JPH0665521A - Pigment dispersant, pigment composition, and pigment dispersion - Google Patents

Abstract

PURPOSE:To enable excellent dispersion into a wide variety of resins and to improve flowability, coating film gloss, brightness, and storage stability. CONSTITUTION:A pigment dispersant comprising an acrylic polymer having a saturated aliphatic polycyclic group and either a group derived from an organic pigment or a heterocyclic ring; a pigment composition containing the dispersant; and a pigment dispersion. The dispersant is produced, for example, by polymerizing isobornyl (meth)acrylate with an acrylic monomer having a carboxy or other reactive group and reacting the resulting acrylic polymer having a saturated alicyclic group with an organic pigment having a reactive group, e.g. aminomethylquinacridone or a heterocyclic compound having a reactive group, e.g. 5-aminophthalimide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dispersant and a pigment composition used for dispersing a pigment in paints, printing inks and the like, and a pigment dispersion containing the dispersant and the pigment composition.

[0002]

2. Description of the Related Art In paints, printing inks, etc., the dispersibility and dispersion stability of organic pigments often pose problems. For example,
In the manufacturing process of the organic pigment, the crystal particles of the pigment cause strong agglomeration, and strong shearing force is required to disperse them. Therefore, a large amount of energy is required to produce a pigment dispersion such as paint or ink. Furthermore, the affinity between the organic pigment and the dispersion medium is often insufficient, causing problems such as pigment flocculation and increased viscosity of paints and inks, poor leveling, insufficient gloss, and reduced coloring strength. ing. Further, the pigment particles dispersed by strong shearing force re-aggregate with time, resulting in problems such as thickening during storage, insufficient gloss when using a paint or ink after storage, and reduction in coloring power. .

For the purpose of solving such problems, various pigment dispersants have been conventionally used, for example, (1) a polymer dispersant comprising an acrylic resin containing a heterocyclic group having a basic nitrogen atom in the ring ( JP-A-1-16429),
(2) A pigment dispersant composed of an acrylic resin containing a quaternary ammonium salt of a tertiary amino group and sulfonated copper phthalocyanine (JP-A-47-8785) has been proposed.

[0004]

However, since the above-mentioned pigment dispersant (1) has insufficient affinity with the pigment, and the pigment dispersant (2) has insufficient affinity with the resin, they are dispersed. The use of a pigment composition as an agent has a drawback that the fluidity, coating gloss, and image clarity are insufficient depending on the type of pigment or resin. In addition, coatings, inks, etc. made of these pigment compositions have poor storage stability and have a decrease in fluidity during storage, and coating films coated with these and printed surfaces have a reduced gloss. have.

[0005]

In view of these circumstances, the inventors of the present invention have conducted diligent research to solve the drawbacks of the prior art, and as a result, a saturated alicyclic ring (A) composed of two or more rings and an organic dye atom. The pigment dispersant characterized by comprising an acrylic polymer (I) having a group or a heterocycle (B) can be used not only in a wide range of resins but also in fluidity and dispersibility represented by gloss, They found that the dispersion stability represented by storage stability is excellent, and completed the present invention.

That is, the present invention is characterized by comprising an acrylic polymer (I) having a saturated alicyclic ring (A) having two or more rings and an organic dye atomic group or a heterocyclic ring (B). A pigment dispersant, a pigment composition characterized by containing a pigment dispersant comprising the acrylic polymer (I) and an organic pigment, and further comprising the above pigment dispersant or pigment composition. The present invention provides a pigment dispersion characterized by the above.

The pigment dispersant of the present invention may be any acrylic polymer having a saturated alicyclic ring (A) consisting of two or more rings and an organic dye atomic group or heterocyclic ring (B). Although not particularly limited, for example, from two or more rings having at least one reactive group selected from the group consisting of a carboxyl group, a sulfonic acid group, a primary amino group, a secondary amino group, a hydroxyl group and an epoxy group. A saturated alicyclic ring-containing acrylic polymer (hereinafter, abbreviated as saturated alicyclic ring-containing acrylic polymer), and a carboxyl group, a sulfonic acid group, a primary amino group, a secondary amino group, a hydroxyl group and an epoxy group. Organic dyes having one or more reactive groups selected from the group (hereinafter abbreviated as reactive group-containing organic dyes) or heterocyclic compounds (hereinafter abbreviated as reactive heterocyclic compounds),
Examples thereof include those obtained by reacting in a non-reactive solvent in the presence or absence of a catalyst so as to form an amide bond, an ester bond or an amino bond.

Examples of the saturated alicyclic ring-containing acrylic polymer include, for example, a saturated alicyclic ring-containing acrylic monomer having two or more rings (hereinafter abbreviated as saturated alicyclic ring-containing acrylic monomer), a carboxyl group and a sulfonic acid group. , An acrylic monomer having at least one reactive group selected from the group consisting of a primary amino group, a secondary amino group, a hydroxyl group and an epoxy group (hereinafter abbreviated as reactive group-containing acrylic monomer).
And, if necessary, those obtained by polymerizing other monomers capable of polymerizing with these monomers in a solvent, among them, saturated alicyclic ring-containing acrylic monomers and acrylic monomers having a carboxyl group or an epoxy group. What is polymerized as an essential component is preferable. Instead of the saturated alicyclic ring-containing acrylic monomer and the reactive group-containing acrylic monomer, an acrylic monomer having both a saturated alicyclic ring and a reactive group may be used.

Examples of the saturated alicyclic ring-containing acrylic monomer used here include isobornyl acrylate, isobornyl methacrylate, bornyl acrylate, bornyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicycloacrylate. Examples thereof include pentenyl, dicyclopentenyl methacrylate, adamantyl acrylate, adamantyl methacrylate, dimethyladamantyl acrylate, dimethyladamantyl methacrylate, etc. Among them, isobornyl acrylate and isobornyl methacrylate are preferable.

As the acrylic monomer having a carboxyalkyl group, for example, acrylic acid, methacrylic acid,
Examples thereof include crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid, and among them, acrylic acid and methacrylic acid are preferable.

Examples of the acrylic monomer having a sulfonic acid group include butyl acrylamide sulfonic acid. Examples of the acrylic monomer having a primary or secondary amino group include aminoethyl acrylate,
Aminopropyl acrylate, Methylaminoethyl acrylate, Methylaminopropyl acrylate, Ethylaminoethyl acrylate, Ethylaminopropyl acrylate,
Acrylic aminoethylamide, acrylic acid aminopropylamide, acrylic acid methylaminoethylamide, acrylic acid methylaminopropylamide, acrylic acid ethylaminoethylamide, acrylic acid ethylaminopropylamide, methacrylic acid amide, aminoethyl methacrylate, methacrylic acid Aminopropyl acid, methylaminoethyl methacrylate, methylaminopropyl methacrylate,
Ethylaminoethyl methacrylate, ethylaminopropyl methacrylate, aminoethylamide methacrylate, aminopropylamide methacrylate, methylaminoethylamide methacrylate, methylaminopropylmethacrylate methacrylate, ethylaminoethylamide methacrylate, ethylaminopropyl methacrylate Examples include amides.

Examples of the acrylic monomer having a hydroxyl group include hydroxymethyl acrylate and acrylic acid-
Examples thereof include 2-hydroxyethyl, 2-hydroxypropyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N-methylol acrylamide and allyl alcohol.

Examples of the acrylic monomer having an epoxy group include glycidyl acrylate and glycidyl methacrylate. Examples of the other monomer include methyl acrylate, ethyl acrylate, isopropyl acrylate, -n-propyl acrylate, -n-butyl acrylate, -t-butyl acrylate, 2-ethylhexyl acrylate, acrylate- n-octyl, lauryl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, -n-propyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -t-butyl methacrylate, methacryl (Meth) acrylic acid ester such as 2-ethylhexyl acid acid, n-octyl methacrylate, lauryl methacrylate, stearyl methacrylate, tridecyl methacrylate, benzyl methacrylate; addition reaction of stearic acid and glycidyl methacrylate Etc. Addition reaction product of oil fatty acid and (meth) acrylic acid ester monomer having oxirane structure; addition reaction product of oxirane compound containing alkyl group having 3 or more carbon atoms and (meth) acrylic acid; styrene, α -Methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,
Styrene-based monomers such as p-tert-butylstyrene; itaconic acid esters such as benzyl itaconate; maleic acid esters such as dimethyl maleate;
Examples include fumaric acid esters such as dimethyl fumarate; acrylonitrile, methacrylonitrile, vinyl acetate and the like.

The saturated alicyclic ring-containing acrylic polymer can be obtained, for example, by heating and aging the above-mentioned various monomers, the polymerization initiator and the non-reactive solvent in a reaction vessel, and the composition of the various monomers used here. The ratio is usually 5 to 90% by weight, preferably 30 to 70% by weight, when the total amount of the monomers is 100% by weight.
% By weight, 0.1 to 50 reactive group-containing acrylic monomer
% By weight, preferably 10 to 30% by weight, other monomers in the range 0 to 80% by weight, preferably 0 to 30% by weight.

The reaction conditions vary depending on the polymerization initiator and the solvent, but the reaction temperature is 30 to 150 ° C., preferably 60 to 120 ° C., and the reaction time is 30 minutes to 20 hours, preferably 2 hours to 5 hours. .

As the non-reactive solvent, for example, hexane,
Aliphatic hydrocarbon solvents such as mineral spirits; aromatic hydrocarbon solvents such as benzene, toluene, xylene; ester solvents such as butyl acetate; alcohol solvents such as methanol, butanol; dimethylformamide, dimethyl Examples include aprotic polar solvents such as sulfoxide, N-methylpyrrolidone and pyridine. You may use these solvents together.

Examples of the polymerization initiator include t-butylperoxybenzoate, di-t-butylperoxide,
Peroxides such as cumene peroxide, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, etc .; azobisisobutyl nitrile, azobis-
Examples thereof include azo compounds such as 2,4-dimethylvaleronitrile and azobiscyclohexanecarbonitrile.

As the saturated alicyclic ring-containing acrylic polymer used in the present invention, those which are soluble in the non-reactive solvent used in the reaction are preferable, and those having a number average molecular weight of 500 to 30,000 are usually used, but especially 1000 to Those of 10,000 are particularly preferable.

The reactive group-containing organic dyes include at least one reactive group selected from the group consisting of a carboxyl group, a sulfonic acid group, a primary amino group, a secondary amino group, a hydroxyl group and an epoxy group. 1 or more, for example, a dye or pigment originally having one or more reactive groups, or one obtained by introducing one or more reactive groups into a dye or pigment, 1
Organic dyes such as dyes and pigments synthesized by using a raw material having one or more reactive groups can be mentioned.

Examples of the organic dye used here include quinacridone, quinacridonequinone, dioxazine, phthalocyanine, anthrapyrimidine, ansanthrone, indanthrone, flavanthrone, perylene, and perinone.
Examples thereof include diketopyrrolopyrrole, quinophthalone, anthraquinone, thioindigo, benzimidazolone, and azo dyes and pigments.

The method for obtaining the reactive group-containing organic dye is not particularly limited, but, for example, a method for obtaining an organic dye having a carboxyl group by introducing a phthalimide group into the organic dye by a conventional method and then subjecting it to alkali hydrolysis, Furthermore, a method of acid-hydrolyzing this to obtain an organic dye having an aminomethyl group, a method of obtaining an organic dye having a sulfonic acid group by dissolving the organic dye in sulfuric acid and heating to sulfonate, -O- Group, -COO- group, -CON
A method for obtaining an organic dye having a hydroxyl group by diazotizing a hydroxyalkylaniline which may have an H-group or a -SO2NH- group by a conventional method, and then performing a coupling reaction with a coupler of various organic dyes. Alkyl aniline is converted into acetoacetic acid anilide derivative by a conventional method, and then a method for obtaining an organic dye having a hydroxyl group by coupling reaction with a coupler of various organic dyes, an organic dye having an amino group is reacted with epichlorohydrin to form an epoxy group. Examples thereof include a method of obtaining the organic dye.

The reactive group-containing heterocyclic compounds include carboxyl group, sulfonic acid group, primary amino group,
Any heterocyclic compound having at least one reactive group selected from the group consisting of a secondary amino group, a hydroxyl group and an epoxy group may be used. For example, anthraquinone-2-carboxylic acid,
N-phthalimidoacetic acid, anthraquinone-2-sulfonic acid, 1-aminoanthraquinone, 2-aminoanthraquinone, 4-aminophthalimide, 5-aminobenzimidazolone, 1-hydroxyanthraquinone, 2-hydroxymethylanthraquinone, N-hydroxyphthalimide, Examples thereof include N-hydroxyethyl phthalimide, 2-hydroxy-9-fluorenone, N- (2,3-epoxypropyl) phthalimide and the like.

The method for producing the pigment dispersant of the present invention includes:
For example, (1) polymerizing a saturated alicyclic ring-containing acrylic polymer in a non-reactive solvent and then forming an amide bond, an ester bond or an amino bond with the polymer, a reactive group-containing organic dye or a reactive group A method of performing esterification, amidation or amination reaction with a group-containing heterocyclic compound in the presence or absence of a catalyst under reflux for 10 minutes to 5 hours, and then removing the solvent, (2) reactivity A group-containing acrylic monomer and a reactive group-containing organic dye or a reactive group-containing heterocyclic compound capable of forming an amide bond, an ester bond, or an amino bond with the group-containing acrylic monomer are esterified, amidated or Examples include a method of performing an amination reaction, and then polymerizing the reaction product with a saturated alicyclic ring-containing acrylic monomer and, if necessary, another monomer, and then removing the solvent.

In this case, the equivalent ratio of the reactive group in the organic dye or the heterocyclic compound to the reactive group in the acrylic polymer or monomer is usually 0.01: 1 to 2: 1, preferably 0. It is used so as to be 0.5 to 1: 1. In addition, the non-reactive solvent is usually used in an amount of 1 to 10 times by weight the acrylic polymer.

Examples of the catalyst include tin, lead,
An organometallic compound such as manganese or a metal chelate compound,
Examples thereof include metal acyl compounds of fatty acids. The method for preparing the pigment composition of the present invention includes, for example, a method of mixing an organic pigment and a pigment dispersant with a Henschel mixer, an air mixer, a V-type blender, a ball mill, an attritor, a two-roll, a three-roll, an additive. A method in which an organic pigment and a pigment dispersant are kneaded and ground by a pressure kneader, an aqueous dispersion of a wet pigment or a powder pigment is mixed with an organic solvent solution of the pigment dispersant to form an emulsion, and the pigment dispersant on the pigment surface. The method of depositing, followed by filtration, washing with water, and drying may be mentioned. The amount of the pigment dispersant used in this case is usually 0.1 to 30 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the organic pigment.

The organic pigment used here is not particularly limited, but for example, a quinacridone pigment, a quinacridone quinone pigment, a dioxazine pigment, a phthalocyanine pigment, an anthrapyrimidine pigment, an anthanthrone pigment, an indanthrone pigment. , Flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments,
Examples thereof include thioindigo pigments, benzimidazolone pigments and azo pigments.

The pigment dispersant of the present invention is dispersed in a pigment and a resin varnish, and the pigment composition is dispersed in a resin varnish to prepare a pigment dispersion such as paint or printing ink. The paints and printing inks are excellent in fluidity, coating gloss, image clarity and storage stability.

[0028]

EXAMPLES The present invention will now be specifically described with reference to production examples, examples and comparative examples, but the present invention is not limited to the following examples. In the following, all parts and percentages are by weight unless otherwise specified.

Production Example 1 (Production of Reactive Group-Containing Organic Dyes) 300 parts of 98% concentrated sulfuric acid was poured into a reaction vessel, 25 parts of quinacridone was added at 20 to 30 ° C., and the mixture was stirred at 40 ° C. for 2 hours. 13 parts of phthalimide and 2.6 parts of paraformaldehyde were added and reacted at 50-60 ° C for 3 hours. The reaction solution was poured into 5000 parts of ice water, filtered, washed with water and dried to obtain 37 parts of phthalimidomethylquinacridone.

Next, 400 parts of water and 37 parts of phthalimidomethylquinacridone were put into a reaction vessel, 73 parts of 20% aqueous sodium hydroxide solution was injected, and the mixture was stirred at 85 ° C. for 4 hours, and then 105 parts of 20% hydrochloric acid. Is injected at 85 ° C for 4
Stir for hours. After cooling to room temperature, 45 parts of a 20% aqueous sodium hydroxide solution was added, followed by filtration, washing with water and drying to obtain 27.9 parts of aminomethylquinacridone.

Example 1 In a reaction vessel equipped with a thermometer, a condenser and a stirrer, butyl acrylate 3.8 parts methacrylic acid 2.6 parts isobornyl acrylate 6.2 parts t-butyl peroxybenzoate 0.3 parts 30.0 parts of xylene was charged and the reaction was carried out at 120 ° C. for 3 hours while stirring to obtain a saturated alicyclic ring-containing acrylic polymer having a number average molecular weight of 6000. Aminomethylquinacridone 5 in the polymer
Parts and 50 parts of xylene are added with stirring, the temperature is gradually raised, the reaction is carried out under reflux for 3 hours, and then the solvent is distilled off under reduced pressure at 70 ° C. to obtain 16.2 parts of the red pigment dispersant. (1) was obtained.

0.5 part of the pigment dispersant (1) and a quinacridone pigment (CI Pigment Violet 19, hereinafter the same) 9.5
Parts were mixed with a Henschel mixer to obtain a pigment composition, which was then used as a melamine alkyd resin for paint [manufactured by Dainippon Ink and Chemicals, Inc .; Beckosol 57-1362 / Beckosol EY-3002-65 / Super Beckamine L. -117-60 solids weight ratio = 5.6 / 1.4 / 3
To a pigment content of 9% (20 PHR) to prepare a melamine alkyd paint.

Then, the above pigment composition was mixed with an acrylic resin for coating [manufactured by Dainippon Ink and Chemicals, Inc .; mixture of Acridic 47-712 / Super Beckamine L-117-60 in solid content weight ratio = 4/1]. ] The pigment content is 5.6%
It was blended so as to be (15 PHR) to prepare an acrylic paint.

Viscosity (temperature 20 ° C., rotation speed 6 rpm and 60 rpm) by B type viscometer and gloss of coating film (60 °)
Of the measurement results immediately after dispersion and after storage at 25 ° C for 30 days-
As shown in Table 1, these paints were excellent in fluidity, coating film clarity, and gloss, and were also good in storage stability.

Comparative Example 1 A quinacridone pigment was prepared in the same manner as in Example 1 without using the pigment dispersant (1).
A paint was prepared in the same manner as in Example 1 except that 0 part was used,
Then, a paint test was conducted in the same manner. The results are shown in Table 1, and the fluidity of the coating material was poor, and the surface of the coating film was rough and had low gloss.

Comparative Example 2 (Dispersant according to Example 11 of JP-A-1-16429) Isobornyl acrylate 6.2 parts Butyl acrylate 9.0 in a reaction vessel equipped with a thermometer, a cooling tube and a stirrer. Parts Styrene 3.1 parts Acrylonitrile 1.1 parts Vinylimidazole 4.7 parts t-Butylperoxybenzoate 0.5 parts Xylene 30.0 parts Charged and reacted with stirring at 120 ° C. for 3 hours, basic nitrogen A polymer (2 ′) having a heterocyclic group having an atom in the ring was obtained.

A pigment composition and a melamine were prepared in the same manner as in Example 1 except that 0.5 part of the pigment dispersant (2 ') (as a solid content) was used instead of 0.5 part of the pigment dispersant (1). An alkyd paint and an acrylic paint were prepared, and then the viscosity and gloss were measured in the same manner. The results are shown in Table 1. These paints were inferior in the fluidity, the clearness of the coating film, the gloss, and the storage stability as compared with the paint of Example 1 above.

Example 2 In a reaction vessel equipped with a thermometer, a cooling tube and a stirrer, methyl methacrylate 3.0 parts styrene 1.6 parts glycidyl methacrylate 2.1 parts isobornyl methacrylate 16.7 parts azobisisobutyrate. Ronitrile 0.4 parts Xylene 30.0 parts were charged, and the reaction was carried out at 80 ° C. for 3 hours while stirring,
A saturated alicycle-containing acrylic polymer having a number average molecular weight of 5000 was obtained. 5 parts of aminomethylquinacridone and 50 parts of xylene were added to the polymer while stirring, and the temperature was gradually raised to 8
After reacting at 0 ° C for 3 hours, the solvent was distilled off at 70 ° C under reduced pressure to obtain 27.4 parts of a red pigment dispersant (2).

A pigment composition and a melamine alkyd paint were prepared in the same manner as in Example 1 except that the pigment dispersant (2) was used in place of the pigment dispersant (1), and then the viscosity and gloss were similarly obtained. Was measured. The results are shown in Table 1, and the coating composition was excellent in fluidity, coating film clarity and gloss, and was also good in storage stability.

Example 3 In a reaction vessel equipped with a thermometer, a condenser and a stirrer, styrene 3.1 parts acrylic acid 1.8 parts isobornyl acrylate 7.3 parts azobisisobutyronitrile 0.4 parts xylene 30 0.0 part was charged and the reaction was carried out at 80 ° C. for 3 hours while stirring.
A saturated alicyclic ring-containing acrylic polymer having a number average molecular weight of 7,000 was obtained. Aminomethylquinacridone (5 parts) and xylene (50 parts) were added to the polymer while stirring, the temperature was gradually raised, and the reaction was carried out under reflux for 3 hours. Then, the solvent was distilled off under reduced pressure at 70 ° C. 2.8 parts of red pigment dispersant (3) was obtained.

A pigment composition and a melamine alkyd-type coating material were prepared in the same manner as in Example 1 except that the pigment dispersant (3) was used in place of the pigment dispersant (1), and then the viscosity and gloss were similarly obtained. Was measured. The results are shown in Table 1, and the coating composition was excellent in fluidity, coating film clarity and gloss, and was also good in storage stability.

Example 4 In a reaction vessel equipped with a thermometer, a cooling tube and a stirrer, 3.5 parts of methyl methacrylate 2.2 parts of methacrylic acid isobornyl methacrylate 6.7 parts azobisisobutyronitrile 0.4 parts Charge 30.0 parts of xylene, react with stirring at 80 ° C. for 3 hours,
A saturated alicyclic ring-containing acrylic polymer having a number average molecular weight of 5,500 was obtained. Aminomethylquinacridone (5 parts) and xylene (50 parts) were added to the polymer while stirring, the temperature was gradually raised, the reaction was carried out under reflux for 3 hours, and then the solvent was distilled off at 70 ° C. under reduced pressure. 0.0 part of a red pigment dispersant (4) was obtained.

A pigment composition and a melamine alkyd paint were prepared in the same manner as in Example 1 except that the pigment dispersant (4) was used in place of the pigment dispersant (1), and then the viscosity and the gloss were similarly obtained. Was measured. The results are shown in Table 1, and the coating composition was excellent in fluidity, coating film clarity and gloss, and was also good in storage stability.

Example 5 In a reaction vessel equipped with a thermometer, a condenser and a stirrer, butyl acrylate 3.8 parts methacrylic acid 2.6 parts dicyclopentanyl acrylate 6.2 parts azobisisobutyronitrile 0 4 parts xylene 30.0 parts were charged, and the reaction was carried out at 80 ° C. for 3 hours while stirring,
A saturated alicycle-containing acrylic polymer having a number average molecular weight of 4000 was obtained. Aminomethylquinacridone (5 parts) and xylene (50 parts) were added to the polymer while stirring, the temperature was gradually raised, the reaction was carried out under reflux for 3 hours, and then the solvent was distilled off at 70 ° C. under reduced pressure. 2 parts of red pigment dispersant (5) was obtained.

A pigment composition and a melamine alkyd paint were prepared in the same manner as in Example 1 except that the pigment dispersant (5) was used in place of the pigment dispersant (1). Was measured. The results are shown in Table 1, and the coating composition was excellent in fluidity, coating film clarity and gloss, and was also good in storage stability.

Example 6 In a reaction vessel equipped with a thermometer, a cooling tube and a stirrer, methyl methacrylate 3.5 parts acrylic acid 2.2 parts adamantyl acrylate 6.2 parts azobisisobutyronitrile 0.4 parts Charge 30.0 parts of xylene, react with stirring at 80 ° C. for 3 hours,
A saturated alicyclic ring-containing acrylic polymer having a number average molecular weight of 5,500 was obtained. Aminomethylquinacridone (5 parts) and xylene (50 parts) were added to the polymer while stirring, the temperature was gradually raised, and the reaction was carried out under reflux for 3 hours. Then, the solvent was distilled off under reduced pressure at 70 ° C. 0.5 part of a red pigment dispersant (6) was obtained.

A pigment composition and a melamine alkyd-based paint were prepared in the same manner as in Example 1 except that the pigment dispersant (6) was used in place of the pigment dispersant (1), and then the viscosity and gloss were similarly obtained. Was measured. The results are shown in Table 1, and the coating composition was excellent in fluidity, coating film clarity and gloss, and was also good in storage stability.

Example 7 Cyclohexyl methacrylate 5.0 parts Acrylic acid 2.2 parts Isobornyl methacrylate 6.7 parts Azobisisobutyronitrile 0.4 parts in a reaction vessel equipped with a thermometer, a condenser and a stirrer. Charge 30.0 parts of xylene, react with stirring at 80 ° C. for 3 hours,
A saturated alicyclic ring-containing acrylic polymer having a number average molecular weight of 6,500 was obtained. Aminomethyldimethylquinacridone (5 parts) and xylene (50 parts) were added to the polymer while stirring, the temperature was gradually raised, and the reaction was carried out under reflux for 3 hours, then at 70 ° C. under reduced pressure.
The solvent was distilled off with 17.4 parts of a red pigment dispersant (7).
Got

A pigment composition and a melamine alkyd paint were prepared in the same manner as in Example 1 except that the pigment dispersant (7) was used in place of the pigment dispersant (1). Was measured. The results are shown in Table 1, and the coating composition was excellent in fluidity, coating film clarity and gloss, and was also good in storage stability.

Example 8 In a reaction vessel equipped with a thermometer, a cooling tube and a stirrer, vinyltoluene 3.5 parts methacrylic acid 2.6 parts isobornyl acrylate 6.2 parts azobisisobutyronitrile 0.4 parts xylene Charge 30.0 parts, react with stirring at 80 ° C. for 3 hours,
A saturated alicyclic ring-containing acrylic polymer having a number average molecular weight of 6000 was obtained. Aminomethyldichloroquinacridone (5 parts) and xylene (50 parts) were added to the polymer while stirring, the temperature was gradually raised, and the reaction was carried out under reflux for 3 hours, then at 70 ° C. under reduced pressure.
The solvent was distilled off with 15.9 parts of a red pigment dispersant (8).
Got

A pigment composition and a melamine alkyd paint were prepared in the same manner as in Example 1 except that the pigment dispersant (8) was used in place of the pigment dispersant (1). Was measured. The results are shown in Table 1, and the coating composition was excellent in fluidity, coating film clarity and gloss, and was also good in storage stability.

Example 9 In a reaction vessel equipped with a thermometer, a condenser and a stirrer, butyl acrylate 3.8 parts methacrylic acid 2.6 parts isobornyl acrylate 6.2 parts azobisisobutyronitrile 0.4 parts Charge 30.0 parts of xylene, react with stirring at 80 ° C. for 3 hours,
A saturated alicycle-containing acrylic polymer having a number average molecular weight of 6000 was obtained. 5-aminobenzimidazolone 2 was added to the polymer.
And 50 parts of xylene are added with stirring, the temperature is gradually raised, and the reaction is carried out under reflux for 3 hours. Then, the solvent is distilled off at 70 ° C. under reduced pressure to disperse 13.4 parts of a pale yellow pigment. Agent (9)
Got

A pigment composition and a melamine alkyd paint were prepared in the same manner as in Example 1 except that the pigment dispersant (9) was used in place of the pigment dispersant (1), and then the viscosity and gloss of the pigment composition were similarly obtained. Was measured. The results are shown in Table 1, and the coating composition was excellent in fluidity, coating film clarity and gloss, and was also good in storage stability.

Example 10 In a reaction vessel equipped with a thermometer, a condenser and a stirrer, butyl acrylate 3.8 parts methacrylic acid 2.6 parts isobornyl acrylate 6.2 parts azobisisobutyronitrile 0.4 parts Charge 30.0 parts of xylene, react with stirring at 80 ° C. for 3 hours,
A saturated alicycle-containing acrylic polymer having a number average molecular weight of 6000 was obtained. 2-Aminophthalimide (2 parts) and xylene (50 parts) were added to the polymer with stirring, the temperature was gradually raised, the reaction was carried out under reflux for 3 hours, and then the solvent was distilled off at 70 ° C. under reduced pressure. 13.4 parts of pale yellow pigment dispersant (10) was obtained.

A pigment composition and a melamine alkyd paint were prepared in the same manner as in Example 1 except that the pigment dispersant (10) was used in place of the pigment dispersant (1), and then the viscosity and gloss were similarly obtained. Was measured. The results are shown in Table 1, and the coating composition was excellent in fluidity, coating film clarity and gloss, and was also good in storage stability.

Example 11 In a reaction vessel equipped with a thermometer, a condenser and a stirrer, butyl acrylate 3.8 parts methacrylic acid 2.6 parts isobornyl acrylate 6.2 parts azobisisobutyronitrile 0.4 parts Charge 30.0 parts of xylene, react with stirring at 80 ° C. for 3 hours,
A saturated alicyclic ring-containing acrylic polymer having a number average molecular weight of 6000 was obtained. Diaminoanthraquinonyl 12.5 was added to the polymer.
And 50 parts of xylene are added with stirring, the temperature is gradually raised, the reaction is carried out under reflux for 3 hours, and then the solvent is distilled off at 70 ° C. under reduced pressure to give 23.1 parts of a red pigment dispersant. (11)
Got

After 0.5 part of the pigment dispersant (11) and 9.5 parts of diaminoanthraquinonyl pigment (CI Pigment Red 177, the same applies below) were mixed by a Henschel mixer to obtain a pigment composition, this was carried out. A melamine alkyd resin for paint similar to that used in Example 1 has a pigment content of 4.5%.
The mixture was blended to give (10 PHR), a paint was prepared, and then the viscosity and gloss were measured in the same manner. The results are shown in Table-1
As shown, the paint was excellent in fluidity, clearness of the coating film, gloss, and storage stability.

Comparative Example 3 A melamine alkyd paint was prepared in the same manner as in Example 11 except that the pigment dispersant (11) was not used and 10 parts of diaminoanthraquinonyl pigment was used. The gloss was measured. The results are shown in Table 1, and the fluidity of the coating material was poor, and the surface of the coating film was rough and had low gloss.

Example 12 In a reaction vessel equipped with a thermometer, a cooling tube and a stirrer, butyl acrylate 3.8 parts methacrylic acid 2.6 parts isobornyl acrylate 6.2 parts azobisisobutyronitrile 0.4 parts Charge 30.0 parts of xylene, react with stirring at 80 ° C. for 3 hours,
A saturated alicyclic ring-containing acrylic polymer having a number average molecular weight of 6,500 was obtained. 11.6 parts of aminomethylperylene and 50 parts of xylene were added to the polymer while stirring, and the temperature was gradually raised,
After reacting for 3 hours under reflux, the solvent was distilled off at 70 ° C. under reduced pressure to obtain 22.3 parts of a red pigment dispersant (12).

0.5 part of the pigment dispersant (12) and 9.5 parts of perylene pigment (CIPigment Red 178, the same applies hereinafter) were mixed by a Henschel mixer to obtain a pigment composition, which was used in Example 1. The same melamine alkyd resin for paint as that used was blended so that the pigment content was 9% (20 PHR) to prepare a paint, and then the viscosity and gloss were measured in the same manner. The results are shown in Table 1, and the coating composition was excellent in fluidity, coating image clarity, and gloss, and was also excellent in storage stability.

Comparative Example 4 10% perylene pigment was prepared without using the pigment dispersant (12).
A paint was prepared in the same manner as in Example 10 except that the parts were used.
Then, the viscosity and gloss were measured in the same manner. The results are shown in Table 1, and the fluidity of the coating material was poor, and the surface of the coating film was rough and had low gloss.

Example 13 In a reaction vessel equipped with a thermometer, a cooling tube and a stirrer, butyl acrylate 3.8 parts methacrylic acid 2.6 parts isobornyl acrylate 6.2 parts azobisisobutyronitrile 0.4 parts Charge 30.0 parts of xylene, react with stirring at 80 ° C. for 3 hours,
A saturated alicyclic ring-containing acrylic polymer having a number average molecular weight of 6,500 was obtained. Aminomethyldiketopyrrolopyrrole (6.3 parts) and xylene (50 parts) were added to the polymer with stirring, the temperature was gradually raised, and the reaction was carried out under reflux for 3 hours, followed by reducing the pressure to 7
The solvent was distilled off at 0 ° C. to obtain 17.4 parts of a red pigment dispersant (13).

0.5 parts of the pigment dispersant (13) and 9.5 parts of diketopyrrolopyrrole pigment (CIPIgment Red 254, the same applies below) were mixed by a Henschel mixer to obtain a pigment composition, which was then carried out. A melamine alkyd resin for paint similar to that used in Example 1 had a pigment content of 9% (20 PH
R) to prepare a paint. The results of the paint test are shown in Table 1. The paint was excellent in fluidity, coating clarity, gloss, and storage stability.

Comparative Example 5 A coating composition was prepared in the same manner as in Example 13 except that 10 parts of the diketopyrrolopyrrole pigment was used without using the pigment dispersant (13), and then the viscosity and gloss of the coating composition were similarly prepared. The measurement was performed. The results are shown in Table-1, but the fluidity of the coating is poor,
The surface of the coating film was rough and had low gloss.

Example 14 In a reaction vessel equipped with a thermometer, a condenser and a stirrer, butyl acrylate 3.8 parts methacrylic acid 2.6 parts isobornyl acrylate 6.2 parts azobisisobutyronitrile 0.4 parts Charge 30.0 parts of xylene, react with stirring at 80 ° C. for 3 hours,
A saturated alicyclic ring-containing acrylic polymer having a number average molecular weight of 6000 was obtained. Aminomethyldioxazine (9.3 parts) and xylene (50 parts) were added to the polymer while stirring, the temperature was gradually raised, the reaction was carried out under reflux for 3 hours, and then the solvent was distilled off at 70 ° C. under reduced pressure. 20.1 parts of purple pigment dispersant (14)
Got

0.5 parts of the pigment dispersant (14) and a dioxazine pigment (CI Pigment Violet 23, the same applies hereinafter)
After 9.5 parts were mixed with a Henschel mixer to obtain a pigment composition, this was added to a melamine alkyd resin for paint similar to that used in Example 1 with a pigment content of 4.5% (10 PH).
R) was blended to prepare a paint, and then the viscosity and gloss were measured in the same manner. The results are shown in Table-1, and the paint is excellent in fluidity, coating film clarity, and gloss.
Storage stability was also good.

Example 15 In a reaction vessel equipped with a thermometer, a cooling tube and a stirrer, butyl acrylate 3.8 parts methacrylic acid 2.6 parts isobornyl acrylate 6.2 parts azobisisobutyronitrile 0.4 parts Charge 30.0 parts of xylene, react with stirring at 80 ° C. for 3 hours,
A saturated alicyclic ring-containing acrylic polymer having a number average molecular weight of 6000 was obtained. 2-Aminoanthraquinone (2 parts) and xylene (50 parts) were added to the polymer while stirring, the temperature was gradually raised, the reaction was carried out under reflux for 3 hours, and then the solvent was distilled off at 70 ° C. under reduced pressure. 13.4 parts of pale yellow pigment dispersant (15) was obtained. After 0.5 part of the pigment dispersant (15) and 9.5 parts of dioxazine pigment (CI Pigment Violet 23, the same applies below) were mixed with a Henschel mixer to obtain a pigment composition, this was used in Example 1. The same melamine alkyd resin for paint was blended so that the pigment content was 4.5% (10 PHR) to prepare a paint, and then the viscosity and gloss were measured in the same manner. The results are shown in Table 1, and the coating composition was excellent in fluidity, coating image clarity, and gloss, and was also excellent in storage stability.

Comparative Example 6 A paint was prepared in the same manner as in Example 14 except that 10 parts of the dioxazine pigment was used without using the pigment dispersant (14), and then the viscosity and gloss were measured in the same manner. It was The results are shown in Table 1, and the fluidity of the coating material was poor, and the surface of the coating film was rough and had low gloss.

Example 16 In a reaction vessel equipped with a thermometer, a cooling tube and a stirrer, , And react at 80 ° C for 3 hours with stirring,
A saturated alicyclic ring-containing acrylic polymer having a number average molecular weight of 7,000 was obtained. Copper phthalocyanine sulfonic acid 6.3 was added to the polymer.
And 50 parts of xylene were added with stirring, the temperature was gradually raised, and the reaction was carried out under reflux for 10 hours while removing water flowing out. Then, the solvent was distilled off at 70 ° C. under reduced pressure to
8.6 parts of blue pigment dispersant (16) were obtained.

0.5 parts of the pigment dispersant (16) and a copper phthalocyanine pigment (CI Pigment Blue 15, hereinafter the same).
After 9.5 parts were mixed with a Henschel mixer to obtain a pigment composition, this was added to a melamine alkyd resin for paint similar to that used in Example 1 with a pigment content of 4.5% (10 PH).
R) was blended to prepare a paint, and then the viscosity and gloss were measured in the same manner. The results are shown in Table-2. The paint is excellent in fluidity, clearness of coating film, and gloss,
Storage stability was also good.

Comparative Example 7 A paint was prepared in the same manner as in Example 16 except that 10 parts of copper phthalocyanine pigment was used without using the pigment dispersant (16), and then the viscosity and gloss were measured in the same manner. went.
The results are shown in Table 2, and the fluidity of the coating material was poor, and the surface of the coating film was rough and had low gloss.

Comparative Example 8 (according to Example 7 of JP-A-47-8785) A reaction vessel equipped with a thermometer, a cooling tube and a stirrer was used. Was charged, the mixture was reacted under reflux with stirring for 1 hour, and then the mixture was cooled. 2-Ethylhexyl acrylate 18.5 parts Azobisisobutyronitrile 0.3 parts Acetone 1.3 parts n-Propanol 2.0 parts are added to this mixture, and the mixture is reacted under reflux with stirring for 10 hours. Then, n-propanol was removed by azeotropic distillation together with xylene, and the mixture was diluted with 65 parts of xylene.

A 10N sodium hydroxide solution was added to a mixture of 86 parts of a copper phthalocyanine sulfonic acid aqueous paste having a weight concentration of 18% and 392 parts of water with sufficient stirring to adjust the pH to 9 to obtain a solution.

The polymer reaction solution was added to this copper phthalocyanine sulfonate solution, and the mixture was heated under reflux for 1 hour, and then water was removed by azeotropic distillation to remove a heavy solvent containing a solubilizing group, an ionic group and a salt-forming component. A combined pigment dispersant (8 ') was obtained.

A pigment composition and a melamine were prepared in the same manner as in Example 16 except that 0.5 part (as a solid content) of the pigment dispersant (8 ') was used instead of 0.5 part of the pigment dispersant (16). An alkyd paint was prepared and then viscosity and gloss were measured in the same manner. The results are shown in Table-2. These paints were clearly inferior to the paint of Example 16 in fluidity, clearness of coating film and gloss.

Example 17 In a reaction vessel equipped with a thermometer, a cooling tube and a stirrer, , And react at 80 ° C for 3 hours with stirring,
A saturated alicyclic ring-containing acrylic polymer having a number average molecular weight of 6000 was obtained. To the polymer, 7.2 parts of Watching Red and 50 parts of xylene were added with stirring, the temperature was gradually raised, the reaction was carried out under reflux for 10 hours, and then the solvent was distilled off at 70 ° C. under reduced pressure. , 19.4 parts of a red pigment dispersant (17) was obtained.

After 0.5 part of the pigment dispersant (17) and 9.5 parts of the Watching Red pigment were mixed by a Henschel mixer to obtain a pigment composition, the urethane varnish for gravure ink had a pigment content of 5% ( 60PHR) to make an ink, and use a B-type viscometer to measure the viscosity (temperature 2
0 ° C., rotation speed 6 rpm and 60 rpm) were measured.
Further, the gloss of the coating film spread on the acetate film was measured with a 0.15 mm bar coater. The results are shown in Table-2. The ink had excellent fluidity, coating film gloss, and storage stability.

Comparative Example 9 An ink was prepared in the same manner as in Example 14 except that 10 parts of Watching Red pigment (CIPigmentRed 48-3, hereinafter the same) was used without using the pigment dispersant (17). Similarly, the viscosity and the gloss of the coating film were measured. The results are shown in Table 2, but the fluidity of the ink was poor and the gloss was also poor.

Example 18 A pigment composition containing 0.5 part of the pigment dispersant (16) obtained in Example 16 and 9.5 parts of a copper phthalocyanine pigment was added to a urethane varnish for gravure ink to obtain a pigment content of 5%.
(60PHR) blend to make ink, B
The viscosity (temperature: 20 ° C., rotation speed: 6 rpm and 60 rpm) was measured by a mold viscometer. Further, the gloss of the coating film spread on the acetate film was measured with a 0.15 mm bar coater. The results are shown in Table-2. The ink had excellent fluidity, coating film gloss, and storage stability.

Comparative Example 10 An ink was prepared in the same manner as in Example 18 except that 10 parts of copper phthalocyanine pigment was used without using the pigment dispersant (16), and then the viscosity and coating film of the ink were similarly prepared. Was measured for gloss. The results are shown in Table 2, but the fluidity of the ink was poor and the gloss was also poor.

[0081]

[Table 1] * 1) Paint 1: Melamine alkyd paint * 2) Paint 2: Acrylic paint * 3) After storage at 25 ° C for 30 days

[0082]

[Table 2] * 1) Paint 1: Melamine alkyd paint * 3) After storage at 25 ° C for 30 days

[0083]

[Table 3] * 1) Paint 1: Melamine alkyd paint * 3) After storage at 25 ° C for 30 days * 4) Ink 1: Urethane gravure ink

[0084]

The pigment dispersant of the present invention can be produced relatively easily, and the pigment composition using the pigment dispersant is an excellent pigment for a wide range of resins such as melamine alkyd resins and acrylic resins. Shows dispersibility. Furthermore, the pigment dispersion containing the pigment dispersant or the pigment composition of the present invention is excellent in fluidity, coating gloss, image clarity and storage stability.

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Claims (10)

[Claims] 1. A pigment dispersant comprising an acrylic polymer (I) having a saturated alicyclic ring (A) having two or more rings and an organic dye atomic group or a heterocycle (B). 2. The acrylic polymer (I) comprises an acrylic polymer having a saturated alicyclic ring (A) consisting of two or more rings and an organic dye atomic group or a heterocycle (B), an amide bond or an ester. The pigment dispersant according to claim 1, which is a polymer having a structure bonded by a bond or an amino bond. 3. The acrylic polymer (I) comprises one or more reactive groups selected from the group consisting of a carboxyl group, a hydroxyl group and an epoxy group and a saturated alicyclic ring (A) consisting of two or more rings. The acrylic polymer and the organic dye or heterocycle (B) having at least one reactive group selected from the group consisting of a sulfonic acid group or a primary amino group, which are amide bond, ester bond or The pigment dispersant according to claim 1, which is obtained by reacting with a combination that forms an amino bond. 4. The pigment dispersant according to claim 1, 2 or 3, wherein the saturated alicyclic ring (A) consisting of two or more rings is a bicyclo group. 5. A pigment composition comprising the pigment dispersant according to claim 1 and an organic pigment. 6. The acrylic polymer (I) comprises an acrylic polymer having a saturated alicyclic ring (A) consisting of two or more rings and an organic dye atomic group or a heterocycle (B), an amide bond or an ester. The pigment composition according to claim 5, which is a polymer having a structure bonded by a bond or an amino bond. 7. The acrylic polymer (I) comprises one or more reactive groups selected from the group consisting of a carboxyl group, a hydroxyl group and an epoxy group and a saturated alicyclic ring (A) consisting of two or more rings. The acrylic polymer and the organic dye or heterocycle (B) having at least one reactive group selected from the group consisting of a sulfonic acid group or a primary amino group, which are amide bond, ester bond or The pigment composition according to claim 5, which is obtained by reacting with a combination that forms an amino bond. 8. The pigment composition according to claim 5, 6 or 7, wherein the saturated alicyclic ring (A) consisting of two or more rings is a bicyclo group. 9. A pigment dispersion comprising the pigment dispersant according to any one of claims 1 to 4 and an organic pigment. 10. A pigment dispersion comprising the pigment composition according to any one of claims 5 to 8.