JPH0319873B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to pigment dispersion compositions and coating compositions. Conventionally, the pigment dispersion method uses a part of the resin that will be the main component resin of the final paint product as a pigment dispersion resin, first prepares a so-called dispersion base composition in which pigment is dispersed, and then a suitable dispersion base composition is prepared. The common method was to dilute it with a resin and a solvent to form a paint.
In recent years, the paint industry has seen a trend towards the production of a wide variety of paints in small quantities due to the diversification of user requirements. However, since the surface characteristics of pigments used in paints are not uniform, a different dispersing resin must be selected for each type of pigment, and there is a problem in that it is not possible to reduce costs through mass production. If various pigments could be dispersed in large amounts in a single dispersing resin and then mixed or diluted with the necessary resin and solvent to create a product according to the purpose of use, there would be immeasurable gains in paint production. Unfortunately, such a general-purpose dispersing resin has not yet been found, although there may be unknowns. Therefore, an object of the present invention is to provide a general-purpose dispersing resin that has good affinity for various pigments with different surface characteristics and good compatibility with various resins used as paint vehicles. Another object of the present invention is to provide a dispersion composition comprising such a dispersion resin and a pigment. P.Sφrensen is a Journal of Paint
Technology - 47 (602) 31 (1975) explains the affinity between various pigments and resins using the concepts of acids and bases,
It has been reported that good affinity can be obtained between pigments and resins that have contradictory properties, and therefore good dispersibility can be obtained. The present inventors focused on Sφrensen's concept of acids and bases, and based on the acidic and basic resins used as paint vehicles, we developed an amphoteric resin that has both acidic and basic properties through their reaction. We thought that if we could obtain a resin, it would have good compatibility with various paint vehicles used as raw materials, and would also show good dispersibility for various pigments with different surface properties. The present invention was arrived at as a result of intensive research into various bonding methods between the basic resin and the resulting resin, and the suitability of the resulting resin as a dispersion resin. That is, according to the present invention, an acidic resin (A) having active hydrogen and/or an active alkoxy group, or a functional group that reacts with active hydrogen and/or an active alkoxy group, and an electron accepting group; a functional group that reacts with the group;
Alternatively, a dispersion composition consisting of a pigment and an amphoteric resin for dispersion obtained by addition or condensation with a basic resin and/or basic low molecular weight compound (B) having an active hydrogen and/or active alkoxy group and an electron donating group. things are provided. Briefly, the dispersing resin used in the present invention is made by combining an acidic resin with an electron-accepting group and a basic resin (and/or a basic low molecular weight compound) with an electron-donating group, one of which contains active hydrogen. It is an amphoteric resin obtained by addition or condensation reaction of active alkoxy and/or active alkoxy and active hydrogen and/or active alkoxy and a functional group that reacts with each other. The term "active hydrogen" used in this specification refers to hydrogen bonded to oxygen, sulfur, nitrogen, etc. contained in primary, secondary, and tertiary hydroxyl groups, amide bonds, urethane bonds, carboxyl groups, etc. The term "active alkoxy group" refers to a highly reactive alkoxy group such as a group in which the terminal hydrogen atom of active methylol is substituted with alkyl; Nohki”
The term refers to primary, secondary and tertiary hydroxyl groups,
It refers to groups that easily react with active hydrogen, such as isocyanate groups and glycidyl groups; the term "functional groups that react with active alkoxy" refers to groups that easily react with active alkoxy groups, such as primary, secondary, and tertiary hydroxy groups. The term "electron-accepting group" refers to groups that tend to withdraw electrons from other sources, such as carboxyl groups, sulfone groups, and nitro groups, with hydrogen as the standard in the molecule; and the term "electron-donating group" The term ``acidic resin'' refers to groups that have -N- with a lone pair of electrons, halogens, alkyls, etc. that tend to donate electrons to others when hydrogen is the standard in the molecule, and the term ``acidic resin'' is usually used in the paint field. The term "basic resin" refers to resins with acidic groups such as oil-free polyether resins, long-oil or short-oil alkyd resins, acrylic resins, vinyl resins, etc., which are used in the paint field, such as urea resins, melamine resins, polyamides, etc. The term "basic low molecular weight compound" refers to resins having basic groups such as resins and polyurethane resins, and also refers to hydroxylamine compounds (e.g. monoethanolamine, diethanolamine, aminopentanol, etc.) used as prepolymers or monomers of basic resins. aminobenzyl alcohol, 2-dimethylaminoethanol, etc.), amino acids (e.g. 3-dimethylaminobenzoic acid, 2-amino-isobutyric acid, 4-amino-n-
butyric acid, etc.), primary or secondary amine compounds (such as n
-butylamine, n-propylamine, dibutylamine, di(2-ethylhexyl)amine, etc.). Active hydrogen and/or active alkoxy group; Presence of a functional group that reacts with active hydrogen and/or active alkoxy group in an acidic resin, basic resin, or basic low molecular weight compound means that a suitable resin having these groups can be used. This can be easily achieved by selecting or blending compounds having these groups during resin production. The raw material resin used for producing the amphoteric resin for dispersion in the present invention will be further explained as follows. Oil-free polyester resin used as acidic resin is obtained by condensation of polyhydric carboxylic acid and polyhydric alcohol, and polyhydric carboxylic acids include trimellitic acid, trimellitic anhydride, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, Adipic acid, etc., and polyhydric alcohols such as pentaerythol, trimethylolpropane, trimethylolethane, glycerin, polyethylene glycol, 1,6-hexanediol, neopentyl glycol, propylene glycol, and ethylene glycol are commonly used. There is. In addition to the above-mentioned polycarboxylic acids and polyhydric alcohols, long oil or short oil alkyd resins contain fatty acids such as soybean oil fatty acids, castor oil fatty acids,
Tall oil fatty acids, coconut oil fatty acids, cottonseed oil fatty acids, etc., or vegetable oils such as soybean oil, castor oil, tall oil, coconut oil, cottonseed oil, linseed oil, etc. are used. Therefore, the oil-free polyester resin and long-oil or short-oil alkyd resin obtained by reacting the above-mentioned raw materials can contain primary, secondary or tertiary hydroxyl groups and/or carboxyl groups, so that they can be directly used in the present invention. Active hydrogen and/or active alkoxy groups in basic resins or basic low molecular weight compounds, or isocyanate groups of functional groups that react with them, are used as the acidic resin component (A) of the raw material for the production of dispersion resins, It can be reacted with glycidyl groups. Furthermore, when producing the above-mentioned oil-free polyester resins and long-oil or short-oil alkyd resins, compounds having isocyanate groups or glycidyl groups may be present as part of the raw materials to produce resins, or resins having active hydrogen may be prepared. If a compound having an isocyanate group or a compound having a glycidyl group is added to the already obtained resin and allowed to react so that free isocyanate groups or glycidyl groups remain in the resin, a basic resin or a basic low molecular weight resin can be obtained. The compound can carry an active hydrogen group that reacts with these isocyanate groups and glycidyl groups. Examples of compounds having an isocyanate group include diisocyanates such as hexamethylene diisocyanate, xylene diisocyanate, and isophorone diisocyanate, and polyvalent isocyanates such as Desmodyur N and Desmodyur L. Preferably used compounds include triglycidyl isocyanurate, ethylene glycol diglycidyl ether, and the like. Acrylic resins or vinyl resins can also be used as acidic resins (A). These resins as acidic resins useful in the present invention include (1) neutral monomers, (2)
an acid monomer and (3) a monomer having a functional group corresponding to active hydrogen and/or active alkoxy group;
Alternatively, (3)' can be obtained by copolymerizing monomers having active hydrogen and/or active alkoxy groups. Typical neutral monomers include ethylene, propylene, butadiene, isoprene, chloroprene, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, methyl vinyl ether, acrylic esters (e.g. methyl, ethyl, butyl ester, etc.), Methacrylic acid esters (e.g. methyl, ethyl, butyl esters, etc.), nitrile derivatives (e.g. acrylonitrile, methacrylonitrile, etc.), styrene, styrene derivatives (e.g. α
-methylstyrene), etc. Examples of acid monomers include carboxyl-containing monomers such as allyl acid, methacrylic acid, itaconic acid, and maleic acid, and examples of sulfonic acid-containing monomers include α-styrenesulfonic acid. On the other hand, examples of the functional group-containing monomer in (3) above include glycidyl acrylate, glycidyl methacrylate, etc. as glycidyl group-containing monomers.
Vinyl isocyanate, etc. can be selected as the isocyanate group-containing monomer, and vinyl chloride, vinylidene chloride, etc. can be selected as the chlorine-containing monomer. As the active hydrogen group-containing monomer in (3)' above, amide group-containing monomers such as acrylamide and methacrylamide can be used, and as active alkoxy group-containing monomers, N-methoxymethylolacrylamide, N-butoxymethylolacrylamide, etc. can be used. . Alternatively, as the functional group-containing monomer of (3) or the active hydrogen group-containing monomer of (3)', 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-
Hydroxyl-containing monomers such as hydroxypropyl methacrylate, N-methylolacrylamide, etc. can also be used. By appropriately selecting these monomer units for producing vinyl resins, acidic vinyl resins having functional groups that react with active hydrogen and/or active alkoxy groups, or active hydrogen and/or active alkoxy groups, and electron-accepting groups can be obtained. The amphoteric resin for dispersion useful in the present invention can be obtained by reaction with a base resin and/or a low molecular weight basic compound that are appropriately selected corresponding to each of the above. In addition, a basic resin and/or a basic resin is prepared by blending and reacting a polyvalent isocyanate compound or a glycidyl compound with a vinyl resin obtained using a monomer containing an active hydrogen group so that free isocyanate groups or glycidyl groups remain. It can also be a vinyl resin that can react with active hydrogen in a low molecular weight compound. As the basic resin which is component (B) of the dispersing resin, urea resins, melamine resins, polyamide resins, polyurethane resins, etc. commonly used in the paint field are used. Urea resins and melamine resins are obtained by condensing urea or melamine with formaldehyde, and if necessary, alcohols (such as methyl alcohol,
(ethyl alcohol, propyl alcohol, butyl alcohol, etc.) can be used as part of the raw materials for producing the resin and used as an alkylated methylol urea resin or an alkylated methylol melamine resin. Polyamide resins are obtained by the condensation reaction of aliphatic diamines and dibasic acids, or the ring-opening polymerization reaction of cyclic lactams.
1,2-ethanediamine, 1,6-hexanediamine, etc., and dibasic acids such as succinic acid, adipic acid, and sebacic acid are appropriately selected. Examples of cyclic lactams include α-pyrrolidone,
ε-caprolactam, ω-caprolactam, etc. are used. In the above-mentioned production process, active hydrogen or active alkoxy groups are introduced into such basic resins along with electron-donating groups, which can be subjected to an addition or condensation reaction with the functional groups in the acidic resin (A). Polyurethane resins are obtained by addition reacting polyhydroxy compounds such as oil-free polyester resins having hydroxyl groups, long oil or short oil alkyd resins, acrylic resins or polyether resins with isocyanate compounds. The polyether resin in the polyhydroxy compound is a resin obtained by polymerizing propylene oxide, ethylene oxide, etc. using an initiator such as sorbitol, pentaerythritol, sucrose, or starch.
As the isocyanate compound, diisocyanates such as hexamethylene diisocyanate, tolylene diisocyanate, and xylylene diisocyanate, or polyvalent isocyanates such as Desmodyur N and Desmodyur L are used. A group that reacts with active hydrogen, such as an isocyanate group or a glycidyl group, is also introduced into the basic resin as described above by reacting the resin with a polyvalent isocyanate compound or a glycidyl compound, resulting in an active hydrogen group (A). An amphoteric resin for dispersion can also be obtained by reacting with an acidic resin. In place of the basic resin (B) or as a part thereof, the present inventors have proposed an electron-donating group and an active hydrogen and/or an active alkoxy group, or a functional group that reacts with an active hydrogen and/or an active alkoxy group. Using a basic low molecular weight compound having a group (A)
It has been found that an amphoteric resin for dispersion useful in the present invention can be obtained even by carrying out an addition or condensation reaction with an acidic resin. Examples of such basic low molecular weight compounds include various hydroxylamine compounds corresponding to the prepolymers or monomers of the above-mentioned various basic resins, such as monoethanolamine, diethanolamine, aminopentanol, aminobenzyl alcohol, 2-dimethylaminoethanol, etc., and amino acid compounds. For example, 3-dimethylaminobenzoic acid, 2
-amino-isobutyric acid, 4-amino-n-butyric acid, etc.
Primary or secondary amine compounds such as n-butylamine, n-propylamine, dibutylamine, di(2-ethylhexyl)amine, etc. The above acidic resin (A) and basic resin and/or basic low molecular weight compound (B) have active hydrogen and/or active alkoxy groups on one side, and active hydrogen and/or active alkoxy groups on the other side. (A) and (B) each carry a reactive functional group.
These supported groups can easily react with each other by addition or condensation, and an amphoteric resin having both an electron-accepting group and an electron-donating group can be obtained very easily. Addition or condensation does not require any special processing means; it is sufficient to simply mix the two resin raw materials and heat them. The amphoteric resin thus obtained is different from a mere mixture of an acidic resin and a basic resin; it is a reaction product of both, so it has excellent stability and does not separate into raw material resins, and is compatible with various acidic resins used for paints. Since it is compatible with basic resins and has both acidic and basic properties, it showed good dispersibility for various pigments with different surface characteristics, as expected. As described above, the present invention provides a novel dispersion composition in which a pigment is dispersed in the above-mentioned dispersing amphoteric resin. In the paint industry, a wide variety of inorganic and organic pigments are used, and their surface properties are also very different. Even if we think of pigments in terms of acids and bases, their acidity and basicity vary widely. Therefore, it is naturally expected that the degree of acidity and basicity in the dispersing resin will vary from pigment to pigment if the optimal one is sought for each pigment.
Therefore, the present inventors thought that there might be an acidity and basicity of the dispersing amphoteric resin that exhibits good dispersibility in terms of the greatest common denominator for many of the pigments that are widely used today, and Pigments were actually dispersed in the above-mentioned dispersing resin, and the relationship between the acidity and basicity of the resin and the pigment dispersion effect was investigated. However, there is no known simple method for measuring the acidity and basicity of amphoteric resins in non-aqueous systems.
The present inventors dissolved the sample dispersion resin in aniline, quantitatively determined it by non-aqueous potentiometric titration using n-tetrabutylammonium hydroxide as a titration reagent, and calculated the acidity of the resin from the number of moles of reagent required for neutralization. Unique acidity in non-aqueous systems, determined by non-aqueous potentiometric titration using perchloric acid as a titration reagent using an acetic acid solution of the sample, and determining basicity from the number of moles of reagent required for neutralization. We developed a basicity measurement method and evaluated the acidity and basicity of amphoteric resins. As a result of the test, the inventors found that the acidity of the above amphoteric dispersion resin was
The basicity is in the range of 1.0 to 1.0×10 ^-2 m mol/g solid, particularly preferably 0.8 to 2.0×10 ^-2 m mol/g solid, and the basicity is 1.0 to 5×10 ^-3 m mol/g solid,
Particularly preferably 1.0 to 1×10 ^-2 m mol/g solid
It has been found through experience that when the pigment is within the range of , good dispersibility is exhibited for various inorganic and organic pigments for paints. Accordingly, a preferred embodiment of the present invention provides a dispersion composition comprising a dispersing resin and a pigment that exhibits acidity and basicity within the above ranges according to the test methods described herein. On the other hand, the dispersing resin must not only have good dispersibility for the pigments mentioned above, but also good compatibility with various resins used for dilution or solubility in various solvents, and also because the paint will ultimately be used as a coating film. Therefore, it is naturally required that the coating film has excellent coloring properties, physical properties, chemical properties, durability, and weather resistance, that is, the final coating film properties are good. As a result of our research, the present inventors found that the weight ratio of the mixture in the reaction between the acidic resin (A) and the basic resin (B) is 99.5 with respect to the solid content of the resin (A).
% to 40% versus (B) 0.5% to 60%, most preferably
(A) 99.5% to 60% and (B) 0.5% to 40%, while the polymerization ratio of the blend in the reaction of the above acidic resin (A) and basic low molecular weight compound (B) is the solid content of the resin ( A)99.9~50%
, (B) 0.1~50%, most preferably (A) 99.9~
70%, (B) is 0.1 to 30%; the molecular weight of the resulting dispersion resin measured by gel permeation chromatography is 500 to 500 in terms of polystyrene.
100000 most preferably 1000~50000; glass transition temperature -30℃~80℃, preferably -10℃~
It was also found that a temperature of 50°C gave the best results. Therefore, in the most preferred embodiment of the present invention, a resin that satisfies the various parameters described above in addition to the acidity and basicity of the dispersing resin is used for dispersing the pigment. The dispersion composition of the present invention is obtained by dispersing various pigments using the dispersing resin specified in this specification. In this case, various inorganic and organic pigments commonly used in paints are used as pigments, such as zinc white, titanium oxide, antimony white, iron black, red iron oxide, red lead, cadmium yellow, zinc sulfide, Litopone, barium sulfate, lead sulfate, barium carbonate, lead white, alumina white, etc., and organic pigments include azo, polycondensed azo, metal complex azo, benzimidazolone, phthalocyanine, (blue, green ), thioindigo series, anthraquinone series, flavanthrone series, indanthrene series, anthrapyridine series, pyranthrone series, isoindolinone series,
Pigments of the perylene, perylene and quinacridone series are advantageously used. The blending ratio of the above-mentioned dispersion resin and pigment is not critical and can be selected arbitrarily since it is further diluted with resin or solvent when making a paint, but it takes into consideration the economic efficiency of dispersion-based production, dispersion efficiency, etc. death,
Usually the ratio is 10-90% by weight of resin (solids content) and 90-10% by weight of pigment, preferably 30% by weight of resin (solids content).
Used in an allocation of ~70% by weight and pigment 70-30% by weight. The dispersion composition of the present invention comprises the above acidic resin (A) and a basic resin and/or basic low molecular weight compound (B).
The dispersing resin obtained by the reaction is mixed with one or more of the above pigments, and if necessary, a solvent commonly used in the paint industry, such as toluene, xylene, Solvetsuso 100, Solvetsuso, etc.
Add one or more of hydrocarbon solvents such as 150, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as MEK and MIBK, and use a conventional dispersion machine such as a roll mill dispersion machine, a ball mill dispersion machine, or a sand Manufactured using grind mill dispersion machines, planetary mixers, high-speed dispersion machines, etc. The dispersion composition thus obtained exhibits extremely good pigment dispersibility, and has excellent stability during storage.
It has excellent compatibility with various resins and solvents, and is extremely useful as a pigment dispersion composition. When the pigment dispersion base composition of the present invention is made into a paint by blending a crosslinking agent, a coating film-forming resin, and various other additives according to a conventional method, it not only maintains pigment dispersibility and stability but also exhibits excellent gloss. , clay properties, etc., it is expected that significant improvements will be made in terms of coating film performance, painting workability, coating film durability, etc. Of course, if desired, the dispersion composition of the present invention may not be used as a so-called dispersion base composition;
It can also be used as is as a paint. The present invention will be explained below with reference to typical production examples and examples of the dispersing resin used in the present invention. In these production examples and examples, parts or %
By weight unless otherwise specified. Production example 1 Production of short oil alkyd/urea resin dispersion resin 573 parts of reed oil, 218 parts of trimethylolethane and 0.3 parts of lithium naphthenate were heated to a reaction temperature of 240°C to transesterify, and then 174 parts of trimethylolethane part, 176 parts of neopentyl glycol, 528 parts of phthalic anhydride, and 254 parts of isophthalic acid, and heated to 220°~
The mixture was heated at 230°C until the solid acid value reached 2.0 to carry out a dehydration reaction. Cool the reaction mixture and add Solbetsuso 100 (mixed solvent manufactured by Etsuso Standard Oil Co., Ltd.)
Diluted with 1009 parts and 58 parts of cellosolve acetate, viscosity U-V by bubble viscometer, non-volatile content 60
%, a short oil alkyd resin (acidic resin) with a color number of 1 was obtained. Tg - 5℃, number average molecular weight (M) 2300 For 90 parts of solid content of this acidic resin, urea resin
Add 10 parts of solid content of UFR-65 (Mitsui Toatsu Co., Ltd., non-volatile content > 98%) and 16 parts of xylene (for non-volatile content adjustment), and add the varnish as it is at a reaction temperature of 110°C to 120°C to reduce the bubble viscosity. Heat the condensation reaction until the viscosity becomes W-X as determined by the meter, and the acidity becomes 3.65×10 ^-2 m mol/g.
A dispersion resin with a basicity of 1.67×10 ⁻¹ mmol/g solid was obtained. Tg -6℃, M2530 Example 1 130 parts each of the acidic resin and dispersion resin obtained in Production Example 1, 66 parts of Shinkashare Y (manufactured by DuPont, quinacridone organic pigment) and 100 and 104 parts of Solbetsuso as a dispersion solvent. Add each,
It was dispersed using an attritor (Mitsui Miike Manufacturing Model MA-01C) using glass beads with a diameter of 5 mm. 60° specular gloss (Murakami gloss meter)
GM-3M type) was used for tracking, and the results shown in Figure 1 were obtained. It can be seen that when the dispersing resin of the present invention is used (solid line in FIG. 1), the dispersion rate is significantly increased compared to the acidic resin (broken line in FIG. 1). On the other hand, the viscosity during the dispersion process is measured using a cone-plate viscometer (E-type viscometer,
The results shown in Figure 2 were obtained using a Tokyo Keiki Co., Ltd.
By using a dispersion resin (solid line in Figure 2),
A significant decrease in viscosity was observed. Production example 2 Production of long oil alkyd/low molecular weight basic compound based dispersion resin Phthalic anhydride 438 parts, maleic anhydride 22 parts, tall oil fatty acid 1080 parts, pentaerythritol 322 parts
1 part, 64 parts of ethylene glycol and heated to 240℃
Heating at 250°C until the solid acid value is 5.0 or less and the viscosity as determined by a bubble viscometer (dissolved in xylene to make the non-volatile content 60%) is W or more, followed by a dehydration reaction.
After cooling, dilute with 1414 parts of xylene and measure the viscosity W-X by bubble viscometer, non-volatile content 56%, and solid acid value.
4.8, a long oil alkyd resin (acidic resin) with a color number of 6 to 7 was obtained. Tg-26℃, M3420 To 100 parts of solid content of this acidic resin, 5 parts of isophorone diisocyanate (Huls) was added.
The varnish was allowed to react at a reaction temperature of 80°C until the reaction rate of isophorone diisocyanate reached 50% (as determined by an infrared spectrometer). This isophorone diisocyanate has both aliphatic and cycloaliphatic isocyanate groups, but since the aliphatic isocyanate group is 10 times more reactive than the cycloaliphatic one, the reaction of isophorone diisocyanate is rate 50%
At the time point, the hydroxyl group of the long oil alkyd resin and the aliphatic isocyanate group seem to have reacted, and the cycloaliphatic isocyanate seems to have remained unreacted. Then the temperature is 80℃
1.4 parts of monoethanolamine was added while maintaining the temperature, and the unreacted isocyanate groups were reacted. After confirming with an infrared spectrometer that all the isocyanate groups had reacted, it was cooled and the acidity was 8.56×10 ^-2 m mol/g
A dispersion resin with a basicity of 0.11 mmol/g solid was obtained. Tg-24℃, M3620 Example 2 Titanium oxide (CR made by Ishihara Sangyo Co., Ltd.) was added to 40 parts each of the acidic resin and dispersion resin obtained in Production Example 2.
-92) 80 parts and 40 parts of MIBK as a dispersion solvent were added and dispersed for 60 minutes using a paint shaker using 1.58 mmφ glass beads. The gloss and viscosity of the dispersion were measured in the same test as in Example 1, and the results are shown in Table 1.

[Table] It can be seen that the use of the dispersing resin of the present invention can lead to an increase in gloss and a decrease in viscosity. Production Example 3 Production of resin for dispersion in short oil alkyd/polyamide resin meter Isophorone diisocyanate (Huls) was added to 100 parts of the solid content of the acidic resin obtained in Production Example 1.
2 parts were added, and the varnish was allowed to react at a reaction temperature of 70° C. until the reaction rate of isophorone diisocyanate reached 50% (as determined by an infrared spectrometer). Next, while maintaining the temperature at 70°C, 1.30 parts (equivalent to unreacted NCO) of Versamide 140 (polyamide resin manufactured by Henkel Japan Co., Ltd., amine value 370-400, viscosity 2-5 poise (75°C)) was added, and unreacted NCO was added. After confirming with an infrared spectrometer that the reacted isocyanate group has completely reacted with the primary or secondary amino group of Versamide 140, it is cooled and the acidity is 1.43×10 ^-1 m.
mol/g solid, basicity 2.78×10 ^-2 m mol/g
A solid dispersion resin was obtained. Tg-3℃,
M2410 Example 3 Mapico Yellow LLXLO (Titan Kogyo Co., Ltd.) was produced using the dispersion resin obtained in Production Example 3 and an acidic resin.
was dispersed in a paint shaker for 120 minutes. The composition of the dispersion product is 36.3 parts of resin and Mapico Yellow.
46 parts of LLXLO and 17 parts of toluene were used as a solvent. The obtained dispersion was measured in the same manner as in Example 1, and when the dispersion resin was used, the gloss was 75 and the viscosity was 75.
However, when acidic resin was used, the gloss was 60 and the viscosity was 200 cp. Production Example 4 Production of long oil alkyd/urethane resin dispersion resin For 100 parts of the solid content of the acidic resin obtained in Production Example 2, Desmodyur Z4273 (Bayer, 73
% xylene liquid) was added, the varnish was heated to a reaction temperature of 80°C, and after confirming with an infrared spectrometer that all the isocyanate had reacted, it was cooled and the acidity was 2.57×10 ^-1 m mol/g solid, basicity 1.11×
A dispersion resin of 10 ^-2 mmol/g solid was obtained.
Tg-18℃, M3680 Example 4 Carbon black FW-200B (manufactured by Degussa Corporation) was added to 45 parts each of acidic resin and dispersion resin.
10 parts and 45 parts of MIBK as a dispersion solvent were added, and the mixture was dispersed for 5 hours using a paint shaker using 1.58 mmφ glass beads. When the gloss and viscosity of the obtained dispersion were measured in the same manner as in Example 1, it was found that the dispersion resin containing the basic component had no gloss.
70 and viscosity of 50 cp, whereas the acidic resin had a viscosity of 60 and a viscosity of 200 cp, indicating that the use of the dispersing resin of the present invention yields favorable results. Production example 5 587 parts of isifthalic acid, 60 parts of trimethylolethane
130 parts of neopentyl glycol and 235 parts of diethylene glycol were added to a reactor and heated at 220 to 240°C until the solid acid number reached 6.0 to conduct a dehydration reaction. After cooling, the mixture was diluted with 175 parts of cellosolve acetate and 409 parts of xylene. , viscosity U to UV by Gardner Holt bubble viscometer, non-volatile content 60%, chromaticity 1
Oil-free polyester resin (acidic resin)
I got it. Tg14℃, M3380 Melamine resin U-20SE (Mitsui Toatsu Co., Ltd., non-volatile content 60 parts)
%) was added, and the varnish was heated to the reaction temperature.
Heat at 90 to 100℃ until the viscosity reaches Y to Z as measured by a bubble viscometer to perform a condensation reaction and achieve an acidity of 0.107m.
mol/g solid, basicity 0.556m mol/g
A solid dispersion resin was obtained. Tg 16°C, M3620 Example 5 Various pigment dispersion compositions were prepared according to the formulations shown in Table 2 below, and a solvent and resin were further added to prepare coating compositions. Next, each of these paint compositions was applied to a tin plate using a bar coater #26, and then placed in an electric furnace according to a conventional method.
Baking treatment was performed at 230°C for 90 seconds. The gloss (20° gloss) was measured and the results are shown in Table 3. In Table 3, "conventional product" refers to a conventional product manufactured in the same manner using Super Lac DIF OX-97 (oil-free polyester resin, manufactured by Nippon Paint Co., Ltd.) instead of dispersing resin V in Table 2. means the coating composition of the product.

【table】

【table】

[Table] Next, the above paint compositions (primary colors) were mixed in the following formulations to make gray, brown and pale blue paint compositions.

[Table] Immediately after blending each primary color, each mixed color was stirred with a dispensing bar, coated on a tin plate with bar coater #26, and baked in an electric furnace at 230℃ for 90 seconds, and used as a reference plate. One week after blending, the color difference ΔE from the reference plate was measured for each blended color, which was mixed by hand and with a disk bar, and then painted and baked in the same manner.
From the results in Table 5, it is clear that the coating composition of the present invention shows little discoloration over time.

[Table] Production Example 6 573 parts of coconut oil, 218 parts of trimethylolethane, and 0.3 parts of lithium naphthenate were heated to a reaction temperature of 240°C to transesterify, and then 174 parts of trimethylolethane, 176 parts of neopentyl glycol, and phthalic anhydride were added. Add 528 parts and 254 parts of isophthalic acid to 200-230 parts.
Heat and dehydrate at °C until the solid acid value reaches 6.0. After cooling, dilute with 1009 parts of Solbetsuso 100 (mixed solvent manufactured by Etsuso Standard Oil Co., Ltd.) and 58 parts of Cellsolve Acetate to obtain a resin acid value of 5.8 and varnish. Viscosity (Gardner viscosity 25℃) P~Q, nonvolatile content
A short oil alkyd resin (acidic resin) with 60.3% and color number 1 was obtained. Tg-5℃, M2300 Melamine resin (Super Betsucomin G-821, non-volatile content)
60%, manufactured by DIC Corporation) was added, and the varnish was heated at a reaction temperature of 90 to 100°C until the varnish viscosity was U, causing a condensation reaction, and the acidity was 0.14 m mol/
A dispersing resin with a basicity of 0.18 mmol/g solid and a nonvolatile content of 59.8% was obtained. Tg-4℃,
M2460 Example 6 44 parts each of the acidic resin and dispersion resin obtained in Production Example 6 and Shinka Shared Y (manufactured by Toyo Ink Co., Ltd.)
16 parts and 40 parts of Suzol 1000 (manufactured by Maruzen Sekiyu Co., Ltd.) were mixed and dispersed for 10 hours using a reed devil. Each of the resulting dispersed pastes, 50 parts, was dissolved in 20 parts of acidic resin and 12 parts of melamine resin U-128. Primary colors (using acidic resin)
and primary color' (using a dispersing resin) were obtained. On the other hand, 25 parts each of acidic resin and dispersion resin, 50 parts of Anchored FR110G (manufactured by Toho Pigment Co., Ltd.), and Swasol.
Mix 20 parts of 1000 and disperse with a red devil for 3 hours, and add 50 parts of each of the resulting dispersed pastes to acidic resin.
62 parts of melamine resin U-128 and 22 parts of melamine resin U-128 were dissolved to obtain primary colors (using acidic resin) and primary colors' (using dispersing resin). Separately, the above acidic resin, dispersing resin, and melamine resin U-128 were mixed in a weight ratio of 100/100/67 to prepare a transparent resin solution. 73 parts of primary color and 24 parts of primary color, transparent resin solution
62 parts were added to make paint. Separately, 62 parts of a transparent resin solution was added to 73 parts of primary color 'and 24 parts of primary color' to prepare a paint. Electrodeposit the paint and paint onto a dull steel plate that has been coated with an intermediate coat, and bake it for 20 minutes at 140°C. ), and the results shown in Table 6 were obtained.

[Table] Color fading was significantly improved with paints using dispersing resin. We again examined the sagging phenomenon and finished appearance of spray-coated panels under booth conditions of 27℃/50% humidity to 26℃/60% humidity, and found that the sagging phenomenon and appearance were improved with paint using a dispersion resin. I was sure that. The results are shown in Table 7.

[Table] The following reference examples show that the amphoteric resin used in the present invention has good compatibility with other resins, has excellent workability, and provides a good coating film. Reference Example 1 Commercially available melamine resins U-128 and G-821 (DIC
company's product, non-volatile content 60%) mixed at a weight ratio of 75/25,
It was dropped onto a glass plate and baked at 140°C for 20 minutes. As an evaluation of compatibility with melamine resin, the state of microcells generated on the transparent film was examined, and the results shown in Table 8 were obtained.

[Table] It can be seen that the compatibility with the melamine resin is improved by using a dispersing resin added with the melamine resin. Furthermore, the self-dust property was investigated by spray painting a tinplate plate using the above amphoteric resin and melamine resin mixture and then dusting the plate. On the other hand, machine oil was applied to a tin plate and spray painting was performed to examine the oil staining properties, and the results are shown in Table 9.

[Table] By using a dispersing resin with added melamine resin, self-dust and oil staining properties are significantly improved. Reference Example 2 Melamine resin U-128 was mixed with the acidic resin obtained in Production Example 6 and the dispersion resin at a weight ratio of 75/25,
It was applied to a tin plate and baked at 140°C for 20, 40 and 60 minutes to obtain a transparent film. The gel fraction of these coating films was measured using a Bun tensile tester (manufactured by Toyo Baldwin Co., Ltd.) using a mixed liquid extraction method of acetone/methanol (1/1).
As a result of measuring the film strength and elongation using UTM-type), it was found that although there was almost no difference between the two in terms of gel fraction and strength, significantly better results were obtained with respect to elongation by using a dispersing resin.

[Brief explanation of the drawing]

Figure 1 shows the dispersion effect over time when the pigment is dispersed in the amphoteric resin of the present invention (solid line) and when it is dispersed in the conventional acidic resin (broken line), with time on the horizontal axis and 60% on the vertical axis.゜It is a diagram showing specular gloss,
Figure 2 shows the change in viscosity during the dispersion process on the horizontal axis.
It is a diagram showing 60° specular gloss and viscosity (P) plotted on the vertical axis.

Claims (1)

[Scope of Claims] 1. At least one active group selected from active hydrogen and active alkoxy groups is added to one of an acidic resin having an electron-accepting group and a basic resin or compound having an electron-donating group; A pigment dispersion composition comprising a pigment and an amphoteric resin for dispersion, which is obtained by supporting at least one reactive functional group that reacts with a group and subjecting the two to an addition or condensation reaction. 2 The amphoteric resin for dispersion is hydroxylated in an aniline solution.
- Acidity 1.0 to 1.0×10 ^-2 m mol/g expressed in moles of reagent required for neutralization by non-aqueous potentiometric titration using tetrabutylammonium as a titration reagent.
solid, and basicity expressed as the number of moles of reagent required for neutralization by non-aqueous potentiometric titration using perchloric acid as the titration reagent in an acetic acid solution: 1.0 to 5.0×10 ^-3 m
2. The composition according to claim 1, which has mol/g solid. 3 The amphoteric resin for dispersion is an acidic resin in the resin solid content.
99.9-40% by weight and basic resin or compound 0.1-60%
The claimed scope is a resin having a number average molecular weight (gel permeation chromatography measurement, polystyrene equivalent) of 500 to 10,000 and a glass transition temperature of -30% to 80°C, obtained by reacting at a blending ratio of % by weight. The composition according to item 1 or 2. 4. The composition according to any one of claims 1 to 3, wherein the blending ratio of the dispersing amphoteric resin and the pigment is 10 to 90% resin solids and 90 to 10% pigment in weight percent. At least one type of active group selected from active hydrogen and active alkoxy group is added to one of the acidic resin having an accepting group and the basic resin or compound having an electron donating group, and at least one type of active group that reacts with the active group is added to the other side. 1 to 99% by weight of a pigment dispersion composition consisting of a pigment and an amphoteric resin for dispersion obtained by supporting a reactive functional group and carrying out an addition or condensation reaction with the two, and 99 to 1% by weight of another resin. A paint composition made of 6. The composition according to claim 5, wherein the other resin is selected from the group consisting of alkyd resins, polyester resins, acrylic resins, and melamine resins.