JPS58154762A - Dispersion base composition - Google Patents

Abstract

PURPOSE:To provide a dispersion base composition having excellent dispersion stability and brilliancy, consisting of an amphoteric resin for dispersion obtd. by reacting an acidic resin with a melamine/ formaldehyde resin, and a pigment. CONSTITUTION:A pigment is mixed with an amphoteric resin obtd. by subjecting an acidic resin having electron-accepting group and a malamine/formaldehyde resin having groups of formulasIand/or II as electron-donating groups and a number-average condensation degree of 2-6 of triazine nucleus to an addition reaction or a condensation reaction, one of these resins having functional groups capable of reacting with active hydrogen and/or active alkoxy groups. Examples of the acidic resins are oil-free polyester resins obtd. by condensing a polycarboxylic acid with a polyhydric alcohol, and long-oil or short-oil alkyd resins obtd. from a polycarboxylic acid, a polyhydric alcohol and a fatty acid or a vegetable oil as a fat and oil component. Vinyl resins may also be used as the acidic resin.

Description

[Detailed Description of the Invention] The present invention relates to a pigment dispersion base composition, and more specifically, it is composed of a pigment and an amphoteric resin for dispersion obtained by the reaction of an acidic resin and a specific basic resin, and the dispersion stability and sharpness are improved. The present invention relates to a dispersion base composition having particularly excellent properties.

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 resin and solvent to make it into 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 it were possible to prepare a large fraction of various pigments in a single dispersing resin and then mix them according to the purpose of use or dilute them with the necessary resins and solvents, there would be immeasurable gains in paint production. There may be unknowns, but unfortunately no general-purpose dispersing resin has been found.

Now, P, Sφrensen n Journal Op Paint Technology 47 (602) 31 (1975) explains the affinity between various pigments and resins using the concept 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 acidic resins and basic resins used as paint vehicles, we created amphoteric resins that have both acidic and basic properties through their reaction. If pine resin could be obtained, we thought that it would have good compatibility with the famous paint vehicle used as a raw material, and would also show good dispersibility for various pigments with different surface properties. As a result of research into various bonding methods between resins and basic resins, and the suitability of the resulting resin as a dispersion resin, active hydrogen and/or
or with an acidic resin (8) having 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 active hydrogen and/or an active alkoxy group, or The amphoteric resin obtained by addition or condensation with a basic resin (6) having an active hydrogen and/or active alkoxy group and an electron-donating group meets the above objectives and is extremely useful as a general-purpose dispersion resin. Upon learning of this, he filed a patent application for a dispersion base composition comprising the amphoteric resin and pigment (Japanese Patent Application No. 120866/1983). Note that the term "active hydrogen" used in the patent application specification refers to 1st class, 2nd class
means a highly reactive hydrogen atom bonded to oxygen, sulfur, nitrogen, etc. contained in primary and tertiary hydroxyl groups, amide bonds, phrethane bonds, carboxyl groups, etc.;
The term "active alkoxy group" means a highly reactive alkoxy group such as a group in which the terminal hydrogen atom of active methylol is substituted with alkyl; the term "functional group that reacts with active hydrogen" refers to primary, secondary and groups that easily react with active hydrogen, such as tertiary hydroxyl groups, incyanato groups, and glycidyl groups; the term "functional groups that react with active alkoxy" refers to active alkoxy groups such as primary, secondary, and tertiary hydroxyl groups; means a group that easily reacts with; also an "electron-accepting group"
The term "electron-donating group" refers to groups such as carboxyl groups, sulfone groups, nitro groups, etc. that tend to attract electricity from others when hydrogen is used as the standard, and the term "electron-donating group" refers to groups that have a lone pair of electrons. - groups, halogens, alkyls, and other groups that tend to donate electrons to others when hydrogen is the standard in the molecule,
The term "acidic resin" refers to oil-free polyester resins, long-oil or short-oil alkyd resins, commonly used in the coatings field,
Resins with acidic groups such as acrylic resins and vinyl resins are
The term "basic resin" means a resin having a basic group, such as urea resin, melamine resin, polyamide resin, polyurethane resin, etc., which are usually used in the paint field.

The amphoteric resin shown in the above Japanese Patent Application No. 120866/1986 is itself an extremely stable reaction product, and is compatible with various acidic and basic resins used in paints. Since the resin has both the properties of both the surface and the surface, it exhibits good dispersibility for various types of faces H with different surface characteristics, so it was exactly as expected as a resin vehicle for the dispersion base group Ijl.

The present inventors subsequently proceeded with research on individual reaction components, and as a result, found that even among the above-mentioned amphoteric resins, the melamine formal +-:' resin has extremely remarkable specificity. I found out about it later. That is, melamine formaldehyde resin is a polymer resin of methylol melamine obtained by condensing melamine with formaldehyde, or alkylated methylol melamine obtained by further esterifying with alcohol if necessary.
-N- or -N= in the molecule has a lone pair of electrons and acts as an electron-donating group, and at the same time > NH, -NI+,
, an active hydrogen group such as -CH20H, or -CH20
It is one of the important basic resins that can undergo an addition or condensation reaction with an acidic resin due to its R activity and alkoxy group.
It has already been reported in Japanese Patent Application No. 120866-1987 that an amphoteric resin can be obtained which is compatible with various resins and has the property of stably dispersing various pigments with different surface properties if given a certain degree of acidity and basicity. As stated in the issue. However, 1) In the case of melamine formaldehyde resins, the structural factors are not limited to just the degree of chloride, but are deeply related to the properties of the final amphoteric resin. However, if the average number of triazine nuclei (hereinafter referred to as the number average degree of condensation of triazine nuclei) determined from the number average molecular weight of the resin (gel permeation chromatography measurement, epoxy conversion) exceeds a certain critical value, the pigment The dispersion stability of ba, =, t* is significantly improved, and the viscosity becomes too high, causing problems with compatibility with other resins, making it impractical. Surprisingly, when using melamine/formaldehyde resin with a number average condensation degree of the triazine nucleus, which significantly improves pigment dispersion stability, this is not observed at all with amphoteric resins using other basic resins. It has been found that a dispersion base composition with unique effects and excellent image clarity can be obtained. The present invention has been made based on this knowledge.

That is, according to the present invention, [active hydrogen and/or active alkoxy group, or active hydrogen and/-! An acidic resin containing a functional group that reacts with an active alkoxy group and an electron-accepting group, and a functional group that reacts with active hydrogen and/or an active alkoxy group, or an active hydrogen and/or active alkoxy group.
In a dispersion base composition comprising a pigment and an amphoteric resin obtained by an addition or condensation reaction with a basic resin (6) having an electron-donating group and an electron-donating group, the resin has a number average degree of condensation of the triazine nucleus of 2 to 2. Dispersion base composition with excellent image clarity and dispersion stability characterized by being a melamine-formaldehyde resin of No. 6 is provided.

Briefly, the dispersing resin used in the present invention is an acidic resin having an electron-accepting group and a melamine-formaldehyde resin having an electron-accepting group, and has a triazine nucleus having a number average condensation degree of 2 to 6. One of them has active hydrogen and/or
Alternatively, it is an amphoteric resin obtained by adding or condensing activated alkoxy with active hydrogen and/or a functional group that reacts with active alkoxy present on the other side.

Active hydrogen and/or active alkoxy groups; The presence of functional groups that react with active hydrogen and/or active alkoxy groups in acidic resins and melamine-formaldehyde resins requires the selection of appropriate resins having these groups, or the addition of these groups. This can be easily achieved by incorporating a compound having the group into the resin 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 7-ly polyester resin used as acidic resin is obtained by condensation of polyhydric carboxylic acid and polyhydric alcohol.
Examples of polyhydric carboxylic acids include trimellitic acid, trimetic anhydride, fucuric acid, phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, etc., and examples of polyhydric alcohols include pentaerythritol, trimethylolpropane, trimethylolethane, glycerin, polyethylene glycol,
1,6-hexanethiol neopentyl glycol, propylene glycol, ethylene glycol, etc. are commonly used.

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. For example, soybean oil, soybean oil, tall oil, coconut oil, cottonseed oil, linseed oil, etc. are used. Therefore, since the oil-free polyester resin obtained by reacting the above-mentioned raw materials and long oil can contain tertiary hydroxyl groups and/or carboxyl groups, the acidic resin component (A) of the raw material for producing the dispersion resin of the present invention can be used as it is. -NH, -Nl2 or -CH20H in melamine formaldehyde resin
and/or an active alkoxy group such as -CH20R (R is an alkyl group), or a functional group such as an incyanato group or a glycidyl group that reacts with them. 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 incyanato group or a compound having a glycidyl group is added to the resin already obtained and allowed to react so that free incyanato groups or glycidyl groups remain in the resin, the melamine-formaldehyde resin will have these incyanato groups. , a group that reacts with a glycidyl group can be supported. Such polyhydric incyanates include, for example, diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and mixtures thereof, 4,4'-diphenylmethane diisocyanate, and m-phenylene diisocyanate. Isocyanate, 4,4'-
Aromatic diisocyanates such as hifnyl diisocyanate, aliphatic diisocyanates such as tetramethylene diisocyanate, hexanetylene diisocyanate, octamethylene diisocyanate, or aromatic aliphatic diisocyanates such as xylylene diisocyanate. Isocyanate, or triisocyanate such as alicyclic diisocyanate such as inphorone diisocyanate, a, 4/
, 411-triphenylmethane triisocyanate, 2,4.4'-biphenyl triisocyanate, 2,
Examples include 4.4'-diphenylmethane diisocyanate. Other incyanates that can be used include reacting these di- or triisocyanates with a compound having two or more hydroxyl groups in the molecule, such as a diol or triol, so that the reaction product still contains two or more incyanate groups. There are also addition products with incyanate, incyanate polymer compounds, etc.

Further, as the compound having a glycidyl group, triglycidyl isocyanurate, ethylene glycol diglycidyl ether, etc. are preferably used.

Vinyl resins can also be used as acidic resins (4).

Vinyl resins as acidic resins useful in the present invention include (1) neutral vinyl monomers, (2) acid group-containing vinyl monomers, and (3) vinyl monomers having a functional group that reacts with active hydrogen and/or active alkoxy groups. Or (3)
' Obtained by copolymerizing vinyl monomers having active hydrogen and/or active alkoxy groups.

Typical neutral vinyl monomers include ethylene, propylene, butadiene, isoprene, taloloprene, 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, methacrylateril, etc.), styrene, styrene derivatives (e.g. α-
methylstyrene), etc.

Examples of acid group-containing vinyl monomers include carboxyl group-containing vinyl monomers such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid, and examples of sulfonic group-containing monomers include α-styrenesulfonic acid.

On the other hand, the functional group-containing vinyl monomer in (3) above,
For example, glycidyl methacrylate, glycidyl methacrylate, etc. can be selected as the glycidyl group-containing vinyl monomer, and vinyl isocyanate, etc. can be selected as the incyanate group-containing vinyl monomer. As the active hydrogen group-containing vinyl monomer in (3)' above, acrylamide, methacrylamide, etc., which are amide group-containing vinyl monomers, and active alkoxy group-containing vinyl monomers,
N-methoxymethylol acrylamide, N-cytoxymethylol acrylamide, etc. can be used. Alternatively, the functional group-containing monomer of (3) above or FiC3Y
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
Hydroxyl group-containing monomers such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, N-methylolacrylamide, etc. can also be used.

By appropriately selecting one monomer unit for producing these resins, an acidic vinyl resin having a functional group that reacts with active hydrogen and/or an active alkoxy group, or an electron-accepting group and an active hydrogen and/or active alkoxy group can be obtained. The dispersing amphoteric resin useful in the present invention can be obtained by reacting the melamine-formaldehyde resins with appropriately selected melamine-formaldehyde resins. The active hydrogen in the melamine-formaldehyde resin is reacted by blending a polyvalent incyanate compound or a glycidyl compound with a vinyl resin obtained using a vinyl monomer containing an active hydrogen group so that free incyanate groups or glycidyl groups remain. It can also be made into a vinyl resin that reacts with.

As the basic resin which is the other component (6) of the dispersion resin, a melamine-formaldehyde resin having a number average degree of condensation of triazine nuclei of 2 to 6 is selectively used.

Such a melamine-formaldehyde resin can be obtained by condensing melamine and formaldehyde by appropriately selecting the number of moles of melamine and formaldehyde, and if necessary, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol,
Manufacture alcohols such as isobutyl alcohol [tF]
In addition, it can also be used as an alkylated methylolmelamine-formaltech resin.

On the other hand, the melamine-formaldehyde resin obtained by the above reaction method is condensed as it is, or after removing the solvent, by adding an appropriate solvent and mixing one or more of the resins to achieve a predetermined number average degree of condensation of 2. ~6 and can also be used as a melamine-formaltehyde resin as the basic resin of the present invention.

Such melamine-formaldehyde resins act as electron donating groups and at the same time: NH.

Since it has an active hydrogen group such as -NH or -CH20H and/or an active alkoxy group such as -CH20R (R: alkyl group), it can be subjected to an addition or bonding reaction with the functional group in the acidic resin (g).

Furthermore, a group that reacts with active hydrogen, such as an isocyanate group or a glycidyl group, is introduced into the melamine-formaldehyde resin by reacting the resin with a polyvalent isocyanate compound or a glycidyl compound, so that it has an active hydrogen group (
It is also possible to obtain an amphoteric resin for dispersion by reacting with the acidic resin of 8).

Such polyvalent incyanates include, for example, diisocyanates such as 2,4-) lylene diiso'y7+-
), 2, 67) lylene diisocyanate and mixture of both, 4°, 4'-'; phenylmethane diisocyanate, m-7 enylene diisocyanate:/sifsu-), 4,
Aromatic diisocyanates such as 4'-biphenyl diisocyanate, aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, or aromatic fats such as xylylene diisocyanate. As a triisocyanate, such as a group diisocyanate or an alicyclic diisocyanate such as inphorone diisocyanate,
, 4', 4''-)liphenylmethanetriisocyanate), 2,4.4'-biphenyl, triisocyanate, 2,4.4'-diphenylmechntriincyanate, etc.Others can be used. As the incyanate, these di- or triisocyanates are reacted with a compound having a di-hydroxyl group, and the reaction product includes an addition product having two or more incyanate groups, or an incyanate polymer compound. Further, as the compound having a glycidyl group, triglycidyl isocyanurate, ethylene glycol cyclicyl ether, etc. are preferably used.

In order for the dispersing resin of the present invention to exhibit good dispersion performance for various pigments, it is essential that the resin has acidic and basic amphoteric properties. It has been found that there are different genders. That is, the number average degree of condensation, which indicates the number of triazine nuclei, determined from the number average molecular weight (gel perminsion chromatography measurement, epoxy conversion) of the melamine-water formaldehyde 41 fat to be added or condensed is 2.0 to 6. If it is within the range of .0, the dispersion stability of the pigment increases dramatically, especially in the range of 2.0 to 5.
．． The effect is remarkable in OK. The reason why the number of triazine nuclei is so related to pigment dispersion stability is not clear, but to date, it has been reported that when the number average degree of condensation, which indicates the number of triazine nuclei, is 2.0 or less, It is believed that the melamine-formaldehyde resin incorporated in the pigment may not be able to perform adequately as a basic component and therefore not exhibit the best performance in terms of pigment dispersion rate and storage stability. Furthermore, if the number average degree of condensation exceeds 6.0, the viscosity of the synthetic dispersion resin will increase significantly, which will have a negative effect on the pigment dispersion stability and also cause problems in compatibility with other resins. It is possible that it will come.

Furthermore, CB)1. melamine with a number average degree of condensation of the triazine nucleus of 2 to 6.
By selectively using formaldehyde resin, we can give the coating film exceptional clarity, such as gloss and texture, which was not observed at all in the case of amphoteric resins for dispersion due to the suspension reaction between other basic resins and acidic resins. It has also been found that In the present invention, in which a specific melamine-formaldehyde resin is selected and used as the C basic resin, the pigment dispersion stability is dramatically increased, and important properties as a paint, such as imparting sharpness, are achieved. It has now become possible to provide highly useful dispersion-based compositions.

Of course, when the dispersion base composition of the present invention is made into a paint,
Improvements in other coating film properties, such as hiding properties, smoothness, gloss, jet blackness, working properties such as vinyl, durability, weather resistance, etc., are not limited to simply image clarity. This is the same as in the case of both dispersing resins due to the reaction between an acidic resin and an acidic resin. Now, the above acidic resin (4) and melamine
Formaldehyde resin (6) carries active hydrogen and/or an active alkoxy group on one side, and a functional group that reacts with active hydrogen and/or an active alkoxy group on the other side, so (4) and (6) can be easily reacted with the supported groups by addition or condensation, and an amphoteric resin having both an electron-accepting group and an electron-donating group can be obtained extremely easily.

The amphoteric resin thus obtained is different from a simple mixture of an acidic resin and a melamine-formaldehyde resin; it is a reaction product of both, so it has excellent stability and will not separate into raw material resins, and it cannot be used for paints. It is compatible with various acidic resins and basic resins, and as it 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 base 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 vary widely. 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, so the inventors dissolved the sample dispersion resin in aniline.
Quantitate using n-tetrabutylammonium hydroxide as a titration reagent using a non-aqueous potentiometric titration method, determine the acidity of the resin from the number of moles of reagent required for neutralization, and titrate perchloric acid using a sample acetic acid solution. We have developed a unique method for measuring acidity and basicity in a non-aqueous system, in which the reagent is quantified by non-aqueous potentiometric titration, and the basicity is determined from the number of moles of reagent required for neutralization. Acidity and basicity were evaluated. Test results,
The present inventors have determined that the acidity of the amphoteric dispersing resin is 1.0 to 1.
．． OX 10-2m mol/g 5olid, particularly preferably 0.8-2, OX 10-2m mol/g
5 solid, with basicity of 1.0 to 5
10-3m mol/g 5olid1 Particularly preferably 1.0 to I x 10-2m mol/g 5olid
It has been empirically found that when the d is within the range, good dispersibility is exhibited for various inorganic and organic pigments for paints. Accordingly, a preferred embodiment of the present invention provides a dispersion base 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 performance required for a dispersion resin is good compatibility with various resins or solubility in various solvents, and because the paint is ultimately used as a coating film, it has good coloring property in the coating state. Of course, it is also required to have excellent physical properties, chemical properties, durability and weather resistance, that is, good final coating properties. As a result of our research, the present inventors found that the weight ratio of the mixture in the reaction between the acidic resin holes and the melamine-formaldehyde resin CB) was (A) 99% based on the solid content of the resin.
．． of the resulting dispersing resin. Molecular weight measured by Gel Permini-Sicon chromatography and calculated as polystyrene equivalent.
0-100,000, most preferably 1,000-50
,000; glass transition temperature is 130°C to 80°C;
It has also been found that a temperature preferably between -10°C and 50°C gives the best results. Therefore, in the most preferred embodiment of the present invention, a resin that satisfies the above-mentioned various parameters in addition to the acidity and basicity of the dispersion resin is used for dispersing the pigment.

The dispersion base composition of the present invention can be obtained by dispersing various pigments using the dispersing resin specified herein. 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, baritum sulfate, lead sulfate, baritum carbonate, lead white, alumina white, etc., and organic pigments include azo, polycondensed azo, metal complex azo, benzimidacylon, and phthalocyanine (blue, green). , thioindigo, anthraquinone, flavanthrone, indanthrene, anthrapyridine, bilanthrone, isoindolinone, perylene, perinone and quinacridone pigments are advantageously used.

The above blending ratio of the dispersing resin and the pigment is not critical and can be selected arbitrarily, as it is further diluted with resin or solvent when it is made into a paint, but it takes into consideration the economic efficiency of dispersion-based production, dispersion efficiency, etc. Usually resin (solid content) 10-9
0% by weight and 90-10% by weight of pigment, preferably 30-70% by weight of resin (solid content) and 70-30% by weight of pigment.
It is used in proportions of % by weight.

The dispersion base composition of the present invention comprises a dispersion resin obtained by the reaction of the above acidic resin (a) and melamine-formaldehyde tuh (6), and a solvent commonly used in the pigment coating industry, such as toluene. , xylene, hydrocarbon solvents such as Tsurpets 1001 and Tsurpets 150,
Ester solvents such as ethyl acetate and butyl acetate, MEK,
Add one or more types of ketone thread melting such as MIBK and use a normal dispersion machine such as a roll mill dispersion machine, a ball mill dispersion machine, a sand grind mill dispersion machine, a planetary mixer, a high speed dispersion dispersion machine, etc. Manufactured.

The dispersion base composition thus obtained exhibits extremely good pigment dispersibility, has excellent stability during storage, and has excellent compatibility with various resins and solvents, producing a coating material with improved properties. It is extremely useful as a pigment dispersion paste composition.

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 Preparation Examples and Examples, all parts and percentages are by weight, unless stated otherwise.

Production Example 1 200 parts of Mail 325 (Mitsui Toatsu ■, nonvolatile content 80%) was placed in a four-loaf flask equipped with a stirrer and a thermometer, and after removing the solvent in a range of 50 U from room humidity under reduced pressure, toluene, After adding 635 parts of methanol and 0.32 parts of formic acid and stirring the reaction under heating under reflux for 5 hours and 30 minutes, the solvent was removed again under reduced pressure. I) was obtained.

Gelpa-meation chromatography (JASCO)
The number average degree of condensation of the average triazine nucleus in one molecule, determined from the number average molecule and amount obtained by TRI ROTAR-2) measurement and epoxy conversion, is 1.5 for Cymer 325, while 29 for MFIM Fat I. Met.

Production Example 2 140 parts of toluene and 40 parts of n-butanol were charged into a reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a dropping spout, and heated to 105° C. under a nitrogen stream.

211 parts of methyl methacrylate, 1 part of n-butyl acrylate
A mixture of 23 parts of 2-hydroxyethyl meccrylate, 60 parts of acrylic acid, and 12 parts of t-butylperoxy-2-ethylhexanoate was dropped into the above reaction vessel from the dropping funnel at a constant speed over 3 hours. did.

After the completion of the dropwise addition, the temperature was kept at 105°C for 30 minutes, and then a mixture of 20 parts of toluene and 2 parts of t-butylperoxy 2-ethyl hexa/ate was added dropwise from the dropping port 4 at a constant rate over a period of 30 minutes, and then for an additional 1 hour and 30 minutes. After keeping the temperature at 105° C., 240 parts of toluene was added and cooled to obtain a colorless and transparent acrylic resin (acidic resin ■) with a resin solid content of 48% and a viscosity of N measured by a bubble viscometer.

To 96 parts of the solid content of this acidic resin (2), the high molecular weight melamine-formaldehyde resin (MF
Add 4 parts of solid resin (■) and leave the varnish at a reaction temperature of 1.
Heating and binding reaction were carried out at 10°C until the viscosity reached Y as measured by a bubble viscometer, and the acidity was 2.34 x 10-2 m mol.
/ g 5 solid, basicity 1゜39 x 10-
A dispersing resin (ampholytic resin of the present invention) of 5 mol/g 5 solids was obtained.

On the other hand, for comparison, 4 parts of the solid content of Cymer 325 used in Production Example 1 was added to 96 parts of the solid content of drinking water resin I.
It was synthesized using the same reaction method as the above dispersion resin ①, and the viscosity Y1 acidity 2.19 x 10-2 m mol was measured using a bubble viscometer.
/ g 5 solid, basicity 1.30 x 10”
A dispersing resin (amphoteric resin other than the present invention) of m mol/g 5 solid was obtained.

Example 1 Acidic resin ■ obtained in Production Example 2 and dispersion resins I and I
To each 100 parts of t, 22 parts of carbon black FW-200B (Degussa tR) and 1 part of toluene as a dispersion solvent were added.
00 parts of each were added and dispersed for 60 minutes in a paint shaker using 1.58 wn D glass beads.

60 parts of dispersion specular gloss (Murakami gloss meter GM-3M model)
and viscosity (E-type viscometer, Tokyo Keiki ■) were measured and the results shown in Table 1 were obtained.

Table 1 The effects of increasing gloss and decreasing viscosity were observed by using the dispersing resins, and the effects of the dispersing resin (■) were particularly remarkable.

Furthermore, the viscosity change during the storage test at 60°C for each of the obtained dispersion amounts is shown in Figure 1.

As is clear from the figure, the dispersion resin (2) synthesized by co-condensing a melamine-formaldehyde resin with a high number average degree of condensation of triazine nuclei has a remarkable effect on dispersion and storage performance.

For each 100 parts of the resulting dispersion, 28 parts of co-condensed acrylic resin of acrylic and each melamine-formaldehyde resin.
4 parts, 28 parts of toluene, 16 parts of n-butanol, and
On the crosslinking side, melamine-formaldehyde resin, Yunokun 20SE (Mitsui Toatsu ■, nonvolatile content 60%) was added so that the solid content of melamine-formaldehyde resin in the paint was 58 parts, and baked-on acrylic resin paint was added. adjusted.

Apply the obtained paint to a tin plate (0.3 x 50 x 150)
(Japan Test Panel Industry ■) spray painted, 140
The film was baked at ℃ for 30 minutes, and gloss, jet black dust, and sharpness were visually judged. From the results in the %2 table, it can be seen that the paint using dispersing resin (■) is superior.

Table 2 Production Example 3 Production of oil-free polyester dispersion resins ■ and ■ 587 parts of isophthalic acid, 60 parts of trimethylolethane, 130 parts of neopentyl glycol, and 235 parts of diethylene glycol were added, and the solid content was heated at 220°C to 240°C. Acid value is 6
．． After cooling, the mixture was heated to 0 and dehydrated, and after cooling, diluted with 175 parts of cellosolve acetate and 409 parts of xylene to obtain a viscosity U-UV measured by a bubble viscometer, a resin solid content of 60%,
Oil-free polyester resin with 1 color (drinkable resin■)
I got it.

To 92 parts of the solid content of this acidic resin ■, 8 parts of the solid content of the MF resin ■ obtained in Production Example 1 was added, and the viscosity was measured using a bubble viscometer at a reaction temperature of 90°C to 100°C. Y-Z
Heating and condensation reaction until the acidity is 9.8 x 1
0-2m mol/g 5olid.

Basicity 2.58810-'mmol/g 5olid
A dispersing resin ① (ampholytic resin of the present invention) was obtained.

On the other hand, as a comparison, 8 parts of Cymer 325ρ solid content was added to 92 parts of the solid content of acidic resin (■), and the mixture was synthesized using the reaction method described above with the dispersion resin (1).
．． 6 X 10-2 m mol/g 5 solid, basicity 2.54 X 10" m mol/g 5 solid
A dispersing resin ① (ampholytic resin other than the present invention) was obtained.

Example 2 Acidic resin (1) obtained in Production Example 3 and dispersion resin I11.
40 parts each of IV with 1 titanium oxide CR-92 (6 Hara Sangyo ■)
30 parts, 70 parts of Buticello as a dispersion solvent, 1 part of Tsurupets
502 oo parts were added and dispersed in an sG mill for 30 minutes.

In a 10-day storage test at room temperature, the acidic resin (1) produced a hard cake, and the dispersing resin (2) increased the viscosity, but the viscosity of the dispersion using the dispersing resin (2) did not change.

For each 100 parts of the obtained dispersion product, 85 parts each of the corresponding resins ■ and In addition, a baking type oil-free polyester resin paint was prepared so that the solid ul of the melamine-formaldehyde resin contained therein was 28 parts.

After applying each paint to invay rate test paper (Japan Test Panel Industry ■) with a 5 mil doctor blade, bake it at 140℃ for 20 minutes, and measure the color difference △E between the white part and black part of the invay rate test paper using a color difference meter (Toyo Rika). Industrial ■). Furthermore, each paint was diluted to a spray coating viscosity using a diluting solvent and coated on a tin plate 0.3 x 50 x 150 (Japan Test Panel Industry).
) After spray painting, the film clarity was visually judged. The results obtained are shown in Table 3.

Table 3 Production Example 4 Production of Alkyd Dispersing Resins V and (2) 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 transesterified with trimethylol. Ethane 1
Add 74 parts of neopentyl glycol, 176 parts of neopentyl glycol, 528 parts of phthalic anhydride, and 254 parts of inphthalic acid, and heat at 220°C~
Heat and dehydrate at 230°C until the solid acid value reaches 2.0, and after cooling, add 1009 parts of Tsurpets 100 (Ethane Standard Petroleum ■) and 58 parts of Cellosolve Acetate.
A short oil alkyd resin (acidic resin ■) having a viscosity UfV measured by a bubble viscometer, a nonvolatile content of 60%, and a color number of 1 was obtained.

To 92 parts of the solid content of this acidic resin (1), 8 parts of the solid content of the MF resin I obtained in Production Example 1 was added, and the viscosity W- The heating condensation reaction is carried out until the acidity becomes 3.3 X 10
-2m mol/g solid.

Basicity 2.58 x 10-1m mol/g 5o
Resin V (ampholytic resin of the present invention) for dispersing lid was obtained.

On the other hand, for comparison, 8 parts of Cymer 325 was added to 92 parts of the solid content of acidic resin (1), and the mixture was synthesized using the same reaction method as the dispersion resin V. Acidity 3. OX 10-2mmol/g 5olid
, base, degree of strength 2.55 x 10-1 m mol/g
A solid dispersion resin (2) (an amphoteric resin other than the present invention) was obtained.

Example 3 20 parts of Shinkasha Red Y (manufactured by DuPont) were added to 40 parts each of the acidic resin ■ and the dispersion resin ■ and ■ seen in Production Example 4.
As a dispersion solvent, 10,040 parts of Tsurupetz and 120 parts of steel beads were mixed and fractionated for 3 hours using an sGE.

To 100 parts each of the obtained dispersion products, add the corresponding resins ■, V, and W.
25 parts each, and further melamine-formaldehyde resin as a crosslinking agent, Kneepan 128 (Mitsui Toatsu ■, non-volatile content 60
%) and the solid content of melamine-formaldehyde resin in the paint is 22 parts.

In addition, we adjusted the baking type alkyd resin paint.

Each paint was diluted with a diluting solvent to a spray coating viscosity, and sprayed on a tin plate 0.3 x 50 x 150 m+ (Japan Test Panel Industry ■) and baked at 140'C for 30 minutes to achieve good image clarity and 200 specular gloss. were measured and the results shown in Table 4 were obtained.

Table 4 Dispersing resin V is excellent in gloss and image clarity.

4. Brief explanation of the drawings.

FIG. 1 is a diagram showing viscosity changes during storage of pigment dispersion base compositions obtained using various resins described in Example 1.
2 is an acidic resin, 2 is an amphoteric resin for dispersion according to the present invention,
3 represents a composition based on a dispersing amphoteric resin other than the present invention.

Part 1 @ viscosity

Claims (1)

[Scope of Claims]
Pigments and amphoteric resins obtained by addition or condensation reactions with functional groups that react with active hydrogen and/or active alkoxy groups, or with basic resins CB) having active hydrogen and/or active alkoxy groups and electron-donating groups. A dispersion base composition having excellent image clarity and dispersion stability, characterized in that the resin () is a melamine-formaldehyde resin having a number average degree of condensation of triazine nuclei of 2 to 6. (2) Amphoteric resin is resin solid content (8) Resin 99.5
Number average molecular weight (gel permeation chromatography measurement, polystyrene equivalent) obtained by reacting with 4'jt fat at a ratio of 0.5 to 40 weight range.
500 to 100,000 resin. (3) The acidity of the amphoteric resin, expressed as the number of moles of reagent required for neutralization, is determined by non-aqueous potentiometric titration using n-tetraptylammonicum hydroxide as a titration reagent in an aniline solution.
．． 0 to 1.0 x 10 mmol/g 5 solid, and basicity 1.0 to 5.0 x 1.0 x 10 mmol/g 5. OX 10-3 mmol/g 5o
The composition according to claim 1 or 2, which has a lid. (4) The composition according to any one of claims 1 to 3, wherein the blending ratio of the amphoteric resin and the pigment is 10 to 90% resin solids and 90 to 10% pigment.