JPH0724746B2 - Pigment dispersant - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a pigment dispersant. More specifically, a pigment that exhibits good compatibility with a wide range of paint resins, has a sufficient affinity for a pigment dispersion paste with a small amount of dispersion resin, and has good dispersibility and dispersion stability. It relates to a dispersant.

Conventional technology As a pigment dispersion method, a pigment is dispersed by using a part of the main component resin of the paint as a pigment dispersion resin, and a dispersion paste is first prepared, and then a predetermined resin and solvent are diluted to produce the paint. It is generally known. The surface properties of the pigments used in these are acidic, amphoteric and basic. Therefore, by making the dispersion resin amphoteric, the dispersibility, storage stability, color separation, reduction in gloss of the coating film and the like have been improved (JP-A-58-21468).
issue).

It is generally known that in order to obtain good dispersibility in an amphoteric and acidic pigment, a basic functional group may be distributed in the main chain polymer in order to have an affinity for the pigment. It has been proposed that melamine and hydroxyethylethyleneimine are condensation-added to the polyester main chain and that basic monomers are widely distributed in the main chain by copolymerization with an acrylic main chain. These basic resins have a low density of basic functional groups, so the adsorption power is weak, the adsorption layer required for dispersion stability is not formed, and the viscosity at the time of dispersion and dispersion stabilization effect are satisfied. Didn't solve the problem.

As an attempt to solve these problems, JP-A-59-217769
And JP-A-60-166318,
It has been proposed that the dispersibility and temporal stability of the pigment be improved by concentrating and localizing the basic functional group in the main chain. However, a sufficient effect cannot be expected in terms of various properties such as low viscosity when dispersed with a small amount of resin when dispersed and compatibility with a wide range of coating systems, and further improvement in these points has been strongly demanded.

Problems to be Solved by the Invention A wide range of compatibility with various paint resins is obtained, and excellent pigment dispersibility is obtained with a small amount of dispersion resin for pigments, and based on this, storage stability and color mixing It is extremely useful if an excellent coating composition can be obtained, and the present invention was made for the purpose of obtaining such a dispersant.

Means for Solving the Problems The present inventors have used a polyepoxy compound as a base resin for concentrating and localizing a basic functional group, and have an acidic functional group compatible with various resins for paints. A nitrogen compound containing active hydrogen, that is, a compound having a basic functional group, was directly bonded to the epoxy group portion of the base resin while the prepolymer was grafted onto the prepolymer to concentrate and localize the basic functional group. . As a result, a dispersant having a wide range of compatibility with the coating resin and having excellent pigment dispersibility in the dispersion resin with a small amount of the pigment was obtained. Furthermore, it was found that the pigment dispersion stability was extremely good by increasing the epoxy group of the polyepoxy compound to increase the molecular weight, and the storage stability and the color mixing property were excellent.
The present invention has been completed.

That is, according to the invention, the formula (In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group having a substituent or not, an allyl group or a heterocyclic group,
However, except when R ₁ and R ₂ are both hydrogen atoms, R ₁ , R ₂
And a nitrogen atom in the formula can form a heterocycle having or not having a substituent; X is a carbon atom having 25 to 600 carbon atoms, which may contain a carbonyl group, an ether bond or a urethane bond. Represents a hydrogen residue; Z is a number average molecular weight of 300 to
7,000 polyester or acrylic prepolymer chains; n and m each represent a real number of 1 or more satisfying the condition of 140 ≧ n + m ≧ 7), and a pigment dispersant represented by the formula: (In the formula, X represents a hydrocarbon residue having 25 to 600 carbon atoms which may contain a carbonyl group, an ether bond or a urethane bond; n and m are real numbers of 1 or more, each satisfying the condition of 140 ≧ n + m ≧ 7. For a polyepoxy compound (I) represented by (In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group having or not having a substituent, an allyl group or a heterocyclic group, provided that R ₁ and R ₂ are both hydrogen atoms. , R ₁ and R ₂ and a nitrogen atom in the formula can form a heterocycle having or not having a substituent), and an amine compound (II) represented by the formula Z-COOH (formula Medium Z is a prepolymer having a carboxyl group represented by a polyester or acrylic prepolymer chain having a number average molecular weight of 300 to 7,000 (II
A formula characterized by reacting with I) simultaneously or in any order (Wherein R ₁ , R ₂ , X, Z, n and m are as described above), a method for producing a pigment dispersant is provided.

The polyepoxy compound (I) used for producing the pigment dispersant of the present invention needs to contain 7 to 140 epoxy groups in one molecule, and preferably 7 to 70 epoxy groups. If the number of epoxy groups is 7 or less, the storage stability and color mixing property will be poor, and if the number of epoxy groups is 140 or more, the dispersant itself will have an excessively high molecular weight and the viscosity of the dispersion paste will be too high, resulting in poor dispersibility.

Such a polyepoxy compound can be produced by the following method and used.

Polymer Obtained from Polyvalent Glycidyl Ethers: A polymer having a desired number of epoxy groups can be synthesized by combining a polyvalent glycidyl ether having a hydroxy group and a polyvalent isocyanate. For example, as the polyvalent glycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, and as the polyvalent isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and hexamer diisocyanate trimer by buret bond (Sumijour N
-75, manufactured by Sumitomo Bayer Urethane Co., Ltd., etc. are used.

Polymer Obtained from Polymerization of α, β-Ethylenically Unsaturated Glycidyl Monomer: A polymer having a desired number of epoxy groups can be synthesized from each monomer of aryl glycidyl ether and glycidyl methacrylate by a conventional solution polymerization method. .

Next, the amine compound (II) used for producing the pigment dispersant of the present invention has the formula: (In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group with or without a substituent, an aryl group or a heterocyclic group,
However, except when R ₁ and R ₂ are both hydrogen atoms, R ₁ , R ₂
And a nitrogen atom in the formula can form a heterocycle having or not having a substituent). Examples of the amine compound include ethylamine / propylamine, butylamine, isobutylamine, hexylamine, diethylamine, dipropylamine, dibutylamine, dimethylaminoethylamine, diethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, 3
-Alkylamines such as methoxypropylamine, diethylenetriamine or tetraethylenepentamine; N-
Aminopiperidine, 1-amino-4-methylpiperazine, 2-amino-3-nitropyridine, 2-picolylamine, 3-picolylamine, 2-aminopyridine, 3-
Aminoheterocyclic compounds such as aminopyridine, 4-aminopyridine or 2-aminopyrazine; triazole, imidazole, morpholine, piperidinepyrrolidine, 2-
Heterocyclic amines such as pipecoline, 3-pipecoline or 4-pipecoline. These can be used alone or in combination of two or more.

The prepolymer used for producing the pigment dispersant of the present invention is
A prepolymer having a carboxyl group represented by the formula Z-COOH (wherein Z represents a polyester or acrylic prepolymer chain having a number average molecular weight of 300 to 7,000) (II
If the number average molecular weight is 300 or less, the dispersion stability becomes poor. On the other hand, when it is 7,000 or more, both dispersibility and compatibility are poor, which is not preferable. Examples of such prepolymers include carboxyl group-containing polyester resins, acrylic resins, block prepolymers thereof, and modified resins thereof.

In addition, these prepolymers can be produced by the following method and used.

(1) Polyester prepolymer having a terminal carboxyl group: When derived from a lactone, for example, P as an initiator
-Toluenesulfonic acid or dibutyltin laurate, obtained by reacting with a hydroxycarboxylic acid at a temperature of about 100 to 180 ° C. In this case, the hydroxycarboxylic acid used preferably has 4 to 15 carbon atoms. Next, in the case of a polyester obtained by a condensation reaction, condensation of hydroxy fatty acid is mentioned as a typical example. For example, 12-hydroxystearic acid at 160-250 ° C under P-toluenesulfonic acid catalyst
To condense. The number average molecular weight of the obtained polyester prepolymer is preferably 300 to 5000, and more preferably 500 to 3000.

(2) Polyester Prepolymer Having Carboxyl Group at Other Terminal: Obtained by condensation of polyvalent carboxylic acid and polyhydric alcohol. As the polycarboxylic acid, trimellitic acid, trimellitic anhydride, phthalic acid, phthalic anhydride, adipic acid, etc., and as the polyhydric alcohol, pentaerythritol, trimethylolpropane, trimethylolethane, glycerin, polyethylene glycol, 1,6-hexanediol, neopentyl glycol, propylene glycol,
Ethylene glycol and the like are usually used, and fatty acids such as soybean oil fatty acid, castor oil fatty acid, tall oil fatty acid, and coconut oil fatty acid may be used as the oil and fat component in these components. Usually, the solid acid value at the reaction temperature of 200-240 ℃
A polyester prepolymer can be synthesized by reacting until 10 or less. The number average molecular weight of these polyester prepolymers is preferably 300 to 5000, and more preferably 500 to 3000.

(3) Acrylic prepolymer having a terminal carboxyl group: An initiator that is usually used in the polymerization of an acrylic resin using a monomer other than a carboxyl group-containing monomer, for example, 2,2'-azo-bis-isobutyronitrile as an azo-nitrile compound. Further, as the peroxide compound, t-butyl peroxide or the like is used to initiate the polymerization,
By using a compound containing a carboxyl group as the chain transfer agent, for example, mercaptoacetic acid, the carboxyl group can be introduced into the terminal of the acrylic prepolymer. On the other hand, when a monomer other than a carboxyl group-containing monomer is polymerized with an acrylic resin by using a carboxyl group-containing initiator, for example, 4,4'-azo-bis (4-cyanopentanoic acid), the acrylic resin A carboxyl group can be introduced at the end of the prepolymer. Monomers other than the carboxyl group-containing monomer used for the polymerization of the acrylic prepolymer are classified into neutral monomers and functional group-containing monomers. Neutral monomers include ethylene, propylene, butadiene, isoprene, chloroprene, vinyl chloride, vinyl acetate, methyl vinyl ether, acrylic acid esters (eg methyl, ethyl, butyl ester), methacrylic acid esters (eg methyl, ethyl, butyl ester, etc.) ), A nitrile derivative (eg, acrylonitrile, methacrylonitrile, etc.), styrene, a styrene derivative (eg, α-methylstyrene, etc.) and the like. On the other hand, examples of the functional group-containing monomer include amide and methacrylamide as the amide group-containing monomer, N-methoxymethylol acrylamide and N-butoxymethylol acrylamide as the alkoxy group-containing monomer, and 2 as the hydroxyl group-containing monomer.
-Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N-methylol acrylamide and the like can be mentioned. In the polymerization of such an acrylic prepolymer, the total amount is charged by the solution polymerization method, the decomposition temperature of the initiator is higher than the decomposition temperature of the initiator by the initiator dropping method or the monomer dropping method, and usually at a reaction temperature of 70 to 170 ° C. for 1 to 8 hours. A prepolymer can be synthesized by reacting. The number average molecular weight of these acrylic prepolymers is preferably 800-7000, preferably 1000-500.
It is 0.

(4) Acrylic prepolymer having a carboxyl group in addition to the terminal: Obtained by copolymerization of a carboxyl group-containing monomer, a neutral monomer, and a functional group-containing monomer. In the polymerization, a commonly used initiator, for example, an azo-nitrile compound,
It can be obtained by polymerization under the condition (3) above by a solution polymerization method using a peroxide compound. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, maleic acid and fumaric acid. As the neutral monomer and the functional group-containing monomer, the monomers listed in (3) above are used. The number average molecular weight of these acrylic prepolymers is preferably 800 to 7,000, more preferably 1000 to 5
It is 000.

The pigment dispersant of the present invention is the polyepoxy compound (I),
It is produced by reacting the amine compound (II) and the carboxyl group-containing prepolymer (III). In this case, (I), (II) and (III) may be reacted simultaneously or in any order. It doesn't matter. As one of the preferred embodiments, for example, by reacting the polyepoxy compound (I) with the carboxyl group-containing prepolymer (III) in advance to prepare an intermediate substance, and reacting this with the amine compound (II). The method of manufacturing may be mentioned. This will be described below.

Reaction of polyepoxy compound (I) with carboxyl group-containing prepolymer (III): Polyepoxy compound (I) and carboxyl group-containing prepolymer (III) are mixed and, if necessary, reacted with glycidyl group or carboxyl group The reaction is carried out at a reaction temperature of 60 to 180 ° C., preferably 80 to 150 ° C., until the reaction rate measured by the acid value of the unreacted carboxyl groups of the carboxyl group-containing prepolymer is 90% or more. A base catalyst, for example, can be used as a reaction catalyst in the above reaction, if necessary. Examples of the base catalyst include pyridine, isoquinoline, quinoline, N-dimethylcyclohexylamine, α-picoline tri-n-butylamine, triethylamine, N-ethylmorpholine, N, N-dimethylaniline, N- (β-hydroxyethyl) amine, Organic amines such as dimethyl coconut amine derived from N-ethyl-3,5-dimethylmorpholine and coconut oil, and inorganic alkalis such as caustic soda and causticari are used.

The intermediate obtained in the above reaction, that is, the prepolymer-grafted polyepoxy compound, has a carboxyl group-containing prepolymer (III) compatible with various coating resins,
Further, since it is effective for dispersion stability, performances such as compatibility and dispersion stability are preferably imparted. This intermediate has the formula (In the formula, X represents a monovalent hydrogen residue having 25 to 600 carbon atoms which may contain a carbonyl group, an ether bond or a urethane bond; Z represents a polyester or acrylic prepolymer chain having a number average molecular weight of 300 to 7000; n and m are 140 ≧ n
+ M ≧ 7, each represents a real number of 1 or more).

Reaction between prepolymer-grafted polyepoxy compound and amine compound (II): Mix prepolymer-grafted polyepoxy compound and amine compound (II), and optionally add a solvent that does not react with glycidyl group, carboxyl group or amine The reaction is carried out at a reaction temperature of 60 to 150 ° C. until the reaction rate of the epoxy groups of the prepolymer-grafted polyepoxy compound reaches 90% or more, whereby the pigment dispersant of the present invention can be obtained.

The pigment dispersant according to the present invention has the formula (Wherein R ₁ , R ₂ , X, Z, n and m are as described above). The above pigment dispersant formula The hydroxyl group of 1 showed an affinity for the pigment, and an excellent dispersibility effect was obtained, and when it was incorporated into the paint, the effect of improving the adhesion to the coated object was also obtained.

The pigment that can use the pigment dispersant according to the present invention is not limited in kind, but amphoteric and acidic pigments are particularly suitable, and various inorganic and organic pigments can be used. Specific examples of the inorganic pigment include zinc white, titanium oxide, antimony white,
Iron black, red iron oxide, red lead, cadmium yellow, zinc sulfide, lithopone, barium sulfate, lead sulfate, barium carbonate,
Lead white, alumina white and the like can be mentioned, and specific examples of the organic pigment include azo type, polycondensation type, metal complex azo type, benzimidazolone type, phthalocyanine type, thioindigo type, anthraquinone type, flavanthron type, Indanthrene, anthrapyrimidine,
Examples thereof include pyranthrone type, isoindolinone type, perylene type, perinone type and quinacridone type. A basic pigment can also be used if desired.

When a pigment and a dispersed resin are blended and dispersed using a disperser to produce a dispersion base composition, the blending ratio of both is not critical because it is further diluted with a resin or a solvent when it is made into a paint. Although it can be arbitrarily selected, the pigment is usually used in an amount of about 97 to 30% by weight and a dispersant of about 3 to 70% by weight in consideration of the production economy of the dispersion base composition and the dispersion efficiency.

As the disperser, a commonly used disperser, for example, a roll mill, a ball mill, a sand grind mill, a high speed disper, or the like is used.

The thus-obtained dispersion base composition shows extremely good pigment dispersibility and is excellent in stability during storage, and various resins such as alkyd, acrylic, polyester, urethane, vinyl acetate, vinyl chloride, rubber chloride, and epoxy resin. Etc., and is extremely useful as a pigment dispersion base composition.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but all parts and% are based on weight unless otherwise specified.

Production Example 1: Production of polyepoxy compound 400 parts of xylene was charged into a reaction vessel equipped with a dropping funnel, a cooling pipe, a nitrogen introducing pipe, a thermometer, and a stirring blade, and the temperature was raised to 130 ° C, while 500 parts of glycidyl methacrylate was used. , T-
100 parts of butylperoxy 2-ethylhexanoate was placed in a dropping funnel, and the contents of the dropping funnel were added dropwise at a constant rate over 3 hours at 130 ° C under a nitrogen atmosphere. 1 hour after the end of dropping 13
The temperature was maintained at 0 ° C to complete the polymerization. From the above results, a polyepoxy compound [I] having a solid content of 50.2% and a number average molecular weight of 1080 was obtained.

Manufacture example 2: Manufacture of polyepoxy compound By the compounding of manufacture example 2 of Table 1, the polymerization was completed by the method of manufacture example 1. From the above results, a polyepoxy compound [II] having a solid content of 50.0% and a number average molecular weight of 2,100 was obtained.

Production Example 3: Production of polyepoxy compound A reaction vessel equipped with a dropping funnel, a cooling tube, a nitrogen introducing tube, a thermometer, and a stirring blade was charged with 351 parts of cellosolve acetate and heated to 120 ° C, while glycidyl methacrylate 585 And t-butylperoxy 2-ethylhexanoate (13 parts) were placed in a dropping funnel and heated to 120 ° C under a nitrogen atmosphere.
The contents of the dropping funnel were dropped at a constant speed over 3 hours. After completion of dropping, the temperature was kept at 120 ° C. for 30 minutes. Next, 49 parts of cellosolve acetate and 2 parts of t-butylperoxy 2-ethylhexanoate were placed in a dropping funnel, and 120 ° C under a nitrogen atmosphere.
The contents were added dropwise at a constant rate over 1 hour. 1 hour after the end of dropping
The temperature was maintained at 120 ° C to complete the polymerization. From the above results, a solid content of 49.8% and a number average molecular weight of 9800 epoxy compound [III] were obtained.

Production Example 4: Production of polyepoxy compound In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirring blade, 632 parts of cellosolve acetate and Denacol EX-622 8
37 parts (sorbose polyglycidyl ether manufactured by Nagase Kasei Co., Ltd.), 111 parts isophorone diisocyanate,
0.5 parts of dibutyl dilaurate was charged, the temperature was raised to 80 ° C., and the reaction was completed by stirring at 80 ° C. for 2 hours in a nitrogen atmosphere. From the above results, solid content 60.3%, number average molecular weight 2200
To obtain a polyepoxy compound [IV].

Production Example 5: Production of polyepoxy compound By the formulation of Production Example 5 in Table 1, polymerization was completed according to the method of Production Example 1. From the above results, a polyepoxy compound [V] having a solid content of 50.2% and a number average molecular weight of 10100 was obtained.

Manufacture Example 6: Manufacture of acrylic resin prepolymer By the compounding of Manufacture Example 6 in Table 1, polymerization was completed according to the method of Manufacture Example 1. From the above results, solid content 60.2%,
An acrylic resin prepolymer [I] having a number average molecular weight of 5,100, a solid content acid value of 11.1, and a Tg of 30 was obtained.

Manufacture example 7: Manufacture of acrylic resin prepolymer By the compounding of manufacture example 7 of Table 1, polymerization was completed according to the method of manufacture example 1. From the above results, solid content 50.3%,
Number average molecular weight 2700, solid acid value 20.3, OH value 58, Tg 6
An acrylic resin prepolymer [II] of 8.4 was obtained.

Production Example 8: Production of polyester resin prepolymer Cooling pipe, nitrogen introducing pipe, thermometer, 950.0 parts of 12-hydroxystearic acid in a reaction vessel equipped with stirring blades, xylene 48.
1 part and 1.9 parts of dibutyltin oxide were charged, heated to 220 ° C., and dehydrated while stirring to complete the condensation. Based on the above results, a polyester resin prepolymer [I] having a solid content of 95.0%, a number average molecular weight of 1500, an acid value of the solid content of 39.3, and an OH value of 18.5 was obtained.

Production Example 9: Production of Polyester Resin Prepolymer Glycolic acid 34.2 parts, Praxel M (manufactured by Daicel Chemical Industries Ltd., ε-caprolactone) 864.0 parts in a reaction vessel equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer, and a stirring blade. 1.8 parts of dibutyltin oxide was charged and heated to 130 ° C. to complete the reaction with stirring. Based on the above results, solid content 90.2
%, A number average molecular weight of 2100, a solid content acid value of 28.1, and an OH value of 28.2 were obtained as a polyester resin prepolymer [II].

Production Example 10: Production of alkyd resin prepolymer Charge 207 parts of coconut oil, 194.5 parts of trimethylolethane and 0.2 parts of lithium naphthenate into a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirring blade, and raise the temperature to 240 ° C. It was warmed to transesterify. Next, 267 parts of adipic acid and 45.2 parts of 1,6-hexanediol are added, and the mixture is heated at 220 to 230 ° C. until the solid content acid value becomes about 3, dehydration reaction is performed, and after cooling, xylene 35
Dilute with addition of 0 parts, solid content 65.2%, number average molecular weight 260
A polyester resin prepolymer [III] having a solid content acid value of 3.1 and an OH value of 130 was obtained.

Example 1: Production of Dispersant A-1 Step 1 95.1 parts of polyepoxy compound [I] of Production Example 1 and acrylic acid of Production Example 7 were placed in a reaction vessel equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer, and a stirring blade. A solution of resin prepolymer [II] 898.2 parts and triethylamine 5.0 parts was charged and heated to 90 ° C,
The reaction was allowed to stir for 3 hours.

Step 2 Next, 12.3 parts of diethylamine was added to the reaction product of Step 1, and the addition reaction was uniformly stirred at 100 ° C. for 3 hours to obtain a dispersant A-1.

Example 2: Preparation of Dispersant A-2 A reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer, and a stirring blade was charged with 95.1 parts of the polyepoxy compound [I] of Production Example 1 and 12.3 parts of diethylamine, and 90 ° C. The reaction was carried out for 3 hours.

Then, the acrylic resin prepolymer [II] 89 of Production Example 7
8.2 parts were charged and the mixture was stirred at 90 ° C for 3 hours to prepare a dispersant A-
Got 2.

Example 3: Preparation of Dispersant A-3 A reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer, and a stirring blade was placed in a reaction vessel equipped with 95.1 parts of the polyepoxy compound [I] of Production Example 1 and the acrylic resin preform of Production Example 7. 898.2 parts of polymer [II] and 12.3 parts of diethylamine were charged, and the reaction was carried out at 90 ° C. for 5 hours with stirring.

Further, 81.6 parts of xylene was charged, followed by uniform stirring for 30 minutes to obtain a dispersant A-3.

Example 4: Preparation of Dispersant B Step 1 A reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer, and a stirring blade was charged with 396.2 parts of the polyepoxy compound [I] of Production Example 1,
A solution of 598.8 parts of the polyester resin prepolymer of Production Example 8 and 5.0 parts of triethylamine was charged and the temperature was raised to 90 ° C.
The reaction was allowed to stir for 3 hours.

Step 2 Then, n-butylamine 218.4 was added to the reaction product of Step 1.
Parts were charged and the addition reaction was carried out at 90 ° C. for 3 hours. afterwards
A vacuum treatment was carried out at 90 ° C. to remove 320.8 parts of xylene to remove the solvent, and excess amine was removed. Further xylene 782.
After charging 0 part, uniform stirring was carried out for 30 minutes to obtain a dispersant B.

Example 5: Preparation of Dispersant C By the compounding of Example 5 in Table 2, the addition reaction of Steps 1 and 2 was completed according to the method of Example 1 to obtain Dispersant C.

Examples 6 to 8: Preparation of Dispersants DF By the blending of Examples 6 to 8 in Table 2, the addition reaction of Steps 1 and 2 was completed according to the procedure of Example 4 to dispersants DF. Got

Example 9: Preparation of Dispersant G The addition reaction of steps 1 and 2 was completed according to the method of Example 1 by blending Example 9 in Table 2 to obtain Dispersant G.

Comparative Example 1: Preparation of Dispersant H The polyepoxy compound [V] of Production Example 5 was prepared according to the formulation of Comparative Example 1 in Table 2 and using the reaction conditions of Step 2 of Example 1.
Diethylamine was added to to obtain Dispersant H.

Table 3 shows the characteristic values of the dispersants A-1, A-2, A-3 and B to H.

Reference Examples 1 to 14 and Comparative Reference Examples 1 to 2 Various pigments, that is, titanium oxide (Taipaque CR-5) were prepared using the dispersants prepared in the above Examples and Comparative Examples.
0, Ishihara Sangyo Co., Ltd., Carbon Black (Special Black 100, Dexa Co., Ltd.), Yellow Iron Oxide (Mapico Yellow LLXLO, Titanium Industry Co., Ltd.) Organic Red (Fast Red 2203, Fuji Dye Co., Ltd.) Are blended in the respective proportions shown in Table 4, and dispersed with a paint shaker (Red Devil Co.) until the viscosity becomes 10 μ or less.
Dispersion pastes of 14 and Comparative Reference Examples 1 and 2 were obtained. Table 4 shows the properties of these pigment dispersion pastes.

Coating film performance test The pigment-dispersed pastes obtained in each of the reference examples were blended into various paint systems, and compatibility with paint resins and the like were evaluated by coating film performance. The resin varnish characteristics of the paint used in this test are as follows.

Thermoplastic acrylic paint resin varnish (I) Solid content 50%, Tg 15.0, OH value 17.0, solid acid value 7.8, number average molecular weight 8000 Acrylic urethane paint resin varnish (II) solid content 50%, Tg 11.0, OH value 46.0 , Solid content acid value 4.2, number average molecular weight 15000 To 100 parts of coating liquid, Dismodur L-75 (isocyanate compound, Bayer) 10 is mixed and cured Long oil alkyd paint resin varnish (III) Solid content 60%, large Soybean oil modified 60% oil length, OH value 6.3, solid acid value 7.0, number average molecular weight 2400 Medium oil alkyd paint resin varnish (IV) Solid content 50%, soybean oil modified oil length 50%, OH value 45, solid acid value 7.0, number average molecular weight 2600 short oil alkyd paint resin varnish (V) Solid content 60%, coconut oil modified oil length 27%, OH value 102, solid acid value 7.3, number average molecular weight 1960 Butylation for 100 coating liquids Melamine (60% solid content) 10
Chlorinated rubber paint resin varnish (VI) 46 parts chlorinated polyethylene (chlorinated 68%), short oil alkyd resin (oil length 9%) 15 parts, plasticizer phase 23 parts xylene 16 parts solid content 84% paint The coating liquid was adjusted by stirring each component in the above table with a lab mixer for 20 minutes. Then, as shown below, mild steel plates were applied to a test plate which had been treated with # 240 paper and washed with a solvent and dried to obtain a coating film having a dry film thickness of 20 to 30 μm as described below.

With respect to each of the obtained coating films, 60 ° gloss was measured with a gloss meter (manufactured by Suga Test Instruments Co., Ltd.). 2m on the coating
Adhesion was examined by making a peeling test with a cellophane adhesive tape by making 25 cross-cuts with a m cross cut. 90 ~
The case where 100% peeling did not occur was regarded as acceptable. The results of these tests are shown in Table 7.

As is clear from the above, the dispersion paste according to the present invention has excellent compatibility with various coating resins, and provides a high gloss value and good coating adhesion.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09C 3/10 PCE C09D 7/12 PSM

Claims (2)

[Claims] 1. A formula (In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group having a substituent or not, an allyl group or a heterocyclic group,
However, except when R ₁ and R ₂ are both hydrogen atoms, R ₁ , R ₂
And a nitrogen atom in the formula can form a heterocycle having or not having a substituent; X is a carbon atom having 25 to 600 carbon atoms, which may contain a carbonyl group, an ether bond or a urethane bond. Represents a hydrogen residue; Z is a number average molecular weight of 300 to
7,000 polyester or acrylic prepolymer chains; n and m each represent a real number of 1 or more satisfying the condition of 140 ≧ n + m ≧ 7). 2. A formula (In the formula, X represents a hydrocarbon residue having 25 to 600 carbon atoms which may contain a carbonyl group, an ether bond or a urethane bond; n and m are real numbers of 1 or more, each satisfying the condition of 140 ≧ n + m ≧ 7. For a polyepoxy compound (I) represented by (In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group with or without a substituent, an allyl group or a heterocyclic group, provided that R ₁ and R ₂ are both hydrogen atoms. , R ₁ and R ₂ and a nitrogen atom in the formula may form a heterocycle having or not having a substituent), and an amine compound (II) represented by the formula Z-COOH (formula Medium Z is a prepolymer having a carboxyl group represented by a polyester or acrylic prepolymer chain having a number average molecular weight of 300 to 7,000 (II
A formula characterized by reacting with I) simultaneously or in any order (Wherein R ₁ , R ₂ , X, Z, n and m are as described above).