JP3534859B2 - Pigment dispersant, coating composition and printing ink composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paint, a pigment dispersant comprising an amino group-containing compound for improving the dispersibility of a pigment in the production of ink, a coating composition and a printing ink composition using the amino group-containing compound. .

[0002]

2. Description of the Related Art In the production of paints and inks, the dispersibility of pigments is improved, the storage stability of paints, the shortening of dispersion time,
Various dispersants are used for the purpose of preventing color separation and increasing the gloss of the coating film. The dispersant used for such a purpose generally has a portion adsorbing to a pigment and a polymer chain such as polyester or acryl which is compatible with a vehicle for paint or ink. Further, although various functional groups are used as the pigment adsorbing group, many dispersants having an amino group as the pigment adsorbing group have been reported. For example, JP-A-53-103988 discloses low molecular weight amino compounds such as N, N-dimethylaminopropylamine, and JP-A-61-174939 discloses polyethyleneimine which is a high molecular weight amine compound. A pigment dispersant using is reported. The molecular structure of these pigment dispersants connects the polyester chain to the polyamines through an amide bond.

[0003]

However, the compound having an amide bond has a very high cohesive force, and when it is used as a pigment dispersant, it has a problem that it has a low solubility in many paint solvents. To be Further, since the nitrogen constituting the amide group becomes extremely low in basicity, nitrogen having an amide bond does not exhibit adsorptivity to the pigment. Therefore, when a large amount of polyester chains are grafted to polyamines for the purpose of forming an effective steric repulsion layer on the pigment surface and improving the dispersion stability, the amount of adsorbing groups decreases and conversely the dispersibility decreases. There is a problem that it ends up. Furthermore, when a polyester chain is reacted with a polyamine and grafted, a reaction temperature of at least 100 ° C. to 150 ° C. is required to obtain an appropriate reaction rate. When a reaction composition containing amines is heated at such a reaction temperature, coloring of the reaction product is unavoidable in many cases, and the problem that the coating film is colored pale yellow in light-colored paints, especially white Had a point.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies in view of the above-mentioned problems of the adsorbing group of the pigment dispersant, and as a result, have found that a functional group capable of Michael addition with an amino group at one end. , A specific amino group-containing compound derived from polyesters and polyamines has good compatibility with a wide range of resins, and has extremely good dispersion performance with a wide range of pigments. They have found that they are extremely effective as pigment dispersants, and have completed the present invention.

That is, the present invention contains, as an essential component, a unit having a functional group capable of undergoing a Michael addition reaction with an amino group at a terminal and having a polyester chain formed by ring opening of a lactone compound represented by the general formula (2). The present invention provides a pigment dispersant comprising an amino group-containing compound obtained by reacting a polyester compound represented by the general formula (1) and a polyamine compound.

[0006]

[Chemical 3]

The amine value of the amino group-containing compound is
It is intended to provide the pigment dispersant in the range of 10 to 500 mg KOH / g. The average molecular weight of the polyester compound represented by the general formula (1) is 100 to 10,0.
00, or the average molecular weight of the polyamine compound is in the range of 100 to 100,000. Also provided are a pigment dispersant comprising a quaternary ammonium chloride amino group-containing compound obtained by chlorinating a free amino group of an amino group-containing compound, and the pigment dispersant wherein the polyamine compound is polyethyleneimine, polyallylamine or polyvinylamine. To do. Further, the above pigment dispersant is provided in which the unit having a polyester chain formed by ring-opening of a lactone compound is ε-caprolactone, methylcaprolactone, or a copolymer of methylcaprolactone and ε-caprolactone. is there. Further, the present invention provides the pigment dispersant in which the functional group capable of Michael addition is a (meth) acryloyl group. In addition, the polyester dispersant represented by the general formula (1) is the acrylic dispersant represented by the general formula (3).

[0008]

[Chemical 4]

Further, the present invention provides a dispersion obtained by dispersing fine solids in the pigment dispersant, a coating composition containing the pigment dispersant, or a printing ink composition. Hereinafter, the present invention will be described in more detail.

The amino group-containing compound obtained by reacting the polyester compound and the polyamine compound in the present invention is a very effective pigment dispersant. In the pigment dispersant of the present invention, the functional group X of the polyester compound as a raw material undergoes an addition reaction with the amino group of the polyamine compound, but the reacted amino group acts as an amine, so that the pigment adsorbing ability is not impaired. Further, since no amide group is formed, the solubility in the solvent and the compatibility with the paint are not impaired.

In order to produce the pigment dispersant of the present invention, as a first step, the lactone compound represented by the general formula (2) is subjected to ring-opening polymerization to contain a unit having a polyester chain. A polyester compound (1) having an amino group and a functional group (X) capable of addition reaction with the amino group at the terminal is synthesized.

The polyester compound (1) having a polyester chain and having a functional group capable of addition-reacting with an amino group at the end used in the present invention can be synthesized by various methods. However, only one end of the polyester chain has an amino group. It is desirable that a functional group capable of addition reaction with is present. Although there are various functional groups as the functional group capable of addition-reacting with the amino group, a (meth) acryloyl group is convenient in terms of synthesis and reactivity. Polyester having a (meth) acryloyl group only at one end is hydroxyethyl (meth)
Addition reaction of lactone compound to hydroxyl group-containing (meth) acrylate such as acrylate, or (meth)
It can be synthesized by an insertion reaction utilizing an ester exchange reaction between an acrylic ester and a lactone compound, or an addition reaction between a polyester having a carboxyl group at one end and an epoxy group-containing (meth) acrylate such as glycidyl methacrylate. These reaction methods will be described below.

Addition reaction of lactone compound to hydroxyl group-containing (meth) acrylate: As the hydroxyl group-containing (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate represented by the general formula (4), Hydroxybutyl (meth) acrylate or the like can be used.

[0014]

[Chemical 5]

Examples of the lactone compound include ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, 4-methylcaprolactone, 2-methylcaprolactone, β-propiolactone, γ-butyrolactone and the like. The lactones represented by can be used. These may be used alone or as a mixture. Among these, the lactone compound having a side chain disrupts the crystallinity of the polyester chain, and the resulting amino group-containing compound has excellent compatibility with resins and solubility in solvents, and has a reduced viscosity of the millbase and a coating at low temperature. Excellent stability.

The reaction is carried out by charging these hydroxyl group-containing (meth) acrylates and lactones in a reactor having a condenser, a stirrer and an air introduction tube and heating them. The heating temperature is 50 to 150 ° C, preferably 80 to 120 ° C. If the temperature is lower than 50 ° C., the reaction is extremely slow, and if the temperature exceeds 150 ° C., the hydroxyl group-containing (meth) acrylate is polymerized and the desired compound is not provided.

As the reaction catalyst, a titanium-based catalyst such as tetrabutyl titanate or tetraisopropyl titanate, a tin-based catalyst such as stannous chloride, tin octylate or monobutyltin oxide, or an acid such as p-toluenesulfonic acid can be used. I can. The amount of catalyst used is 0.1
〜3,000ppm, preferably 1〜100ppm. When the amount of the catalyst exceeds 3,000 ppm, the resin becomes severely colored, which adversely affects the stability of the product.

The reaction is preferably carried out in the presence of a polymerization inhibitor in order to prevent the polymerization of the hydroxyl group-containing (meth) acrylate. As the polymerization inhibitor, hydroquinone,
Known polymerization inhibitors such as methylhydroquinone and phenothiazine can be used. Further, in order to prevent the polymerization of hydroxyl group-containing (meth) acrylates, it is desirable to carry out the reaction in the presence of a slight amount of oxygen.

Insertion reaction utilizing transesterification reaction of (meth) acrylic acid ester and lactone compound: (meth) acrylic acid is used for insertion reaction utilizing transesterification reaction of (meth) acrylic acid ester and lactone compound. The (meth) acrylic acid ester represented by the general formula (5) such as methyl, ethyl (meth) acrylate, butyl (meth) acrylate, and octyl (meth) acrylate can be used.

[0020]

[Chemical 6]

Examples of the lactone compound include ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, 4-methylcaprolactone, 2-methylcaprolactone, β-propiolactone, γ-butyrolactone and the like. ) The lactones represented by) can be used. These may be used alone or as a mixture.
Among these, the lactone compound having a side chain, crystallinity of the polyester chain is destroyed, the compatibility of the resulting amino group-containing compound with the resin, the solubility in the solvent is excellent, the viscosity reduction of the mill base, at low temperature Excellent paint stability. Even when lactones having no side chains are used and cannot be liquefied at room temperature, they can be liquefied by copolymerizing lactones having side chains.

The reaction takes place by charging these (meth) acrylic acid esters and lactones into a reactor having a dehydration tube and a condenser and heating them. Reaction temperature is 5
It is 0 to 150 ° C, preferably 80 to 120 ° C. Fifty
If the temperature is lower than 0 ° C, the reaction is extremely slow, and if the temperature exceeds 150 ° C, the (meth) acrylic acid ester is polymerized to give no target compound.

As the reaction catalyst, titanium-based catalysts such as tetrabutyl titanate and tetraisopropyl titanate, tin-based catalysts such as stannous chloride, tin octylate and monobutyltin oxide, and acid-based catalysts such as p-toluenesulfonic acid. Although it can be used, p-toluenesulfonic acid is particularly preferable. The amount of catalyst used is 0.1 ppm
˜1%, preferably 1 to 1,000 ppm. When the amount of the catalyst exceeds 1%, coloring of the resin becomes severe and the stability of the product is adversely affected.

The reaction is preferably carried out in the presence of a polymerization inhibitor in order to prevent the polymerization of the (meth) acrylic acid ester. As the polymerization inhibitor, known polymerization inhibitors such as hydroquinone, methylhydroquinone and phenothiazine can be used. Further, in order to prevent the polymerization of the (meth) acrylic acid ester, it is desirable to carry out the reaction in the presence of a slight amount of oxygen.

Addition reaction of a polyester having a carboxyl group at one end with an epoxy group-containing (meth) acrylate such as glycidyl methacrylate: a polyester having a carboxyl group at one end is an addition reaction of a lactone to a monocarboxylic acid or a hydroxy group. It can be synthesized by addition reaction of lactones to carboxylic acids.

In the reaction in which the lactone compound is added to the monocarboxylic acid, a carboxylic acid-modified polylactone compound having a molecular weight higher than the expected molecular weight is produced from the molar ratio of the monocarboxylic acid as the initiator and the lactone compound, or the lactone compound is produced. Whereas the high molecular weight homopolymer and the monocarboxylic acid may remain, when a hydroxycarboxylic acid is used as an initiator, a polylactone compound having a designed molecular weight can be easily obtained.

As the monocarboxylic acid that can be used here, various aliphatic and aromatic carboxylic acids can be used, and examples thereof include acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, lauric acid, Examples thereof include stearic acid, abietic acid, phenylacetic acid, methoxyacetic acid and the like. These may be used alone or in combination.

Examples of the lactone compound include 4-methylcaprolactone, 2-methylcaprolactone, ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, β-propiolactone, γ-butyrolactone and the like. The lactones represented by can be used. These may be used alone or in combination.
Among these, lactones having a side chain, crystallinity of the polyester chain is destroyed, the compatibility of the resulting amino group-containing compound with the resin, the solubility in the solvent is excellent, the viscosity reduction of the mill base, at low temperature Excellent paint stability.

As the hydroxycarboxylic acid which can be used, aliphatic, aromatic and unsaturated hydroxycarboxylic acids can be used. Examples thereof include ricinoleic acid, ricinoleic acid and 12-hydroxystearic acid. , Castor oil fatty acid, hydrogenated castor oil fatty acid, δ-
Hydroxyvaleric acid, ε-hydroxycaproic acid, P-hydroxyethyloxycarboxylic acid, 2-hydroxynaphthalene-3-carboxylic acid, 2-hydroxynaphthalene-
6-carboxylic acid, 2,2-dimethylolpropionic acid,
2,2-dimethylol valeric acid, 2,2-dimethylol pentanoic acid, malic acid, tartaric acid, lactic acid, glycolic acid, gluconic acid, hydroxypivalic acid, 11-oxyhexadecanoic acid, 2-oxidedecanoic acid, salicylic acid, etc. are used. it can. These may be used alone or in combination.

A carboxyl group-terminated polyester compound containing as an essential component a unit having a polyester chain formed by ring-opening of a lactone compound is a dicarboxylic acid or its anhydride, a diol component, a lactone compound, a hydroxy group, like ordinary polyesters. It is also possible to synthesize it from a raw material such as a carboxylic acid compound or a monocarboxylic acid compound.

Examples of the dicarboxylic acid or acid anhydride thereof include maleic acid, succinic acid, glutaric acid, fumaric acid, adipic acid, sebacic acid, azelaic acid, dodecane diacid, phthalic acid, isophthalic acid, terephthalic acid and hexahydro. Known components such as phthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, trimellitic acid, methyltetrahydrophthalic acid or its anhydride can be used.

As the diol component, various aliphatic branched, linear structure, alicyclic or aromatic alcohols can be used. For example, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1 , 3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, 3-methylpentanediol, 1,5
-Pentanediol, 1,6-hexanediol, trimethylolpropane, cyclohexanedimethanol,
1,4-dibenzyl alcohol or the like can be used. Further, monoepoxides such as α-olefin monoepoxide and Cajuula E (monoepoxide of versatic acid glycidyl ether; manufactured by Yuka Shell Epoxy Co., Ltd.) can also be used.

The carboxyl group-terminated polyester is synthesized by charging the polyester raw material into a reactor connected to a dehydration tube and a condenser and polymerizing it in a nitrogen stream. For the reaction, a suitable dehydrating solvent such as toluene or xylene can be used. The solvent used in the reaction can be removed by an operation such as distillation after the reaction is completed, or can be used as it is as a part of the product.

The synthesis temperature of the carboxyl group-terminated polyester compound is 120 to 220 ° C., preferably 160 to 21.
Perform in the range of 0 ° C. If the reaction temperature is lower than 120 ° C, the reaction rate is extremely slow, and if it exceeds 210 ° C, side reactions other than the addition reaction of lactones such as decomposition of lactone polymer into lactone monomer and formation of cyclic lactone dimer are likely to occur. It is difficult to synthesize carboxyl group-terminated polylactones having a target molecular weight. In addition, the produced copolymer is likely to be colored.

Examples of the esterification catalyst that can be used include tin octylate, dibutyltin oxide, dibutyltin laurate, monobutyltin hydroxybutyl oxide, and other organotin compounds, stannous oxide, stannous chloride, and other tin compounds, and tetra. Butyl titanate, tetraethyl titanate, tetrapropyl titanate and the like can be used. The amount of the catalyst used is 0.1 to 3,000 ppm, preferably 1 to 100 ppm. The amount of catalyst is 3,000pp
When it exceeds m, coloring of the resin becomes severe, which adversely affects the stability of the product. On the contrary, if the amount of the catalyst used is less than 1 ppm, the ring-opening polymerization rate of the lactone becomes extremely slow, which is not preferable. In addition, it tends to be colored when reacted in the presence of air, so it is desirable to react in an inert atmosphere such as a nitrogen stream.

Next, the obtained carboxyl group-terminated polyester is reacted with an epoxy group-containing (meth) acrylate. As the epoxy group-containing (meth) acrylate, those of the general formula (6) can be used, but glycidyl methacrylate, which is industrially produced and available,
β-methylglycidyl methacrylate, 2,3-epoxycyclohexylmethyl (meth) acrylate and the like are preferable.

[0037]

[Chemical 7]

The reaction is carried out by charging these epoxy group-containing (meth) acrylate and carboxyl group-terminated polyester into a reactor having a dehydration tube and a condenser and heating. The reaction temperature is 50 to 150 ° C, preferably 80 to 120 ° C. If the temperature is lower than 50 ° C, the reaction is extremely slow, and if the temperature exceeds 150 ° C, the epoxy group-containing (meth) acrylate is polymerized and the target compound is not provided.

As the reaction catalyst, amine catalysts such as N, N-dimethylbenzylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, triphenylphosine and tetra A phosphorus-based catalyst such as a halogen ion salt of phenylphosphonium or the like, or a halogen ion salt of ethyltriphenylphosphonium or the like can be used. The amount of catalyst used is 0.1
It is 3,000 ppm, preferably 1 to 500 ppm. When the amount of the catalyst exceeds 3,000 ppm, the resin becomes severely colored, which adversely affects the stability of the product.

The reaction is preferably carried out in the presence of a polymerization inhibitor in order to prevent the polymerization of the epoxy group-containing (meth) acrylate. As the polymerization inhibitor, known polymerization inhibitors such as hydroquinone, methylhydroquinone and phenothiazine can be used. Further, in order to prevent the polymerization of the epoxy group-containing (meth) acrylates, it is desirable to carry out the reaction in the presence of a slight amount of oxygen.

In addition to these methods, the hydroxyl group is
It is also possible to synthesize a monofunctional polyester having an individual unit, then react with a bifunctional isocyanate to synthesize a prepolymer, and then react with a hydroxyl group-containing (meth) acrylate to prepare a raw material for the dispersant. However, in this case, a monofunctional polyester having one hydroxyl group of 2 mol and a polyester obtained by reacting 1 mol of diisocyanate are easily mixed as impurities. In addition, when unreacted isocyanate remains, a cross-linking reaction may occur when reacting with polyamines in the next step, and a gel product may be produced.

The average molecular weight of the polyester compound represented by the general formula (1) thus synthesized is 100 to 2
It is preferably in the range of 10,000. More preferably, it is in the range of 500 to 10,000. When the molecular weight of the polyester is less than 100, the resulting amino group-containing compound cannot form a sufficient steric repulsion layer around the pigment, and when the molecular weight exceeds 20,000, the molecular weight of the amino group-containing compound obtained is If it becomes too large, the compatibility with paints and vehicles for ink is lowered, and the pigment dispersibility is also lowered.

Next, in the second step, the ester compound obtained above and the polyamine compound are reacted to synthesize a pigment dispersant comprising an amino group-containing compound. The polyamine compound used in the present invention has a molecular weight of 100 to 10
10,000 is desirable. If the molecular weight is less than 100, the molecular weight of the adsorbed portion of the pigment is too low to have the effect of using the polyamine compound. If the molecular weight exceeds 100,000, the molecular weight of the entire pigment dispersant becomes too large. There is a possibility that it may lead to a meeting and decrease the dispersion. In addition, the viscosity of the pigment dispersant at the time of melting is high, and synthesis is difficult. Further, as a polyamine compound, in order to improve compatibility with coating resins and solvent solubility, a monoepoxide of α-olefin, a reaction product of a monoepoxide such as Cajuula E and a polyamine, or methyl (meth) is used.
It is also possible to use polyamines modified with acrylic monomers such as acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, cyclohexyl (meth) acrylate. Specifically, as the polyamines, polyethyleneimine, polyallylamine, polyvinylamine and the like can be preferably used.

The reaction ratio of the polyester compound having a Michael-addable functional group at one end and the polyamine compound is preferably such that the molar ratio of the Michael-addable functional group and the amino group is in the range of 1: 1 to 1:99. The range of 2: 3 to 1:65 is preferable. The reaction can be obtained by charging a polyamine compound and a polyester compound having a functional group capable of Michael addition at one end into a reactor connected to a dehydration tube and a condenser to cause a reaction. The reaction is
Even at room temperature, it proceeds rapidly and almost quantitatively with some heat generation. Therefore, the reaction temperature is 10 ° C to 1
It is 30 ° C., preferably 20 ° C. to 100 ° C. 10 ° C
At lower temperatures, the reaction is slow and an industrially reasonable reaction rate cannot be obtained. On the other hand, when the temperature exceeds 130 ° C., problems such as reaction between functional groups capable of Michael addition and coloring of reaction products are likely to occur.

For the reaction, it is possible to use a solvent which does not participate in the addition reaction. Such paint solvents and solvents, xylene, toluene, aromatic solvents such as Solvesso,
Acetone, methyl ethyl ketone, methyl isobutyl ketone and other ketones, butanol, isopropanol and other alcohols, dimethyl adipate, dimethyl succinate,
Esters such as dimethyl glutarate may be used. The solvent used in the reaction can be removed by an operation such as distillation after the reaction is completed, or can be used as it is as a part of the product.

The average molecular weight of the polyester portion contained in the dispersant thus synthesized is 100 to 5,000.
It is preferably 0. The molecular weight of polyester is 10
If it is less than 0, a sufficient steric repulsion layer cannot be formed around the pigment, and if the molecular weight exceeds 5,000, the dispersant as a whole has too large a molecular weight and is compatible with paints and vehicles for inks. And the pigment dispersibility are also reduced.

In the pigment dispersant thus synthesized, when the end of the polyester chain in the dispersant on the side opposite to the amino group is terminated with a hydroxyl group, in the baking step after forming into a paint. , The pigment dispersant of the present invention by reacting with a melamine resin or an isocyanate,
Firmly incorporated as part of the coating. Therefore, bleeding or crystallization of the pigment dispersant in the coating film does not occur, and bleeding or reaggregation of the pigment does not easily occur in the pigment captured by the pigment dispersant.

Further, by using a lactone compound-containing polyester having an appropriate molecular weight as a polyester compound as a reaction intermediate, it can be applied to pigment dispersion using a solvent having a relatively high polarity such as alcohol and cellosolves. Is possible.

The above-mentioned pigment dispersant of the present invention is an inorganic pigment such as titanium oxide, zinc oxide, cadmium sulfide, yellow iron oxide, red iron oxide, yellow lead, carbon black, phthalocyanines, insoluble azo pigments, azo lake pigments, condensation pigments. It has excellent pigment dispersibility for polycyclic pigments (slene-based, indigo-based, perylene-based, perinone-based, phthalone-based, dioxazine-based, quinacridone-based, isoindolinone-based, diketopyrrolopyrrole-based pigments) The manufactured mill base has good fluidity and storage stability.

[0050]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. In the examples, all "parts" indicate parts by weight.

(Production Example 1: Intermediate 1 (PCL FA1
Synthesis of 0) 116 parts of hydroxyethyl acrylate, ε in a 2 liter glass reaction flask equipped with stirrer, Dimroth condenser, thermometer and air inlet tube.
-1140 parts of caprolactone, 0.012 parts of monobutyltin oxide and 1.3 parts of methylhydroquinone were added and reacted at 100 ° C for 10 hours until the residual ε-caprolactone was 1% or less.

(Production Example 2: Intermediate 2 (PCL FA1
Synthesis of 5)) 116 parts of hydroxyethyl acrylate in a 2 liter glass reaction flask equipped with a stirrer, Dimroth condenser, thermometer, and air introduction tube.
1710 parts of ε-caprolactone, 0.018 part of monobutyltin oxide and 1.8 parts of methylhydroquinone were added, and the reaction was carried out at 100 ° C for 10 hours until the remaining ε-caprolactone was 1% or less.

(Production Example 3: Intermediate 3 (PCL FA2
Synthesis of 0)) 116 parts of hydroxyethyl acrylate in a 3 liter glass reaction flask equipped with a stirrer, Dimroth condenser, thermometer, and air introduction tube,
2280 parts of ε-caprolactone, 0.025 part of monobutyltin oxide and 2.5 parts of methylhydroquinone were added, and the reaction was carried out at 100 ° C for 10 hours until the remaining ε-caprolactone was 1% or less.

(Production Example 4: Intermediate 4 (PCL FM1
Synthesis of 5)) Hydroxyethyl methacrylate 130 in a 3 liter glass reaction flask equipped with stirrer, Dimroth condenser, thermometer, and air inlet tube.
Parts, 1710 parts of ε-caprolactone, 0.020 part of monobutyltin oxide and 2.0 parts of methylhydroquinone were added, and the mixture was reacted at 100 ° C. for 10 hours until the remaining ε-caprolactone was 1% or less.

(Production Example 5: Intermediate 5 (PCL FA20
Synthesis of 00-30)) Hydroxyethyl acrylate 1 in a 3 liter glass reaction flask equipped with stirrer, Dimroth condenser, thermometer, and air inlet tube.
16 parts, ε-caprolactone 1400 parts, 4-methylcaprolactone 600 parts, monobutyltin oxide 0.
021 parts and 2.1 parts of methylhydroquinone were added, and the mixture was reacted at 100 ° C. for 10 hours until the total amount of remaining ε-caprolactone and 4-methylcaprolactone was 1% or less.

(Production Example 6: Intermediate 6 (PCL FA20
Synthesis of 00-20)) Hydroxyethyl acrylate 1 in a 3 liter glass reaction flask equipped with stirrer, Dimroth condenser, thermometer, and air inlet tube.
16 parts, ε-caprolactone 1600 parts, 4-methylcaprolactone 400 parts, monobutyltin oxide 0.
021 parts and 2.1 parts of methylhydroquinone were added, and the mixture was reacted at 100 ° C. for 10 hours until the total amount of remaining ε-caprolactone and 4-methylcaprolactone was 1% or less.

(Production Example 7: Synthesis of Intermediate 7) 116 parts of caproic acid and 1400 of ε-caprolactone were placed in a 3 liter glass reaction flask equipped with a stirrer, Dimroth condenser, thermometer, and nitrogen inlet tube. Part, 600 parts of 12-hydroxystearic acid and 0.05 part of tetrabutyl titanate were added and reacted at 190 ° C. for 14 hours. The product was a viscous liquid with an acid value of 28 mg KOH / g. Next, the above polyester was cooled to 80 ° C., 1 part of triphenylphosphine as a catalyst was added and dissolved,
Next, 142 parts of glycidyl methacrylate was added dropwise and reacted until the acid value became 1 mgKOH / g.

Example 1 Synthesis of Dispersant 1 900 parts of Intermediate 1 was placed in a 2 liter glass reaction flask equipped with a stirrer, Dimroth condenser, thermometer, and nitrogen inlet tube. Heated to 60 ° C. Then, 100 parts of polyethyleneimine "SP200" (manufactured by Nippon Shokubai Co., Ltd .; molecular weight 10,000) was added and reacted with stirring. It was confirmed by proton NMR that the acrylic group had disappeared, and the reaction was terminated. The reaction product has an amine value of 10
2mgKOH / g wax, hue when melting is APH
It was 130 in A.

Example 2 Synthesis of Dispersant 2 950 parts of Intermediate 1 was placed in a 2 liter glass reaction flask equipped with a stirrer, Dimroth condenser, thermometer, and nitrogen inlet tube. Heated to 60 ° C. Then, 50 parts of polyethyleneimine "SP200" (manufactured by Nippon Shokubai Co., Ltd .; molecular weight 10,000) was added and reacted with stirring. It was confirmed by proton NMR that the acrylic group had disappeared, and the reaction was terminated. The reaction product has an amine value of 55 mg.
KOH / g wax, the hue when melting is APHA 1
It was 20.

(Example 3: Synthesis of Dispersant 3) 900 parts of Intermediate 2 was placed in a 2 liter glass reaction flask equipped with a stirrer, Dimroth condenser, thermometer, and nitrogen introducing tube. Heated to 60 ° C. Then, 100 parts of polyethyleneimine "SP200" (manufactured by Nippon Shokubai Co., Ltd .; molecular weight 10,000) was added and reacted with stirring. It was confirmed by proton NMR that the acrylic group had disappeared, and the reaction was terminated. The reaction product has an amine value of 105.
With wax of mgKOH / g, the hue when melting is APHA
Was 130.

Example 4 Synthesis of Dispersant 4 950 parts of Intermediate 2 was placed in a 2 liter glass reaction flask equipped with a stirrer, Dimroth condenser, thermometer, and nitrogen inlet tube. Heated to 60 ° C. Then, 50 parts of polyethyleneimine "SP200" (manufactured by Nippon Shokubai Co., Ltd .; molecular weight 10,000) was added and reacted with stirring. It was confirmed by proton NMR that the acrylic group had disappeared, and the reaction was terminated. The reaction product has an amine value of 54 mg.
KOH / g wax, the hue when melting is APHA 1
It was 20.

Example 5 Synthesis of Dispersant 5 950 parts of Intermediate 3 was placed in a 2 liter glass reaction flask equipped with a stirrer, Dimroth condenser, thermometer, and nitrogen introducing tube. Heated to 60 ° C. Then, 50 parts of polyethyleneimine "SP200" (manufactured by Nippon Shokubai Co., Ltd .; molecular weight 10,000) was added and reacted with stirring. It was confirmed by proton NMR that the acrylic group had disappeared, and the reaction was terminated. The reaction product has an amine value of 55 mg.
KOH / g wax, the hue when melting is APHA 1
It was 90.

Example 6 Synthesis of Dispersant 6 900 parts of Intermediate 2 was placed in a 2 liter glass reaction flask equipped with a stirrer, Dimroth condenser, thermometer, and nitrogen inlet tube. Heated to 60 ° C. Then, 100 parts of polyethyleneimine "SP018" (manufactured by Nippon Shokubai Co., Ltd .; molecular weight 1,800) was added and reacted with stirring. It was confirmed by proton NMR that the acrylic group had disappeared, and the reaction was terminated. The reaction product has an amine value of 104 m
With gKOH / g wax, the hue when melted was 200 for APHA.

Example 7 Synthesis of Dispersant 7 950 parts of Intermediate 2 was placed in a 2 liter glass reaction flask equipped with a stirrer, Dimroth condenser, thermometer, and nitrogen introducing tube. Heated to 60 ° C. Then, with stirring, 50 parts of polyethyleneimine "SP018" (manufactured by Nippon Shokubai Co., Ltd .; molecular weight 1800) was added and reacted.
It was confirmed by proton NMR that the acrylic group had disappeared, and the reaction was terminated. The reaction product has an amine value of 55 mg KO.
H / g wax with a hue of 180 when melted
Met.

Example 8 Synthesis of Dispersant 8 900 parts of Intermediate 4 was placed in a 2 liter glass reaction flask equipped with a stirrer, Dimroth condenser, thermometer, and nitrogen introducing tube. Heated to 60 ° C. Then, 100 parts of polyethyleneimine "SP018" (manufactured by Nippon Shokubai Co., Ltd .; molecular weight 1800) was added and reacted with stirring. It was confirmed by proton NMR that the methacrylic group had disappeared, and the reaction was terminated. The reaction product has an amine value of 100.
With wax of mgKOH / g, the hue when melting is APHA
Was 150.

Example 9 Synthesis of Dispersant 9 900 parts of Intermediate 5 was placed in a 2 liter glass reaction flask equipped with a stirrer, Dimroth condenser, thermometer, and nitrogen introducing tube. Heated to 60 ° C. Then, 100 parts of polyethyleneimine "SP200" (manufactured by Nippon Shokubai Co., Ltd .; molecular weight 10,000) was added and reacted with stirring. It was confirmed by proton NMR that the acrylic group had disappeared, and the reaction was terminated. The reaction product has an amine value of 102.
Viscous liquid of mgKOH / g, hue when melting is APH
It was 120 in A.

Example 10 Synthesis of Dispersant 10 900 parts of Intermediate 6 was placed in a 2 liter glass reaction flask equipped with a stirrer, Dimroth condenser, thermometer, and nitrogen introducing tube. Heated to 60 ° C. Then, 100 parts of polyethyleneimine "SP018" (manufactured by Nippon Shokubai Co., Ltd .; molecular weight 1,800) was added and reacted with stirring. It was confirmed by proton NMR that the acrylic group had disappeared, and the reaction was terminated. The reaction product has an amine value of 104.
Viscous liquid of mgKOH / g, hue when melting is APH
It was 180 in A.

Example 11: Synthesis of Dispersant 11 900 parts of Intermediate 7 was placed in a 2 liter glass reaction flask equipped with a stirrer, Dimroth condenser, thermometer, and nitrogen introducing tube. Heated to 60 ° C. Then, 100 parts of polyethyleneimine "SP200" (manufactured by Nippon Shokubai Co., Ltd .; molecular weight 10000) was added and reacted with stirring. It was confirmed by proton NMR that the acrylic group had disappeared, and the reaction was terminated. The reaction product has an amine value of 99.
With wax of mgKOH / g, the hue when melting is APHA
Was 250.

Example 12 Synthesis of Dispersant 12 950 parts of Intermediate 4 was placed in a 2 liter glass reaction flask equipped with a stirrer, Dimroth condenser, thermometer, and nitrogen introducing tube. 200 parts of xylene was added and melt | dissolved, and it heated at 40 degreeC. Then, while stirring, 50 parts of polyethyleneimine "SP200" (manufactured by Nippon Shokubai Co., Ltd .; molecular weight 10,000) was added and reacted to obtain proton NMR.
Thus, it was confirmed that the acrylic group had disappeared, and the reaction was terminated. To the reaction product, 200 g of THF was added and dissolved with sufficient stirring. Next, 90 parts of dimethyl sulfuric acid was added and mixed well, then heated to 60 ° C. and stirred for 2 hours. Then, the solvent used in the reaction was removed at 80 ° C. under reduced pressure to obtain a solid product.

Comparative Example 1 Synthesis of Dispersant 13 A 2 liter reactor equipped with a condenser, nitrogen inlet tube, stirrer and thermometer was charged with 116 parts caproic acid, 2,000 parts caprolactone monomer and 2 parts tetrabutyl titanate. Preparation,
The reaction was carried out at 185 ° C. for 18 hours under a nitrogen stream. The acid value of the resulting intermediate polycaprolactone was 26 KOHmg /
It was g. A 2-liter reactor equipped with a condenser, a dehydration tube, a nitrogen introduction tube, a stirrer, and a thermometer was charged with 1,000 parts of the above intermediate, and then polyethyleneimine "SP
200 "(manufactured by Nippon Shokubai Co., Ltd .; molecular weight 10,000) was charged with 600 parts of toluene as a dehydrating solvent and reacted at 150 ° C. The amount of dehydrated water is 14c
The reaction was stopped when it became c. The amine value after removing a part of the solvent of the product (toluene solution) was 70 mg KO.
It was H / g. The hue at the time of melting was 500 as APHA. In addition, from the IR spectrum, the absorption of amide group is 16
It was observed at 50,1550 cm ^-1 and it was confirmed that the polyester chain was grafted to polyethyleneimine via an amide bond.

(Example 13: Fluidity test 1) Titanium oxide (Taipaque CR95 manufactured by Ishihara Sangyo: C.I-Pigm)
75 parts of ent White 6), 1 part of Dispersant 1, 7 parts of xylene, 7 parts of butyl cellosolve acetate, and 100 parts of glass beads were dispersed with a disperser (manufactured by Red Devil Co.) for 60 minutes. The dispersion paste shows good flowability, 1
It showed fluidity even after a week.

Example 14 Fluidity Test 2 Carbon Black (Mitsubishi Chemical Co., Ltd. MA-100: CIP)
IGMENT BLACK 7) 20 parts, dispersant 1 4
Part, xylene 38 parts, butyl cellosolve acetate 38
And 100 parts of glass beads were dispersed for 60 minutes by a disperser (manufactured by Red Devil Co.). The dispersed paste showed good fluidity and showed fluidity even after 1 week.

Example 15 Fluidity Test 3 Phthalocyanine Blue (Chromofine Blue 4 manufactured by Dainichi Seika Kogyo Co., Ltd.)
920: C.I. I-Pigment Blue 15: 3)
25 parts, dispersant 1 10 parts, xylene 32.5 parts, butyl cellosolve acetate 32.5 parts, glass beads 10
0 part was dispersed for 60 minutes with a disperser (manufactured by Red Devil). The dispersed paste showed good fluidity and showed fluidity even after 1 week.

(Example 16: Flowability test 4) Titanium oxide (Taipaque CR95 manufactured by Ishihara Sangyo: C.I-Pigm)
ent White 6) 75 parts, Dispersant 2 1 part, xylene 7 parts, butyl cellosolve acetate 7 parts, and glass beads 100 parts were dispersed with a disperser (manufactured by Red Devil Co.) for 60 minutes. The dispersion paste shows good flowability, 1
It showed fluidity even after a week.

(Example 17: Fluidity test 5) Carbon black (Mitsubishi Kasei MA-100: CI Pigment)
nt Black 7) 20 parts, dispersant 2 4 parts, xylene 23 parts, butyl cellosolve acetate 23 parts, and glass beads 100 parts with a disperser (made by Red Devil Co.) 60
Dispersed for minutes. The dispersed paste shows good flowability,
It showed fluidity even after 1 week.

Example 18 Fluidity Test 6 Phthalocyanine Blue (Chromophine Blue 4 manufactured by Dainichi Seika Kogyo Co., Ltd.)
920: C.I. I-Pigment Blue 15: 3)
25 parts, dispersant 2 10 parts, xylene 32.5 parts, butyl cellosolve acetate 32.5 parts, glass beads 10
0 part was dispersed for 60 minutes with a disperser (manufactured by Red Devil). The dispersed paste showed good fluidity and showed fluidity even after 1 week.

(Example 19: Fluidity test 7) Titanium oxide (Taipaque CR95 manufactured by Ishihara Sangyo: C.I-Pigm)
ent White 6) 75 parts, Dispersant 3 1 part, xylene 7 parts, butyl cellosolve acetate 7 parts, and glass beads 100 parts were dispersed for 60 minutes by a disperser (manufactured by Red Devil). The dispersion paste shows good flowability, 1
It showed fluidity even after a week.

(Example 20: Fluidity test 8) Carbon black (Mitsubishi Kasei MA-100: CI Pigment)
nt Black 7) 20 parts, dispersant 3 4 parts, xylene 23 parts, butyl cellosolve acetate 23 parts, and glass beads 100 parts with a disperser (manufactured by Red Devil Co.) 60
Dispersed for minutes. The dispersed paste shows good flowability,
It showed fluidity even after 1 week.

(Example 21: Flowability test 9) Phthalocyanine blue (Chromophine blue 4 manufactured by Dainichi Seika Kogyo Co., Ltd.)
920: C.I. I-Pigment Blue 15: 3)
25 parts, 10 parts dispersant 3, 32.5 parts xylene, 32.5 parts butyl cellosolve acetate, 10 glass beads
0 part was dispersed for 60 minutes with a disperser (manufactured by Red Devil). The dispersed paste showed good fluidity and showed fluidity even after 1 week.

(Example 22: Fluidity test 10) Phthalocyanine green (Chromofine green 5310, manufactured by Dainichiseika Kogyo Co., Ltd .: CI Pigment Green)
7) 25 parts, 10 parts of dispersant 7, 65 parts of xylene, and 100 parts of glass beads were used with a disperser (manufactured by Red Devil Co.) 60
Dispersed for minutes. The dispersed paste shows good flowability,
It showed fluidity even after 1 week.

(Example 23: Flowability test 11) Benzimidazolone yellow (Chromofine yellow 2080 manufactured by Dainichiseika Kogyo Co., Ltd .: CI Pigment Yell)
ow154) 45 parts, dispersant 8 5 parts, xylene 50
And 100 parts of glass beads were dispersed for 60 minutes by a disperser (manufactured by Red Devil Co.). The dispersed paste showed good fluidity and showed fluidity even after 1 week.

(Example 24: Fluidity test 12) Yellow iron oxide (manufactured by Titanium Industry Co., Ltd. Mapicoello LLXLO: C.I-
Pigment Yellow 42) 60 parts, dispersant 9
2 parts, xylene 38 parts, and glass beads 100 parts were dispersed for 60 minutes with a disperser (manufactured by Red Devil). The dispersed paste showed good fluidity and showed fluidity even after 1 week.

(Example 25: Flowability test 13) 70 parts of Bengara (CI-Pigment Red 101),
2 parts of the dispersant 10, 14 parts of xylene, 14 parts of butyl cellosolve acetate, and 100 parts of glass beads were dispersed for 60 minutes by a disperser (manufactured by Red Devil Co.). The dispersed paste showed good fluidity and showed fluidity even after 1 week.

(Example 26: Fluidity test 14) Quinacridone (Chromofine red 682, manufactured by Dainichi Seika Kogyo Co., Ltd.)
0: C.I. I-Pigment Violet 19) 40
Parts, 2 parts of dispersant 2, 29 parts of MIBK, 29 parts of butyl cellosolve acetate, and 100 parts of glass beads were dispersed for 60 minutes by a disperser (manufactured by Red Devil Co.). The dispersed paste showed good fluidity and showed fluidity even after 1 week.

(Example 27: Flowability test 15) Brilliant carmine 6B (Shimla Brilliant Carmine 6B 236: CI Pigment manufactured by Dainippon Ink and Chemicals, Inc.)
ent Red 57: 1) 45 parts, dispersant 2 2.5
Parts, 52.75 parts of xylene, and 100 parts of glass beads were dispersed for 60 minutes by a disperser (manufactured by Red Devil Co.). The dispersed paste showed good fluidity and showed fluidity even after 1 week.

(Example 28: Flowability test 16) Disazo yellow (Seika Fast Yellow 2 manufactured by Dainichi Seika Kogyo Co., Ltd.)
300: C.I. I-Pigment Yellow12)
40 parts, 2 parts of dispersant 4, 5 parts of xylene, and 100 parts of glass beads were dispersed for 60 minutes with a disperser (manufactured by Red Devil Co.). The dispersed paste showed good fluidity and showed fluidity even after 1 week.

(Example 29: Fluidity test 17) Carbon black (Degussa FW-200: C.I-Pigm)
ent Black 7) 20 parts, dispersant 5 10 parts,
70 parts of xylene and 100 parts of glass beads were dispersed for 60 minutes by a disperser (manufactured by Red Devil Co.). The dispersed paste showed good fluidity and showed fluidity even after 1 week.

(Example 30: Flowability test 18) Carbon black (Degussa FW-200: C.I-Pigm)
ent Black 7) 20 parts, dispersant 6 10 parts,
70 parts of xylene and 100 parts of glass beads were dispersed for 60 minutes by a disperser (manufactured by Red Devil Co.). The dispersed paste showed good fluidity and showed fluidity even after 1 week.

(Example 31: Fluidity test 19) Carbon black (Degussa FW-200: C.I-Pigm)
ent Black 7) 20 parts, dispersant 9 10 parts,
70 parts of xylene and 100 parts of glass beads were dispersed for 60 minutes by a disperser (manufactured by Red Devil Co.). The dispersed paste showed good fluidity and showed fluidity even after 1 week.

(Example 32: Flowability test 20) Diketopyrrolopyrrole (Ciba Geigy DPP Red BO:
C. 45 parts of I-Pigment Red 254), 3 parts of Dispersant 3, 52 parts of xylene, and 100 parts of glass beads were dispersed for 60 minutes by a disperser (manufactured by Red Devil Co.).
The dispersed paste showed good fluidity and showed fluidity even after 1 week.

(Example 33: Flowability test 21) Carbon black (Degussa FW-200: C.I-Pigm)
ent Black 7) 20 parts, dispersant 7 10 parts,
70 parts of xylene and 100 parts of glass beads were dispersed for 60 minutes by a disperser (manufactured by Red Devil Co.). The dispersed paste showed good fluidity and showed fluidity even after 1 week.

(Example 34: Fluidity test 22) Brilliant carmine 6B (Shimura-Brilliant carmine 6B 236: CI-Pig manufactured by Dainippon Ink and Chemicals, Inc.)
ment Red 57: 1) 45 parts, dispersant 12 2.0 parts, xylene 53.25 parts, glass beads 100
The parts were dispersed for 60 minutes with a disperser (manufactured by Red Devil). The dispersed paste showed good fluidity and showed fluidity even after 1 week.

(Comparative Example 2: Flowability test 23) Carbon black (Degussa FW-200: C.I-Pigme)
nt Black 7) 20 parts, dispersant 12 10 parts,
70 parts of xylene and 100 parts of glass beads were dispersed for 60 minutes by a disperser (manufactured by Red Devil Co.). The dispersed paste showed fluidity immediately after the dispersion, but one week later, it became a paste jelly and the fluidity was lost.

(Comparative Example 3: Fluidity test 24) Carbon black (Degussa FW-200: C.I-Pigme)
nt Black 7) 20 parts, alkyd resin (Dainippon Ink and Chemicals Co., Ltd .: Beckol EZ-3530-80, solvent: xylene, NV 80%) 12.5 parts, xylene 6
7.5 parts and 100 parts of glass beads were dispersed for 60 minutes by a disperser (made by Red Devil Co.). The dispersion paste was gel-like and did not show any fluidity.

(Examples 35 to 36, Comparative Example 4: Coating Film Evaluation Test) The pigment pastes produced in Example 15, Example 31, and Comparative Example 2 were made into paints with the compounding compositions shown in Table 1 to obtain paints. Immediately after preparation and after leaving at low temperature (0 ° C., 3 days), a coating film was prepared (baking condition: 135 ° C., 30 minutes), and surface glossiness was measured (60 ° C.). The results are shown in Table-2.

[0096]

[Table 1]

[0097]

INDUSTRIAL APPLICABILITY As described above, the pigment dispersant of the present invention synthesized by adding the polyamine compound and the polyester compound using the Michael addition reaction is superior to the dispersant grafted with an amide group. It has dispersibility and can be applied to various paints and inks. Further, as is clear from Example 36, the pigment dispersant produced from the lactone having a side chain does not have high crystallinity like caprolactone and does not precipitate in the paint even at a low temperature. Even after being left at a low temperature, the gloss does not decrease, which is extremely effective for paint preparation.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI C08G 63/685 C08G 63/685 73/00 73/00 C09D 11/02 C09D 11/02 167/04 167/04 201/00 201 / 00 (56) Reference JP 61-174939 (JP, A) JP 5-271593 (JP, A) JP 5-177123 (JP, A) JP 1-299632 (JP, A) ) JP-A 63-91130 (JP, A) JP-A 63-20303 (JP, A) JP-A 5-271423 (JP, A) JP-A 63-197529 (JP, A) JP-A 4- 352884 (JP, A) JP-A-7-207012 (JP, A) JP-A-8-10601 (JP, A) JP-A-7-149855 (JP, A) JP-A-8-507960 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09D 17/00 B01F 17/16 B01F 17/38 B01F 17/52 C08G 63/08 C08G 63/685 C08G 73/00 C09D 11/02 C09D 167/04 C09D 201/00

Claims (15)

(57) [Claims] 1. A general formula containing as an essential component a unit having a functional group capable of undergoing a Michael addition reaction with an amino group at a terminal and having a polyester chain formed by ring opening of a lactone compound represented by the general formula (2). A pigment dispersant comprising a polyester compound represented by 1) and an amino group-containing compound obtained by reacting with a polyamine compound. [Chemical 1] 2. The amine value of the amino group-containing compound is 10
The pigment dispersant according to claim 1, which is in a range of from about 500 mgKOH / g. 3. The pigment dispersant according to claim 1, wherein the polyester compound represented by the general formula (1) has an average molecular weight of 100 to 20,000. 4. The molecular weight of the polyamine compound is 100 to 1.
The pigment dispersant according to claim 1, which is in the range of 0,000. 5. The pigment dispersant according to claim 1, wherein the polyamine compound is polyethyleneimine. 6. A pigment dispersant comprising a quaternary ammonium chloride amino group-containing compound obtained by chlorinating a free amino group of the amino group-containing compound according to claim 1. 7. The pigment dispersant according to claim 1, wherein the polyamine compound is polyallylamine. 8. The pigment dispersant according to claim 1, wherein the polyamine compound is polyvinylamine. 9. The pigment dispersant according to claim 1, wherein the unit having a polyester chain formed by ring opening of the lactone compound is ε-caprolactone. 10. A unit having a polyester chain formed by ring opening of a lactone compound is methylcaprolactone, or a unit having methylcaprolactone and ε.
The pigment dispersant according to claim 1, which is obtained by copolymerization of caprolactone. 11. The functional group capable of Michael addition is (meth).
The pigment dispersant according to claim 1, which is an acryloyl group. 12. The pigment dispersant according to claim 1, wherein the polyester compound represented by the general formula (1) is a (meth) acrylic acid ester represented by the general formula (3). [Chemical 2] 13. A dispersion liquid obtained by dispersing fine solids in the pigment dispersant according to claim 2. 14. A coating composition containing the pigment dispersant according to claim 1. 15. A printing ink composition containing the pigment dispersant according to claim 1.