JPS61106627A - Branched resin, its production and coating composition - Google Patents

Abstract

PURPOSE:To obtain the titled resin useful to improve compatibility with various resins such as alkyd resins, by reacting a specified polyepoxy compound with a COOH group-containing acrylic prepolymer and another prepolymer. CONSTITUTION:A branched resin represented by formula IV (wherein n+m is 2-6) and having a weight-average MW of 1,000-2,000,000 and a glass transition temperature of -20-100 deg.C is obtained by reacting a polyepoxy resin of formula I (wherein R is an aliphatic, alicyclic, aromatic or heterocyclic hydrocarbon residue and n' is 2-6) with a COOH group-containing acrylic prepolymer of formula II [wherein X is an acrylic prepolymer chain of a weight-average MW of 1,000-100,000, a glass transition temperature of -20-100 deg.C, obtained by using 0.2-0.8wt%, based on the solid content of the prepolymer, COOH group-containing chain transfer agent and/or 0.3-12wt% COOH group-containing initiator) and a COOH group-containing resin other than X, represented by formula III (wherein Y is a prepolymer chain of a resin other than the acrylic resin represented by X), e.g., alkyl resin.

Description

Detailed Description of the Invention: Industrial Field of Application The present invention provides a branched resin that has low viscosity, excellent compatibility with acrylic resins and resins other than acrylic resins, and is also effective as a resin for dispersing various pigments. Regarding.

Prior Art The present inventors have previously discovered that the formula R-(OCH2-CH-CH2)n' (wherein R is an aliphatic, alicyclic, aromatic or heterocyclic hydrocarbon residue, n' is 2 to 6 A polyfunctional epoxy compound represented by the formula
A branched acrylic resin obtained by reacting an acrylic prepolymer with a terminal carboxyl group (acrylic prepolymer chain at 20 to 100°C) has a lower viscosity than a normal acrylic resin at the same molecular weight. Based on this fact, a patent application was filed as Patent Application No. 58-218127.

In general, the branched acrylic resin has an electron accepting group and/or
He discovered that a pigment-dispersing resin with excellent dispersibility with various pigments could be obtained by supporting an electron-donating group.
A patent application was filed as No. 24791.

However, in the paint industry, paints are rarely formulated using only one type of resin; usually, plasticizers, crosslinking agents,
Various resins are mixed and used as a modifier. In this case, if the resins have good compatibility with each other, the desired low viscosity and improved pigment dispersibility can be achieved, but if the compatibility is poor, the intended results may not necessarily be obtained. There is.

Therefore, regardless of the type of resin used, it would be of great benefit to the industry if it had excellent compatibility, maintained low viscosity even in the mixed state, and had good pigment dispersion. , and its low viscosity makes it a high non-volatile paint.
Moreover, a product with excellent coating workability and coating film performance can be obtained.

Means for Solving the Problem The inventors introduced some resin molecules that cause compatibility problems into resin molecules as a means to improve compatibility with various resins (especially alkyd resins and polyester resins). However, the present invention was completed based on the fact that compatibility is improved by newly configuring the molecule.

To explain in detail the content of the present invention, a polyfunctional epoxy compound represented by and a formula X-C00H
Acrylic prepolymer having a carboxyl group represented by (X is an acrylic prepolymer chain) and Y-COOH (
Y is various resin residues, but alkyd and/or polyester residues are particularly preferred). By synthesizing a H OH branched resin and introducing a resin Y different from an acrylic resin, compatibility with various resins that are incompatible with X but compatible with Y is improved. Furthermore, for the purpose of improving the pigment dispersibility, paint, coating, and film performance of such resins, the branched resins may be made to support electron-accepting groups and/or electron-donating groups.

To explain in detail the method for producing the branched resin, X-C0
The carboxyl group-containing acrylic prepolymer represented by OH is prepared by copolymerizing (1) acid monomers or by copolymerizing (2)
) It can be obtained by copolymerizing monomers other than acid monomers using a chain transfer agent having a carboxyl group and/or an initiator having a carboxyl group.

In the case of (1) above, the monomers that can be used include: ■ Acid monomer ■ Neutral monomer ■ Monomer having a functional group that reacts with active hydrogen and/or active alkoxy group or ■ Active hydrogen and/or active alkoxy group It is obtained by copolymerizing monomers having the following.

Typical acid monomers include carboxyl group-containing monomers, such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid.

Neutral monomers include ethylene, propylene, butadiene, imprene, polypropylene, vinyl bromide, vinyl fluoride, acrylic esters (such as methyl, ethyl, butyl esters), and methacrylic esters (such as methyl, ethyl, butyl esters). etc.), nitrile derivatives (eg, acrylonitrile, methacrylonitrile, etc.), styrene derivatives (eg, α-methylstyrene), and the like.

On the other hand, examples of the functional group-containing monomer mentioned in (2) above include glycidyl acrylate, glycidyl acrylate, etc.
Glycidyl methacrylate, etc. can be selected, 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 (2) above, acrylamide, methacrylamide, etc. can be used as an amide group-containing monomer, and N-methoxymethylolacrylamide, N-butoxymethylolacrylamide, etc. can be used as an active alkoxy group-containing monomer. Alternatively, as the functional group-containing monomer of (1) or the active hydrogen group-containing monomer of (2), 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate,
Hydroxyl-containing polymers such as -hydroxypropyl methacrylate or N-methylol acrylamide can also be used.

In such a carboxyl group-containing acrylic prepolymer, the amount of carboxyl groups contained is on average 0.1 mol to 1.5 mol per molecule, preferably 0.2 mol to 1.2 mol, calculated based on the number average molecular weight. It is. The viscosity of the carboxyl branched resin increases, and if it is less than 0.1 mol, a sufficient branched structure cannot be achieved, making it impossible to achieve the object of the present invention.

On the other hand, in the case of (2) above, the monomer other than the acid monomer is the above-mentioned (1) neutral monomer, (2) active hydrogen and/or active alkoxy group having a functional group that reacts with it, or (2) active hydrogen and/or active alkoxy group. When polymerizing an acrylic resin, a monomer having the following is used as a commonly used initiator: □For example, 2'-azo-bis-isobutyronitrile, 1 as an azo-nitrile compound.
．． 1'-Azo-bis-1-cyclobutanenitrile, 2
, 2'-azo-bis-2methylbutyronitrile, etc., 2,3-diazo-bicyclo[2.2.

1] Heptene, 2.2.2'-azo-bis-propane, 1.1'-azo-bis-1-phenylethane, etc., and peroxide compounds such as t-butyl peroxide, benzoyl peroxide, t- Polymerization is initiated using butyl hydroperoxide, cumene hydroperoxide, etc., and (1) as a chain transfer agent, a compound containing a carboxyl group, such as mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptoacetic acid, etc. A carboxyl group can be introduced at the end of the acrylic prepolymer by using dropionic acid, 0-mercaptobenzoic acid, or the like.

On the other hand, monomers other than carboxyl group-containing monomers,
When polymerizing the acrylic resin, (2) using a carboxyl group-containing initiator, such as 4,4'-azo-bis(4-cyanopentanoic acid), peroxide diglutaric acid, etc.
Carboxyl groups can also be introduced at the ends of the acrylic prepolymer by initiating polymerization. In general, a carboxyl group can also be introduced at the end of an acrylic prepolymer by using both a carboxyl group-containing compound as the chain transfer agent (α) and a carboxyl group-containing initiator (β). I can do it.

In the polymerization of the carboxyl group-containing acrylic prepolymer obtained by the methods (1) and (2) above, polymerization methods such as bulk polymerization, solution polymerization, and if necessary suspension polymerization are used to prepare all m. method, initiator dropping method or monomer dropping method, the temperature is higher than the decomposition temperature of the initiator, usually 70 to 170°C.
A prepolymer can be synthesized by reacting at a reaction temperature of 1 to 8 hours. When synthesizing such a prepolymer, the amount of the carboxyl group-containing chain transfer agent used in method (α) used to introduce carboxyl groups at the terminals of the acrylic prepolymer obtained by method (2) depends on the solidity of the prepolymer. The mold weight ratio is in the range of 0.2 to 8 weight percent, preferably 0.3 to 5 weight percent. on the other hand,
When a carboxyl group-containing initiator is used in method (β), the m used is 0.3 in terms of the solid fraction of the prepolymer.
-12% by weight, preferably 0.4-8% by weight. If the amount of the carboxyl group-containing chain transfer agent used in method (1) exceeds the above 8% by weight, and the amount of the carboxyl group-containing initiator used in method (2) exceeds the above 12% by weight, The molecular weight of the polymer decreases significantly, and therefore the molecular weight of the acrylic resin, which is the object of the present invention, decreases, making it impossible to exhibit sufficient effects in terms of durability such as weather resistance and chemical resistance. On the other hand, if the amount of the carboxyl group-containing chain transfer agent used is less than 0.2% by weight, or if the amount of the carboxyl group-containing initiator used is less than 0.3% by weight, the molecular weight of the prepolymer increases significantly and The reactivity with the glycidyl group of the functional engineering (boxy) compound decreases (1.6).For this reason, it takes a long time to synthesize the acrylic resin, which is the objective of the present invention, and The molecular weight of certain acrylic resins becomes too large, resulting in increased viscosity and problems such as being unsuitable for use as paint resins.

The acrylic prepolymer having a carboxyl group synthesized under the above polymerization conditions does not impair the durability such as weather resistance and chemical resistance, solvent resistance, mechanical strength, etc. of the acrylic resin, which is the object of the present invention. In order to maintain a low viscosity, the weight average molecular weight of the acrylic prepolymer II (measured by gel permeation chromatography, polystyrene conversion >1
ooo~1000001 Also glass transition temperature -20~10
Preferably it is 0°C.

On the other hand, at least one or more prepolymers Y-C00H other than the above-mentioned acrylic resins having carboxyl groups include oil-free polyester resins having carboxyl groups;
Examples include long oil or short oil alkyd resins. On the other hand, in polyhydroxy resins such as polyether resins, polyurethane resins, and epoxy resins, such hydroxyl groups are converted into acid anhydrides,
For example, at least one or more of acetic anhydride, succinic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride is added by a conventional method to incorporate carboxyl groups into the resin. Can be put to use. Oil-free polyester 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. However, as polyhydric alcohols, pentaerythritol, trimethylolpropane, trimethylolethane, glycerin, polyethylene glycol, 1,6-hexanediol, neopentyl glycol, propylene glycol, ethylene glycol, etc. are commonly used.

In addition to the above-mentioned polyhydric carboxylic acids and polyhydric alcohols, the long oil or short oil alkyd resin contains fatty acids as oil components, 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.

The above polyether resin is obtained by polymerizing propylene oxide, ethylene oxide, etc. using a polyhuman oxygen compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, sorbitol, pentaerythritol, sucrose, starch, or other initiator. It is resin.

Polyurethane resins are obtained by addition-reacting polyhydroxy resins, such as oil-free polyester resins having hydroxyl groups, long oil or short oil alkyd resins, acrylic resins or polyether resins, and isocyanate compounds.

Epoxy resins can generally be obtained by reacting a phenol compound with epichlorohydrin, a polyhydric alcohol with epichlorohydrin, or another acid with epichlorohydrin.

Prepolymer having the above carboxyl group, Y-COO
The amount of carboxyl groups contained in the resin in H is an average of 0°1 mol to 1.5 mol per molecule calculated by number average molecular weight,
Preferably it is 0.2 mol - 1.2 mol. When 1.5 mol of carboxyl Jjffi is added, the viscosity of the branched resin increases and 1. Moreover, if it is less than 0.1 mole, the object of the present invention cannot be achieved, such as not being able to obtain a sufficient branched structure.

Acrylic prepolymers containing carboxyl groups synthesized under these conditions, X-C0OH and other resins containing carboxyl groups, and Y-C0OH are added to glycidyl groups of polyfunctional epoxy compounds having two or more glycidyl groups. By reacting, a branched resin with good compatibility, which is the object of the present invention, can be synthesized.

The polyfunctional epoxy compound is a substance having two or more glycidyl groups, and these compounds may be saturated or unsaturated aliphatic, alicyclic, aromatic or heterocyclic compounds, and chlorine, These compounds may be monomeric or polymeric, optionally substituted with substituents such as hydroxyl groups, ether groups, etc.

Kinoe Akira's polyfunctional epoxy compounds include epoxidized esters of unsaturated alcohols and polyvalent aliphatic acids, such as di(2,3-epoxyhexyl adipate).
, di(2,3-epoxybutyl) oxuate, di(2,3-epoxyhexyl) succinate, di(2,3-epoxyphthalate)
Nitrogen compounds containing glycidyl groups, such as epoxybutinori,
Examples include diglycidylaniline and di- and triglycidylamine.

Particularly preferred polyfunctional epoxy compounds for use in the production of the novel acrylic resins of the present invention are glycidyl ethers, especially glycidyl ethers of polyhydric phenols and polyhydric alcohols. Glycidyl ethers of polyhydric phenols and polyhydric alcohols can be obtained by reacting shrimprochlorohydrin with desired polyhydric phenols or polyhydric alcohols in the presence of an alkali. For example, diglycidyl ether of bisphenol A, diglycidyl ether of resorcinol, 7
0 glucinol triglycidyl 1 ether,
Triglycidyl ether of trihydroxydibipuenyl, polyglycidyl ether of phenol/formaldehyde/novolak, 0-cresol formaldehyde/
Polyglycidyl ether of novolac, diglycidyl ether of butanediol, diglycidyl ether of polypropylene glycol, diglycidyl ether of neopentyl glycol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of pentaerythritol, Polyglycidyl ether of sorbitol and other polyfunctional epoxy compounds include epoxy compounds derived from aromatic dicarboxylic acids such as diglycidyl isophthalate, diglycidyl phthalate, diglycidyl ester of linole trimer acid, and isocyanuric acid. Also included are triglycidyl, tetraphenylolethane epoxy, and the like.

The reaction between the polyfunctional epoxy compound having two or more glycidyl groups and the carboxyl group-containing acrylic prepolymer is based on the number of moles of glycidyl groups in the polyfunctional epoxy compound and the number of moles of carboxyl groups in the carboxyl group-containing acrylic prepolymer. and in the range of 1:0.6 to 1:1.4, preferably in the range of 10.8 to 1:1.2, while the blending ratio of carboxyl group-containing acrylic prepolymer and other carboxyl group-containing resin is the former 99-10w
t%, add a solvent that does not react with glycidyl groups or carboxylic groups as necessary at 1 to 1 g□wt% of the latter, and adjust the reaction temperature to 80 to 180°C, preferably 100 to 160°C.
At 0°C, the reaction rate is 80% as measured by the acid value of unreacted carboxyl groups in the carboxyl-terminated acrylic prepolymer.
Do the above.

For the reaction between the glycidyl group and the carboxyl group, for example, a base catalyst can be used as a reaction catalyst, if necessary. Examples of the base catalyst include pyridine, isoquinoline, quinoline, and N.

N-dimethylcyclohexylamine, α-picolithryn-butylamine, triethylamine, N-ethylmorpholine, N,N-dimethylaniline, N-(β- and droxyethyl)amine, N-ethyl-3,5-dimethylmorpholine and coconut oil. Organic amines such as dimethyl coconut amine or inorganic alkalis such as caustic soda and caustic potash are used.

The branched resin obtained by this method has improved compatibility with various resins, and the resin itself has a low viscosity.
A high non-volatile paint with excellent coating workability and film performance can be obtained.

However, since pigments used in paints do not have uniform surface properties, the branched resins described above may not always exhibit good dispersion performance depending on the pigment.

Based on the fact that pigment surface characteristics are classified according to the concepts of acids and bases, the present inventors modified the resin itself to be acidic or/and basic according to the pigment surface characteristics using the branched resin, ``The low viscosity property and solubility of the 41-year-old acrylic resin make it possible to improve the dispersion performance of various pigments, especially the dispersion speed, viscosity of the dispersion paste, yield value, stability over time, and paint coating. It has been found that the composition has excellent characteristics in terms of color mixing stability under various conditions, non-volatile content during coating, coating workability, and color tone, gloss, and sharpness as a coating film.

Among the branched resins for pigment dispersion having such excellent dispersion, paint, painting, and coating performance, (1) the branched resin having an electron-accepting group is an acid anhydride and/or a branched resin that retains active hydrogen. Alternatively, free electron-accepting groups can be supported within the molecule by reacting with a sultone compound.

On the other hand, (2) a branched resin having an electron-donating group is obtained by copolymerizing a polymerizable basic compound monomer during the synthesis of a carboxyl group-containing acrylic prepolymer, and using a prepolymer that retains such a base to produce a branched resin. It can be obtained by synthesizing. Furthermore, (1) reacting the active hydrogen contained in the branched resin and the optionally introduced active alkoxy group with a basic low molecular weight compound and/or basic resin having an active alkoxy group and/or active hydrogen; obtained by.

Furthermore, (3) the amphoteric branched resin having an electron-donating group and an electron-accepting group is
) Can be easily obtained by combining with ■.

The term "active hydrogen" used in this specification refers to reactions that bond 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 an alkyl. The term "" refers to groups that easily react with active hydrogen, such as primary, secondary and tertiary hydroxyl groups, isocyanate groups, glycidyl groups, etc., and "functional groups that react with active alkoxy"
The term "electron-accepting group" refers to a group that easily reacts with an active alkoxy group, such as a primary, secondary, or tertiary human oxyl group, and the term "electron-accepting group" refers to a group that easily reacts with an active alkoxy group, such as a primary, secondary, or tertiary human oxyl group, and the term "electron-accepting group" refers to a group that easily reacts with an active alkoxy group, such as a primary, secondary, or tertiary human oxyl group. When hydrogen is used as a standard, groups that tend to attract electrons from others are called "electron-donating groups" and have -N-, which has a lone pair of electrons, so hydrogen is used as a standard in molecules such as halogens and alkyls. The term "basic resin" refers to groups that tend to donate electrons to others when The term "basic low molecular weight compound" refers to hydroxylamine compounds (e.g. monoethanolamine, jetanolamine,
aminopentanol, aminobenzyl alcohol, 2-
dimethylaminoethanol, etc.), amino acids (e.g. 3-
Dimethylaminobenzoic acid, 2-amino-isobutyric acid, 4-
amino-n-butyric acid, etc.).

A detailed explanation of the manufacturing method of (A) a branched resin having an electron accepting group, (8) a branched resin having an electron donating group, and (C) an amphoteric branched resin having an electron accepting group and an electron donating group in this application. do.

(A> In the synthesis of a branched resin having an electron-accepting group, an active hydrogen group-containing compound is used to synthesize the acrylic prepolymer having a carboxyl group and other resins having a carboxyl group. Active hydrogen groups may be retained in polymers and other resins, or acrylic prepolymers and other resins that do not retain active hydrogen groups may be used.

The branched resin obtained by reacting these acrylic prepolymers having carboxyl groups and other resins having carboxyl groups with a polyfunctional epoxy compound has the formula ? H holds a secondary hydroxyl group in the molecule 1
and can be utilized as an active hydrogen group.

In order to support electron-accepting groups on the branched resin holding active hydrogen groups obtained by such a method, any substance can be used as long as it is a compound that reacts with active hydrogen groups to generate free acidic groups. However, typically, for example, compounds that react with active hydrogen groups to produce carboxyl groups, acid anhydrides such as acetic anhydride, succinic anhydride, phthalic anhydride,
Maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, etc., as well as compounds that react with active hydrogen groups to produce sulfone m groups, fatty acid sultones, such as 1,3-propanesultone ,
1.3-putanesultone, 2゜4-putanesultone, 1
．． ．． 4-putanesultone, 1,3-octanesultone,
It is also possible to use 2,3-decanesultone or the like, or anhydrous anhydrides such as metaphosphoric acid.

In such an addition reaction of a sultone compound, a sultone-modified branched resin can be synthesized by reacting a solution consisting of a branched resin and fatty acid sultone at a reaction temperature of 60 to 150°C for 2 to 10 hours. . In the synthesis of such a sultone-modified branched resin, the amount of sultone used when adding sultone is 0.101% to 6% by solid weight of the branched resin, preferably 0.02% to 6%.
It is in the range of 4% by weight. If the amount used exceeds 6% by weight, the melt viscosity of the polymer increases, making it difficult to manufacture the polymer.

On the other hand, in the synthesis of a branched resin having an electron-donating group (B), a polymerizable basic compound such as dimethylamine ethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate is used in the synthesis of an acrylic prepolymer having a carboxyl group. , diethylaminoethyl methacrylate, butylaminoethyl methacrylate, butylaminoethyl acrylate, 2-
Vinylpyridine, 4-vinylpyridine, 2-methyl5-
Vinyl lysine, 2-ethyl 5-vinyl pyridine, dimethylallylamine, diallylamine, vinylbilroline,
Vinylisoquinoline, NN-dimethylaminoethyl vinyl ether, 2 (NN dimethylamino) 4 vinylpyrimidine, trans 1゜2 dipyridylethylene, 3 cinnamoylpyridine, 2-methyl 5-cinnamoylpyridine, 4.6 diamino 2-vinyl 5- By copolymerizing triazine or the like and synthesizing a branched resin using such a prepolymer, an electron donating group can be supported within the molecule.

Alternatively, when synthesizing an acrylic prepolymer having a carboxyl group and other resins having a carboxyl group, an active alkoxy group-containing compound and/or an active hydrogen group-containing compound as needed may be copolymerized, and such prepolymers and other resins can be synthesized. The branched resin synthesized using this method is loaded with active hydrogen and an active alkoxy group introduced as necessary, and the branched resin obtained by this method is reacted with a low molecular weight basic compound and/or a basic resin. By this, a branched resin having an electron donating group can be synthesized.

In addition, a basic resin and/or a basic low molecular weight compound is prepared by blending and reacting a polyhedral isocyanate compound or a glycidyl compound with a branched resin that supports active hydrogen groups so that free isocyanate groups or glycidyl groups remain. It can also be a branched resin that can react with active hydrogen therein.

As the basic resin, urea resins, melamine resins, polyamide resins, polyurethane resins, etc., which are commonly used in the paint field, are used.

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.) are used as part of the raw materials for resin production, if necessary. , alkylated methylol urea resins or alkylated methylol melamine resins.

The polyamide resin is obtained by a condensation reaction of an aliphatic diamine and a dibasic acid, or a urea condensation reaction of a cyclic lactam. Examples of the aliphatic diamine include 1.2 ethanediamine, N,N'-dimethyl-1°)11' −”9 ＞
'7s->1, 6-'-4''''>'yz>, etc., and succinic acid, adipic acid, sebacic acid, etc. are appropriately selected as the dibasic acid.

Examples of the cyclic lactam that can be used include α-pyrrolidone, δ-caprolactam, and ω-capryllactam.

In the above manufacturing process, active hydrogen or active alkoxy groups are introduced into such basic resins along with electron donating groups (
It can be subjected to an addition or condensation reaction with the functional group in the acidic resin of A).

The above (A>branched resin having an electron accepting group and (B)
(C) A branched resin having an electron accepting group and an electron donating group can be synthesized by combining techniques used in the synthesis of a branched resin having an electron donating group.

The thus obtained branched resins (A), (B), and (C) have the same -
It has the characteristic that the viscosity becomes lower depending on the molecular weight. In addition, by appropriately using branched resins (A), (B), and (C) according to the pigment surface characteristics, we can improve dispersion, paint, painting, and coating performance compared to when ordinary resins are modified. Demonstrates excellent effects.

However, 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 optimum one is sought for each pigment. Therefore, the present inventors thought that it might be possible for the acidity and basicity of the dispersion resin to exhibit good dispersibility in terms of the greatest common denominator for many of the pigments that are widely used today. was actually dispersed in the above-mentioned dispersing resin, and the relationship between the acidity and basicity of the resin and the dispersion effect of the pigment was investigated. However, since there is no known simple method for measuring the acidity and basicity of amphoteric pigments in a non-aqueous system, the present inventors dissolved the dispersion resin of the sample in aniline and used n-tetrabutylammonium hydroxide. The acidity of the resin is determined from the number of moles of the reagent required for neutralization by non-aqueous potentiometric titration using a titration reagent, and the acidity of the resin is determined by non-aqueous potentiometric titration using perchloric acid as a titration reagent using an acetic acid solution of the sample. We have developed a unique method for measuring acidity and basicity in non-aqueous systems that determines basicity from the number of moles of reagent required for neutralization. It was worth it. As a result of the test, the present inventors found that the acidity of the amphoteric dispersion resin was 1.0 to 1. OX 104 ■1dol/g,s
ol id , particularly preferably from 0.8 to 2. Ox104
It is in the range of m n+ol/a, 5olid, and the basicity is 1.0 to 5 xlo-3m m+ol/iJ.

5olid, particularly preferably 1.0 to 1 x 104
When within the range of m mof/g, 5olid,
It has been found through experience that it exhibits good dispersibility in various inorganic and organic pigments for paints. Therefore, in preferred embodiments of the present invention, resins exhibiting acidity and basicity within the above ranges in the test method described herein are preferably used.

As a result of our research, the present inventors found that the blending ratio in the reaction between the active hydrogen groups in the above-mentioned branched resin and the acid anhydride and/or sultone compound was 099.9 to 50 in solid content of the resin.
% ■0.1-50%, most preferably ■99.9
~70%, 00.1~30%, and further supports the above active hydrogen and optionally introduced active alkoxy group, ■branched resin, ■low molecular weight basic compound, and/or ■basic The blending ratio in the reaction with the resin is 00.1 to 5% compared to the solid content of the resin of 099.9 to 50%.
■o for 0%, most preferably 099.9-10%;
i ~ 30%, and on the other hand, the weight ratio of the mixture in the reaction of the above branched resin and basic resin is 0 in terms of the solid content of the resin.
99.5-40%, most preferably 00.5-60%, most preferably 99.5-60% and 00.5-60%, and the molecular weight of the obtained dispersing resin is 2,000 in terms of polystyrene
~200°000, preferably 4.000~ioo,o
o.

It has also been found that the best results are given when the glass transition temperature is between 120 and 100°C, preferably between 110 and 80°C. Therefore, in the most preferred embodiment of the present invention, a resin that satisfies the above various parameters in addition to the acidity and basicity of the dispersing resin is used for dispersing the pigment.

The coating 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, and examples of inorganic pigments include carbon black, zinc white, titanium oxide, antimony white, iron black, red iron, red lead, cadmium yellow, Zinc sulfide, lithopone, barium sulfate, 1iIFl! Lead, barium carbonate, lead white, alumina white, etc., and organic pigments include azo, polycondensed azo, metal complex azo, benzimidacylon, phthalocyanine (blue, green), thioindigo, and anthraquinone. Various pigments of the type, flavanthrone, indanthrene, anthrapyridine, bilanthrone, isoindolinone, perylene, perinone and quinacridone are used advantageously.

The blending ratio of the above-mentioned dispersing resin and pigment is not critical and can be selected arbitrarily as it is further diluted with resin or solvent when making a paint, but it is subject to the economic efficiency of dispersion-based production, dispersion efficiency, etc. Considering that, usually resin (solid content) 1
0 to 9011% by weight and 90 to 10% pigment, preferably 30 to 70% by weight resin (solid content) and 7% pigment.
It is used at a ratio of 0 to 30%.

The coating composition of the present invention comprises a dispersing resin carrying the above-described electron-accepting group and/or electron-donating group, and, if necessary, other resins such as acrylic resins, alkyd resins, polyester resins other than those of the present invention, One or more of polyether resin, cellulose nitrate, urethane resin, vinyl acetate resin, polyvinyl alcohol resin, vinyl chloride resin, phenol resin, melamine resin, guanamine resin, urea resin, epoxy resin, etc., and the above pigments. Solvents commonly used in the paint industry, for example, hydrocarbon solvents such as toluene, xylene, Tsurupetz 100 and Tsurupetz 150, ester solvents such as ethyl acetate and butyl acetate, by mixing one or more of them, if necessary. M.E.K., M.E.K.
It is produced by adding one or more ketone solvents such as IBK and using 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. .

The coating composition thus obtained exhibits extremely good pigment dispersibility, excellent stability during storage, and excellent compatibility with various resins and solvents, making it extremely useful as a coating 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.

By weight unless otherwise specified.

Synthesis Example-1 (branched resin incorporating a carboxyl group-containing acrylic prepolymer and a carboxyl group-containing alkyd resin) 24 parts of xylene and acetic acid were placed in a reaction vessel equipped with a dropping funnel, a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring blade. Charge 200 parts of butyl and raise the temperature to 130°C. 2- and 45 parts of droxyethyl methacrylate, 336 parts of methyl methacrylate,
A solution containing 60 parts of normal butyl acrylate, 127 parts of styrene monomer, 3 parts of acrylic acid, and 10.8 parts of azobisisobutyronitrile was charged into a 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 1.2 parts of azobisisobutyronitrile and 176 parts of xylene was charged into the dropping funnel.

This was added dropwise at a uniform rate over 30 minutes. 1 hour after completion of dripping IJ1
The temperature was maintained at 30°C to complete polymerization. Bunacol EX here
-41113 parts, Firmin DMG 1.11 parts, and in-house alkyd resin α (Mn8500, Mw 30000
．． Acid 1i1[io, 2noKOH/g solid content, OH number 551110KOH10 solid content, heating residue 60%) 16
Charge 2 parts and keep at 130°C for 9 hours. Next, 115 parts of xylene and 115 parts of butyl acetate were added to complete the reaction. After cooling, the contents were taken out to obtain a branched acrylic resin A incorporating an alkyd resin. The characteristics of the obtained resin are shown in Table-1.

Synthesis example-2 (terminal carboxyl group acrylic pre)”:□
(B9.?- and force, ■ki,, group-containing a, branched resin incorporating chito resin) xylene was placed in a reaction vessel equipped with a dropping funnel, a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring blade. 27HIB to butyl acetate20
Charge 0 parts and raise the temperature to 130°C. 45 parts of 2-hydroxyethyl methacrylate, 336 parts of methyl methacrylate, 60 parts of n-butyl acrylate, 127 parts of styrene monomer, 116.5811 parts of thioglycol. A solution of 2.7 parts of azobisisobutyronitrile is 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 0.3 parts of azobisisobutyronitrile and 176 parts of xylene was charged into the dropping funnel. This was added dropwise at a uniform rate over 30 minutes. 1:00 after completion of dripping 12113
The temperature was maintained at 0°C to complete the polymerization.

Here is Bunacol EX-41128 part, Firmin DM
G 1.11 parts, and in-house alkyd resin α 275
and kept at 130°C for 9 hours. Next, 130 parts of xylene and 130 parts of butyl acetate were added to complete the reaction. After cooling, the contents were taken out to obtain a branched acrylic resin B. The characteristics of the obtained resin are shown in Table-1.

Synthesis Example 3 (Acid Addition Branched Resin) To the branched resin synthesized by the method of Synthesis Example 1 in a reaction vessel equipped with a cold section tube, nitrogen introduction tube, thermometer, and stirring blade 865
A solution of 1 part, 9.1 parts of phthalic anhydride, and 44 parts of DBTOo (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a Kolben and heated to 130°C.
The temperature rises to After the temperature was raised, the temperature was maintained at 130° C. for 1 hour to complete the addition reaction, and acid addition branched resin C was obtained. The special numbers of C are shown in Table-2.
Shown below.

Synthesis Example 4 (Acid-added branched resin) A phthalic anhydride-added branched resin was synthesized using the same method as in Synthesis Example 3 using the formulation shown in Table 2.

Synthesis Example 5 (base addition branched resin) 33 parts of xylene and 156 parts of butyl acetate are charged into a reaction vessel equipped with a dropping funnel, a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring blade, and the temperature is raised to 130°C. 45 parts of 2-hydroxyethyl methacrylate, 336 parts of methyl methacrylate,
60 parts of normal butyl acrylate, 127 parts of styrene monomer, N.

11.5 parts of N dimethylaminoethyl methacrylate, thioglycol! A solution of 6.5 parts of azobisisobutyronitrile and 2.7 parts of azobisisobutyronitrile was charged into the dropping funnel. Under nitrogen atmosphere 1
At 30° C., the contents of the dropping funnel are added dropwise at a constant rate over a period of 3 hours. After the completion of dropping, the temperature was kept at 130°C for 30 minutes.

Next, a solution of 0.3 parts of azobisisobutyronitrile and 123 parts of xylene is charged into the dropping funnel.

This was added dropwise at a uniform rate over 30 minutes. 1 hour after completion of dripping
Maintain at 30°C. Next, a solution of 17 parts of Bunacol EX-411 (manufactured by Nagase Kasei Kogyo Co., Ltd.) and 1.44 parts of Fu-1-mine DMC was charged and kept at 130°C for 7 hours to complete the addition reaction, and 144 parts of xylene and 144 parts of butyl acetate were added. was charged and cooled to obtain a base-added branched resin E. The special values of E are shown in the table-
Not shown in 3.

Synthesis Example-6 (Acid/base addition branched resin) Synthesis example in a reaction vessel equipped with a cooling tube, nitrogen introduction tube, thermometer, and W11 root.
665 parts of base-added branched resin E synthesized by method 5, 9.1 parts of phthalic anhydride, 0 DBTO (manufactured by Wako Pure Chemical Industries, Ltd.)
．． The 44 solutions were charged into a Kolben and heated to 130'C. After raising the temperature, the temperature was maintained at 130° C. for 1 hour to complete the addition reaction. The special properties of the acid/base addition branched resin F are shown in Table 4.

Example-1 Patent 1982-218127 already filed by the present inventors
3 shows the synthesis method of branched acrylic resin. lζ synthesizes branched acrylic resin β using in-house alkyd resin α (carboxyl group-containing alkyd resin) from the formulation shown in Synthesis Example 2 of this patent according to this method. did. In order to investigate the compatibility between the in-house alkyd resin α and the branched resins (β, A and B), a solution prepared by thoroughly mixing the two resins was applied to a transparent glass plate using a 711 film applicator (
The resin film was adjusted using a machine (manufactured by Taisuke Machine Co., Ltd.).

Next, after drying in a jet oven at 140° C. for 1 hour, the resin film was evaluated when cooled to room temperature. The planning results are shown in Table-5. From this result, it was observed that the compatibility was improved by introducing a portion of the alkyd resin molecules that cause problems in compatibility into the 111'' (branched acrylic resin) and constructing new molecules.

Example-2 Patent No. 58-218127 filed by the present inventors in J.
3 shows the synthesis method of acid addition branched acrylic resin,
According to this method, an acid-added branched acrylic resin γ was synthesized by removing the in-house alkyd resin α from the formulation shown in Synthesis Example 2 of this patent.

The method of Example 1 was followed to examine the compatibility between the in-house alkyd resin α (carboxyl group-containing alkyd resin) and the acid addition branched resins (γ, C, and D). The evaluation results are shown in Table 6.
Shown below. From this result, it was observed that compatibility can be improved by introducing a portion of alkyd resin molecules that cause problems in compatibility into a branched acrylic resin and configuring new molecules.

Example 3 Branched resin B obtained in Synthesis Examples 2 and 4 and
Using □D, each pigment was dispersed with a paint shaker (Red Devil Co., Ltd.) according to the dispersion formulation shown in Table 7, and the specular gloss (Murakami gloss needle GM-26D type) of the dispersed product was measured. In addition, the viscosity of each of the obtained dispersion pastes was measured using a cone-plate viscometer (E-type viscometer manufactured by Tokyo Keiki Co., Ltd.), and the results shown in Table 7 were obtained.

From these results, it is observed that when an acid-added branched resin is used, the viscosity of the dispersed paste is about 1/3 of that of a branched resin containing almost no acid, in the case of phthalocyanine blue. It is also observed that the gloss is about 30% higher in the case of phthalocyanine blue.

(Margins below) Table-1 (1) Gel permeation chromatography (polystyrene equivalent) Table-2 Table-3 Table-4 ×...Display of cloudy white, shrinking procedural amendment 1 case 1982 Patent Application No. 229565 2 Name of the invention: Branched resin, its manufacturing method, and relationship with the Paint Composition 3 Amendment Case Patent Applicant Address: 2-1-2 Oyodokita, Oyodo-ku, Osaka Name: Nippon Paint Co., Ltd. Representative: Masao Suzuki 4: Agent Address: 6th floor, River Center Building, 3-57 Kyobashi, Higashi-ku, Osaka, Osaka 540 Name: Takeo Ito, Patent Attorney (6871) Date of 5° amendment order (voluntary) 6 Subject of amendment Name and description of the invention in the application (Title of the Invention, Claims, and Detailed Description Column (2) The acrylic prepolymer represented by ” he corrected.

2. The scope of claims is amended as follows.

(1) Formula % Formula %) (In the formula, R is an n+m-valent aliphatic, alicyclic, aromatic or cyclic hydrocarbon residue; X is an acrylic prepolymer chain, and Y is a non-acrylic resin represented by Branched resin with a weight average molecular weight (measured by gel permeation chromatography, polystyrene equivalent) of 1000 to 200000 and a glass transition temperature of -20 to 100°C .

The resin according to claim 1, which has a weight average molecular weight of 1,000 to 100,000 and a glass transition temperature of -20 to 100°C.

(3) A polyfunctional epoxy compound represented by the formula (wherein R is an aliphatic, alicyclic, aromatic or heterocyclic hydrocarbon residue 11 n / is a real number from 2 to 6).

formula% formula% (in the formula or weight average molecular weight 1,000 to 100,00
0, an acrylic prepolymer chain with a glass transition temperature of -20 to 100°C) and an acrylic prepolymer having a carboxyl group represented by Y-COOH.

Resin prepolymer chains other than X having carboxyl groups (
○H (0-CH, -CH-CH, -0-Go-X)n(0-
CHz-CH-CHz-〇-Go-Y)mH (in the formula, R, X and Y are each as described above: n+m is 2 to
A method for producing a branched resin represented by a real number of 6).

(4) the acrylic prepolymer represented by 4. The method of claim 3, wherein the method is made using an initiator containing.

(5) The method according to claim 4, wherein the carboxyl group-containing chain transfer agent is selected from the group consisting of mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, and 0-mercaptobenzoic acid.

(6) The method according to claim 5, wherein the carboxyl group-containing initiator is 4,4'-azobiscyanopentanoic acid or peroxide diglutaric acid.

(7) The resin according to claim 1, wherein the resin other than X having a carboxyl group represented by Y-COOH is a polyester resin or an alkyd resin.

(8) The method according to claim 3, wherein the polyfunctional epoxy compound is selected from neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and sorbitol polyglycidyl ether.

(9) A patent claim obtained by reacting a branched resin having an active hydrogen group represented by the formula % (in which R, X, Y and n+m are as described above) with an acid anhydride and/or a sultone. A branched resin carrying an electron-accepting group according to item 1.

(10) A patent claim synthesized using at least one of acetic anhydride, succinic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and trimellitic anhydride as an acid anhydride. The branched resin according to item 9.

(11) Branched type according to claim 2 synthesized using 1,3-propanesultone, 1,3-butanesultone, 1,3-octanesultone, 1,3-decanesultone as the sultone compound resin.

(12) A branched resin having an active hydrogen group and/or an active alkoxy group introduced as necessary, represented by the formula % (in which R, X, Y, and n+m are as described above) and an activated alkoxy A branched resin carrying an electron-donating group according to claim 1, which is obtained by reacting the group and/or a basic compound having active hydrogen.

(13) A polyfunctional epoxy compound represented by the formula (in which R and n' are as described above) and a carboxyl compound represented by 1 formula % (in the formula, X' is an acrylic polymer chain having a basic group) A branched resin carrying an electron-donating group according to claim 1, which is obtained by reacting with a group-containing acrylic prepolymer.

(1□4) The method described in Section 2 above and Section 5 and/or
Alternatively, the branched resin according to claim 1, which is formed by carrying an electron accepting group and an electron donating group by using the method described in claim 6.

3, page 9, line 8 "acrylic resin" A certain thing "Resin other than X" I am corrected.

4. Line 6 from the bottom of page 9 "acrylic resin" A certain thing "Acrylic resin represented by X" I am corrected.

5, page 16, line 12 "above" A certain thing "The above represented by X" I am corrected.

6. Insert the following between lines 16 and 17 on page 18.

r Also, Y-C, OOH is X containing a carboxyl group
Acrylic resins other than the above can also be used. 7, page 19, between lines 11 and 12, insert the following:

In addition, some of the carboxylic acid resin prepolymers represented by X-COOH and Y-COOH above may have various substituents that do not affect the reaction between the carboxyl group and the glycidyl group (for example, F, C1, etc.), and It may also contain a heteroatom such as Si. J8, on page 20, line 8, ``acrylic resin'' is corrected to ``branched resin.''

Claims (14)

[Claims] (1) Formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is an n+m-valent aliphatic, alicyclic, aromatic, or cyclic hydrocarbon residue; X is an acrylic prepolymer chain, and Y is an acrylic resin. Other resin prepolymer chains: n+m is 2 to
Weight average molecular weight (gel permeation chromatography measurement, polystyrene equivalent) expressed as 6 real numbers)
1000-200000, glass transition temperature -20-10
Branched resin at 0℃. (2) The acrylic prepolymer has a weight average molecular weight of 100
0 to 100,000C and a glass transition temperature of -20 to 100C. (3) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Functional epoxy compound and formula X-COOH (wherein X is a weight average molecular weight of 1,000 to 100,000
, an acrylic prepolymer chain with a glass transition temperature of -20 to 100°C) having a carboxyl group, and a resin prepolymer chain other than an acrylic resin having a carboxyl group represented by Y-COOH (Y is a resin other than an acrylic resin) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R, X, and Y are each as mentioned above, and n+m is 2 to 6.
A manufacturing method for branched resin expressed as a real number). (4) The acrylic prepolymer contains a carboxyl group-containing chain transfer agent corresponding to 0.2 to 8% by weight and/or a carboxyl group-containing initiator corresponding to 0.3 to 12% by weight based on the solid content of the prepolymer. The method according to claim 3, which is made using the method. (5) The method according to claim 4, wherein the carboxyl group-containing chain transfer agent is selected from the group consisting of mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, and 0-mercaptobenzoic acid. (6) The method according to claim 5, wherein the carboxyl group-containing initiator is 4,4'-azobiscyanopentanoic acid or peroxide diglutaric acid. (7) Polyester resin as a resin other than acrylic resin having a carboxyl group represented by Y-COOH,
The resin according to claim 1, which is an alkyd resin. (8) The method according to claim 3, wherein the polyfunctional epoxy compound is selected from neopentyl glycol sidaline sol ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and sorbitol polyglycidyl ether. (9) A branched resin represented by a formula having an active hydrogen group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, R, A branched resin carrying an electron-accepting group according to claim 1. (10) A patent claim synthesized using at least one of acetic anhydride, succinic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and trimellitic anhydride as an acid anhydride. The branched resin according to item 9. (11) Branched type according to claim 2 synthesized using 1,3-propanesultone, 1,3-butanesultone, 1,3-octanesultone, 1,3-decanesultone as the sultone compound resin. (12) Branched resin having an active hydrogen group and/or an active alkoxy group introduced as necessary, represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, R, X, n+m are as described above) A branched resin carrying an electron-donating group according to claim 1, which is obtained by reacting a basic compound having an active alkoxy group and/or an active hydrogen. (13) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R and n' are as described above) A polyfunctional epoxy compound represented by the formula X'-COOH (In the formula, X' has a basic group) The branched resin carrying an electron-donating group according to claim 1, which is obtained by reacting a carboxyl group-containing acrylic prepolymer represented by (acrylic polymer chain). (14) The method described in Section 2 above, and Section 5 and/or
Alternatively, the branched resin according to claim 1 is formed by carrying an electron accepting group and an electron donating group by using the method described in claim 6.