JP3379587B2 - Dispersants, dispersions and paints - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly versatile dispersant which is also effective as a difficult-to-disperse pigment, a dispersant containing this dispersant, and a paint comprising this dispersant.

[0002]

2. Description of the Related Art Introducing a solid such as a pigment into a liquid medium requires a strong mechanical force, which is very costly and time consuming. This is due substantially to the wettability of the solid by the surrounding medium as well as its affinity for the medium. In order to reduce the dispersion due to such mechanical force, a dispersant that facilitates dispersion is widely used.

Examples of these dispersants include Japanese Patent Publication No. 2-
Urethane dispersants and the like described in, for example, 19844 are cited. This urethane dispersant has an average of 2.5-
Produced by reacting a polyisocyanate having 6 functional groups with a polyester having one hydroxyl group, further reacting with polyethylene glycol, and then reacting with a nitrogen atom-containing basic compound having —NH ₂ group. To be done. These are used directly as a pigment or in a relatively small amount added to a medium.

[0004]

However, there are known pigments which are still difficult to disperse even when the above urethane dispersant is used. These are so-called hardly dispersed pigments, and specific examples thereof include Irgadine DPP-RED-B.
Examples thereof include O and carbon black.

The object of the present invention is to provide a dispersant which is effective for the above-mentioned difficult-to-disperse pigments and has high versatility, a dispersion containing this dispersant, and a paint comprising this dispersion. That is.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an isocyanate compound is a hydroxy compound having a tertiary amino group and an ester bond or an amide bond. It has an added structure but does not have a polymerized structure of ethylenically unsaturated double bonds.
With have urethane compound, effective for flame dispersed pigment, and found that the versatile urethane dispersant is obtained, and have completed the present invention.

Namely, the present invention includes a tertiary amino group, a hydroxy compound having an ester bond or amide bond (A), has a structure formed by adding the isocyanate compound (B) ethylenically unsaturated double Bond polymerization structure
A dispersant characterized by comprising a compound (Z) which does not have an active ingredient, a dispersion characterized by containing a dye / pigment and the dispersant, and a dispersion comprising the dispersion. Regarding the paint to do.

The hydroxy compound (A) used in the present invention may be any compound having a tertiary amino group and an ester bond or an amide bond, for example, an amino alcohol having a tertiary amino group and / or a tertiary amino group. A compound having a structure obtained by subjecting a polyamine (a ₁ ) having an amino group and a primary or secondary amino group and a carboxylic acid (a ₂ ) having a lactone or a hydroxyl group to an esterification reaction or an amidation reaction, An amino alcohol and / or polyamine (a ₁ ) and a polycarboxylic acid (a ₃ ) are subjected to an esterification reaction or an amidation reaction to form a compound having a tertiary amino group and a hydroxyl group, and then a polyol or an epoxy compound (a ₄ ) and a compound having a structure formed by reaction with the above. However, when a polycarboxylic acid ester is used as the polycarboxylic acid in the above, the subsequent reaction is limited to the reaction with the polyol.

The hydroxy compound (A) has a total of 2 ester bonds and / or amide bonds.
Those having at least two are preferable from the viewpoint of improving the dispersibility, and further, polyester compounds having at least two ester bonds in total are more preferable from the viewpoint of improving the dispersibility.

When the hydroxy compound (A) is a polyester compound, its number average molecular weight is 200 to 5,0.
The range of 00 is more preferable from the viewpoint of improving dispersibility. Next, the hydroxy compound (A) used in the present invention
The above raw materials (a ₁ ), (a ₂ ), (a
₃ ) and (a ₄ ) will be described.

Among the above amino alcohols and / or polyamines (a ₁ ), examples of amino alcohol compounds having a tertiary amino group include dimethylaminoethanol, diethylaminoethanol, dibutylaminoethanol, 3-dimethylaminopropanol and 3-diethylamino. Propanol, 3-dimethylamino-2-propanol, N-isobutyldiethanolamine, N-methyldiethanolamine, triethanolamine, N-hydroxyethoxyethylpiperazine, 1-benzyl-3
-Hydroxypyrrolidine, N-methyl-2-hydroxyethylpyrrolidine, N, N-dibenzylethanolamine, 1-benzyl-4-hydroxypiperidine, N-methyl-3-piperidineethanol, N-methyl-3-hydroxypiperidine, N-ethyl-3-hydroxypiperidine, N-methyl-4-hydroxypiperidine, N-
(2-Hydroxyethyl) -morpholine, 1-piperidine ethanol, 4- (2-hydroxyethyl) -piperazine-1-ethanesulfonic acid, 4- (2-hydroxyethyl) -piperazine-1-ethanesulfonic acid sodium salt, N An aliphatic amino alcohol, such as methyl-2-pyrrolidine ethanol,

2-pyridinemethanol, 3-pyridinemethanol, 4-pyridinemethanol, 2,6-pyridinedimethanol, 2-pyridineethanol, 4-pyridineethanol, 6-methyl-2-pyridineethanol, 5
-Ethyl-2-pyridine ethanol, 2- (2-pyridyl) -1,3-propanediol, 2-hydroxymethyl-2- (4-pyridyl) -1,3-propanediol, 2-hydroxypyridine, 3- Hydroxypyridine, 4-hydroxypyridine, 2,3-dihydroxypyridine, 2,6-dihydroxypyridine, 3-hydroxy-6-methylpyridine, 2- (4-pyridyl) -4-
Amino-6-hydroxypyrimidine, 2- (4-pyridyl) -4-hydroxy-6-methylpyrimidine, 2-
A hydroxypyridine such as (4-pyridyl) -4,6-dihydroxypyrimidine,

5- (2-hydroxyethyl) -4-methylthiazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-thiouracil, glyoxal-bis (-2-hydroxyanyl) -4,5- Diamino-6-hydroxy-2-mercaptopyrimidine,
2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1- (2-hydroxyethyl) imidazole, 2-dimethylaminophenol, 3-dimethylaminophenol, 4- Non-pyridine type monocyclic aromatic amino alcohols such as dimethylaminophenol,

8-hydroxyquinaldine, N- (2-
Hydroxyethyl) -phthalimide, 1-hydroxybenzotriazole, 7- (2,3-dihydroxypropyl) -theophylline, 2-hydroxybenzimidazole, 2-quinoxalinol, 3- (2-hydroxyethyl) -indole, allopurinol, Examples thereof include condensed polycyclic amino alcohols such as 1-hydroxybenzotriazole.

Examples of polyamines having a tertiary amino group and a primary or secondary amino group among amino alcohols and / or polyamines (a ₁ ) include, for example, dimethylaminoethylamine, diethylaminoethylamine,
N, N-dimethyl-1,3-propanediamine, N, N
-Diethyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, 3- (2- (N, N
-Dimethyl-amino) -ethoxy) -propylamine,
Diethanolaminopropylamine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-
Aminopropylpiperidine, N-aminopropyl-2-
Pipecoline, N-aminopropyl-4-pipecoline, N
-Aminoethylmorpholine, N-aminopropylmorpholine, methyliminobispropylamine, N-aminopiperidine, N-amino-4-pipecoline, 4-piperidinopiperidine, 1- (2-aminoethyl) -pyrrolidine, 1- Amino-4-methylpiperazine, N-hydroxyethoxyethylpiperazine, 1,4-bisaminopropylpiperazine, N-methylhomopiperazine, N-acylhomopiperazine, N-methylpiperazine, N-aminopropylpiperazine, N-carbetoxy Piperazine, N
-Formylpiperazine, 1- (o-chlorophenyl)
-Piperazine, 1- (m-chlorophenyl) -piperazine, 1- (p-chlorophenyl) -piperazine, 1-
Aliphatic polyamines such as (2-pyrimidyl) -piperazine, 1-amino-4-cyclopentylpiperazine, 1-cyclopentylpiperazine, 1-aminoethylpiperazine and the like,

2-aminomethylpyridine, 3-aminomethylpyridine, 4-aminomethylpyridine, 2-methylaminoethylpyridine, 4-alkylaminoethylpyridine, 2-amino-3-nitropyridine, 2-amino-
5-nitropyridine, 2,2'-dipyridylamine, 2
-Chloro-4-aminopyridine, 2-amino-5-chloropyridine, 2-amino-3,5-dichloropyridine,
2-amino-3,5-dichloro-6-methylpyridine,
2-amino-3,5-dichloro-3-methylpyridine,
2-amino-3,5-dichloro-4-methylpyridine,
2-amino-3,5-dichloro-4,6-dimethylpyridine, 2-amino-3,5-dichloropyridine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,6-diaminopyridine, 2,3,6-triaminopyridine, 2-amino-3-methylpyridine, 2-
Amino-4-methylpyridine, 2-amino-6-methylpyridine, 2-amino-4-ethylpyridine, 2-amino-4-propylpyridine, 2-amino-4,6-dimethylpyridine, 2,6-diamino -4-Methylpyridine, 2- (4-pyridyl) -4-amino-6-hydroxypyrimidine, 2- (4-pyridyl) -cycloformazine, 2,4-diamino-6- (4-pyridyl) -s −
Triazine, n- (2-pyridyl) -piperazine, 2,
Substituted pyridines such as 2'-dipyridylamine and the like;

1H-imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1- (3-aminopropyl) -imidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2 -Phenyl-4-methylimidazole, 1-aminoethyl-2-methylimidazole, 1
-(Cynoethylaminotyl) -2-methylimidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2 ′ -Undecyl imidazolyl-
(1 ')]-Ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1)']-ethyl-s-triazine, 2-phenyl-4- Methyl-5-hydroxymethylimidazole, 2
-Phenyl-4,5-dihydroxymethyl imidazole, 4-formyl imidazole, 2-methyl-4-formyl imidazole, 2-phenyl-4-formyl imidazole, 2-phenyl-4-formyl imidazole, 4-methyl -5-formyl imidazole, 2-
Ethyl-4-methyl-5-formylimidazole, 2
-Phenyl-4-methyl-5-formyl imidazole, 4-methyl imidazole, 4-methyl-5-hydroxymethyl imidazole, histamine, histidine, 1
-Imidazoles such as aminoethylimidazole,

2-amino-4-methylpyrimidine, 2-
Mercaptopyrimidine, 3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 1,2,4-triazole, 5-amino-1H-tetrazole, 2-amino-4,6 -Dimethylpyrimidine, 2-aminothiazole, 2-amino-5-nitrothiazole, 2-amino-5-mercapto-1,3,4-
Thiadiazole, 3-amino-5-methylisoxazole, 2-aminopyrimidine, aminopyrazine, 4
(6) -Aminouracil, 2-amino-1,3,4-thiadiazole, 4-methyl-4H-1,2,4-triazole-3-thiol, 5-anilino-1,2,3,4
An aromatic monocyclic amine such as thiatriazole, melamine, benzoguanamine, acetoguanamine, etc.,

6-aminopurine (adenine), 4-aminoquinaldine, guanine, 2-aminobenzimidazole, benzimidazole, allopurinol, benzotriazole, theophine, xanthine (2,6-dihydroxypurine), theobromine (2,6) -Dihydroxy-
3,7-dimethylpurine), theophylline (3,7-dihydro-1,3-dimethylxanthine) 5 (6) -nitrobenzimidazole, 3-methyl-2-benzothiazolinone todrazonium, 2-mercaptobenz Imidazole, 2-aminobenzothiazole, 1-hydroxybenzotriazole, guanine (2-amino-6-hydroxypurine), gramine (3-dimethylaminomethylindole), 4-aminoquinaldine, 2-aminoquinaldine, 5- Methyl-s-triazolo [1,5-a]
Pyrimidin-7-ol, 3-methyl-2-quinoxalinol, 6-methylquinoline, 2-mercaptobenzothiazole, 2- (4-thiazolyl) -benzimidazole, 2-amino-6-methoxybenzothiazole, 2-
Amino-6-chlorobenzothiazole, 2-amino-6
-Nitrobenzothiazole, 2-amino-6-ethoxybenzothiazole, aminocarbazole, amino-N-
9-alkylcarbazole, aminophenylbenzothiazole, aminobenztriazole, 2-amino-4-
Methoxybenzthiazole, 2-amino-5,6-dimethylbenzthiazole, 2-amino-5-methoxybenzthiazole, 2- (4-aminophenyl) -6-methylbenzthiazole, 8-aminoquinaldine, 4-amino Fused polycyclic aromatic amines such as quinaldine,

1,5,7-triazabicyclo- [4,4
And condensed polycyclic aliphatic amines such as 4,0] -dec-5-ene (TBD).

Next, as the lactone or carboxylic acid having a hydroxyl group (a ₂ ) used for producing the hydroxy compound (A), an esterification reaction with an amino alcohol compound and / or a polyamine compound (a ₁ ) and / or Any compound capable of undergoing an amidation reaction may be used, and examples thereof include lactone, carboxylic acid having a hydroxyl group, carboxylic acid ester having a hydroxyl group, carboxylic acid anhydride having a hydroxyl group, and carboxylic acid halide having a hydroxyl group. Among them, lactone, carboxylic acid having a hydroxyl group or carboxylic acid ester having a hydroxyl group is preferable.

Examples of the lactone include propiolactone, valerolactone, caprolactone and substituted derivatives thereof, and examples of the carboxylic acid having a hydroxyl group include ricinoleic acid, 9-hydroxystearic acid and 10-hydroxystearic acid. blend,
12-Hydroxystearic acid, dimethylolpropionic acid, and poly (hydroxycarboxylic acid) obtained by dehydration condensation of these alone or as a mixture thereof are examples of the carboxylic acid ester having a hydroxyl group, such as ricinoleic acid methyl ester. , Methyl ester of a mixture of 9-hydroxystearic acid and 10-hydroxystearic acid, 12-hydroxystearic acid methyl ester, 12-hydroxystearic acid ethyl ester, 12-hydroxystearic acid butyl ester and the like, respectively.

The polycarboxylic acids (a ₃ ) used for producing the hydroxy compound (A) include, for example, polycarboxylic acids, polycarboxylic acid anhydrides or polycarboxylic acid esters.

Examples of the polycarboxylic acid include succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid,
Isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
Sebacic acid, azelaic acid, brazilic acid, trimellitic acid, pyromellitic acid, itaconic acid and the like, polycarboxylic acid anhydrides, for example, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, anhydrous Phthalic acid, trimellitic anhydride, pyromellitic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, itaconic anhydride and the like, as polycarboxylic acid ester, for example, dimethyl succinate, dimethyl maleate, dimethyl adipate, Examples thereof include dibutyl phthalate, dimethyl isophthalate, dimethyl terephthalate, and dimethyl sebacate.

Further, among the polyols or epoxy compounds (a ₄ ) used in the production of the hydroxy compound (A) used in the present invention, examples of the polyol include ethylene glycol, diethylene glycol, polyethylene glycol, 1,2-propylene glycol. , 1,3
-Propylene glycol, dipropylene glycol, polypropylene glycol, 1,4-butanediol, polytetramethylene glycol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, glycerol, tri Methylolethane, trimethylolpropane,
Examples include pentaerythritol.

Among the polyols or epoxy compounds (a ₄ ) used for producing the hydroxy compound (A) used in the present invention, examples of the epoxy compound include allyl glycidyl ether, n-butyl glycidyl ether, phenyl glycidyl ether, Examples thereof include glycidyl ether, bishexamethylene glycidyl ether, cyclohexene oxide, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, versatic acid glycidyl ester (Cardura E), bisphenol A diglycidyl ether, and epoxy resin.

Next, the hydroxy compound used in the present invention
(A) is the above raw material (a₁ ), (A ₂ ), (A₃ ),
(A_Four ) Describes the reaction conditions when manufacturing
To do. Amino alcohol having tertiary amino group and / or
Or has a tertiary amino group and a primary or secondary amino group
Polyamine (a₁ ) With a lactone,
Ring-opening esterification reaction and / or ring-opening amidation reaction of
Is (a₁ ) And a lactone mixture of 160 to 20
By heating to 0 ° C and reacting for 30 minutes to 5 hours
Done.

When (a ₁ ) is reacted with a carboxylic acid or polycarboxylic acid having a hydroxyl group, its dehydration esterification reaction and / or dehydration amidation reaction is
It is carried out by heating a mixture of (a ₁ ) and a carboxylic acid or polycarboxylic acid having a hydroxyl group to 160 to 250 ° C. and reacting for 2 to 30 hours while removing water out of the system.

When (a ₁ ) is reacted with a polycarboxylic acid anhydride, the ring-opening esterification reaction and / or ring-opening amidation reaction is carried out by mixing a mixture of (a ₁ ) and the polycarboxylic acid anhydride with 80 It is carried out by heating to ˜150 ° C. and reacting for 30 minutes to 5 hours.

When (a ₁ ) is reacted with a carboxylic acid ester or polycarboxylic acid ester having a hydroxyl group, the dealcoholization transesterification reaction and / or the dealcoholation ester-amide exchange reaction is
₁ ) and a hydroxyl group-containing carboxylic acid ester or polycarboxylic acid ester in a mixture of 150 to 2
It is carried out by heating to 50 ° C. and reacting for 30 minutes to 10 hours while removing alcohol out of the system.

The ester compound and / or amide compound having a carboxyl group obtained by reacting (a ₁ ) with a polycarboxylic acid, a polycarboxylic acid anhydride or a polycarboxylic acid ester as described above is converted into a polyol. When the ring-opening esterification reaction is performed with a mixture of the above ester compound and / or amide compound having a carboxyl group and a polyol,
It is carried out by heating to 50 ° C. and reacting for 2 to 30 hours while removing water from the system.

When the ester compound and / or amide compound having a carboxyl group obtained by reacting (a ₁ ) with a polycarboxylic acid or a polycarboxylic acid anhydride as described above is reacted with an epoxy compound. The ring-opening esterification reaction is carried out by heating a mixture of the above-mentioned ester compound and / or amide compound having a carboxyl group and an epoxy compound at 160 to 210 ° C. and reacting for 30 minutes to 5 hours.

For these various reactions, if necessary, a solvent,
You may use a catalyst etc. together. As the solvent used here, a high boiling point solvent such as toluene, xylene, Solvesso 100, Solvesso 150, and HRS (aromatic high boiling point solvent) is preferable. Further, as the catalyst, tetrabutyl titanate, dibutyltin dilaurate or an oxide, hydroxide, or the like of lead, zinc, calcium, lithium or sodium,
An organic acid salt or the like is used.

Further, these reactions are preferably carried out in an atmosphere of an inert gas such as nitrogen while stirring the reaction system. The method for producing the hydroxy compound (A) used in the present invention is not necessarily limited to the above method, and may be a known production method used for producing an alkyd resin, a polyester resin, a polyamide resin or the like. .

The isocyanate compound (B) used in the present invention has various structures, and examples thereof include monoisocyanate and polyisocyanate. Examples of the above-mentioned monoisocyanate include phenyl isocyanate and n-butyl isocyanate.

As the polyisocyanate, diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and 2,4
-And a mixture of 2,6-tolylene diisocyanate,
4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, hexamethylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, 1-isocyanate-3,
3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate), lysine diisocyanate, isopropylidene bis (4-cyclohexyl isocyanate), and the like, and more than two isocyanate groups on average per molecule. As the compound having, for example, polyphenyl-polymethylene polyisocyanate (crude MDI, trade name Millionate MDI), triphenylmethane-4,4 ′, 4 ″ -triisocyanate (Desmodur R), obtained by adding diisocyanate to polyol Desmodur L represented by the following structural formula (1), coronate HL represented by the following structural formula (2), urethane modified polyisocyanate such as Takenate D110N represented by the following structural formula (3),
Biuret-modified polyisocyanate such as Desmodur N represented by the following structural formula (4) obtained from diisocyanate by Biuret reaction, Desmodule IL represented by the following structural formula (5) produced by ring formation of diisocyanate, and the following structure Desmodur HL represented by the formula (6), Borlene KC represented by the following structural formula (7), Tolylene diisocyanate-isophorone diisocyanate represented by the following structural formula (8), and Trimeric represented by the following structural formula (9). Isophorone diisocyanate, coronate EH represented by the following structural formula (10),
Examples thereof include polyisocyanates having an isocyanurate ring such as trimeric tolylene diisocyanate represented by the following structural formula (11).

[0037]

[Chemical 1]

[0038]

[Chemical 2]

[0039]

[Chemical 3]

[0040]

[Chemical 4]

The above-mentioned compound having an average of more than two isocyanate groups per molecule is a commercial product, and is often not a pure form of the compound represented by the above chemical formula, but has a certain molecular weight distribution. , A mixture with compounds having certain similar structures.

As the isocyanate compound (B) used in the present invention, monoisocyanate can be used, but polyisocyanate is preferable because of its high effect of improving dispersibility. Among them, those having an isocyanurate ring are pigments, In particular, it has a high affinity with organic pigments and is particularly preferable.

When the above-mentioned isocyanate compound (B) is a polyisocyanate, the addition of the above-mentioned hydroxy compound (A) does not have to be carried out for all the isocyanate groups in the polyisocyanate, but for at least one isocyanate group. It has only been done. The free isocyanate group remaining in the compound having a structure in which a part of the isocyanate group in the polyisocyanate is added may be reacted with an active hydrogen group such as a hydroxyl group present in the thermosetting resin, or hydroxy. It may be reacted with a compound (C) having active hydrogen other than the compound (A).

As the above-mentioned compound (C), those having various structures can be used, and examples thereof include alcohols, phenols, primary and secondary amines, thiols, malonic acid esters, acetoacetic acid esters, acetylacetone, water, urea, Examples include urethane, amide, ammonia, amidine, and guanidine. These compounds may contain one active hydrogen group in one molecule, and may simultaneously contain two or more same or different active hydrogen groups.

Further, the compound (C) may be an active hydrogen compound having a functional group such as a tertiary amino group. As the active hydrogen compound having a tertiary amino group, not only the above-mentioned amino alcohol compound having a tertiary amino group or the polyamine (a ₁ ) having a tertiary amino group and a primary and / or secondary amino group, Thiol having a tertiary amino group, phenol having a tertiary amino group, malonic acid ester having a tertiary amino group, acetoacetic acid ester having a tertiary amino group, acetylacetone having a tertiary amino group, having a tertiary amino group Examples thereof include urea, urethane having a tertiary amino group, and amide having a tertiary amino group.

Further, as the compound (C), a compound such as a polyhydroxy compound or an amino alcohol which can leave a free hydroxyl group after reacting with an isocyanate group may be used. Examples of such compounds include glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, trishydroxymethylaminomethane, diethanolamine, monoethanolamine, 1- (2-hydroxyethyl) -piperazine and the like.

The compound (Z) having a free hydroxyl group remaining, which is obtained as described above, reacts with the curing agent at the time of thermosetting and is fixed in the coating film when used by adding it to the thermosetting resin. Therefore, it is convenient because it does not bleed on the surface of the coating film.

The reaction of adding the hydroxy compound (A) or the active hydrogen compound (C) to the isocyanate compound (B) using the above raw materials is carried out under various conditions depending on the structure of the reaction substrate. This addition reaction is usually carried out at room temperature or with stirring under heating conditions depending on the reaction rate. Generally, when the reaction substrate is an amine, the reaction is carried out at room temperature, and when the reaction substrate is an alcohol,
Heat to react. When the reaction substrate contains a functional group that promotes dimerization or trimerization of isocyanate groups with each other, the structure of the reaction product can be controlled by changing the reaction conditions. For example, when an alcohol having a tertiary amino group is reacted with an excess isocyanate compound for a long time, an isocyanurate ring can be formed in addition to the urethane bond. Therefore, the molecular weight and the isocyanurate ring content of the reaction product can be increased or decreased by adjusting the excess ratio of the isocyanate group.

The reaction conditions between the reaction substrate other than the above-mentioned compounds and the isocyanate compound (B) depend on the reactivity with the isocyanate group of the reaction substrate. Further, a catalyst may be used in the above-mentioned addition reaction, dimerization and trimerization reaction, and examples of such a catalyst include amine compounds such as triethylenediamine and tetramethylbutanediamine, dibutyltin dilaurate and dibutyltin oxide, Examples include metal catalysts such as iron acetylacetonate.

The above-mentioned addition reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen, because it is not disturbed by moisture or the like. Further, a solvent may be used in combination in the reaction, if necessary.

As such a solvent, various solvents may be used depending on the solubility of the addition compound to be formed, but examples thereof include aromatic solvents such as toluene and xylene, ethyl acetate,
Ester solvents such as butyl acetate and ethyl cellosolve, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone, ether solvents such as dioxane, polar solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide, water And so on.

The compound (Z) used in the present invention can be directly produced as described above by the addition reaction of the hydroxy compound (A) to the isocyanate compound (B), but can be produced by other methods. May be. As such another production method, after reacting a hydroxy compound other than the hydroxyl compound (A) with the isocyanate compound (B), the addition compound is modified to give the isocyanate compound (B) and the hydroxy compound (A). Examples thereof include a method for producing a compound having the same structure as the addition compound.

The compound (Z) thus obtained is produced in the above-mentioned manner and then directly in the form obtained by the production method, or by adding a solvent if necessary, or by a method such as heating or decompression. It may be used in a form that is easy to handle by removing.

The compound (Z) is usually used in an amount of 0.1 to 30 parts by weight, based on 100 parts by weight of the solid to be dispersed.
-30 parts by weight is preferred.

When the compound (Z) has a high basicity, the amount of its use is practically limited in a coating material using a melamine resin. This is because, in general, the basic compound in the coating composition remarkably inhibits the melamine curability and also reduces the acid resistance of the final coating film. Therefore, the compound (Z)
When many tertiary amino groups having a high basicity (pKa) are contained therein, the amount of the compound (Z) used is preferably determined in consideration of the above-mentioned physical properties such as curability and acid resistance. For example, the pKa of the tertiary amino group in the compound (Z) is 7 or more, and the solid-state amine value of the compound (Z) is 5
When it is 0 or more, the amount used is preferably less than 3% by weight of the resin solid content in the final paint.

The dispersant of the present invention containing the compound (Z) as an active ingredient may be added at any step in the step of obtaining a dispersion or a coating, but it can be applied before the solid is dispersed.

The dispersant of the present invention exerts a sufficient dispersing effect by itself, but this does not limit the use of other dispersants. That is, the dispersant of the present invention is a commonly used pigment derivative or a dispersant such as a resin-type dispersant other than the present invention, or addition of a wetting agent, a leveling agent, a rheology control agent, a silane coupling agent, or the like. It may be used together with the agent.

The method for preparing a dispersion using the dispersant of the present invention and a particulate solid such as a dye or pigment is not particularly limited, and the present invention may be used in place of the conventional dispersant or together with the conventional dispersant. The dispersant may be used, and examples thereof include a method in which the dispersant of the present invention, a dye and a pigment, and a solvent are mixed and dispersed by a disperser such as a paint conditioner or a ball mill.

Examples of the pigment used together with the dispersant of the present invention include inorganic pigments, organic pigments and extender pigments, among which inorganic pigments and organic pigments are preferable. Examples of the inorganic pigment include titanium dioxide, iron oxide, zinc oxide,
Examples include lead chromate and carbon black.

Examples of the organic pigment include dye-based pigments such as azo, thioindigo, and anthraquinone, copper phthalocyanine, its nuclear halogenated derivatives, phthalocyanine pigments such as copper tetraphenylphthalocyanine and octaphenylphthalocyanine, and dianthraquinonyl red. , Indanthrone blue, etc.
Indigo-based pigments such as thioindigocobalt, perinone-based pigments such as perinone orange, perylene-based pigments such as perylene maroon, perylene red, perylene violet, phthalone-based pigments such as quinophthalo yellow, carbazole violet, etc. Quinacridone pigments such as dioxazine pigments, unsubstituted quinacridone, quinacridone magenta, dichloroquinacridone and quinacridone scarlet, isoindolinone pigments such as isoindolinone yellow R, metal complex pigments such as copper azomethine yellow, DPP red, etc. And diketopyrrolopyrrole pigments, methine / azomethine pigments, and the like.

The method for preparing the above-mentioned coating material of the present invention is not particularly limited, and the dispersant of the present invention or the conventional dispersant or the dispersant may be used instead of or together with the conventional dispersant or the dispersant. A dispersion may be used, for example, a method of adding a resin to the dispersion of the present invention and dispersing with a disperser such as a paint conditioner or a ball mill, or a mixture of the dispersant of the present invention, a dye / pigment, a solvent, and a resin once. And the like.

The resin used for producing the coating material of the present invention may have various structures, for example, alkyd / melamine, acrylic / melamine, acrylic /
Thermosetting resins such as isocyanate, polyester / isocyanate, epoxy, phenol, unsaturated polyester, polyvinyl chloride, polyolefin, polyamide,
Examples thereof include thermoplastic resins such as polycarbonate, polystyrene and polyurethane.

[0063]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to such examples.

Production Example 1 ε-caprolactone 114 parts N, N-dimethyl-1,3-propanediamine 102 parts Tetrabutyl titanate 1 part A mixture of 9 parts at 160 to 180 ° C. under a nitrogen atmosphere at 9 ° C.
The reaction was carried out for 0 minutes while stirring to obtain a viscous amide alcohol having a number average molecular weight of 216.

Production Example 2 ε-caprolactone 398 parts N, N-dimethyl-1,3-propanediamine 102 parts Tetrabutyl titanate 1 part except that a mixture of 1 part was used, and the reaction was carried out in the same manner as in Production Example 1 to give a number average molecular weight. A polyester alcohol having 500 amide bonds was obtained.

Production Example 3 δ-Valerolactone 898 parts N, N-Dimethyl-1,3-propanediamine 102 parts Tetrabutyl titanate 1 part except that a mixture of 1 part was used, the reaction was carried out in the same manner as in Production Example 1, and the number average was obtained. A polyester alcohol having an amide bond with a molecular weight of 1000 was obtained.

Production Example 4 ε-caprolactone 1875 parts 1- (3-aminopropyl) imidazole 125 parts Tetrabutyl titanate 1 part except that a mixture was used and reacted in the same manner as in Production Example 1 to give an amide having a number average molecular weight of 2000. A polyester alcohol having a bond was obtained.

Production Example 5 ε-caprolactone 4900 parts N-methylpiperazine 100 parts Tetrabutyl titanate 1 part except that a mixture was used and reacted in the same manner as in Production Example 1 to give a polyester alcohol having an amide bond having a number average molecular weight of 5000. Got

Production Example 6 ε-caprolactone 1405 parts 2-aminopyrimidine 95 parts Tetrabutyl titanate A polyester alcohol having an amide bond with an amide bond having a number average molecular weight of 1500 was reacted in the same manner as in Production Example 1 except that a mixture of 1 part was used. Got

Production Example 7 ε-caprolactone 850 parts 2-aminobenzothiazole 150 parts Tetrabutyl titanate 1 part A mixture of 9 parts at 190 to 220 ° C. under a nitrogen atmosphere at 9 ° C.
The reaction was carried out for 0 minutes with stirring to obtain a polyester alcohol having an amide bond having a number average molecular weight of 1000.

Production Example 8 A mixture of 100 parts of N-methylpiperazine and 154 parts of hexahydrophthalic anhydride was reacted under nitrogen atmosphere at 80 ° C. for 60 minutes while stirring to obtain a carboxylic acid having an amide bond.

Production Example 9 A mixture consisting of 254 parts of the carboxylic acid obtained in Production Example 8 and 240 parts of Curdula E was heated at 180 to 200 ° C. for 9 hours under a nitrogen atmosphere.
The reaction was carried out for 0 minutes with stirring to obtain an ester compound.

Production Example 10 12-Hydroxystearic acid 100 parts Xylene 5 parts Tetrabutyl titanate 0.5 part A mixture of 1 part at 170 to 200 ° C. under a nitrogen atmosphere.
The reaction was carried out with stirring for 0 hours, and water generated by the condensation reaction was removed from the reaction system using a Dean Stark trap to obtain a polyester resin solution having an acid value of 25.

Production Example 11 Polyester resin solution obtained in Production Example 10 100 parts N, N-dibutyl-1,3-propanediamine 8.5 parts Tetrabutyl titanate 1 part HRS (aromatic high boiling point solvent) 5 parts Mix the mixture at 180-210 ° C under nitrogen atmosphere 4
The mixture was reacted with stirring for a period of time, and water produced by the condensation reaction was removed from the reaction system using a Dean Stark trap to obtain a polyester resin solution having an amide bond.

Preparation Example 12 Polyester resin solution obtained in Preparation Example 10 100 parts 1- (3-aminopropyl) imidazole 7.0 parts Tetrabutyl titanate 1 part HRS (aromatic high boiling solvent) 5 parts A mixture was used. Except that it was reacted in the same manner as in Production Example 11 to obtain a polyester resin solution having an amide bond.

Production Example 13 1,3-butylene glycol 95 parts adipic acid 130 parts tetrabutyl titanate 1 part A mixture of 5 parts at 160 to 210 ° C. under a nitrogen atmosphere.
The reaction is carried out while stirring for a period of time, and water produced by the condensation reaction is removed from the water cooling tube to the outside of the reaction system to give a hydroxyl value of 55.
Of polyester diol was obtained.

Production Example 14 100 parts of the polyester diol obtained in Production Example 13 A mixture of 12.5 parts of the carboxylic acid obtained in Production Example 8 was added at 160 to 220 ° C. under a nitrogen atmosphere for 4 hours.
The reaction was carried out while stirring for a period of time, and the water produced by the condensation reaction was removed from the water cooling tube to the outside of the reaction system to obtain a polyester resin having an amide bond.

Production Example 15 A mixture of 192 parts of trimellitic anhydride, 95 parts of aminopyrazine, and 15 parts of xylene was reacted under stirring in a nitrogen atmosphere at 100 ° C. for 1 hour, and then the temperature was raised to 150 to 200 and further 3 times. After reacting for a period of time, water generated by the ring closure reaction was removed to the outside of the reaction system using a Dean Stark trap to obtain a carboxylic acid solution having an imide bond.

Production Example 16 carboxylic acid solution obtained in Production Example 15 284 parts Cardura E 240 parts Trimethylbenzylammonium chloride 0.5 part A mixture of 9 parts at 170-200 ° C. under nitrogen atmosphere.
The reaction was carried out for 0 minutes with stirring to obtain an ester compound having an imide bond.

Production Example 17 A mixture of 284 parts of the carboxylic acid solution obtained in Production Example 15 and 134 parts of trimethylolpropane was added under nitrogen atmosphere at 160 to 210 ° C. for 4 hours.
The reaction was carried out with stirring for a period of time, and water generated by the condensation reaction was removed from the reaction system by using a Dean Stark trap to obtain an ester compound having an average of two hydroxyl groups in one molecule.

Production Example 18 ε-caprolactone 114 parts 3-dimethylamino-1-propanol 103 parts tetrabutyl titanate 1 part A mixture of 2 parts at 170 to 200 ° C. under a nitrogen atmosphere at 2 ° C.
The mixture was reacted with stirring for a period of time to obtain a viscous ester alcohol having a number average molecular weight of 217.

Production Example 19 Polyester monomonomer having a number average molecular weight of 1500 was reacted in the same manner as in Production Example 18 except that a mixture consisting of ε-caprolactone 1369 parts 3-diethylamino-1-propanol 131 parts tetrabutyl titanate 1 part was used. Got all.

Production Example 20 δ-Valerolactone 827 parts 3-Dibutylamino-1-propanol 173 parts Tetrabutyl titanate 1 part A reaction was conducted in the same manner as in Production Example 18 except that a mixture consisting of 1 part was used. I got polyester monool.

Production Example 21 ε-caprolactone 385 parts 1- (2-hydroxyethyl) pyrrolidine 115 parts Tetrabutyl titanate 1 part except that a mixture of 1 part was used and reacted in the same manner as in Production Example 18 to give a number average molecular weight of 500. I got polyester monool.

Production Example 22 ε-caprolactone 877 parts 4- (2-hydroxyethyl) pyridine 123 parts Tetrabutyl titanate 1 part except that a mixture of 1 part was used and reacted in the same manner as in Production Example 18 to give a number average molecular weight of 1000. I got polyester monool.

Preparation Example 23 ε-caprolactone 357 parts 4-methyl-5-thiazoleethanol 143 parts Tetrabutyl titanate 1 part A mixture of 2 parts at 190 to 220 ° C. under a nitrogen atmosphere.
The reaction was carried out with stirring for a period of time to obtain a polyester monool having a number average molecular weight of 500.

Production Example 24 A mixture of 191 parts of N- (2-hydroxyethyl) phthalimide and 154 parts of hexahydrophthalic anhydride was reacted under nitrogen atmosphere with stirring at 100 ° C. for 1 hour to give a carboxylic acid having an ester bond. Obtained.

Production Example 25 A mixture consisting of 345 parts of the carboxylic acid obtained in Production Example 24, 240 parts of Cardura E, 240 parts of trimethylbenzylammonium, and 2 at 170-200 ° C. under a nitrogen atmosphere.
The mixture was reacted with stirring for a period of time to obtain a polyester monool having a number average molecular weight of 590.

Production Example 26 Polyester resin solution obtained in Production Example 10 100 parts 4- (2-hydroxyethyl) morpholine 6 parts Tetrabutyl titanate 1 part A mixture of 4 parts at 160 to 210 ° C. under a nitrogen atmosphere.
The reaction was carried out with stirring for an hour. A polyester monol having a number average molecular weight of 2400 was obtained.

Production Example 27 Polyester diol obtained in Production Example 13 100 parts Carboxylic acid obtained in Production Example 24 16.9 parts Tetrabutyl titanate 1 part A mixture consisting of 4 parts at 160 to 210 ° C. under a nitrogen atmosphere.
The number average molecular weight is 2,400 by reacting while stirring for 2 hours.
Then, a polyester alcohol having an average of one hydroxyl group in one molecule was obtained.

Production Example 28 A mixture of 345 parts of the carboxylic acid obtained in Production Example 24 and 134 parts of trimethylolpropane was added under nitrogen atmosphere at 160 to 210 ° C. for 4 hours.
The number average molecular weight is 460
Then, a polyester polyol having an average of two hydroxyl groups in one molecule was obtained.

Production Example 29 N-Methyldiethanolamine 119 parts ε-caprolactone 881 parts Tetrabutyl titanate 1 part A mixture of 2 parts at 170 to 200 ° C. under a nitrogen atmosphere.
The mixture was reacted with stirring for a period of time to obtain a viscous polyester diol having a number average molecular weight of 1,000.

Example 1 217 parts of amide alcohol obtained in Preparation Example 1 119 parts of phenyl isocyanate 119 parts of dibutyltin dilaurate 0.03 parts 250 parts of methyl ethyl ketone The mixture was reacted under nitrogen atmosphere at 70 to 80 ° C. for 4 hours while stirring. A solution containing a urethane compound having a number average molecular weight of 335 was obtained. Hereinafter, this solution is referred to as a dispersant (I-1).

Example 2 Reaction was carried out in the same manner as in Example 1 except that a mixture of the amide alcohol obtained in Preparation Example 1 217 parts 2,4-tolylene diisocyanate 87 parts dibutyltin dilaurate 0.03 part methyl ethyl ketone 300 parts was used. Thus, a solution containing a urethane compound having a number average molecular weight of 606 was obtained. Hereinafter, this solution is referred to as a dispersant (I-2).

Example 3 Polyester alcohol obtained in Preparation Example 501 501 parts Isophorone diisocyanate 111 parts Dibutyltin dilaurate 0.03 parts Methyl ethyl ketone 400 parts The reaction was conducted in the same manner as in Example 1 except that a mixture was used, and a number average molecular weight was obtained. A solution containing about 1200 urethane compounds was obtained. Hereinafter, this solution is referred to as a dispersant (I-3).

Example 4 Reaction was carried out in the same manner as in Example 1 except that a mixture of the polyester alcohol obtained in Production Example 3 1001 part 2,4-tolylene diisocyanate 87 parts dibutyltin dilaurate 0.03 part methyl ethyl ketone 500 parts was used. Thus, a solution containing a urethane compound having a number average molecular weight of about 2200 was obtained. Hereinafter, this solution is referred to as a dispersant (I-4).

Example 5 Polyester alcohol obtained in Production Example 4 2001 parts Desmodur IL (solution containing 49% butyl acetate) 525 parts Dibutyltin dilaurate 0.03 parts Methyl ethyl ketone 1500 parts Except that a mixture was used. A similar reaction was performed to obtain a solution containing a urethane compound having a number average molecular weight of about 8000. Hereinafter, this solution is referred to as a dispersant (I-5).

Example 6 Polyester alcohol obtained in Preparation Example 5 500 parts 2,4-Tolylene diisocyanate 8.7 parts Dibutyltin dilaurate 0.003 parts Methyl ethyl ketone 300 parts The same as in Example 1 except that a mixture was used. The reaction was carried out to obtain a solution containing a urethane compound having a number average molecular weight of about 10,000. Hereinafter, this solution was used as a dispersant (I-6).
Called.

Example 7 Polyester alcohol obtained in Preparation Example 1500 1500 parts Desmodur IL (solution containing 49% butyl acetate) 525 parts Dibutyltin dilaurate 0.03 parts Methyl ethyl ketone 800 parts Toluene 500 parts Except that a mixture of 500 parts was used. The reaction was performed in the same manner as in Example 1 to obtain a solution containing a urethane compound having a number average molecular weight of about 6000. Hereinafter, this solution is referred to as a dispersant (I-7).

Example 8 Polyester alcohol obtained in Production Example 7 1001 parts Desmodur HL (liquid containing 40% butyl acetate) 400 parts Dibutyltin dilaurate 0.03 parts Methyl ethyl ketone 700 parts Toluene 300 parts Implemented except using a mixture The reaction was performed in the same manner as in Example 1 to obtain a solution containing a urethane compound having a number average molecular weight of about 4000. Hereinafter, this solution is referred to as a dispersant (I-8).

Example 9 Same as Example 1 except that a mixture of the ester compound obtained in Production Example 9 494 parts 1,6-hexamethylene diisocyanate 84 parts dibutyltin dilaurate 0.03 parts cyclohexanone 400 parts xylene 400 parts was used. To obtain a solution containing a urethane compound having a number average molecular weight of about 1100. Hereinafter, this solution is referred to as a dispersant (I-9).

Example 10 Example 1 except that a mixture of the polyester resin solution obtained in Production Example 11 111 parts Desmodur HL (liquid containing 40% butyl acetate) 18 parts dibutyltin dilaurate 0.03 part methyl ethyl ketone 80 parts was used. The reaction was carried out in the same manner as in 1. to obtain a solution containing a urethane compound having a number average molecular weight of about 10,000. Hereinafter, this solution was used as a dispersant (I-1
0).

Example 11 Polyester resin solution obtained in Preparative Example 12 106 parts Desmodur IL (solution containing 49% butyl acetate) 23.5 parts Dibutyltin dilaurate 0.03 parts Methyl ethyl ketone 110 parts Implemented except using a mixture. The reaction was carried out in the same manner as in Example 1 to obtain a solution containing a urethane compound having a number average molecular weight of about 10,000. Hereinafter, this solution was used as a dispersant (I-1
1).

Example 12 Polyester resin obtained in Production Example 14 228 parts Desmodur HL (solution containing 40% butyl acetate) 40 parts Dibutyltin dilaurate 0.03 parts Methyl ethyl ketone 150 parts Xylene 100 parts Implemented except that a mixture of 100 parts was used. The reaction was carried out in the same manner as in Example 1 to obtain a solution containing a urethane compound having a number average molecular weight of about 10,000. Hereinafter, this solution was used as a dispersant (I-1
2).

Example 13 Ester compound obtained in Preparative Example 16 554 parts Desmodur HL (liquid containing 40% butyl acetate) 400 parts Dibutyltin dilaurate 0.03 parts Methyl ethyl ketone 600 parts Xylene 400 parts Implemented except that a mixture of 400 parts was used. Reaction was carried out in the same manner as in Example 1 to obtain a solution containing a urethane compound having a number average molecular weight of about 3000. Hereinafter, this solution was used as a dispersant (I-13).
Called.

Example 14 Ester compound obtained in Preparative Example 17 430 parts Desmodur IL (solution containing 49% butyl acetate) 525 parts Dibutyltin dilaurate 0.03 parts Methyl ethyl ketone 850 parts Except that a mixture was used. A similar reaction was performed to obtain a solution containing a urethane compound having a number average molecular weight of about 2,500. Hereinafter, this solution was used as a dispersant (I-14).
Called.

Example 15 Ester alcohol obtained in Preparation Example 218 parts Phenylisocyanate 119 parts Dibutyltin dilaurate 0.03 parts Methyl ethyl ketone 350 parts It was reacted in the same manner as in Example 1 except that a mixture was used, and a number average molecular weight was obtained. A solution containing 336 urethane compounds was obtained. Hereinafter, this solution is referred to as a dispersant (I-15).

Example 16 Ester alcohol obtained in Preparation Example 18 218 parts 2,4-Tolylene diisocyanate 87 parts Dibutyltin dilaurate 0.03 part Methyl ethyl ketone 300 parts except that a mixture was used and reacted in the same manner as in Example 1. Thus, a solution containing a urethane compound having a number average molecular weight of 608 was obtained. Hereinafter, this solution is referred to as a dispersant (I-16).

Example 17 Polyester monool obtained in Preparative Example 19 150 parts Isophorone diisocyanate 11.1 parts Dibutyltin dilaurate 0.003 parts Methyl ethyl ketone 75 parts Cyclohexanone 75 parts except a mixture was used. Then, a solution containing a urethane compound having a number average molecular weight of about 3200 was obtained. Hereinafter, this solution was used as a dispersant (I-17).
Called.

Example 18 Polyester monool obtained in Preparative Example 20 101 parts 2,4-Tolylene diisocyanate 8.7 parts Dibutyltin dilaurate 0.03 parts Methyl ethyl ketone 50 parts Toluene 25 parts except that a mixture was used. The reaction was performed in the same manner as in 1 to obtain a solution containing a urethane compound having a number average molecular weight of about 2200. Hereinafter, this solution was used as a dispersant (I-18).
Called.

Example 19 Polyester monool obtained in Production Example 501 501 parts Desmodur IL (49% butyl acetate solution) 525 parts Dibutyltin dilaurate 0.03 parts Methylethylketone 400 parts Toluene 300 parts except that a mixture was used. The reaction was performed in the same manner as in Example 1 to obtain a solution containing a urethane compound having a number average molecular weight of about 2,800. Hereinafter, this solution was used as a dispersant (I-19).
Called.

Example 20 Polyester monool obtained in Preparation Example 22 100 parts Desmodur HL (40% butyl acetate solution) 40 parts Dibutyltin dilaurate 0.03 parts Methyl ethyl ketone 80 parts Xylene 50 parts except that a mixture of 50 parts was used. The reaction was carried out in the same manner as in Example 1 to obtain a solution containing a urethane compound having a number average molecular weight of about 5,000. Hereinafter, this solution was used as a dispersant (I-20).
Called.

Example 21 Polyester monool obtained in Preparative Example 23 501 parts Desmodur IL (liquid containing 49% butyl acetate) 525 parts Dibutyltin dilaurate 0.03 parts Methyl ethyl ketone 500 parts except that a mixture of 500 parts was used. The reaction was performed in the same manner as in 1. to obtain a solution containing a urethane compound having a number average molecular weight of about 2800. Hereinafter, this solution was used as a dispersant (I-21).
Called.

Example 22 Polyester monool obtained in Preparative Example 25 498 parts Isophorone diisocyanate 111 parts Dibutyltin dilaurate 0.03 part Cyclohexanone 500 parts of cyclohexanone were reacted in the same manner as in Example 1 except that a mixture was used, and the number average was obtained. A solution containing a urethane compound having a molecular weight of about 1200 was obtained. Hereinafter, this solution was used as a dispersant (I-22).
Called.

Example 23 Polyester monool obtained in Preparation Example 26 106 parts Desmodur HL (solution containing 40% butyl acetate) 18 parts Dibutyltin dilaurate 0.03 parts Methyl ethyl ketone 50 parts Xylene 40 parts except that a mixture was used. The reaction was carried out in the same manner as in Example 1 to obtain a solution containing a urethane compound having a number average molecular weight of about 10,000. Hereinafter, this solution was used as a dispersant (I-2
3).

Example 24 Polyester alcohol obtained in Preparative Example 27 228 parts Desmodur IL (solution containing 49% butyl acetate) 52.5 parts Dibutyltin dilaurate 0.03 parts Methyl ethyl ketone 150 parts Toluene 100 parts except that a mixture was used. Was reacted in the same manner as in Example 1 to obtain a solution containing a urethane compound having a number average molecular weight of about 10,000. Hereinafter, this solution was used as a dispersant (I-2
4).

Example 25 Polyester polyol obtained in Preparative Example 28 373 parts Desmodur HL (liquid containing 40% butyl acetate) 40 parts Dibutyltin dilaurate 0.03 parts Methyl ethyl ketone 250 parts Xylene 200 parts Implemented except using a mixture. The reaction was performed in the same manner as in Example 1 to obtain a solution containing a urethane compound having a number average molecular weight of about 2,500. Hereinafter, this solution was used as a dispersant (I-25).
Called.

Example 26 Polyester alcohol obtained in Production Example 2 401 parts Desmodur IL (solution containing 49% butyl acetate) 525 parts Dibutyltin dilaurate 0.03 parts Methyl ethyl ketone 500 parts A mixture of 70-80 ° C. under a nitrogen atmosphere. After stirring for 1 hour with stirring, trishydroxymethylaminomethane (24 parts) was added, and the mixture was further reacted for 2 hours under the same reaction conditions to obtain a solution containing a urethane-urea compound having a number average molecular weight of about 2,500. . Hereinafter, this solution is referred to as a dispersant (I-26).

Example 27 Polyester alcohol obtained in Preparation Example 105 105 parts Desmodur IL (solution containing 49% butyl acetate) 52.5 parts Dibutyltin dilaurate 0.003 parts Methyl ethyl ketone 150 parts A mixture of 70 to 70 parts under a nitrogen atmosphere. After reacting at 80 ° C. for 1 hour with stirring, 4- (2-hydroxyethyl) -morpholine (4 parts) was added, and the mixture was further reacted for 2 hours under the same reaction conditions to contain a urethane compound having a number average molecular weight of about 6000. A solution was obtained. Hereinafter, this solution is referred to as a dispersant (I-27).

Example 28 Polyester monool obtained in Production Example 20 50 parts Desmodur IL (solution containing 49% butyl acetate) 52.5 parts Dibutyltin dilaurate 0.003 parts Methyl ethyl ketone 125 parts A mixture of 70 parts under a nitrogen atmosphere. After reacting at -80 ° C for 1 hour with stirring, 9 parts of 2-amino-6-chlorobenzothiazole were added, and 2 more were added under the same reaction conditions.
Urethane with a number average molecular weight of about 3500
A solution containing a urea compound was obtained. Hereinafter, this solution is referred to as a dispersant (I-28).

Example 29 Polyester alcohol obtained in Production Example 5 300 parts Desmodur IL (solution containing 49% butyl acetate) 52.5 parts Dibutyltin dilaurate 0.003 parts Methyl ethyl ketone 450 parts A mixture of 65 to 65 under a nitrogen atmosphere. After reacting at 70 ° C. for 30 minutes with stirring, 13 parts of the ester alcohol obtained in Preparation Example 18 was added, and the reaction was further conducted under the same reaction conditions to obtain 2 more portions.
After reacting for a time, a solution containing a urethane compound having a number average molecular weight of about 10,000 was obtained. Hereinafter, this solution is referred to as a dispersant (I-29).

Example 30 Ester Compound Obtained in Production Example 9 39.5 Parts Desmodur IL (Butyl Acetate 49% Liquid) 52.5 parts Dibutyltin Dilaurate 0.003 parts Methyl Ethyl Ketone 110 parts under a nitrogen atmosphere. After reacting at 65 to 70 ° C for 30 minutes with stirring, 1.2 parts of trishydroxymethylaminomethane and 1.5 parts of 2-aminobenzothiazole were added, and the mixture was further reacted for 2 hours under the same reaction conditions. A solution containing a urethane-urea compound having an average molecular weight of about 2500 was obtained. Hereinafter, this solution was added with a dispersant (I-
30).

Example 31 Polyester monool obtained in Production Example 19 22.5 parts Desmodur IL (solution containing 49% butyl acetate) 52.5 parts A mixture of 100 parts methyl ethyl ketone at 60 to 65 ° C. under a nitrogen atmosphere. After reacting with stirring for 1 hour, 8.0 parts of aminopyrazine was added, and the mixture was further reacted for 3 hours under the same reaction conditions, and then 45.5 parts of methyl ethyl ketone was added and reacted to contain a urethane-urea compound. A slightly cloudy viscous liquid was obtained. Hereinafter, this solution is referred to as a dispersant (I-31).

Example 32 Polyester monool obtained in Preparation Example 25 29.5 parts Desmodur HL (liquid containing 40% butyl acetate) 40 parts Dibutyltin dilaurate 0.003 parts Methyl ethyl ketone 75 parts A mixture of 70 parts under a nitrogen atmosphere. After reacting at -80 ° C for 2 hours with stirring, 3.3 parts of N- (2-hydroxyethyl) morpholine and 2.5 parts of 3-amino-5-methylisoxazole were added, and the mixture was further added under the same reaction conditions. The reaction was carried out for 2 hours to obtain a solution containing a urethane-urea compound having a number average molecular weight of about 2500. Hereinafter, this solution is referred to as a dispersant (I-32).

Example 33 Polyester alcohol obtained in Production Example 6 60 parts Polyoxyethylene nonyl phenyl ether (molecular weight 600) 6 parts Desmodur IL (solution containing 49% butyl acetate) 52.5 parts Dibutyltin dilaurate 0.003 parts Methyl ethyl ketone After reacting a mixture of 250 parts under nitrogen atmosphere at 65 to 70 ° C. for 1 hour while stirring, 4.6 parts of 1- (2-hydroxyethyl) pyrrolidine and 0.5 part of glycerol were added, and the same reaction conditions were applied. The reaction was further continued for 2 hours under the conditions to obtain a polyurethane resin solution. Hereinafter, this solution was added with a dispersant (I-
32).

Example 34 Polyester diol obtained in Preparative Example 29 100 parts Tolylene diisocyanate 17.4 parts Methyl ethyl ketone 160 parts A mixture was reacted under nitrogen atmosphere at 65 to 70 ° C. for 5 hours while stirring to give a polyurethane. A resin solution was obtained. Hereinafter, this solution is referred to as a dispersant (I-34).

Comparative Example 1 1-nonanol 2.9 parts ε-caprolactone 95.1 parts tetrabutyl titanate 0.1 part A mixture of 9 parts at 170 to 190 ° C. under a nitrogen atmosphere at 9 ° C.
After reacting with stirring for 0 minutes and cooling to 100 ° C., a mixture of polyethylene glycol (number average molecular weight 400) 3.5 parts dibutyltin dilaurate 0.01 part xylene 180 parts ethyl cellosolve 75 parts was added, and the temperature was about 40 ° C. Kept at. Next, after adding 31.5 parts of Desmodur HL (a liquid containing 40% butyl acetate), the mixture was reacted under stirring in a nitrogen atmosphere at 70 to 80 ° C. for 3 hours, and further 2- (2-hydroxyethyl)
-Pyridine (4.5 parts) was added, and the mixture was further reacted for 2 hours under the same conditions to obtain a solution containing a urethane compound. Hereinafter, this solution is referred to as a dispersant (I'-1).

Examples 35-48 and Comparative Examples 2-8 150 parts of glass beads (3 mmφ) and a solvent of the composition shown in Table 1, Table 2 or Table 3 [xylene / butanol =
3/1 (weight ratio)], an alkyd resin, a pigment and a dispersant are mixed in a dispersion container, and then dispersed for 2 hours with a paint conditioner to obtain a mill base, and 87 parts of the obtained mill base (however, glass beads (Excluding weight) and Beckozole 57-1362 [Alkyd resin manufactured by Dainippon Ink and Chemicals, Inc., containing 35% of Solvesso 100] 68 parts and Super Beckamine L-117 [Melamine resin manufactured by Dainippon Ink and Chemicals, Inc.] 45% of a mixed solvent of xylene / butanol 40%] was further dispersed for 5 minutes with a paint conditioner to obtain an alkyd / melamine paint.

To the obtained alkyd / melamine paint, a mixed solvent of Solvesso 100 / xylene / butanol / cellosolve acetate = 40/30/20/10 (weight ratio) was added to adjust the viscosity to 18 seconds with an Iwata viscosity cup. After that, it was poured onto a test panel plate tilted at an angle of 80 °, left in the air for about 30 minutes, and dried by heating at 140 ° C for 20 minutes to obtain a cured coating film, and the gloss (20 °) of the coating film was obtained. The dispersibility was evaluated by measuring. The results are shown in Table 1, Table 2 and Table 3.

The alkyd resins and pigments used are shown below. * Alkyd resin H-1: Beckosol EY-3002 [Dainippon Ink and Chemicals, Inc., xylene / butanol mixed solvent 35%
Contained] H-2: Beccosol EY-4006 [manufactured by Dainippon Ink and Chemicals, Inc., containing 40% xylene / Solvesso 100 mixed solvent] * Pigment P-1: titanium oxide P-2: carbon black P-3: copper Phthalocyanine (CI Pigment Blue 15) P-4: Dianthraquinolyl (CI Pigment Red 177) P-5: Perylene (CI Pigment Red 179) P-6: Quinacridone (CI Pigment Red 179). Pigment Violet 19) P-7: Diketopyrrolopyrrole (CI Pigment Red 254, manufactured by Ciba Geigy)

[0131]

[Table 1]

[0132]

[Table 2]

[0133]

[Table 3]

Examples 49 to 61 Instead of the dispersant (I-1), the dispersants (I-5) and (I-
6), (I-10), (I-14), (I-15),
(I-17), (I-18), (I-22), (I-2
5), (I-29), (I-32), (I-33) or (I-34) was used, and an alkyd / melamine paint was prepared in the same manner as in Example 41.

A cured coating film was obtained in the same manner as in Example 41 except that the obtained alkyd / melamine coating composition was used, and the gloss (20 °) of the coating film was measured. All were 70 or more. Examples 62 to 68 150 parts of glass beads (3 mmφ), a solvent [xylene / butanol = 3/1 (weight ratio)] having a composition shown in Table 4, an acrylic resin, a pigment and a dispersant were mixed in a dispersion container. Then, the mixture was dispersed with a paint conditioner for 2 hours to obtain a mill base, and then 75 parts of the obtained mill base (excluding the weight of the glass beads) and Acridic 47-712 [acrylic resin manufactured by Dainippon Ink and Chemicals, Inc., Containing 50% toluene / butyl acetate mixed solvent] 98
And 27 parts of Super Beckamine L-117 [containing melamine resin manufactured by Dainippon Ink and Chemicals, Inc., 40% xylene / butanol mixed solvent] were further dispersed with a paint conditioner for 5 minutes to obtain an acrylic / melamine paint. .

A cured coating film was obtained in the same manner as in Example 35 except that the obtained acrylic / melamine coating material was used, and the dispersibility was evaluated by measuring the gloss (20 °) of the coating film.
The results are shown in Table 4.

The pigments used are the same as in Examples 35 to 48, and the acrylic resins used are shown below. * Acrylic resin (K) K-1: Acridic A-430 [manufactured by Dainippon Ink and Chemicals, Inc., containing 40% xylene / butanol mixed solvent] K-2: Acridic 47-712 [Dainippon Ink and Chemicals] Co., Ltd., toluene / butyl acetate mixed solvent 50%
Containing]

[0138]

[Table 4]

Examples 69 to 70 150 parts of glass beads (3 mmφ), a solvent having a composition shown in Table 5 [xylene / butanol = 3/1 (weight ratio)], a pigment and a dispersant were mixed in a dispersion container. Then, the mixture was dispersed with a paint conditioner for 2 hours to obtain a pigment dispersion, and then 58 parts of the obtained pigment dispersion (however, the weight of glass beads was excluded) and Beckosol 57-1362.
[Dainippon Ink and Chemicals Incorporated alkyd resin, 35% containing Solvesso 100] 97 parts and Super Beckamine L-117 [Dainippon Ink and Chemicals Incorporated melamine resin, xylene / butanol mixed solvent 40% included ] 45 parts was further dispersed for 5 minutes with a paint conditioner to give an alkyd / melamine paint.

A cured coating film was obtained in the same manner as in Example 35 except that the obtained alkyd / melamine coating material was used, and the dispersibility was evaluated by measuring the gloss (20 °) of the coating film.
The results are shown in Table 5.

Example 71 150 parts of glass beads (3 mmφ), a solvent having the composition shown in Table 5 [xylene / butanol = 3/1 (weight ratio)], a pigment and a dispersant were mixed in a dispersion container, and then mixed. The pigment was dispersed for 2 hours with a paint conditioner to obtain a pigment dispersion, and then 42 parts of the obtained pigment dispersion (excluding the weight of the glass beads) and Acridic 47-712 [acrylic resin manufactured by Dainippon Ink and Chemicals, Inc.]. ,toluene/
Butyl acetate mixed solvent 50% contained] 131 parts and Super Beckamine L-117 [Dainippon Ink and Chemicals, Inc. melamine resin, xylene / butanol mixed solvent 40% contained] 27 parts with a paint conditioner for a further 5 minutes. Dispersed into an acrylic / melamine paint.

A cured coating film was obtained in the same manner as in Example 35 except that the obtained acrylic / melamine coating material was used, and the dispersibility was evaluated by measuring the gloss (20 °) of the coating film.
The results are shown in Table 5.

[0143]

[Table 5]

[0144]

INDUSTRIAL APPLICABILITY The dispersant of the present invention is effective for highly dispersible pigments and has high versatility, and dispersions and paints obtained using this dispersant have good dispersion of solids such as pigments And has excellent gloss.

Claims (15)

(57) [Claims] And 1. A tertiary amino group, Gae having hydroxy compound having an ester bond or amide bond (A), a structure formed by adding the isocyanate compound (B)
A dispersant comprising a compound (Z) having no polymerized structure of a silenic unsaturated double bond as an active ingredient. 2. A compound (Z) containing a tertiary amino group
Having an ethyl bond or an amide bond
The hydroxy compound (A) having no heavy bond is converted to ethylene.
Isocyanate Compounds Not Containing Polyunsaturated Double Bond
An ethylenically unsaturated diamine having a structure added to (B)
The compound having no polymer structure of heavy bonds.
Dispersant . 3. The dispersant according to claim 1, wherein the hydroxy compound (A) is a compound having two or more ester bonds. 4. The hydroxy compound (A) is an amino alcohol having a tertiary amino group and / or a polyamine (a having a tertiary amino group and a primary or secondary amino group.
The dispersant according to claim 1, which is a compound having a structure obtained by reacting ₁ ) with a lactone or a carboxylic acid having a hydroxyl group (a ₂ ). 5. The dispersant according to claim 4, wherein the carboxylic acid (a ₂ ) is a lactone, a carboxylic acid having a hydroxyl group or a carboxylic acid ester having a hydroxyl group. 6. The hydroxy compound (A) is an amino alcohol having a tertiary amino group and / or a polyamine (a having a tertiary amino group and a primary or secondary amino group.
The dispersant according to claim 1, which is a compound having a structure obtained by reacting ₁ ) with a polycarboxylic acid (a ₃ ) and then with a polyol or an epoxy compound (a ₄ ). 7. The dispersant according to claim 6, wherein the polycarboxylic acid (a ₃ ) is a polycarboxylic acid, a polycarboxylic acid anhydride or a polycarboxylic acid ester. 8. The hydroxy compound (A) is 200 to
The dispersant according to any one of claims 2 to 7, which is a polyester having a number average molecular weight of 5,000. 9. The dispersant according to any one of claims 1 to 8, wherein the isocyanate compound (B) is a polyisocyanate compound. 10. The dispersant according to claim 9, wherein the isocyanate compound (B) has an isocyanurate ring. 11. The compound (Z) comprises a hydroxy compound (A) having a tertiary amino group, an ester bond or an amide bond, and a compound (C) having active hydrogen other than the hydroxy compound (A). The dispersant according to claim 10, which is a compound having a structure formed by addition to polyisocyanate. 12. The dispersant according to claim 11, wherein the compound (C) is a polyhydroxy compound other than the compound (A) or an amino alcohol other than the compound (A). 13. A dye / pigment and any one of claims 1-12.
And a dispersant according to item 1. 14. A dye and pigment and any one of claims 1 to 12.
A coating material containing the dispersant and the resin described in 1. 15. A paint comprising the dispersion according to claim 13 and a resin.