecular weight of 5800.

(Examples 29 and 30)
Synthesis was performed in the same manner as in Example 28 except that the raw materials and preparation amounts shown in Table 1 were used to obtain a polyester dispersant.

(Example 31)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 100 parts of n-butyl methacrylate and 100 parts of n-butyl acrylate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution in which 0.1 part of 2,2′-azobisisobutyronitrile was dissolved in 12 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 12 parts of PMA, 21 parts of trimellitic anhydride, 245 parts of cyclohexanone, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. . Thereafter, 3 parts of neopentyl glycol was added, and it was confirmed that 98% or more of the acid anhydride was half-esterified by measuring the acid value. The reaction was terminated, and the polyester dispersant had an acid value of 74 and a weight average molecular weight of 7500. Got.

(Examples 32-34)
Synthesis was performed in the same manner as in Example 32 except that the raw materials and preparation amounts shown in Table 1 were used to obtain a polyester dispersant.

(Example 35)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 12 parts of 3-mercapto-1,2-propanediol, 19 parts of PMA, and 31 parts of cyclohexanone and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., and 100 parts of n-butyl methacrylate and 100 parts of benzyl methacrylate were charged. 200 parts of cyclohexanone solution in which 0.5 part of 2,2'-azobisisobutyronitrile was dissolved was added and reacted for 10 hours. The solid content measurement confirmed that the polymerization had progressed 95%, and the reaction was completed. A polyester dispersant having an acid value of 43 and a weight average molecular weight of 9000 was obtained.

(Examples 36 to 38)
Synthesis was performed in the same manner as in Example 35 except that the raw materials and preparation amounts shown in Table 1 were used to obtain a polyester dispersant.

(Example 39)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 12 parts of 3-mercapto-1,2-propanediol, 37 parts of PMA, 11 parts of neopentyl glycol, and 60 parts of cyclohexanone and replaced with nitrogen gas. . The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., and 80 parts of methyl methacrylate, 80 parts of butyl acrylate, 2-hydroxypropyl methacrylate 40 parts were charged, 200 parts of a cyclohexanone solution in which 0.5 part of 2,2′-azobisisobutyronitrile was dissolved was added and reacted for 10 hours. The solid content measurement confirmed that the polymerization had progressed 95%, and the reaction was completed. A polyester dispersant having an acid value of 73 and a weight average molecular weight of 13,000 was obtained.

(Examples 40 to 42)
Synthesis was performed in the same manner as in Example 35 except that the raw materials and preparation amounts shown in Table 1 were used to obtain a polyester dispersant.

(Example 43)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 12 parts of 3-mercapto-1,2-propanediol, 12 parts of PMA, 11 parts of trimellitic anhydride, and 35 parts of cyclohexanone. Replaced. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride is half-esterified by measuring the acid value, the temperature in the system is cooled to 70 ° C., and 80 parts of methyl methacrylate, 80 parts of butyl acrylate, 20 parts of hydroxyethyl methacrylate Then, 20 parts of 2-hydroxypropyl methacrylate was charged, and 200 parts of a cyclohexanone solution in which 0.5 part of 2,2′-azobisisobutyronitrile was dissolved was added and reacted for 10 hours. The solid content measurement confirmed that the polymerization had progressed 95%, and the reaction was completed. A polyester dispersant having an acid value of 53 and a weight average molecular weight of 10,000 was obtained.

(Examples 44 to 46)
Synthesis was performed in the same manner as in Example 35 except that the raw materials and preparation amounts shown in Table 1 were used to obtain a polyester dispersant.

(Example 47)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 12 parts of 3-mercapto-1,2-propanediol, 15 parts of PMA, 11 parts of neopentyl glycol, 14 parts of trimellitic anhydride, 52 parts of cyclohexanone Was replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., and 80 parts of methyl methacrylate, 100 parts of butyl acrylate, 2-hydroxypropyl methacrylate 20 parts were charged, and 200 parts of a cyclohexanone solution in which 0.5 part of 2,2′-azobisisobutyronitrile was dissolved was added and reacted for 10 hours. The solid content measurement confirmed that the polymerization had progressed 95%, and the reaction was completed. A polyester dispersant having an acid value of 63 and a weight average molecular weight of 9000 was obtained.

(Examples 48 to 50)
Synthesis was performed in the same manner as in Example 35 except that the raw materials and preparation amounts shown in Table 1 were used to obtain a polyester dispersant.

  The raw materials and properties of the polyester dispersants obtained in Examples 1 to 34 are shown in Tables 1 to 4, and the raw materials and properties of the polyester dispersants obtained in Examples 35 to 50 are shown in Tables 5 and 6, respectively.

PMA: pyromellitic anhydride (manufactured by Daicel Chemical Industries)
BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride (Mitsubishi Chemical Corporation)
BPAF: 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.)
DMBA: dimethylol butanoic acid (manufactured by Perstorp)
C-1015N: bifunctional polycarbonate polyol, trade name Kuraray polyol C-1015N (hydroxyl value 112 mgKOH / g, manufactured by Kuraray Co., Ltd.)
C-2015N: bifunctional polycarbonate polyol, trade name Kuraray polyol C-2015N (hydroxyl value 56 mgKOH / g, manufactured by Kuraray Co., Ltd.)
DBU: 1,8-diazabicyclo- [5.4.0] -7-undecene (manufactured by Sun Apro Co., Ltd.)

(Comparative Example 1)
In a four-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel, 559 parts of dimethyl terephthalate, 420 parts of propylene glycol, 21.2 parts of glycerin, 0.2 part of zinc acetate, tetrabutyl ortho 0.025 parts of titanate was charged, and a transesterification reaction was performed at 160 to 220 ° C. with stirring under a nitrogen stream. When 95% (175 g) or more of the theoretical amount of methanol was distilled, the inside of the flask was gradually depressurized and reacted at 1 to 3 torr and 240 ° C. for 3 hours to obtain a polyester having a hydroxyl group at the terminal. Next, the flask was depressurized with nitrogen and gradually cooled to 200 ° C. When the temperature reached 200 ° C., 65 parts of succinic anhydride was added and reacted for 1 hour to obtain a polyester dispersant having an acid value of 40 and a weight average molecular weight of 12,000 (= comparative dispersant 1; hereinafter the same).

(Comparative Example 2)
A 4-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel was charged with 75 parts of cyclohexanone, 17.8 parts of neopentyl glycol, and 31.9 parts of pyromellitic anhydride, 150 to 160 The temperature was raised to 0 ° C., and the reaction was performed for 5 hours in a nitrogen gas atmosphere. When the resin acid value became 334 or less, the mixture was cooled, 249.7 parts of ε-caprolactone and 0.6 parts of tetrabutyl titanate were added, and the mixture was stirred at 150 ° C. for 5 hours. The mixture was cooled when the heating residue reached 76% or more, and 625 parts of cyclohexanone was added to obtain a polyester dispersant having an acid value of 54 and a weight average molecular weight of 12900. The polyester dispersant prepared in Comparative Example 2 corresponds to the polyester dispersant described in Patent Document 2.

(Comparative Example 3)
In a four-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel, 25.4 g of 1,2,4,5-benzenetetracarboxylic acid, 39.0 g of 2-ethylhexyl alcohol, and 50 mL of xylene Then, 0.2 g of tetrabutyl titanate was added thereto, and heated and refluxed at 160 to 180 ° C. for 18 hours in a nitrogen stream, and the generated water was separated by a Gene Stark trap. After completion of the reaction, xylene was removed under reduced pressure at 150 ° C. A light brown polyester dispersant having an acid value of 96.0 g KOH / g was obtained. The polyester dispersant prepared in Comparative Example 3 corresponds to the polyester dispersant described in Patent Document 1.

(Comparative Example 4)
In a four-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel, 19.8 parts of xylene, 2.1 parts of octanol, 77.9 parts of ε-caprolactone, 0.16 parts of tetrabutyl titanate Was heated to 150 to 160 ° C. and reacted for 5 hours in a nitrogen gas atmosphere. After confirming that the heating residue was 78% or more, the mixture was cooled to obtain a polyester monool. 31.86 parts of the synthesized polyester monool and 0.98 parts of trimellitic anhydride were charged and reacted at 150 to 160 ° C. in a nitrogen atmosphere. When the resin acid value became 22.7 or less, YED122 (trade name alkylphenol monoglycidyl ether, epoxy equivalent 250, manufactured by Japan Epoxy Resin Co., Ltd.) and 2.55 parts were charged and reacted at the same temperature. When the resin acid value became 1.1 or less, 1.96 parts of trimellitic anhydride was added and reacted at the same temperature, and when the resin acid value became 38.7 or less, YED122, 5.1 parts And the reaction is carried out at the same temperature. When the resin acid value becomes 1.8 or less, 3.92 parts of trimellitic anhydride is added and the reaction is carried out at the same temperature, and the resin acid value is reduced to 60.1 or less. At that time, the reaction mixture was cooled and 53.6 parts of xylene was added to terminate the reaction. A polyester dispersant having an acid value of 58.9 and a weight average molecular weight of 11,000 was obtained. The polyester dispersant prepared in Comparative Example 4 corresponds to the polyester dispersant described in Patent Document 3.

(Comparative Example 5)
26.6 parts (0.18 mol) of phosphorus oxychloride was dissolved in 70 parts of tetrahydrofuran, placed in a reaction vessel, and cooled to −50 ° C. 100 parts of PLACCEL FM4 (manufactured by Daicel Chemical Industries), 16.7 g (0.17 mol) of triethylamine and 0.1 part of hydroquinone monomethyl ether were dissolved in 150 parts of tetrahydrofuran and put into a dropping funnel. While blowing dry nitrogen gas, the phosphorus oxychloride solution was stirred and the Plaxel 4A solution was added dropwise. During dropwise keeping the -45 to-50 ° C., kept at -45 ° C. for 20 minutes between time After completion of the dropwise addition 1. Thereafter, the temperature was raised to 0 ° C., and a solution obtained by dissolving 15 parts of water and 37.9 parts of triethylamine in 100 parts of tetrahydrofuran was added dropwise. After completion of the dropwise addition, the mixture was stirred for 15 hours under ice cooling to complete the hydrolysis of the P-C1 bond. Thereafter, the precipitated triethylammonium chloride was filtered off, and tetrahydrofuran was removed under reduced pressure at a temperature of 30 ° C. or lower. The obtained solid was washed with 0.3N hydrochloric acid aqueous solution. Next, after washing several times with toluene, it was dried under reduced pressure at room temperature to obtain a polyester dispersant having a phosphate group at the terminal. The polyester dispersant prepared in Comparative Example 5 corresponds to the polyester dispersant described in Patent Document 4.

[Production Example 1 of pigment derivative (Y) having a basic group]
After 50 parts of copper phthalocyanine as a pigment component was chlorosulfonated, it was reacted with 14 parts of N, N-dimethylaminopropylamine as an amine component to obtain 62 parts of a pigment derivative (Y1) having a basic group.

Pigment derivative having basic group (Y1)

  CuPc represents a copper phthalocyanine residue.

[Production Example 2 of pigment derivative (Y) having a basic group]
After 50 parts of copper phthalocyanine as a pigment component was chloromethylated, it was reacted with 40 parts of dibutylamine as an amine component to obtain 95 parts of a pigment derivative (Y2) having a basic group.

Pigment derivative having basic group (Y2)

  CuPc represents a copper phthalocyanine residue.

[Production Example 3 of pigment derivative (Y) having a basic group]
After 50 parts of quinacridone as a pigment component were chloroacetamidomethylated, it was reacted with 40 parts of N-methylpiperazine as an amine component to obtain 103 parts of a pigment derivative (Y3) having a basic group.

Pigment derivative having basic group (Y3)

[Production Example 4 of pigment derivative (Y) having a basic group]
A pigment derivative (Y4) having a basic group was obtained in the same manner as in Production Example 1 using diphenyl diketopyrrolopyrrole as the dye component and N-aminopropylmorpholine as the amine component.

Pigment derivative having basic group (Y4)

[Production Examples 5 to 10 of pigment derivative (Y) having basic group]
The following pigment derivatives, anthraquinone derivatives, acridone derivatives or triazine derivatives were obtained by the same method as in Production Examples 1 to 4 of the pigment derivative (Y) having the basic group.

Pigment derivative having basic group (Y5)

Pigment derivative having basic group (Y6)

Pigment derivative having basic group (Y7)

Pigment derivative having basic group (Y8)

Pigment derivative having basic group (Y9)

Pigment derivative having basic group (Y10)

(Examples 51 to 59) <Production of pigment composition>
As shown in Table 7, the pigment (CI Pigment Blue 15: 3), the polyester dispersant synthesized in Examples 1 to 9, the pigment derivative (Y1) having a basic group synthesized in Production Example 1, In addition, 100 parts of zirconia beads having a diameter of 2 mm were added and dispersed with a paint conditioner for 3 hours to prepare a pigment composition.

(Comparative Examples 6 and 7) <Production of pigment composition>
A pigment composition was prepared in the same manner as in Examples 51 to 59 except that the carboxyl group-containing polyester synthesized in Comparative Examples 1 and 2 was used.

(Evaluation of pigment composition)
In order to evaluate the performance of the pigment composition of the present invention, the viscosity of the obtained composition was measured with a B-type viscometer (25 ° C., rotation speed 100 rpm), and 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 haze, the lower 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 7.

  As is clear from the above evaluation results, the pigment compositions of Examples 51 to 59 using the polyester dispersant of the present invention showed a low initial viscosity and a good stability with little increase in viscosity over time. Yes. Furthermore, the haze is also low. In contrast, in the pigment compositions of Comparative Examples 6 and 7, both the viscosity and haze were high, and it was found that there was a problem in dispersibility.

(Example 60)
9 parts of Pigment Blue 15: 3, 1 part of pigment derivative (Y1) having a basic group, 1 part of dispersant 3 (solid), alkyd resin (Hitachi Chemical Co., Ltd., “Phthalkid 133-60”) 29 Part and 60 parts of cyclohexanone were charged into a mayonnaise bottle, 250 parts of zirconia beads having a diameter of 0.5 mm were charged as a dispersion medium, and this dispersion was performed with a paint shaker to obtain a pigment dispersion.

  The viscosity of the obtained pigment dispersion was measured with a B-type viscometer, and the performance of the dispersion was evaluated based on the viscosity and TI value (viscosity at 6 rpm / viscosity at 60 rpm). The viscosity at 6 rpm was 110 mPa · s, the viscosity at 60 rpm was 100 mPa · s, and the TI value was 1.11. Further, the obtained pigment dispersion was stored in a thermostat at 50 ° C. for 1 week and accelerated with time, and the change in viscosity of the pigment dispersion before and after aging was measured. The viscosity at 6 rpm was 105 mPa · s and the rate of change was −5%. After the pigment dispersion was coated on glass and the solvent was removed, the weight loss% before and after heating at 200 ° C. for 1 hour was 8.5%.

(Examples 61 to 119)
In the same manner as in Example 60, pigment dispersions were obtained with the blending ratios (weight ratios) shown in Tables 8 and 9, respectively. Moreover, it evaluated by the method similar to Example 60 (The lower the viscosity, the better, the closer the TI value to 1, the better).

(Evaluation of pigment dispersion)
Viscosity stability was evaluated as ○ when the rate of change in viscosity before and after storage at 50 ° C. for 1 week was within ± 10%, and × when exceeding ± 10%. The weight loss of the coating film was determined to be ○ when the weight loss before and after heating at 200 ° C. for 1 hour was within 10% after removing the coating film and solvent on the glass, and x when exceeding 10%. The results are shown in Tables 10 and 11.

(Comparative Examples 8-24)
In the same manner as in Example 60, pigment dispersions were obtained according to the blending ratios (weight ratios) shown in Table 12. Moreover, it evaluated by the method similar to Example 60 (The lower the viscosity, the better, the closer the TI value to 1, the better). When the rate of change in viscosity before and after storage at 50 ° C. for 1 week was within ± 10%, it was rated as ○, and when it exceeded ± 10%, it was marked as ×. The weight loss of the coating film was determined to be ○ when the weight loss before and after heating at 200 ° C. for 1 hour was within 10% after removing the coating film and solvent on the glass, and x when exceeding 10%. The results are shown in Table 13.

  As is clear from the above evaluation results, the pigment dispersions of Examples 60 to 119 using the polyester dispersant of the present invention have a low initial viscosity and almost no increase in viscosity with time, and exhibit good stability. Yes. In addition, the coating has high resistance. On the other hand, in the pigment dispersions of Comparative Examples 8 to 24, the viscosity is high and the amount of dispersant used must be increased. Further, since many dispersants having a low molecular weight were used, it was found that there was a problem in the durability of the coating film even if there was no problem in viscosity.

The polyester dispersant according to the present invention can be suitably used in fields such as paints and colored resin compositions, and specifically, suitable for offset ink, gravure ink, color filter resist ink, ink jet ink, and the like. Can be used. When the polyester dispersant of the present invention is used, a dispersion excellent in non-aggregability, fluidity, and storage stability can be produced.
As mentioned above, although this invention was demonstrated along the specific aspect, the deformation | transformation and improvement obvious to those skilled in the art are included in the scope of the present invention.

Claims (28)

Vinyl polymer produced by radical polymerization of an ethylenically unsaturated monomer in the presence of compound (a1) having two hydroxyl groups and one thiol group in the molecule, and having two hydroxyl groups in one terminal region A hydroxyl group in (a);
An acid anhydride group in tetracarboxylic acid anhydride (b);
A polyester dispersing agent for pigments produced by reacting. Vinyl polymer produced by radical polymerization of an ethylenically unsaturated monomer in the presence of compound (a1) having two hydroxyl groups and one thiol group in the molecule, and having two hydroxyl groups in one terminal region A hydroxyl group in (a) and a hydroxyl group in a polyol compound (c) other than the vinyl polymer (a);
An acid anhydride group in tetracarboxylic acid anhydride (b);
A polyester dispersing agent for pigments produced by reacting. Vinyl polymer produced by radical polymerization of an ethylenically unsaturated monomer in the presence of compound (a1) having two hydroxyl groups and one thiol group in the molecule, and having two hydroxyl groups in one terminal region A hydroxyl group in (a);
An acid anhydride group in tetracarboxylic acid anhydride (b) and an acid anhydride group in tricarboxylic acid anhydride (d);
A polyester dispersing agent for pigments produced by reacting. Vinyl polymer produced by radical polymerization of an ethylenically unsaturated monomer in the presence of compound (a1) having two hydroxyl groups and one thiol group in the molecule, and having two hydroxyl groups in one terminal region A hydroxyl group in (a) and a hydroxyl group in a polyol compound (c) other than the vinyl polymer (a);
An acid anhydride group of the tetracarboxylic acid anhydride (b) and an acid anhydride group in the tricarboxylic acid anhydride (d);
A polyester dispersing agent for pigments produced by reacting. Presence of compound (a2) produced by reacting a hydroxyl group in compound (a1) having two hydroxyl groups and one thiol group in the molecule with an acid anhydride group in tetracarboxylic anhydride (b) Below, a polyester dispersant for pigments produced by radical polymerization of an ethylenically unsaturated monomer. A hydroxyl group in the compound (a1) having two hydroxyl groups and one thiol group in the molecule and a polyol compound (c ′) having no thiol group, and an acid anhydride group in the tetracarboxylic anhydride (b); A polyester dispersant for pigments produced by radical polymerization of an ethylenically unsaturated monomer in the presence of the compound (a3) produced by reacting with. Hydroxyl group in compound (a1) having two hydroxyl groups and one thiol group in the molecule, acid anhydride group in tetracarboxylic acid anhydride (b) and acid anhydride group in tricarboxylic acid anhydride (d) A polyester dispersant for pigments produced by radical polymerization of an ethylenically unsaturated monomer in the presence of the compound (a4) produced by reacting with. A compound having two hydroxyl groups and one thiol group in the molecule (a1) and a hydroxyl group in the polyol compound (c ′) having no thiol group and an acid anhydride group in the tetracarboxylic acid anhydride (b); Polyester dispersant for pigment produced by radical polymerization of ethylenically unsaturated monomer in the presence of compound (a5) produced by reacting with acid anhydride group in tricarboxylic acid anhydride (d) . The weight average molecular weight is 2000-35000, and the acid value is 5-200, The polyester dispersant for pigments as described in any one of Claims 1-8. The polyester dispersant for a pigment according to any one of claims 1 to 9, wherein the tetracarboxylic acid anhydride (b) 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), Q ₁ represents 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 polyester dispersant for pigments according to any one of claims 1 to 10, wherein the vinyl polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer has a weight average molecular weight of 1,000 to 10,000. The polyester dispersant for pigments according to any one of claims 1 to 11, wherein a glass transition temperature of a vinyl polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer is -50 to 70 ° C. The polyester dispersant for a pigment according to any one of claims 1 to 12, wherein the ethylenically unsaturated monomer contains benzyl (meth) acrylate in an amount of 20% to 70% by weight based on the whole monomer. The polyester dispersant for pigments according to any one of claims 1 to 13, wherein the ethylenically unsaturated monomer contains a monomer represented by the following general formula (3).
General formula (3)

[In General Formula (3), R is a linear or branched alkyl group having 1 to 4 carbon atoms. ] The pigment composition containing the polyester dispersing agent for pigments as described in any one of Claims 1-14, 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 15. The pigment composition according to Item 15.   A pigment dispersion obtained by dispersing the pigment composition according to claim 15 or 16 in a varnish. In the presence of the compound (a1) having two hydroxyl groups and one thiol group in the molecule, the ethylenically unsaturated monomer is radically polymerized to give a vinyl polymer having two hydroxyl groups in one terminal region (a Step A1 for manufacturing)
A step B1 of reacting the vinyl polymer (a) with the tetracarboxylic acid anhydride (b);
The manufacturing method of the polyester dispersing agent containing this. In the presence of the compound (a1) having two hydroxyl groups and one thiol group in the molecule, the ethylenically unsaturated monomer is radically polymerized to give a vinyl polymer having two hydroxyl groups in one terminal region (a Step A2 for manufacturing)
A step B2 of reacting the vinyl polymer (a), the tetracarboxylic acid anhydride (b), and a polyol compound (c) other than the vinyl polymer (a);
The manufacturing method of the polyester dispersing agent containing this. In the presence of the compound (a1) having two hydroxyl groups and one thiol group in the molecule, the ethylenically unsaturated monomer is radically polymerized to give a vinyl polymer having two hydroxyl groups in one terminal region (a Step A3 for manufacturing)
A step B3 of reacting the vinyl polymer (a) with a tetracarboxylic acid anhydride (b) and a tricarboxylic acid anhydride (d);
The manufacturing method of the polyester dispersing agent containing this. In the presence of the compound (a1) having two hydroxyl groups and one thiol group in the molecule, the ethylenically unsaturated monomer is radically polymerized to give a vinyl polymer having two hydroxyl groups in one terminal region (a Step A4 for manufacturing)
A step B4 of reacting the vinyl polymer (a), the tetracarboxylic acid anhydride (b), the polyol compound (c) other than the vinyl polymer (a), and the tricarboxylic acid anhydride (d);
The manufacturing method of the polyester dispersing agent containing this. Step B5 for producing a compound (a2) by reacting a hydroxyl group in the compound (a1) having two hydroxyl groups and one thiol group in the molecule with an acid anhydride group in the tetracarboxylic acid anhydride (b). When,
A step A5 of radically polymerizing an ethylenically unsaturated monomer in the presence of the compound (a2);
The manufacturing method of the polyester dispersing agent containing this. Hydroxyl group in compound (a1) having two hydroxyl groups and one thiol group in the molecule and hydroxyl group in polyol compound (c ′) having no thiol group and acid anhydride in tetracarboxylic acid anhydride (b) A step B6 of producing a compound (a3) by reacting a substance group;
A step A6 of radically polymerizing an ethylenically unsaturated monomer in the presence of the compound (a3);
The manufacturing method of the polyester dispersing agent containing this. Hydroxyl group in compound (a1) having two hydroxyl groups and one thiol group in the molecule, acid anhydride group in tetracarboxylic acid anhydride (b), and acid anhydride in tricarboxylic acid anhydride (d) A step B7 of reacting a group to produce a compound (a4);
A step A7 of radically polymerizing an ethylenically unsaturated monomer in the presence of the compound (a4);
The manufacturing method of the polyester dispersing agent containing this. In the polyol compound (c ′) having no hydroxyl group in the compound (a1) having two hydroxyl groups and one thiol group in the molecule, the acid anhydride group in the tetracarboxylic acid anhydride (b), and the thiol group A step B8 of producing a compound (a5) by reacting a hydroxyl group of the compound with an acid anhydride group in the tricarboxylic acid anhydride (d);
A step A8 of radically polymerizing an ethylenically unsaturated monomer in the presence of the compound (a5);
The manufacturing method of the polyester dispersing agent containing this. The method for producing a polyester dispersant according to any one of claims 18 to 25, wherein the tetracarboxylic acid anhydride (b) 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), Q ₁ represents 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. ]   27. The polyester dispersant according to any one of claims 18 to 26, wherein the ethylenically unsaturated monomer contains benzyl (meth) acrylate in an amount of 20% to 70% by weight based on the whole monomer. Production method. The method for producing a polyester dispersant according to any one of claims 18 to 27, wherein the ethylenically unsaturated monomer contains a monomer represented by the following general formula (3).
General formula (3)

[In General Formula (3), R is a linear or branched alkyl group having 1 to 4 carbon atoms. ]