JPS6310675A - Coating resin - Google Patents

Abstract

PURPOSE:To obtain the title resin which allows excellent pigment dispersion and gives a pigment paste having excellent storage stability, by reacting an Al chelate compound with a resin having active hydrogen atoms and/or epoxy groups attached to an electron attracting atom (group). CONSTITUTION:An aluminum chelate compound is reacted with a resin which has active hydrogen atoms and/or epoxy groups attached to an electron attracting atom or group and preferably has an acid value of 10 or less (e.g., a polyether polyol resin or an epoxy resin), giving an objective coating resin. Examples of suitable aluminum chelate compounds include a diisopropoxyaluminum monoalkyl acetoacetate and an aluminum tris-alkyl acetoacetate. The suitable amount of the chelate compound in the reaction is 2-20pts.wt. based on 100pts.wt. resin.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a coating resin that exhibits good dispersibility for a wide range of pigments and is capable of providing a pigment paste with good storage stability. .

(Background of the Invention) Pigments are blended into compositions such as paints and inks for coloring, but this work is extremely difficult due to the poor dispersibility of pigments. Conventionally, in order to disperse this pigment in a composition such as a paint, a small amount of resin and the pigment are thoroughly mixed in advance to form a so-called pigment paste, and this is lubricated with a specified resin and solvent to form a paint or a pigment. It is generally formed into a composition such as ink. Therefore, the performance required of the resin is that it has extremely high affinity with pigments and does not adversely affect the performance of the target paint composition.

By the way, it is understood that most pigments themselves have amphoteric properties, such as acids and bases, and it has been reported that groups with opposite properties to those of the pigments are introduced into resins to improve dispersibility. . For example, it has been proposed to introduce acidic groups, basic groups, or both into resins to increase their affinity with pigments. In addition, regarding the form of resins, star-shaped resins have been proposed in which a polymerization reaction starts from a central substance with several active sites, and chains extend from the center. . In the case of this star-shaped resin, since the resin itself has a low viscosity, it is easy to obtain a pigment paste with a low viscosity. Furthermore, efforts have been made to further improve the performance by introducing acidic groups and/or basic groups into this star-shaped resin.

However, none of the above methods is completely satisfactory, and further improvement in performance is desired.

(Contents of the Invention) As a result of various studies, the present inventors discovered that aluminum chelate was obtained by reacting an aluminum chelate compound with a resin having active hydrogen and/or epoxy groups bonded to electron-withdrawing atoms or atomic groups. It has been found that the compound-modified resin has extremely excellent pigment dispersibility, and paints prepared from it maintain extremely good values for various properties. In other words, the aluminum chelate compound-modified resin exhibits good dispersibility for a wide range of pigments, regardless of whether they are acidic, basic, or amphoteric, and as a result, the resulting pigment paste has improved tinting power, gloss, fluidity, etc. is recognized.

In order to improve the dispersibility of the pigment, a method of chemically treating the surface of the pigment particles, such as a method of treating the surface with an aluminum chelate compound (Japanese Unexamined Patent Publication No. 125475/1983,
JP-A-57-195163) and a method of treating with a titanium compound (JP-A-50-145448) are also known, but in these methods, the pigment and metal compound are mixed in a mortar before dispersing the pigment. It is necessary to thoroughly mix the mixture using a method such as a method, and the work is complicated.

As described above, the present invention involves modifying a specific resin with an aluminum chelate compound, and is clearly different from the above method in which a pigment is treated with an aluminum chelate compound.

Conventionally, it is known that paint compositions containing aluminum chelate compounds tend to cause gelation of the resin components during storage, and gelation also occurs when aluminum compounds are reacted with the specific resins mentioned above. There were concerns about the progress of

However, in reality, such gelation does not proceed;
The reaction between the specific resin and the aluminum chelate compound proceeded smoothly.

The present invention was completed based on the above findings, and
Its gist lies in a coating resin obtained by reacting an aluminum chelate compound with a resin having an active hydrogen and/or epoxy group bonded to an atomic group similar to an electron-withdrawing atom.

The resin used in the present invention is usually a variety of resins used for paints, but it is required to have an active hydrogen and/or epoxy group bonded to an electron-withdrawing atomic group. Paint resins usually include polyol resins, polyester resins, alkyd resins, acrylic resins, urea resins,
Examples include melamine resin, polyamide resin, polyurethane resin, and epoxy resin. When the above resin has active hydrogen and/or epoxy groups bonded to electron-withdrawing atoms or atomic groups, it can be used as is in the present invention.

If these are not present, they can be introduced by known methods. The electron-withdrawing atom or atomic group refers to a hydrogen atom bonded to an electron-withdrawing atom such as an oxygen atom or an electron-withdrawing atomic group such as a phosphoric acid group or a sulfonic acid group. For example, when introducing an epoxy group into a resin, a compound having a reactive glycidyl group may be reacted with the resin. For example, in the case of an acrylic resin, glycidyl acrylate or a glycidyl group-containing monomer such as glycidyl acrylate The epoxy group may be introduced by coexisting with the acrylic resin raw material monomer.

A polyol compound means a compound having a plurality of hydroxyl groups in its molecule, and generally preferably has at least one polymer chain. Especially focusing on compound molecules having several hydroxyl groups,
Those having a structure in which a polymer chain extends from each hydroxyl group and a hydroxyl group is present at the end of each polymer chain are preferably used. In general, it is preferable that the polyol compound has a low viscosity.
124922 specification, JP-A-60-115624 specification, JP-A-60-137924 specification, JP-A-Sho 60 specification
Polyether polyols, polyester polyols, polyether polyester polyols, and the like having a star structure described in Japanese Patent No. 137,967 are preferably used. For example, the formula: %Formula%] [R is a residue obtained by removing a hydroxyl group from a polyhydroxy compound, Ro is a hydrogen atom or a methyl group, Q and m are each 0 or a positive integer, but Q+1B is at least 61
and n is an integer of 3 or more. ] Compounds represented by the following are most preferably used.

Polyester resins are obtained by condensation of polyhydric carboxylic acids and polyhydric alcohols, and examples of the polyhydric carboxylic acids include trimellitic acid, trimellitic anhydride, phthalic acid, phthalic anhydride, inphthalic acid, terephthalic acid, and adipic acid. It will be done.

Examples of polyhydric alcohols that are commonly used include pentaerythritol, trimethylolpropane, trimethylolethane, glycerin, polyethylene glycol, 1,6-hexanediol, neopentyl glycol, propylene glycol, and ethylene glycol.

In addition to the above-mentioned polycarboxylic acids and polyhydric alcohols, 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, etc. Tall oil, coconut oil, cottonseed oil, linseed oil, etc. are used.

Acrylic resins are obtained by reacting (meth)acrylic acid or derivatives thereof with other copolymerizable monomers if desired. Examples of derivatives of acrylic acid include acrylic esters (e.g. methyl, ethyl, butyl esters, etc.)
, methacrylic acid esters (eg, methyl, ethyl, butyl esters, etc.), nitrile derivatives (eg, acrylonitrile, methacrylonitrile, etc.), styrene, styrene derivatives (eg, α-methylstyrene), and the like.

Urea resins and melamine resins are obtained by condensing formaldehyde with urea or melamine, and alcohols (e.g. 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 resin is obtained by condensation reaction of aliphatic diamine and dibasic acid or ring-opening polymerization reaction of cyclic lactam.
Examples of aliphatic diamines include l.

2-ethanediamine, N,N'-dimethyl-1,2-
Ethanediamine, 1,6-hexanediamine, etc. are used. Further, as examples of the dibasic acid, succinic acid, adipic acid, sebacic acid, etc. are appropriately selected. Examples of the cyclic lactam include α-pyrrolidone, ε-caprolactam, and ω-capryllactam.

Polyurethane resins are obtained by 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. Examples of the isocyanate compound include diisocyanates such as hexane ethylene diisocyanate, tolylene diisocyanate, and xylylene diisocyanate, and polyvalent isocyanates such as Desmodur N1 and Desmodur L.

The number average molecular weight of the resin is 5oo to too, oo.

is common. Number average molecular weight is determined by gel permeability chromatography using polystyrene standards. In the case of polyol compounds, the molecular weight of the resin is
20,000 or less (preferably 10,000 or less), 1°000 to 50,000 in the case of acrylic resin, 500 to 10,000 in the case of polyester resin, 200 to 4,000 in the case of epoxy resin and 1,000 to 20,000 in the case of polyurethane resin. It is particularly preferred that the polyol compound has a weight average molecular weight/number average molecular weight of 3.5 or less, preferably 3.0 or less. When the number average molecular weight exceeds 20,000, the viscosity of the coating resin obtained by the reaction with the aluminum chelate compound increases significantly, and gelation is likely to occur. Furthermore, when the weight average molecular weight/number average molecular weight exceeds 3.5, the viscosity of the paint resin similarly increases and gelation tends to occur.

In the present invention, an aluminum chelate compound having an active hydrogen and/or epoxy group bonded to the electron-withdrawing atom and atomic group is reacted.
Based on the theory that the pigment described above is considered to be a base, acid, or amphoteric, it is thought that dispersibility is improved when an acid group or a base or both are introduced into the N+ group as necessary. Introduction of acid groups and introduction of bases can be carried out by methods known to those skilled in the art.

When the resin has an acid value, the acid value of the resin is 10 or less, preferably in the range of 1 to 5.

Generally, an acidic group is introduced by using an acidic group-introducing reagent, and the acidic group referred to herein means an electron-accepting group, and examples thereof include a carboxylic acid group and a sulfonic acid group. As acidic group-introducing reagents, reagents capable of introducing carboxyl groups are most commonly used, and representative examples include phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, and tetrahydroanhydride. Phthalic acid, hexahydrophthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, hetacetic anhydride, himic anhydride, maleic anhydride, fumaric acid, itaconic acid, trimellitic anhydride, methylcyclohexentricarboxylic anhydride, pyroanhydride Examples include mellitic acid. Among these, it is particularly preferable to use tribasic acid anhydrides such as phthalic anhydride and maleic anhydride.

The basic group introduced by the basic group introduction reagent means an electron donating group, and a typical example thereof is a group containing a nitrogen atom having a lone pair of electrons. As a basic group introduction reagent,
Isocyanate compounds such as naphthalene diisocyanate, phenylene diisocyanate, isophorone diisocyanate, tolyl isocyanate, diphenyl ether diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and other monomer compounds, or their molecular weight can be increased to reduce toxicity. This compound (hexamethylene diisocyanate-based “Duranate EXPD-101 (Asahi Kasei),” “Desmodur TPL-2291 (Sumitomo Bayer),” “Coronet” E H (Japan Polyurethane), xylylene diisocyanate-based “Takenate D12ON” (Formula (Japan Pharmaceutical), isophorone diisocyanate type ("Desmodur Z-4370" (Sumitomo Bayer), etc.), melamine compounds, such as compounds obtained by condensing melamine and formaldehyde, or compounds obtained by adding alcohol to the condensation. (“Cymel 303” and “Cymel 300” as methylated melamine (Mitsui Toatsu)
, “Sumimar 40W” (Sumitomo Chemical), “Kneepan 20SE-60” (Mitsui Toatsu) as n-butylated melamine
, isobutylated melamine such as "MFQ13" (Nippon Paint), hydroquinolamine compounds such as monoethanolamine, jetanolamine, aminopentanol, aminobenzyl alcohol, 2-dimethylaminoethanol, etc., amino acid compounds such as 3-dimethylamino Examples include polyamide compounds such as benzoic acid, 2-aminoisobutyric acid, and 1-amino-n-butyric acid. Among these, it is particularly desirable to use isocyanate compounds and melamine compounds.

As the aluminum chelate compound, those represented by the following formula are preferably used.

[R" is a lower alkyl group, R"° is CR, -CH=CR
Y (wherein R1 and R2 are each a lower alkyl group or a lower alkoxy group), m is an integer of I to 3,
n is an integer from O to 2, m+n is 3]. In the above formula, only the alcoholate moiety (R-0-) reacts with active hydrogen or epoxy groups in the resin.

However, the chelate moiety (...O-R"'-0-
) is considered to remain as is.

Specific examples of aluminum chelate compounds include diisopropoxyaluminum monooleyl acetoacetate,
Diisopropoxyaluminum monolauryl acetoacetate, diisopropoxyaluminum monostearylacetoacetate, diisopropoxyaluminum monoisostearylacetoacetate, diisopropoxyaluminum ethyl acetoacetate, monoisopropoxyaluminum bisoleylacetoacetate, monoisopropoxyaluminum mono Examples include oleate monoethylacetoacetate, aluminum trisethylacetoacetate, aluminum monoacetylacetonate bisethylacetoacetate, aluminum trisacetylacetonate, but are not necessarily limited to these.

It is desirable that the reaction ratio between the resin and the aluminum chelate compound is 2 to 20 parts by weight of the latter per 100 parts by weight of the former; if more than this is blended, gelation may proceed during the reaction, and if the blend is less than this, gelation may proceed during the reaction. , the resin cannot have sufficient pigment dispersibility.

The reaction temperature is usually below 150°C, preferably around 80°C. If the temperature is 150°C or higher, gelation may proceed.

The coating resin thus obtained has excellent storage stability. The resin is thought to have at least one unreacted chelate group, and when the pigment is dispersed, the unreacted chelate group forms a covalent bond with a functional group corresponding to acidity or basicity present on the surface. It seems that they are combined.

The pigment paste obtained by dispersing the pigment in the above paint resin has excellent storage stability, so even if it is stored for a long time, it will cause an increase in viscosity, a decrease in pigment dispersibility, a change in coloring power, and a decrease in gloss. No deterioration is observed.

There is no particular limitation on the range of pigments that can be used, and various inorganic and organic pigments can be used. Specific examples of inorganic pigments include zinc white, titanium oxide, antimony white, carbon black, iron black, red iron black, red lead, cadmium yellow, zinc sulfide, lithopone, barium sulfide, lead sulfate, barium carbonate, lead white, and alumina white. can be mentioned,
Specific examples of organic pigments include azo, polycondensed S metal complex azo, benzimidacylon, phthalocyanine (blue, green), thioindigo, anthraquinone, flavanthrone, indanthrene, and anthraquinone. Examples include pyridine series, pyranthrone series, isoindolinone series, perylene series, perinone series, and quinacridone series.

The amount of pigment used is usually 1% based on the total weight of resin and pigment.
0-90% (by weight), preferably 30-70% (by weight)
It is.

The pigment paste may be composed only of the coating resin of the present invention and the pigment as described above, but as long as it does not have an essentially adverse effect on its dispersibility, it may also contain appropriate resins, solvents, additives, and other additives as necessary. A curing agent or the like may be added.

The pigment paste prepared as described above is stored and mixed uniformly with another coating resin to prepare a coating composition.

Various resins can be used as other paint resins, specific examples of which are as follows: nioleum-free polyester resin, long oil alkyd resin, short oil alkyd resin,
Acrylic resin, melamine resin, epoxy resin, polyurethane resin, polyamide resin, urea resin, polyether resin, etc. Note that the star-type purchased polyol compound used in the preparation of the resin composition for paint of the present invention and the resin for paint of the present invention can be used as a resin for paint other than the above.

There is no particular restriction on the blending ratio of pigment paste and paint resin, but it is usually 1.99 to 99=1 (weight ratio). Note that appropriate resins, solvents, modifiers, etc. may be blended as necessary.

In the above description, specific examples of solvents that can be appropriately blended into pigment pastes and coating compositions include hydrocarbon solvents (e.g., toluene, xylene, Solhetsuso 100,
Solbevso 150), ester solvents (eg, ethyl acetate, butyl acetate), ketone solvents (eg, methyl ethyl ketone, methyl isobutyl ketone), and the like.

In the preparation of the pigment paste or coating composition, any conventional dispersing and mixing means may be employed, such as a dispersing machine such as a roll mill, ball mill, sand mill, planetary mixer, or high-speed disperser.

The coating composition prepared as described above has an excellent coating appearance and can form a solid coating film.

Next, the present invention will be explained in more detail with reference to comparative examples and examples.

Example 1 Pentaerythritol polymer (prepared by polymerizing pentaerythritol and propylene oxide by the method described in JP-A-58-15933; Mn = 2°000) 1000
300g of ε-caprolactone and 1?g of di-n-butyltin oxide. was added and reacted at about 180°C for 2 hours. The obtained reaction product A has Mn 2.600, Mw
/: An= 1.45 and Metsu f.

To the reaction product A 1009, 10.59% of diisopropoxyaluminum ethyl acetoacetate and 12.39% of xylene were added, and the reaction was carried out at 70°C for about 1 hour. A resin was obtained.

Example 2 2.8 phthalic anhydride was added to the reaction product A1009 of Example 1.
9 and Kijirole 12.09 were added and refluxed at 150°C for about 2 hours to obtain an acidic polymer (Mn=2.672; Mw
/Mn=1,51, acid value=lO,3).

6 g of quinolol and 2.589 g of diisopropoxyaluminum ethyl acetoacetate were added to the obtained r-acidic polymer 509 (non-volatile content 100%), and the mixture was heated to about 1
When reacted for a period of time, a low viscosity, pale yellow oil-like paint resin was obtained.

Example 3 4.5% of phthalic anhydride was added to the reaction product Al009 of Example 1.
9 and Kijirole 12.09 were added and refluxed at 1'50°C for about 2 hours to form an acidic polymer (Mn=2,710:M
w/Mn=1,55, acid value=16.3).

To 50 g of the obtained acidic polymer (nonvolatile content 100%), 6 g of Kijirole and 1.539 g of diisopropoquine aluminum ethyl acetoacetate were added, and the mixture was heated at 70°C to about 1
When reacted for a period of time, a pale yellow oil-like paint resin with low viscosity was obtained.

Example 4 Phthalic anhydride 6 to the reaction product A I O09 of Example 1
．． Add 29 and Kijirole I +, 99, 150°
The acidic polymer (Mn=2,758
:M#/Mn=1.60, acid value=22.1).

To the obtained acidic polymer 509 (non-volatile content 100%) was added 6 g of Kijirole and 0.529 g of diisopropoxyaluminum ethyl acetoacetate, and the mixture was heated at 70°C to about 1
When reacted for a period of time, a pale yellow oil-like paint resin with low viscosity was obtained.

3.4% of phthalic anhydride was added to the reaction product A2009 of Example 1.
9 and Quijirol 259 were added and refluxed at 150°C for about 2 hours to form an acidic polymer (Mn=2,640; My/Mn
=I, 50, acid value = 6.3).

To the obtained acidic polymer 509 (non-volatile content 100%) were added Kijirole 69 and diisopropoquinoaluminum ethyl acetoacetate 5.4 i9, and the mixture was heated to about 1 at 70°C.
When reacted for a period of time, a pale yellow oil-like paint resin with low viscosity was obtained.

Example 6 f2 acidic polymer obtained in Example 5 509 (non-volatile content 1
00%), Kinroll 69 and melamine resin knee pants 128 (Mitsui Toatsugetsu, 79 (MX1 = L. +03:
Add Sr / ~1n = 1.89) and heat at 140℃ for about 2
The acid/base modified polymer (Mn=2.720
: Mw/Mn=2.15, acid value=6.2).

Diisopropoxyaluminum ethyl acetoacetate 5.419 was added to the obtained acid/base modified polymer, and 7
When the reaction was carried out at 0° C. for about 1 hour, a low viscosity, pale yellow oil-like coating resin was obtained.

Example 7 Phthalic anhydride 5 to the reaction product A 10 o9 of Example 1
．． 69 and Kijirole 12.69 were added and refluxed at 150°C for about 2 hours to form an acidic polymer (Mn=2.670;
w/Mn=1.53, acid value=20.6).

To the obtained acidic polymer 509 (0,019 moQ) (non-volatile content 100%) were added Kizilol 69 and diisopropoxyaluminum ethyl acetoacetate 5°359 and reacted at 70° C. for about 1 hour, resulting in gelation.

Example 8 Phthalic anhydride 4,5 to the reaction product Al0Q9 of Example 1
Add 12.59 g and Kijirole and heat at 150°C for about 2.
The acidic polymer (Mn=2,714; Mw/
Mn=1,60, acid value=16.3) was obtained.

To 50 g (non-volatile content! 00%) of the obtained acidic polymer were added 69 g of Kijirole and 3.689 g of diisopropoxyaluminum edylacetoacetate), and the mixture was reacted at 70° C. for about 1 hour, resulting in gelation.

Comparative Example 1 The acidic polymer that had not reacted with the aluminum chelate obtained in Example 5 was used as a comparative paint resin.

The acid/base-modified polymer that had not reacted with the aluminum chelate obtained in Example 6 was used as a comparative coating resin.

14.3 parts of coconut oil, 8.3 parts of trimethylolethane, and di-n-butyltin oxide o, oti were charged into a reaction vessel and heated to 220°C under a nitrogen atmosphere to carry out a transesterification reaction. After cooling, 5.2L of ethylene glycol
6.0 parts of trimethylolethane and 31 parts of phthalic anhydride.
Add 6 parts, heat to 230°C, measure the acid value while dehydrating, cool when the acid value reaches 0.8,
．． 0 part was added to obtain polyester resin 1. The number average molecular weight of this resin was 1900 as measured by GPC. Resin I was heated to 80° C., 6.0 parts of diisopropoxyaluminum monoethyl acetoacetate was added, kept warm for 1 hour, and then cooled to obtain alkyd resin IA.

Example 1O 35.1 parts of isophthalic acid, 4.4 parts of azelaic acid, 4.6 parts of trimethylolpropane, 15.4 parts of neopentyl glycol, 8.7 parts of 1.6 hexanediol, and di-
0.01 part of n-butyltin oxide is charged into a reaction vessel and heated to 230° C. under a nitrogen atmosphere, and the acid value is measured while dehydrating. When the acid value reached 8, it was cooled and 40.0 parts of pheasant roll was added to obtain polyester resin 2. The number average molecular weight of this resin was 220 as measured by GPC.
0 and 1 ko. Resin 2 was heated to 80°C, 1090 parts of aluminum trisethyl acetoacetate was added,
After keeping the temperature for 1 hour, it was cooled to obtain polyester resin 2A.

Add 5 parts of Kneepan 128 (manufactured by Mitsui Toatsu Co., Ltd.) to 2.100 parts of the polyester resin obtained in Example 10 above, heat it to 80°C, and continue the reaction until the increase in viscosity becomes constant. Resin 3 was obtained. To resin 3, diisopropoxyaluminum ethyl acetoacetate 3.0 was added at 80°C.
of the mixture was added, kept warm for 1 hour, and then cooled to obtain polyester resin 3A.

Example 12 30.6 parts of isophthalic acid, 14.9 parts of azelaic acid, 3.7 parts of trimethylolpropane, 19.2 parts of neopentyl glycol, 10.9 parts of 1.6-hexanediol (J
and 0.01 part of di-butyltin oxide were charged into a reaction vessel and heated to 230°C under a nitrogen atmosphere, and the acid value was measured while dehydrating. When the acid value reached 10, it was cooled, and 40.0 parts of pheasant roll was added to obtain polyester resin 4. The number average molecular weight of this tree was 1,000 when measured by GPC. Resin 4 was heated to 80°C, 6.0 parts of aluminum trisethyl acetoacetate was added, kept warm for 1 hour, and then cooled to form polyester resin 4.
I got an A.

Example 13 35.4 parts of isophthalic acid, 4.5 parts of azelaic acid, 5.7 parts of trimethylolpropane, 14.5 parts of neopentyl glycol, 8.2 parts of 1.6 hexanediol, and di-
0.01 part of n-butyltin oxide is charged into a reaction vessel and heated to 230°C under a nitrogen atmosphere, and the acid value is measured while dehydrating. When the acid value reached 15, it was cooled, and one bottle of 40.0 parts of pheasant roll was added to obtain polyester resin 5. The number average molecular weight of this resin was 2100 as measured by GPC. Resin 5 was heated to 80° C. and diisopropoxyaluminum ethyl acetoacetate 3.
When 0 part was added, gelation occurred.

Example 14 35.4 parts of isophthalic acid, 4.5 parts of azelaic acid, 5.7 parts of trimethylolpropane, 14.5 parts of neopentyl glycol, 8.2 parts of 1.6 hexanediol, and 0.2 parts of non-n-butyltin oxide. 1 part of O was charged into a reaction vessel and heated to 230°C under a nitrogen atmosphere, and the acid value was measured while dehydrating. When the acid value reached 15, it was cooled and 40.0 parts of pheasant roll was added to obtain 1 piece of polyester resin 6. The number average molecular weight of this resin was 2100 as measured by GPC. Resin 6 was heated to 170°C to form diisopropoxyaluminum ethyl acetoacetate 3.
．． When 0 part was added, gelation occurred.

Comparative Examples 3 to 6 The f-copolyester resin 11 obtained in Example 9, the polyester resin 2 obtained in Example 1O, the polyester resin 3 obtained in Example 11, and the polyester resin 4 obtained in Example 12 were used as Comparative Example 3. 4.5.6 was used for pigment dispersion.

Example 15 1000 parts of xylene is charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring blade, and the temperature is raised to 130°C. Methyl methacrylate 67.1 parts, styrene 542.
A solution containing 5 parts of n-butyl acrylate, 224.8 parts of n-butyl acrylate, 165.6 parts of hydroxyethyl acrylate, and 60 parts of azobisisobutyronitrile was charged into the dropping funnel. The contents of the dropping funnel were added dropwise at a constant rate over 3 hours at 130° C. under a nitrogen atmosphere. After the completion of dropping, the temperature was maintained at 130°C for 30 minutes. Next, a solution of 6 parts of azobisisobutyronitrile and 800 parts of xylene was charged into the dropping funnel, and this was added dropwise at a uniform rate over 30 minutes. After completion of the dropwise addition, the temperature was maintained at 130° C. for 2 hours to complete polymerization and cooled to obtain acrylic resin 1. The number average molecular weight of this acrylic resin 1 was 3,500. This acrylic resin l was heated to 80°C, 30 parts of diisopropoxyaluminum ethyl acetoacetate was added,
The mixture was kept at 80° C. for 1 hour to obtain acrylic resin IA.

Example 16 1000 parts of xylene was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring blade, and the temperature was raised to 140°C! j
L. Methyl methacrylate 55.8 parts, styrene 5
A solution containing 58.6 parts of lauryl methacrylate, 126.9 parts of hydroxyethyl acrylate, 248.4 parts of hydroxyethyl acrylate, 10.3 parts of acrylic acid, and 60 parts of azobisisobutyronitrile was charged into the dropping funnel. The contents of the dropping funnel were added dropwise at a uniform rate over 3 hours at 140°C under a nitrogen atmosphere. After the completion of dropping, the temperature was maintained at 140°C for 30 minutes. Next, a solution of 6 parts of azobisisobutyronitrile and 800 parts of xylene was charged into the dropping funnel, and this was added dropwise at a uniform rate over 30 minutes. After completion of the dropwise addition, the mixture was maintained at 140° C. for 2 hours to complete polymerization and cooled to obtain acrylic resin 2. The number average molecular weight of this acrylic resin 2 was 2,100. This acrylic resin 2 was heated to 80°C.
100 parts of diisopropoxyaluminum ethyl acetoacetate was added, and the mixture was kept at 80° C. for 1 hour to obtain acrylic resin 2A.

Example 17 Add 5 parts of Kneepan 128 (manufactured by Mitsui Toatsu Co., Ltd.) to 2.100 parts of the acrylic resin obtained in Example 16 above, heat it to 808C, and continue the reaction until the viscosity increase becomes constant. Obtained. Further, 3.0 parts of diisopropoxyaluminum ethyl acetoacetate was added to Resin 3 at 80°C, kept warm for 1 hour, and then cooled to obtain Acrylic Resin 3A.

Example 1 18 Two parts of xylene are charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring blade, and the temperature is raised to 130°C. 433°9 parts of methyl methacrylate, 21 parts of styrene
3.9 parts, lauryl methacrylate 202.3 parts, hydroxyethyl acrylate) 124.21.7 'y +
J Rulic acid 25.7 parts, azobisisobutyronitrile 30
of the solution into the dropping funnel. Under nitrogen atmosphere, 130
The contents of the dropping funnel were heated uniformly at ℃ for 3 hours. After the completion of dropping, the temperature was maintained at 130°C for 30 minutes. Next, a solution of 6 parts of azobisisobutyronitrile and 800 parts of xylene was charged into the dropping funnel, and the mixture was heated uniformly for 30 minutes. After completion of the dropwise addition, the mixture was maintained at 130° C. for 2 hours to complete polymerization and cooled to obtain acrylic resin 4. The number average molecular weight of this acrylic resin 4 was 6,000. This acrylic resin 4 to 8
The mixture was heated to 0°C and 30 parts of diisopropoxyaluminum ethyl acetoacetate was added to form a gel.

Comparative Examples 7 to 9 Acrylic resin 11 obtained in Example 15, acrylic resin 2 obtained in Example 16, and acrylic resin 3 obtained in Example 17 were used for pigment dispersion as Comparative Examples 7, 8, and 9, respectively.

Example 19 100 parts of xylene and 100 parts of Epicoat +001 (manufactured by Shell Chemical Co., Ltd.) are charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring blade, and the temperature is raised to 70° C. to completely dissolve. Then, 8 parts of diisopropoxyaluminum ethyl acetoacetate was added and kept at 70°C for 1 hour.
It was cooled to obtain epoxy resin 1.

Add 100 parts of xylene to a reaction vessel equipped with a cooling tube, nitrogen introduction tube, thermometer, and stirring blade, and Epicoat! Add 100 parts of 004 (manufactured by Shell Chemical Co., Ltd.) and raise the temperature to 90°C to completely dissolve it. Thereafter, 10 parts of aluminum trisethyl acetoacetate was added and the mixture was kept at 90° C. for 1 hour and then cooled to obtain epoxy resin 2.

Example 21 100 parts of xylene and 100 parts of Epicoat 1009 (manufactured by Shell Chemical Co., Ltd.) are charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring blade, and the temperature is raised to 170° C. to completely dissolve. Thereafter, 10 parts of diisopropoxyaluminum ethyl acetoacetate was added at 170°C to form a gel.

Comparative Examples 10 to I2 Epikote toot of Example 19, Epikote tOQ4 of Example 20, and Epikote 1009 of Example 2X were used as Comparative Examples 1011L12 for pigment separation.

Example ■ Manufacture of pigment paste 1) Manufacture of blue paste The blue pigment Fastgen Blue NK (
Add 12.5 parts of Dainippon Ink), 16.7 parts of Kijiroll and 50 parts of Glass Peas, and use a paint shaker to
Shake for hours. The properties of the obtained dispersion paste were as shown in Table 1.

2) Production of black paste Black pigment carbon black MA-1 was added to 25.0 parts of the paint resin produced in Example 1-16 and Comparative Example 1-12.
00 (Mitsubishi Carbon), 20 parts of Kinroll, and 50 parts of Glass Peas were added, and the mixture was shaken in a paint shaker for 1 hour. The properties of the obtained f-bidispersion paste were as shown in Tables 1 to 4.

Table 3 1 unit cps: Measured with an E-type viscometer! 20° specular gloss value; measured with a 10μ grind gauge 3
Measured with E-type viscometer Table 4 1 unit cps Measured with HE-type viscometer 320° specular gloss value; Measured with grind gauge 10μ 3
Example of measurement using an E-type viscometer ■ Production of paint The dispersion paste prepared above was added to melamine alkyd white paint New Orga 130 (Nippon Paint) 609.
．． 09 was added to prepare a paint.

Formation of Coating Film The coating prepared as described above was applied by spraying to a matte steel plate whose surface had been previously prepared, and baked at l·10°C for 30 minutes. The surface properties of the resulting coating film were as shown in Table 5.

Further, after storing the paint prepared as described above at 40°C for two weeks, a paint film was formed in the same manner. The surface properties of the resulting coating film were as shown in Table 5.

Claims (1)

[Scope of Claims] 1. A coating resin obtained by reacting an aluminum chelate compound with a resin having active hydrogen and/or epoxy groups bonded to electron-withdrawing atoms or atomic groups. 2. The coating resin according to item 1, wherein the resin is a polyether polyol resin, a polyester resin, an alkyd resin, an acrylic resin, a polyurethane resin, or an epoxy resin. 3. The resin for paint according to item 1, wherein the resin has an acid value of 10 or less. 4. The coating resin according to item 1, wherein the aluminum chelate compound is diisopropoxyaluminum monoalkyl acetoacetate or aluminum trisalkyl acetoacetate. 5. The coating resin according to item 1, wherein the reaction is carried out at a temperature of 0 to 150°C. 6. The first one, in which the reaction ratio of the resin and the aluminum chelate compound is 2 to 20 parts by weight to 100 parts by weight of the former.
Paint resin described in Section 1.