JP3235930B2 - Method for producing pigment dispersant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a dispersant for improving the dispersibility of a pigment in the production of paints and inks, a printing ink containing the dispersant, and a paint composition.

[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 and the like, prevention of color separation,
Various dispersants have been used for the purpose of increasing the gloss of a coating film.

For such a purpose, a dispersant having a structure in which a polyamine compound is combined with a polyester or an acrylic resin is disclosed in JP-A-61-174939, JP-A-63-197529, and JP-A-63-197529. 54-37
No. 082, JP-A-48-79178 and the like are known.

[0004]

Problems to be Solved by the Invention JP-A-54-3708
No. 2, JP-A-48-79178 discloses that a dispersant using a polyester obtained by dehydration-condensation of a long-chain aliphatic hydroxycarboxylic acid such as 12-hydroxystearic acid has a wide dispersing performance for various pigments. Have
High-concentration pigment dispersions have not yet achieved satisfactory performance in terms of fluidity of the dispersions and coloring power of paints and inks. Further, the dispersant having such a structure reduces the adhesion between the coating film and the metal surface in paints and inks applied to metals.

Further, Japanese Patent Application Laid-Open No. 61-174939,
JP-A-63-197529 discloses a dispersant having a polyester chain obtained by ring-opening polymerization of a lactone such as caprolactone with a long-chain carboxylic acid.

However, lactones are generally difficult to be added to carboxylic acids when an ordinary titanium or tin-based catalyst is used, unreacted carboxylic acids remain, and high-molecular-weight lactone homopolymer, Alternatively, a carboxylic acid-modified lactone polymer having a much higher molecular weight than designed is produced. Therefore, in the pigment dispersant, it is difficult to control the molecular weight of the lactone polymer forming the steric repulsion layer, and it is difficult to synthesize a pigment dispersant having a high dispersibility.
In addition, such a high molecular weight lactone polymer has high crystallinity, and when such a dispersant is used in the production of paints and inks, during storage, the dispersant crystallizes in the paint and impairs the appearance of the coating film. Problems arise.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned problems of the prior art, and as a result, since they do not contain a high-molecular-weight lactone homopolymer, they have high compatibility with various vehicles. A structure with excellent pigment dispersing performance that does not crystallize the dispersant in paints for paints or inks, gives an excellent coating appearance, and does not impair the adhesion between the paint and the metal surface. Was found.

That is, the present invention relates to a compound of the formula (I) wherein hydroxycarboxylic acid is used as an initiator.

Embedded image ... (I) << L and m are 1 to 10, n is carbon number 0 to 10,
R ² and R ³ are hydrogen or an aliphatic alkyl group having 1 to 4 carbon atoms. >> A polyalkylene polyamine compound is reacted with a carboxyl group-terminated polylactone compound obtained by ring-opening polymerization of a lactone compound represented by the formula: The method for producing a pigment dispersant described above, the "coating composition comprising a dispersion" and the "printing ink comprising a dispersion".

In the present invention, as a first step, a carboxyl group-terminated polylactone compound obtained by ring-opening polymerization of a lactone compound represented by the above formula (I) using hydroxycarboxylic acid as an initiator is synthesized.

As the hydroxycarboxylic acids that can be used here, aliphatic, aromatic and unsaturated hydroxycarboxylic acids can be used, such as ricinoleic acid, ricinoleic acid, 12-hydroxystearin 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-dimethylolvaleric acid, 2,2-dimethylolpentane Acid, malic acid, tartaric acid, lactic acid, glycolic acid, gluconic acid, hydroxypivalic acid, 11-oxyhexadecanoic acid, 2-oxidedecanoic acid, salicylic acid,
Etc. can be used. As the lactone compound, lactones such as ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, β-propiolactone, and γ-butyrolactone can be used.

These may be used alone or as a mixture.

The molecular weight of the polylactone compound initiated by ring-opening polymerization with hydroxycarboxylic acid is from 100 to 5,000.
And preferably in the range of 500 to 3000. When the molecular weight of the polylactone is 100 or less, a sufficient steric repulsion layer cannot be formed around the pigment,
On the other hand, if the molecular weight is 5,000 or more, the molecular weight of the entire dispersant becomes too large, so that the compatibility with the paint and the vehicle for ink is reduced, and the dispersibility of the pigment is also reduced.

The lactone adduct of hydroxycarboxylic acid is synthesized by charging hydroxycarboxylic acid and lactone into a reactor connected to a dehydrating tube and a condenser, adding a catalyst, and subjecting the lactone to ring-opening polymerization by nitrogen gas stream. I do.

The esterification temperature is from 90 ° C. to 210 ° C.
Preferably, it is performed in the range of 120 ° C to 170 ° C. When the reaction temperature is 90 ° C. or lower, the reaction rate is extremely slow,
In the above, side reactions other than the addition reaction of the lactones, for example, a transesterification reaction and a dehydration condensation reaction are likely to occur, and it is difficult to synthesize a carboxyl group-terminated polylactone having a target molecular weight. Further, at 210 ° C. or higher, the decomposition and coloring of the reaction product are likely to occur.

As the esterification catalyst, tin octylate,
Organic tin compounds such as dibutyltin oxide, dibutyltin laurate, and monobutyltin hydroxybutyl oxide; tin compounds such as stannous oxide and stannous chloride; tetrabutyl titanate, tetraethyl titanate, and tetrapropyl titanate can be used. The amount of the catalyst used is 0.1 PPM to 1000 PPM, preferably 1 PPM to
100 PPM. When the amount of the catalyst is 1000 PPM or more, coloring of the resin becomes intense, which adversely affects the stability of the product.

Conversely, if the amount of the catalyst used is 1 PPM or less, the rate of ring-opening polymerization of lactones becomes extremely slow, which is not preferable. In addition, since the reaction tends to be colored in the presence of air, it is desirable to carry out the reaction in an inert atmosphere such as a nitrogen stream.

Next, as a second step, a polyalkylene polyamine compound is reacted to synthesize a pigment dispersant.

The polyalkylene polyamine used in the present invention preferably has a molecular weight of 100 to 20,000. If the molecular weight is less than 100, the molecular weight of the adsorbed portion of the pigment is too low, so that the effect of using the polyalkylene polyamine compound is not obtained. If the molecular weight is more than 20,000, the molecular weight of the entire pigment dispersant becomes too large. May lead to a meeting of the members or decrease the dispersibility.

Although various compounds can be used as the polyalkylene polyamine, polyethyleneimine is preferred.

The reaction ratio between the carboxyl group-terminated polylactone and the polyalkylene polyamine is preferably such that the molar ratio of the carboxyl group to the amino group is in the range of 1: 1 to 1:99.

In the reaction, a polyalkylene polyamine and a carboxyl-terminated polylactone are charged into a reactor connected to a dehydrating tube and a condenser, and dehydration-condensed in the presence of a suitable dehydrating solvent, for example, toluene or xylene, or under a nitrogen stream. It is synthesized by dehydration condensation. The temperature of the amidation reaction is from 90 ° C to 210 ° C, preferably 1
It is performed in the range of 20 ° C to 170 ° C.

At a temperature of 90 ° C. or lower, the rate of the amidation reaction is extremely slow, and at a temperature of 210 ° C. or higher, the reaction product is liable to be decomposed or colored.

Under mild reaction conditions, that is, a low reaction temperature or a short reaction time, a salt of an amino group and a carboxyl group is formed, and under severe reaction conditions, that is, an amide bond is formed under a high reaction temperature or a long reaction time. You. The synthesized dispersant may contain a mixture of an amide bond, an amino group and a carboxyl group.

The reaction can be carried out in a suitable solvent which does not react with lactones, such as an aromatic solvent such as xylene or toluene, or a ketone solvent such as MIBK or anone. The solvent used in the reaction may be omitted, or may be used as it is.

Examples of the amidation catalyst include organotin compounds such as tin octylate, dibutyltin oxide, dibutyltin laurate, and monobutyltin hydroxybutyl oxide; tin compounds such as stannous oxide and stannous chloride; tetrabutyl titanate; and tetraethyl titanate. And titanium compounds such as tetrapropyl titanate; organic acids such as P-toluenesulfonic acid and methanesulfonic acid; and inorganic acids such as sulfuric acid and phosphoric acid. The amount of catalyst used is 0.
1 PPM to 1000 PPM, preferably 1 PPM to 10
0 PPM. When the amount of the catalyst is 1000 PPM or more, coloring of the resin becomes intense, which adversely affects the stability of the product.

Conversely, if the amount of the catalyst used is 1 PPM or less, the rate of the amidation reaction between the lactone polymer having a carboxyl group terminal and the polyalkylene polyamine compound becomes extremely slow, which is not preferable. In addition, since the reaction tends to be colored in the presence of air, it is desirable to carry out the reaction in an inert atmosphere such as a nitrogen stream.

The pigment dispersant thus synthesized is
The caprolactone end is terminated by a hydroxyl group.
This hydroxyl group reacts with a melamine resin or an isocyanate in a baking step after coating, whereby the pigment dispersant is firmly incorporated as a part of the coating film. Therefore, bleeding or crystallization of the pigment dispersant in the coating film does not occur, and the pigment captured by the pigment dispersant hardly bleeds or re-aggregates the pigment.

Further, by using polycaprolactone having an appropriate molecular weight as a raw material, the present invention can be applied to pigment dispersion using a relatively highly localized solvent such as alcohols.

The above-mentioned pigment dispersants include inorganic pigments such as titanium oxide, zinc oxide, cadmium sulfide, yellow iron oxide, red iron oxide, graphite, carbon black, etc .; phthalocyanines; insoluble azo pigments; azo lake pigments; It has excellent pigment dispersibility for pigments (slen, indigo, perylene, perinone, phthalone, dioxazine, quinacridone, isoindolinone, and diketopyrrolopyrrole pigments). Hereinafter, the pigment dispersant of the present invention will be described with reference to examples, but the present invention is not limited thereto. In the examples, all parts indicate parts by weight.

Example 1 [Intermediate 1] 1365 parts of caprolactone monomer, 135 parts of lactic acid, 0.0075 of stannous chloride were placed in a 2 liter reactor equipped with a condenser, a nitrogen inlet tube, a stirrer, and a thermometer.
The reaction was continued at 170 ° C. under nitrogen flow until the remaining caprolactone monomer became 1% or less. The resulting intermediate has a polycaprolactone OH value of 57.2 KOHm.
g / g and the acid value was 58.0 KOHmg / g.

[Intermediate 2] Condenser, nitrogen inlet tube,
In a 2 liter reactor equipped with a stirrer and a thermometer, 1410 parts of caprolactone monomer, 90 parts of lactic acid and 0.0075 parts of stannous chloride are charged, and the remaining caprolactone monomer is reduced to 1% or less at 170 ° C. under a nitrogen stream. Reacted. The resulting intermediate had a polycaprolactone OH value of 38.0 KOHmg / g and an acid value of 38.5 KOHmg / g.

[Intermediate 3] Condenser, nitrogen inlet tube,
In a 2 liter reactor equipped with a stirrer and a thermometer, 1432.5 parts of caprolactone monomer, 67.5 parts of lactic acid, and 0.0075 part of stannous chloride were charged, and the caprolactone monomer remaining at 170 ° C. under a nitrogen stream was 1%. The reaction was carried out until the following. Intermediate Polycaprolactone O Obtained
The H value was 28.4 KOHmg / g and the acid value was 29.0 KOHmg / g.

[Intermediate 4] Condenser, nitrogen inlet tube,
In a 2 liter reactor equipped with a stirrer and a thermometer, 1191 parts of caprolactone monomer, 309 parts of 12-hydroxystearic acid, and 0.0075 part of stannous chloride were charged, and 1% of the caprolactone monomer remaining at 170 ° C. under a nitrogen stream was 1%. The reaction was carried out until the following. The resulting intermediate has a polycaprolactone OH value of 28.1 KOHmg / g and an acid value of 2
It was 7.9 KOHmg / g.

[Intermediate 5] Condenser, nitrogen inlet tube,
A caprolactone monomer (1443 parts), glycolic acid (57 parts), and stannous chloride (0.0075 part) are charged into a 2 liter reactor equipped with a stirrer and a thermometer, and the caprolactone monomer remaining at 170 ° C. under a nitrogen stream at 170 ° C. becomes 1% or less. Until the reaction. Intermediate Polycaprolactone O Obtained
The H value was 29.5 KOHmg / g and the acid value was 29.9 KOHmg / g.

[Intermediate 6] Condenser, nitrogen inlet tube,
In a 2 liter reactor equipped with a stirrer and a thermometer, 1462 parts of caprolactone monomer, 38 parts of glycolic acid, and 0.0075 part of stannous chloride are charged, and the caprolactone monomer remaining at 170 ° C. under a nitrogen stream becomes 1% or less. Until the reaction. Intermediate Polycaprolactone O Obtained
The H value was 29.5 KOHmg / g and the acid value was 29.9 KOHmg / g.

<Dispersant 1> 1,000 parts of Intermediate 1 was charged into a 2 liter reactor equipped with a condenser, a dehydrating tube, a nitrogen introducing tube, a stirrer, and a thermometer, and then polyethyleneimine (sp-200 manufactured by Nippon Shokubai Kogyo, molecular weight (10000) and 600 cc of toluene as a dehydrating solvent were charged and reacted at 150 ° C. The amount of dehydrated water is 14c
The reaction was stopped when the value reached c. The amine value of the product (toluene solution) after removing part of the solvent was 128.1.
mgKOH / g.

<Dispersant 2> 1000 parts of Intermediate 2 was charged into a 2 liter reactor equipped with a condenser, a dehydrating tube, a nitrogen introducing tube, a stirrer, and a thermometer, and then polyethyleneimine (sp-200 manufactured by Nippon Shokubai Kogyo, molecular weight 10000) and 600 cc of toluene as a dehydrating solvent were charged.
The reaction was performed at 150 ° C. The reaction was stopped when the amount of dehydrated water reached 9 cc. Product (toluene solution)
After removal of some of the solvent, the amine value was 89 mgKOH / g.

<Dispersant 3> 1000 parts of Intermediate 3 was charged into a 2 liter reactor equipped with a condenser, a dehydrating tube, a nitrogen introducing tube, a stirrer, and a thermometer, and then polyethyleneimine (sp-200 manufactured by Nippon Shokubai Kogyo, molecular weight 10000), and 600 cc of toluene as a dehydrating solvent were charged.
The reaction was performed at 150 ° C. The reaction was stopped when the amount of dehydrated water reached 7 cc. Product (toluene solution)
After removing some of the solvent, the amine value was 68 mgKOH / g.

<Dispersant 4> 1,000 parts of Intermediate 1 was charged into a 2 liter reactor equipped with a condenser, a dehydrating tube, a nitrogen introducing tube, a stirrer, and a thermometer, and then polyethyleneimine (Nippon Shokubai Kogyo sp-200, molecular weight (10000) and 600 cc of toluene as a dehydrating solvent were charged and reacted at 150 ° C. The amount of dehydrated water is 14c
The reaction was stopped when the value reached c. The amine value of the product (toluene solution) after removing a part of the solvent is 231 mg KO
H / g.

<Dispersant 5> 1000 parts of Intermediate 2 was charged into a 2 liter reactor equipped with a condenser, a dehydrating tube, a nitrogen introducing tube, a stirrer, and a thermometer, and then polyethyleneimine (sp-200 manufactured by Nippon Shokubai Kogyo, molecular weight (10000) and 600 cc of toluene as a dehydrating solvent were charged and reacted at 150 ° C. The amount of dehydrated water is 9.5
When the reaction reached cc, the reaction was stopped. The amine value of the product (toluene solution) after removing a portion of the solvent was 177 mg.
KOH / g.

<Dispersant 6> 1000 parts of Intermediate 3 was charged into a 2 liter reactor equipped with a condenser, a dehydrating tube, a nitrogen introducing tube, a stirrer, and a thermometer, and then polyethyleneimine (Nippon Shokubai Kogyo sp-200, molecular weight (10000) and 600 cc of toluene as a dehydrating solvent were charged and reacted at 150 ° C. 7cc of dehydrated water
When it became, the reaction was stopped. The amine value of the product (toluene solution) after removing a part of the solvent was 149 mgKOH /
g.

<Dispersant 7> 1000 parts of Intermediate 4 was charged into a 2 liter reactor equipped with a condenser, a dehydrating tube, a nitrogen introducing tube, a stirrer, and a thermometer, and then polyethyleneimine (Nippon Shokubai Kogyo sp-200, molecular weight (10000) was reacted at 120 ° C. The amine value of the product was 115 mg KOH / g.

<Dispersant 8> 1000 parts of Intermediate 5 was charged into a 2 liter reactor equipped with a condenser, a dehydrating tube, a nitrogen introducing tube, a stirrer, and a thermometer, and then polyethyleneimine (Nippon Shokubai Kogyo sp-200, molecular weight (10000) was charged and reacted at 120 ° C. The amine value of the product was 122 mg KOH / g.

<Dispersant 9> 1000 parts of Intermediate 5 was charged into a 2 liter reactor equipped with a condenser, a dehydrating tube, a nitrogen introducing tube, a stirrer, and a thermometer, and then polyethyleneimine (sp-200 manufactured by Nippon Shokubai Kogyo, molecular weight (10000) was charged and reacted at 120 ° C. The amine value of the product was 52 mg KOH / g.

<Dispersant 10> 1000 parts of Intermediate 6 was charged into a 2 liter reactor equipped with a condenser, a dehydrating tube, a nitrogen introducing tube, a stirrer, and a thermometer, and then polyethyleneimine (Nippon Shokubai Kogyo sp-200, molecular weight 10000)
Was charged and reacted at 120 ° C. The amine value of the product was 37 mg KOH / g.

<Dispersant 11> 1000 parts of Intermediate 5 was charged into a 2 liter reactor equipped with a condenser, a dehydrating tube, a nitrogen introducing tube, a stirrer, and a thermometer, and then polyethyleneimine (sp-018, manufactured by Nippon Shokubai Kogyo, molecular weight 1800) was charged and reacted at 120 ° C. The amine value of the product was 49 mg KOH / g.

<Dispersant 12> 1000 parts of the intermediate 5 was charged into a 2 liter reactor equipped with a condenser, a dehydrating tube, a nitrogen introducing tube, a stirrer, and a thermometer, and then polyethyleneimine (sp-003 manufactured by Nippon Shokubai Kogyo, molecular weight 300) to 7
7 parts were charged and reacted at 120 ° C. The amine value of the product was 45 mg KOH / g.

<Dispersant 13> 520 parts of a dispersant was dissolved in 100 CC of tetrahydrofuran, and 5 parts of dimethyl sulfuric acid was added and reacted. After completion of the reaction, the solvent is removed and dispersant 13
I got

<Application Example 1> Titanium oxide (Taipe CR95 manufactured by Ishihara Sangyo Co., Ltd .: CI-Pigment White)
e 6) 70 parts, dispersant 11 parts, xylene 14.5 parts,
14.5 parts of butyl cellosolve acetate and 100 parts of glass beads were dispersed with a disperser (manufactured by Red Devil Co.) over 30 minutes. The dispersion paste exhibited good fluidity and showed fluidity even after one week.

<Application Example 2> Carbon black (Mitsubishi Kasei MA-100: CI-Pigment Black)
7) 50 parts, a dispersant, 14 parts, xylene, 23 parts, butyl cellosolve acetate, 23 parts, and 100 parts of glass beads were dispersed with a dispersing machine (manufactured by Red Devil Co., Ltd.) for 30 minutes. The dispersion paste exhibited good fluidity and showed fluidity even after one week.

<Application Example 3> Phthalocyanine Blue (Chromofine Blue 4920, manufactured by Dainichi Seika Kogyo Co., Ltd .: CI-
Pigment Blue 15: 3) 45 parts, dispersant 1
4 parts, 25.5 parts of xylene, 25.5 parts of butyl cellosolve acetate, and 100 parts of glass beads were dispersed by a dispersing machine (manufactured by Red Devil Co., Ltd.) for one hour. The dispersion paste exhibited good fluidity and showed fluidity even after one week.

<Application Example 4> Titanium oxide (Taipage CR95, manufactured by Ishihara Sangyo Co., Ltd .: CI-Pigment White)
e 6) 70 parts, dispersant 21 parts, xylene 14.5 parts,
14.5 parts of butyl cellosolve acetate and 100 parts of glass beads were dispersed with a disperser (manufactured by Red Devil Co.) over 30 minutes. The dispersion paste exhibited good fluidity and showed fluidity even after one week.

<Application Example 5> Carbon black (Mitsubishi Kasei MA-100: CI-Pigment Black)
7) 50 parts, 24 parts of a dispersant, 23 parts of xylene, 23 parts of butyl cellosolve acetate, and 100 parts of glass beads were dispersed by a dispersing machine (manufactured by Red Devil Co., Ltd.) for 30 minutes.
The dispersion paste exhibited good fluidity and showed fluidity even after one week.

<Application Example 6> Phthalocyanine blue (Chromofine Blue 4920, manufactured by Dainichi Seika Kogyo): CI-
Pigment Blue 15: 3) 45 parts, dispersant 2
4 parts, 25.5 parts of xylene, 25.5 parts of butyl cellosolve acetate, and 100 parts of glass beads were dispersed by a dispersing machine (manufactured by Red Devil Co., Ltd.) for one hour. The dispersion paste exhibited good fluidity and showed fluidity even after one week.

<Application Example 7> Titanium oxide (Taipage CR95 manufactured by Ishihara Sangyo Co., Ltd .: CI-Pigment White)
e 6) 70 parts, dispersant 31 parts, xylene 14.5 parts,
14.5 parts of butyl cellosolve acetate and 100 parts of glass beads were dispersed by a disperser (manufactured by Red Devil Co., Ltd.) for 30 minutes. Dispersed paste shows good fluidity,
After a week, it still showed fluidity.

<Application Example 8> Carbon black (Mitsubishi Kasei MA-100: CI-Pigment Black)
7) 50 parts, 34 parts of a dispersant, 23 parts of xylene, 23 parts of butyl cellosolve acetate, and 100 parts of glass beads were dispersed by a dispersing machine (manufactured by Red Devil Co., Ltd.) for 30 minutes.
The dispersion paste exhibited good fluidity and showed fluidity even after one week.

<Application Example 9> Phthalocyanine Blue (Chromo Fine Blue 4920, manufactured by Dainichi Seika Kogyo): CI-
Pigment Blue 15: 3) 45 parts, dispersant 3
4 parts, 25.5 parts of xylene, 25.5 parts of butyl cellosolve acetate, and 100 parts of glass beads were dispersed by a dispersing machine (manufactured by Red Devil Co., Ltd.) for one hour. The dispersion paste exhibited good fluidity and showed fluidity even after one week.

<Application Example 10> Phthalocyanine Green (Chromo Fine Green 5310 manufactured by Dainichi Seika Kogyo):
C. 45 parts of I-Pigment Green 7), 74 parts of a dispersant, 25.5 parts of xylene, 25.5 parts of butyl cellosolve acetate, and 100 parts of glass beads were dispersed by a dispersing machine (manufactured by Red Devil Co., Ltd.) for one hour. The dispersion paste exhibited good fluidity and showed fluidity even after one week.

<Application Example 11> Benzimidazolone Yellow (Chromo Fine Yellow 208 manufactured by Dainichi Seika Kogyo)
0: C.I. I-Pigment Yellow154) 3
0 parts, 82 parts of dispersant, 34 parts of xylene, 34 parts of butyl cellosolve acetate, and 100 parts of glass beads were dispersed with a dispersing machine (manufactured by Red Devil Co.) over 30 minutes. Dispersed paste shows good fluidity and after one week,
Showed fluidity.

<Application Example 12> Yellow iron oxide (Mapico Yellow LLXLO manufactured by Titanium Industry: CI Pigment)
75 parts of Yellow 42), 91 parts of dispersant, xylene 1
2 parts, 12 parts of butyl cellosolve acetate, and 100 parts of glass beads were dispersed with a disperser (manufactured by Red Devil Co., Ltd.) for 30 minutes. The dispersion paste exhibited good fluidity and showed fluidity even after one week.

<Application Example 13> Benga (C.I-Pig)
men Red 101) 70 parts, dispersant 102 parts,
Xylene 14 parts, butyl cellosolve acetate 14 parts,
100 parts of the glass beads were dispersed with a dispersing machine (manufactured by Red Devil Co., Ltd.) for 30 minutes. The dispersion paste exhibited good fluidity and showed fluidity even after one week.

<Application Example 14> Quinacridone (Chromofine Red 6820 manufactured by Dainichi Seika Kogyo: CI-Pig)
Men's Violet 19) 30 parts, dispersant 23 parts,
MIBK 33.5 parts, butyl cellosolve acetate 3
3.5 parts and 100 parts of glass beads were dispersed with a disperser (manufactured by Red Devil Co.) over 30 minutes. The dispersion paste exhibited good fluidity and showed fluidity even after one week.

<Application Example 15> Brilliant Carmine 6B
(Shimlar Brilliant Carmine 6B 236 manufactured by Dainippon Ink and Chemicals, Inc .: CI Pigment Red)
57: 1) 40 parts, dispersant 134 parts, MIBK 28 parts,
Butyl cellosolve acetate 28 parts, glass beads 10
0 parts were dispersed with a dispersing machine (manufactured by Red Devil Co., Ltd.) for 30 minutes. Dispersed paste shows good fluidity,
Even after one week, it showed fluidity.

<Application Example 16> Disazo Yellow (Seika Fast Yellow 2300 manufactured by Dainichi Seika Kogyo Co., Ltd .: CI-
Pigment Yellow 12) 30 parts, dispersant 8
3 parts, 33.5 parts of MIBK, 33.5 parts of butyl cellosolve acetate, and 100 parts of glass beads were dispersed with a dispersing machine (manufactured by Red Devil Co.) over 30 minutes. The dispersion paste exhibited good fluidity and showed fluidity even after one week.

<Application Example 17> Carbon black (Mitsubishi Kasei MA-100: CI Pigment Blac)
k7) 50 parts, 44 parts of a dispersant, 23 parts of xylene, 23 parts of butyl cellosolve acetate, and 100 parts of glass beads were dispersed with a dispersing machine (manufactured by Red Devil Co.) over 30 minutes. The dispersion paste exhibited good fluidity.

<Application Example 18> Carbon black (Mitsubishi Kasei MA-100: CI-Pigment Blac)
k7) 50 parts, a dispersant 54 parts, xylene 23 parts, butyl cellosolve acetate 23 parts, and glass beads 100 parts were dispersed with a dispersing machine (manufactured by Red Devil Co.) over 30 minutes. The dispersion paste exhibited good fluidity.

<Application Example 19> Carbon black (Mitsubishi Kasei MA-100: CI Pigment Blac)
k7) 50 parts, 64 parts of a dispersant, 23 parts of xylene, 23 parts of butyl cellosolve acetate, and 100 parts of glass beads were dispersed with a dispersing machine (manufactured by Red Devil Co.) over 30 minutes. The dispersion paste exhibited good fluidity.

<Application Example 20> Carbon black (Mitsubishi Kasei MA-100: CI Pigment Blac)
k 7) 50 parts, dispersant 114 parts, xylene 22 parts, butyl cellosolve acetate 23 parts, glass beads 100
The mixture was dispersed with a dispersing machine (manufactured by Red Devil Co., Ltd.) for 30 minutes. The dispersion paste exhibited good fluidity.

<Application Example 21> Carbon black (Mitsubishi Kasei MA-100: CI Pigment Blac)
k 7) 50 parts, dispersant 124 parts, xylene 23 parts, butyl cellosolve acetate 23 parts, glass beads 100
The mixture was dispersed with a dispersing machine (manufactured by Red Devil Co., Ltd.) for 30 minutes. The dispersion paste exhibited good fluidity.

<Intermediate 7: Comparative Example> 92 parts of caproic acid, 1120 parts of caprolactone monomer, and 2 parts of tetrabutyl titanate were charged into a 2 L reactor equipped with a condenser, a nitrogen inlet tube, a stirrer, and a thermometer, and placed under a nitrogen stream. , 18
The reaction was performed at 5 degrees for 18 hours. The acid value of the resulting intermediate polycaprolactone was 38.9 KOHmg / g.

<Dispersant 14: Comparative Example> 1000 parts of Intermediate 7 was charged into a 2 L reactor equipped with a condenser, a dehydrating tube, a nitrogen introducing tube, a stirrer, and a thermometer, and then polyethyleneimine (sp- 200, molecular weight 100
00), 600 cc of toluene as a dehydrating solvent
And reacted at 150 ° C. The reaction was stopped when the amount of dehydrated water reached 14 cc. The amine value of the product (toluene solution) after removing a part of the solvent is 12
It was 8.1 mg KOH / g.

<Application Example 22: Comparative Example> Titanium oxide (Taipage CR95, manufactured by Ishihara Sangyo Co., Ltd .: CI Pigment)
White 6) 65 parts, 141 parts of dispersant, 17 parts of xylene, 17 parts of butyl cellosolve acetate, and 100 parts of glass beads are dispersed in a dispersing machine (manufactured by Red Devil Co., Ltd.) 30
And dispersed. The dispersed paste showed fluidity.

<Application Example 23> Application Example 5 and Application Example 22
The pigment paste produced in the above was made into a paint with the composition shown in Table 1 and left immediately after forming the coating film and at low temperature (0 degree, 3 days)
The subsequent measurement of the surface glossiness (60 degrees) was performed.

Table 1 Composition Paint formulation 1 Paint formulation 2 Alkyd resin * 1) 40 40 Pigment paste (Application example 1) 20 Pigment paste (Application example 12) 20 Solvent xylene 8.6 8.6 Phthylcellosol 10 10 Acetate leveling agent * 2) 0.4 0.4 Melamine resin * 3) Immediately after mixing 10 10 Gloss 96 91 After low temperature test * 4) Gloss 94 70 * 1) Oil-free alkito resin manufactured by Dainippon Ink Co., Ltd.
M6005-60 * 2) Monsanto Modaflow * 3) Dainippon Ink Butylated Melamine Resin Superbecamine J820-60 * 4) Leave at 5 ° C for 10 days. Baking conditions are 150 ° C for 30 minutes.

As described above, it is clear that the pigment dispersant having a carboxyl group-terminated polycaprolactone chain obtained by ring-opening polymerization with hydroxycarboxylic acid has excellent pigment dispersibility. Further, unlike polycaprolactone obtained by ring-opening polymerization with a carboxylic acid, it does not contain a high molecular weight component, and a paint using the same does not cause a decrease in gloss even after being left at a low temperature, and is extremely effective for paint preparation.
(Below)

Claims (12)

(57) [Claims] 1. An aliphatic monohydroxy having 2 to 18 carbon atoms.
Wherein the monocarboxylic acid as an initiator (I) ## STR1 ## ... (I) << L and m are 1 to 10, n is carbon number 0 to 10,
R ² and R ³ are hydrogen or an aliphatic alkyl group having 1 to 4 carbon atoms. >> A polyalkylene polyamine compound is reacted with a carboxyl group-terminated polylactone compound obtained by ring-opening polymerization of a lactone compound represented by the following formula: A method for producing a pigment dispersant. 2. The method for producing a pigment dispersant according to claim 1, wherein the reaction product of the carboxyl group-terminated polylactone compound and the polyalkylene polyamine compound is a salt, an amide, or a mixture thereof depending on the reaction conditions. 3. The method according to claim 1, wherein the carboxyl group- terminated polylactone compound has a molecular weight of 100 to 5,000. 4. The method according to claim 1, wherein the polyalkylene polyamine compound has a molecular weight of 100 to 20,000. 5. The method according to claim 1, wherein the polyalkylene polyamine compound is polyethylene imine. 6. The method for producing a pigment dispersant according to claim 2 , wherein the free amino group is converted to a quaternary ammonium salt. 7. The method according to claim 1, wherein the lactone compound is ε-caprolactone. 8. An aliphatic monohydroxy having 2 to 18 carbon atoms.
The formula (I) according to claim 1, wherein a monocarboxylic acid is used as an initiator.
Obtained by ring-opening polymerization of a lactone compound represented by
Polyalkylene to ruboxyl-terminated polylactone compound
A pigment dispersant obtained by reacting a polyamine compound. 9. A pigment is dispersed in the pigment dispersant according to claim 8.
A dispersion liquid that is dispersed. 10. A coating composition comprising the dispersion according to claim 9 . 11. A printing ink comprising the dispersion according to claim 9 . 12. aliphatic mono hydroxy <br/> shea monocarboxylic acids having 2 to 18 carbon atoms, ricinoleic acid, 12-hydroxystearic acid, castor oil fatty acid, hydrogenated castor oil fatty acid,
The method according to claim 1, wherein the compound is any one or more selected from δ-hydroxyvaleric acid, ε-hydroxycaproic acid, lactic acid, glycolic acid, hydroxypivalic acid, 11-oxyhexadecanoic acid, and 2-oxidedecanoic acid. A method for producing a pigment dispersant.