JPS6154343B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a coating composition whose main component is an acrylic resin emulsion obtained by using a polyester resin having an aminosulfonic acid type zwitterionic group as an emulsifier. The present inventors have created a new polyester resin (alkyd type, oil-free type) having a specific amphoteric ionic group, and have already applied for a patent for this (Japanese Patent Application No. 110865-1983, ―56048
issue). Such polyester resin has the formula, [In the formula, A represents a C ₁ to C ₆ linear or branched alkylene group, phenylene group, or substituted phenylene group. ] Those having an aminosulfonic acid type zwitterionic group shown in the following, especially oil-free systems have good solubility in various organic solvents and are also excellent in miscibility with solvent-based resin compositions, and have an aminosulfonic acid type zwitterionic group. It is said to be useful because it fully exhibits its reaction catalytic function and surfactant function. As a result of extensive research into the uses of such polyester resins, the present inventors have found that acrylic resins obtained by emulsifying and stabilizing a polymer of α,β-unsaturated monomers in an aqueous medium with the above-mentioned polyester resins as emulsifiers. The present inventors discovered that when a resin emulsion is made into a paint, the zwitterionic groups of the polyester resin have a catalytic effect, accelerating the curing speed of the coating film and increasing the degree of crosslinking of the coating film, which led to the completion of the present invention. . That is, the gist of the present invention is to provide a coating composition whose main component is an acrylic resin emulsion comprising a polymer of α,β-unsaturated monomers emulsified and stabilized in an aqueous medium with an emulsifier. A coating composition characterized in that the above-mentioned polyester resin is used as an emulsifier. The above-mentioned polyester resin used in the present invention has, as an alcohol component in its reaction components,
formula, [In the formula, R ₁ is a C ₁ -C ₂₀ alkyl group that has at least one hydroxyl group and may contain -O- or -COO- in the molecular group, R ₂ and
R ₃ is the same or different hydrogen atom, C _1
-C20 alkyl group, alkyl group or cyclic group having at least one hydroxyl group and/or sulfonic acid group, and A have the same meaning as above. ] Except for using the hydroxyl group-containing aminosulfonic acid type zwitterionic compound (hereinafter simply referred to as zwitterionic compound), it may be produced by adopting the raw materials and reaction conditions/methods of ordinary polyester resins. Specifically, it can be produced by subjecting the reaction components to an esterification reaction and, if necessary, a transesterification reaction, in a suitable solvent according to the procedure described in Reference Examples described later. In addition, specific examples of the reaction components of the polyester resin and their usage amounts are as follows. Oil-free system a Zwitterionic compound 0.05-50% (wt%, the same applies hereinafter), preferably 0.5-30%, b Polybasic acid compound 2-90%, if necessary c Polyhydric alcohol 0-90% and/ or d oxirane compound 0-90%. Alkyd-based a zwitterionic compound 0.05-30%, preferably
0.1-20% b polybasic acid compounds 2-90%, c polyhydric alcohols 2-90%, d fatty acids and or oils 1-80%. Examples of the above-mentioned amphoteric ionic compound include N-
(2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted product (N-methyl-N-
(2-hydroxyethyl)aminomethanesulfonic acid, N-ethyl-N-(2-hydroxyethyl)
Aminomethanesulfonic acid, N-isopropyl-N
-(2-hydroxyethyl)aminomethanesulfonic acid, N-(2-ethylhexyl)-N-(2-
hydroxyethyl)aminomethanesulfonic acid, N
-decyl-N-(2-hydroxyethyl)aminomethanesulfonic acid, N-stearyl-N-(2-
(hydroxyethyl) aminomethanesulfonic acid, etc.) and N,N-dialkyl substituted products (N,N-
Dimethyl-N-2-hydroxyethyl)ammoniomethanesulfonic acid betaine, N,N-diethyl-N-(2-hydroxyethyl)ammoniomethanesulfonic acid betaine, N-methyl-N-dodecyl-N-(2- hydroxyethyl)ammoniomethanesulfonic acid betaine, etc.), N-(2-hydroxy-1-methylethyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(2-hydroxy propyl)
Aminomethanesulfonic acid and its N-alkyl substituted products, N,N-dialkyl substituted products, N-(3-
hydroxypropyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(2-propyl-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N -Dialkyl substituent, N-
(2-Methyl-2-ethyl-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl- and N,N-dialkyl-substituted products, N-
(1,2-dimethyl-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-1,1,
2,2-tetramethyl-2-hydroxyethyl)
Aminomethanesulfonic acid and its N-alkyl and N,N-dialkyl substituted products, N-(1-
Methyl-5,5dimethyl-5-hydroxypentyl)aminomethanesulfonic acid and its N-alkyl- and N,N-dialkyl-substituted products, N-
(1,2-diisopropyl-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl- and N,N-dialkyl-substituted products, N-
(2,3 dihydroxypropyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N
-Dialkyl substituted product, N-(1-hydroxymethyl-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, N-(1-hydroxymethyl-
2-Methyl-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(1-hydroxymethyl-3-hydroxypropyl)aminomethanesulfonic acid and its N- Alkyl substituted product and N,N-dialkyl substituted product, N-(1-(γ-hydroxypropyl)-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, N -(1,1
-Bis(hydroxymethyl)-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-
(2,2-bis(hydroxymethyl)-3-hydroxypropyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N,N-bis(2-hydroxyethyl)aminomethanesulfone Acid and its N-alkyl substituted product (N-methyl-N,N-bis(2-hydroxyethyl)ammoniomethanesulfonic acid betaine, N
-Ethyl-N,N-bis(2-hydroxyethyl)ammoniomethanesulfonic acid betaine, N-
Butyl-N,N-bis(2-hydroxyethyl)
Ammoniomethanesulfonic acid betaine, N-dodecyl-N,N-bis(2-hydroxyethyl)ammoniomethanesulfonic acid betaine, N-stearyl-N,N-bis(2-hydroxyethyl)ammoniomethanesulfonic acid betaine etc.), N-
(2-hydroxyethyl)-N-(2-hydroxypropyl)aminomethanesulfonic acid and its N-
Alkyl substituted product, N,N-bis(2-hydroxypropyl)aminomethanesulfonic acid and its N-alkyl substituted product, N,N-bis(4-hydroxybutyl)aminomethanesulfonic acid and its N-alkyl substituted product, N-(2-hydroxyethyl)-N-
(1,1-bis(hydroxymethyl)-2-hydroxyethyl)aminomethanesulfonic acid and its N
-Alkyl substituted product, N-(3-hydroxypropyl)-N-(1,1-hydroxymethyl)-2-
hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted product, N,N-bis(2,3-
dihydroxypropyl) aminomethane sulfonic acid and its N-alkyl substituted product, N,N-bis-(1
-hydroxymethyl)-2-hydroxyethyl)
Aminomethanesulfonic acid and its N-alkyl substituted product, N,N-bis-(1,1-(bishydroxymethyl)-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted product, N,N,
N-tris-(2-hydroxyethyl)ammoniomethanesulfonic acid betaine, N,N-bis-
(2-hydroxyethyl)-N-(3-hydroxypropyl)ammoniomethanesulfonic acid betaine, N,N,N-tris(3-hydroxypropyl)ammoniomethanesulfonic acid betaine, N-(2-hydroxyethyl) Aminoethanesulfonic acid and its N-alkyl substituted products (N-methyl-N-(2-hydroxyethyl)aminoethanesulfonic acid, N-ethyl-N-(2-hydroxyethyl)aminoethanesulfonic acid, N-isopropyl- N-(2-hydroxyethyl)aminoethanesulfonic acid, N-(2-ethylhexyl)-N-
(2-hydroxyethyl)aminoethanesulfonic acid, N-decyl-N-(2-hydroxyethyl)
Aminoethanesulfonic acid, N-stearyl-N-
(2-hydroxyethyl)aminoethanesulfonic acid, etc.) and N,N-dialkyl substituted products (N,
N-dimethyl-N-(2-hydroxyethyl)ammonioethanesulfonic acid betaine, N,N-diethyl-N-(2-hydroxyethyl)ammonioethanesulfonic acid betaine, N-methyl-N-
dodecyl-N-(2-hydroxyethyl)ammonioethanesulfonic acid betaine, etc.), N-(2-hydroxyethyl),
-Hydroxy-1-methylethyl)aminoethanesulfonic acid and its N-alkyl substituted products and N,
N-dialkyl substituted product, N-(2-hydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, N
-(3-hydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted products and N,N-
Dialkyl substituted product, N-(2-propyl-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, N-(2-methyl-2-ethyl-2-hydroxy ethyl)aminoethanesulfonic acid and its N
-Alkyl substituted product and N,N-dialkyl substituted product, N-(1,2-dimethyl-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, N-
(1,1,2,2-tetramethyl-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products,
N-(1-methyl-5,5-dimethyl-5-hydroxypentyl)aminoethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(1,2-diisopropyl-2-hydroxy ethyl)aminoethanesulfonic acid and its N
-alkyl substituted product and N,N-dialkyl substituted product, N-(2,3-dihydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, N-(1-hydroxymethyl -2-hydroxyethyl) aminoethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(1-hydroxymethyl-2-methyl-2-hydroxyethyl)
Aminoethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(1-
Hydroxymethyl-3-hydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted and N,N-dialkyl substituted products, N-(1-
(γ-Hydroxypropyl)-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-
(1,1-bis(hydroxymethyl)-2-hydroxyethyl)aminoethanesulfonic acid and its N
-Alkyl substituted product and N,N-dialkyl substituted product, N-(2,2-bis(hydroxymethyl)-
3-hydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N,N-bis(2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted products (N- Methyl-N,N-bis(2-hydroxyethyl)ammonioethanesulfonic acid betaine, N-ethyl-N,N-bis(2-hydroxyethyl)ammonioethanesulfonic acid betaine, N-butyl-N,N- Bis(2-hydroxyethyl)ammonioethanesulfonic acid betaine,
N-dodecyl-N,N-bis(2-hydroxyethyl)ammonioethanesulfonic acid betaine, N
-Stearyl-N,N-bis(2-hydroxyethyl)ammonioethanesulfonic acid betaine, etc.), N-(2-hydroxyethyl)-N-(2
-Hydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted product, N,N-bis(2-
hydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted product, N,N-bis(4-hydroxybutyl)aminoethanesulfonic acid and its N-alkyl substituted product, N-(2-hydroxyethyl)-N-( 1,1-bis(hydroxymethyl)
-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product, N-(3-hydroxypropyl)-N-(1,1-bis(hydroxymethyl)-2-hydroxyethyl)aminoethanesulfonic acid and Its N-alkyl substituent, N,N
-bis(2,3-dihydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted product,
N,N-bis-(1-(hydroxymethyl)-2
-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product, N,N-bis-(1,
1-(bishydroxymethyl)-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product, N,N,N-tris-(2-hydroxyethyl)ammonioethanesulfonic acid betaine, N,N- Bis-(2-hydroxyethyl)-
N-(3-hydroxypropyl)ammonioethanesulfonic acid betaine, N,N,N-tris(3
-Hydroxypropyl)ammonioethanesulfonic acid betaine, 3-{N-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted product (3{N-methyl-N-(2-hydroxy ethyl)}aminopropanesulfonic acid-(1),3-{N
-ethyl-N-(2-hydroxyethyl)}aminopropanesulfonic acid-(1), 3-{N-isopropyl-N-(2-hydroxyethyl)}aminopropanesulfonic acid-(1), 3-{N -(2-ethylhexyl)-N-(2-hydroxyethyl)}aminopropanesulfonic acid-(1), 3-{N-decyl-N-(2-hydroxyethyl)}aminopropanesulfonic acid-(1), 3-{N-stearyl-N-
(2-hydroxyethyl)}aminopropanesulfonic acid-(1), etc.) and N,N-dialkyl substituted products (3-{N,N-dimethyl-N-(2-hydroxyethyl)}ammoniopropanesulfonic acid- (1)
Betaine, 3-{N,N-diethyl-N-(2-
hydroxyethyl)}ammoniopropanesulfonic acid-(1) betaine, 3-{N-methyl-N-dodecyl-N-(2-hydroxyethyl)}ammoniopropanesulfonic acid-(1)betaine, etc.), 3-
{N-(2-hydroxy-1-methylethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted products and N,N-dialkyl substituted products, 3-
{N-(2-hydroxypropyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted products and N,N-dialkyl substituted products, 3-{N-(3-
hydroxypropyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted products and N,N-
Dialkyl substituted product, 3-{N-(2-propyl-
2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted products and N,N
-Dialkyl substituted product, 3-{N-(2-methyl-
2-ethyl-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted products and N,N-dialkyl substituted products, 3-{N-
(1,2-dimethyl-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted products and N,N dialkyl substituted products, 3-{N
-(1,1,2,2-tetramethyl-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted products and N,N-dialkyl substituted products, 3-{N-(1 -methyl-5,5-dimethyl-5-hydroxypentyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted products and N,N-dialkyl substituted products, 3-{N-
(1,2-diisopropyl-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-
Alkyl substituted product and N,N-dialkyl substituted product, 3-{N-(2,3-dihydroxypropyl)}aminopropanesulfonic acid-(1) and its N-
Alkyl substituted product and N,N-dialkyl substituted product, 3-{N-(1-hydroxymethyl-2-hydroxyethyl)}aminopropanesulfonic acid-
(1) and its N-alkyl substituted products and N,N-dialkyl substituted products, 3-{N-(1-hydroxymethyl-2-methyl-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituents and N,N-dialkyl substituents, 3-{N
-(1-hydroxymethyl-3-hydroxypropyl)}aminopropanesulfonic acid-(1) and its N
-Alkyl substituted product and N,N-dialkyl substituted product, 3-{N-(1-(γ-hydroxypropyl)-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted product and N,N-dialkyl substituted product, 3-{N-(1-
(γ-hydroxypropyl)-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N
-Alkyl substituted product and N,N-dialkyl substituted product, 3-{N-(1,1-bis(hydroxymethyl)-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted product and N,N-dialkyl substituent, 3-{N-(2,2
-Bis(hydroxymethyl)-3-hydroxypropyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted products and N,N-dialkyl substituted products, 3-{N,N-bis(2-hydroxyethyl )}Aminopropanesulfonic acid-(1) and its N-
Alkyl substituted product (3-{N-methyl-N,N-bis(2-hydroxyethyl)}ammoniopropanesulfonic acid-(1) betaine, 3-{N-ethyl-
N,N-bis(2-hydroxyethyl)}ammoniopropanesulfonic acid-(1)betaine, 3-{N
-Butyl-N,N-bis(2-hydroxyethyl)}ammoniopropanesulfonic acid-(1)betaine, 3-{N-dodecyl-N,N-bis(2-hydroxyethyl)}ammoniopropanesulfonic acid -(1)Betaine, 3-{N-stearyl-N,N
-bis(2-hydroxyethyl)}ammoniopropanesulfonic acid-(1)betaine, etc.), 3-{N
-(2-hydroxyethyl)-N-(2-hydroxypropyl)}aminopropanesulfonic acid-(1)
and its N-alkyl substituted product, 3-{N,N-bis(2-hydroxypropyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted product, 3-
{N,N-bis(2-hydroxypropyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted products, 3-{N,N-bis(4-hydroxybutyl)}aminopropanesulfonic acid-( 1) and its N-
Alkyl substituted product, 3-{N-(2-hydroxyethyl)-N-(1,1-bis(hydroxymethyl)-2-hydroxyethyl}aminopropanesulfonic acid-(1) and its N-alkyl substituted product, 3-
{N-3-hydroxypropyl)-N-(1,1
-bis(hydroxymethyl)-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N
-alkyl substituent, 3-{N,N-bis(2,3
-dihydroxypropyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted product, 3-
{N,N-bis-(1-hydroxymethyl)-2
-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted product, 3-{N,N
-Bis-(1,1-(bishydroxymethyl)-
2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted product, 3-{N,
N,N-tris-(2-hydroxyethyl)}ammoniopropanesulfonic acid-(1) betaine, 3-
{N,N-bis-(2-hydroxyethyl)-N
-(3-hydroxypropyl)}ammoniopropanesulfonic acid-(1) betaine, 3-{N, N, N
-Tris(3-hydroxypropyl)}ammoniopropanesulfonic acid-(1) betaine, 5-{N-(2-hydroxyethyl)}aminopentanesulfonic acid-(1) and its N-alkyl substituted product (5- {N-methyl-N-(2-hydroxyethyl)}aminopentanesulfonic acid-(1), 5-
{N-ethyl-N-(2-hydroxyethyl)}aminopentanesulfonic acid-(1), 5-{N-isopropyl-N-(2-hydroxyethyl)}aminopentanesulfonic acid-(1), 5- {N-(2-ethylhexyl)-N-(2-hydroxyethyl)}
Aminopentanesulfonic acid (1), 5-{N-decyl-N-(2-hydroxyethyl)} Aminopentanesulfonic acid (1), 5-{N-stearyl-N
-(2-hydroxyethyl)}aminopentanesulfonic acid-(1), etc.) and N,N-dialkyl substituted products (5-{N,N-dimethyl-N-(2-hydroxyethyl)}ammoniopentanesulfonic acid -(1)Betaine, 5-{N,N-diethyl-N-
(2-Hydroxyethyl)ammoniopentanesulfonic acid-(1) betaine, 5-{N-methyl-N-
dodecyl-N-(2-hydroxyethyl)}ammoniopentanesulfonic acid-(1) betaine, etc.),
5-{N,N-bis-(2-hydroxyethyl)}aminopentanesulfonic acid-(1) and its N-
Alkyl substituted product (5-{N-methyl-N,N-bis(2-hydroxyethyl)}ammoniopentanesulfonic acid-(1) betaine, 5-{N-ethyl-
N,N-bis(2-hydroxyethyl)}ammoniopentanesulfonic acid-(1)betaine, 5-{N
-Butyl-N,N-bis(2-hydroxyethyl)}ammoniopentanesulfonic acid-(1)betaine, 5-{N-dodecyl-N,N-bis(2-hydroxyethyl)}ammoniopentanesulfonic acid -(1)Betaine, 5-{N-stearyl-N,N
-bis(2-hydroxyethyl)}ammoniopentanesulfonic acid-(1)betaine, etc.), 5-
{N,N,N-tris-2-hydroxyethyl)}
Ammoniopentanesulfonic acid - (1) betaine, N-(2-hydroxyethyl)iminodiethanesulfonic acid, N-(2-hydroxypropyl)iminodiethanesulfonic acid, N-(2,3-dihydroxypropyl)imino Diethanesulfonic acid, N
-(1,1-bis(hydroxyethyl)-2-hydroxyethyl)iminodiethanesulfonic acid, N
-(2-hydroxyethyl)iminoethanesulfonic acid propanesulfonic acid, N-(2-hydroxypropyl)iminoethanesulfonic acid propanesulfonic acid, N-(2,3-dihydroxypropyl)
Iminoethanesulfonic acid propanesulfonic acid, N
-(1,1-bis(hydroxymethyl)-2-hydroxyethyl)iminoethanesulfonic acid, propanesulfonic acid, N-(2-hydroxyethyl)orthanylic acid,
N-(2-hydroxyethyl)methanilic acid, N-
(2-hydroxyethyl)sulfanilic acid, N,
Examples include N-bis-(2-hydroxyethyl)orthanilic acid, N,N-bis-(2-hydroxyethyl)methanilic acid, N,N-bis-(2-hydroxyethyl)sulfanilic acid, and these 1 The species or species are provided for use. Such amphoteric ionic compounds may be used as they are or as a salt with a basic substance (eg, ammonia, amine, alkali metal). Examples of the polybasic acid compounds include adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecylcarboxylic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, tetrahydrophthalic anhydride, hymic anhydride, Examples include trimellitic acid, pyromellitic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, and hettic anhydride. One or more of these may be used. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexanediol,
Diethylene glycol, dipropylene glycol, neopentyl glycol, triethylene glycol, hydrogenated bisphenol, glycerin, trimethylolethane, trimethylolpropane,
Examples include pentaerythritol, and one of these
Use one or more species. Examples of the oxirane compounds include phenyl glycidyl ether, methyl glycidyl ether, n-butyl glycidyl ether, versatate glycidyl ester, and α-olefin oxide, and one or more of these may be used. Examples of the above-mentioned fatty acids include soybean oil fatty acids, linseed oil fatty acids, safflower oil fatty acids, tall oil fatty acids, coconut oil fatty acids, dehydrated castor oil fatty acids, tung oil fatty acids, and total fatty acids. Examples of the above-mentioned oils used in combination include castor oil, coconut oil, linseed oil, palm kernel oil, safflower oil, soybean oil, tung oil, dehydrated castor oil, etc., and one or more of each can be used. offer The emulsifier used in the present invention is composed of the polyester resin obtained as described above, and particularly has an acid value of 30 to 150, preferably 40 to 150, and a number average molecular weight (hereinafter referred to as M) of 500 to 150. It may be set to 5000, preferably in the range of 700 to 3000. By adjusting the balance between molecular weight and hydrophilic functional groups in this way, foaming properties as an emulsifier,
Properties such as emulsification and dispersibility are improved. In addition, among the acid groups of the polyester resin, the acid value of at least 30 or more is ammonia, amine (preferably 30 or more).
It may be used in a neutralized state with a class amine) or an alkali metal. Such a neutralized state improves solubility in water. In addition, as conventional polymer emulsifiers, those based on unsaturated polyesters obtained by the esterification reaction of long-chain unsaturated dibasic acids and dihydric alcohols are known (JP-A-54-126290). However, unlike the emulsifier used in the present invention, this does not have the function of catalyzing the reaction of amphoteric ionic groups. The acrylic resin emulsion of the present invention is a system in which a polymer of α,β-unsaturated monomers is emulsified and stabilized in an aqueous medium (water or a water-water-water-miscible organic solvent mixture system) by the polyester resin. For example, it can be produced by using the above polyester resin as an emulsifier when emulsion polymerizing an α,β-unsaturated monomer in an aqueous medium in the presence of a polymerization initiator. The above α,β-unsaturated monomer may be a usual monomer for vinyl polymerization, specifically,
formula, [In the formula, R ₄ is H or CH ₃ , and R ₅ is H or a C ₁ to _{C 12} linear or branched alkyl group,
Represents 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl. ]
Acrylic acid or methacrylic acid and their esters, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, other α,β-unsaturated acids (crotonic acid,
itaconic acid, maleic acid, fumaric acid, etc.) and their esters, styrene or α-methylstyrene and their nuclear alkyl (C ₁ - _{C 4} ) substituted products, vinyl acetate, vinyl chloride, butadiene, isoprene, etc. One or more of these may be used. The polymerization initiator may be a common initiator for emulsion polymerization, such as water-soluble inorganic initiators such as potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, and combinations of these inorganic initiators and pyrosulfite. Examples include redox initiators obtained by combining sodium, sodium bisulfite, divalent iron ions, etc., and water-soluble azo compounds such as azobiscyanovaleric acid and azobis(2-amidinopropane) hydrochloride.
The species or species are provided for use. The amount used is usually 0.05 to 5 parts, preferably 0.1 to 5 parts, based on 100 parts (parts by weight, the same applies hereinafter) of the above α,β-unsaturated monomer.
The selection can be made within the range of 4 parts. In addition to the polymerization initiator, benzoyl peroxide,
Organic peroxides such as t-butyl peroxide and cumene hydroperoxide, azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile, and also conventional chain transfer agents can be used. In addition, when using a polymerization initiator, water, a hydrophilic organic solvent or α,
The β-unsaturated monomer may be provided in the form of a solution. The above emulsion polymerization method may be carried out under normal conditions and techniques, for example, except for using the polyester resin as an emulsifier (dissolved in an α,β-unsaturated monomer or an aqueous medium). ~
It may be carried out in batches or in whole or in part by dropping at 100° C. for 5 minutes to 72 hours. The amount of polyester resin used is usually 0.5 to 200 parts, preferably 1.0 to 200 parts, per 100 parts of α,β-unsaturated monomer.
You can choose within the range of 100 copies. If the amount is less than 0.5 part, a large amount of agglomerated particles will tend to be produced during synthesis, and if it exceeds 200 parts, there will be no particular problem, but if such a large amount is used, the acrylic resin emulsion will be meaningless. Further, the nonvolatile content of the emulsion to be produced is usually set to 60% or less, preferably 20 to 55%. In addition, without using such an emulsion polymerization method, for example, after preparing an acrylic resin in advance by solution polymerization or bulk polymerization of the above α,β-unsaturated monomer by a conventional method, this is prepared in the presence of the polyester resin. The acrylic resin emulsion may be produced by emulsifying and dispersing it in an aqueous medium. In this way, an acrylic resin emulsion is obtained, but conventionally, when using a low molecular weight emulsifier, a relatively large amount (4 to 8
%), and in the past, the emulsifier often remained in the emulsion film and deteriorated the physical properties of the emulsion resin, but in the present invention, the amount used can be as small as 0.5%. Moreover, even if the emulsifier remains, since the emulsifier itself has an M of 500 to 5,000, the above-mentioned deterioration in physical properties is eliminated. Furthermore, such emulsions have excellent stability (storage stability, mechanical stability, miscibility stability) and can be easily blended with other water-soluble polymers. The coating composition according to the present invention has the above-mentioned acrylic resin emulsion as a main component, and specifically, the main component can be used alone or in combination with a conventional resin vehicle (melamine resin, urea resin, guanamine resin, etc.) as necessary. Aminoplast resins such as resins,
(phenoplast resin, epoxy resin, etc.), organic or inorganic coloring pigments, extender pigments, anti-rust pigments, other additives (fillers, extenders, thickeners, etc.), surfactants, PH regulators, water It is prepared by mixing an appropriate amount of a hydrophilic organic solvent and dispersing the mixture at room temperature. This coating composition is applied to a suitable object to be coated (metal plate, wood, paper type substrate, building, etc.) by a normal method to a film thickness of 5 to 500 μm, and
A good cured coating is formed by drying at a temperature of 20 seconds to 72 hours. In the coating composition of the present invention constructed as described above, the acrylic resin emulsion is designed to be an acid-catalyzed thermosetting system such as an activated methylol crosslinked system (i.e., in combination with an aminoplast resin, etc.)
In this case, the crosslinking reaction is promoted by the catalytic action of the amphoteric ionic group, making it possible to cure at a low temperature, and the resulting cured coating film has excellent water resistance and solvent resistance, as well as high hardness and extremely good gloss. Furthermore, since the polyester resin used as an emulsifier has hydroxyl groups and carboxyl groups in its molecules that can react with active methylol groups, it is incorporated into a three-dimensional network structure through a crosslinking reaction, and is not a residual substance like a normal emulsion. No deterioration in physical properties due to emulsifiers.
Moreover, the excellent properties of so-called polyester resins can be imparted to the cured coating film. That is,
This makes it possible to create high-gloss paints that have both high hardness and flexibility, and have superior weather resistance, stain resistance, and chemical resistance. Next, the present invention will be specifically explained with reference to Reference Examples, Examples, and Comparative Examples. Reference example 1 In a two-colben equipped with a stirrer, nitrogen inlet tube, temperature controller, condenser, and decanter, 191 parts of hydroxyethyl taurine, 140 parts of ethylene glycol, 170 parts of triethylene glycol, 331 parts of adipic acid, and 168 parts of phthalic anhydride were added. part and xylene 40
Prepare the ingredients and raise the temperature. Water produced by the reaction is removed by azeotropic reflux with xylene. The temperature was raised to 190° C. over about 2 hours from the start of reflux, and stirring and dehydration were continued until the acid value equivalent to carboxylic acid became 10 or less to complete the reaction. The obtained polyester resin had an acid value of 79, a hydroxyl value of 79, and an M of 708. Reference Example 2 134 parts of bishydroxyethyl taurine, 130 parts of neopentyl glycol, 236 parts of alaic acid, 186 parts of phthalic anhydride, and 27 parts of xylene were placed in a 2-colben equipped with a stirrer, nitrogen inlet tube, temperature control device, condenser, and decanter. Prepare the ingredients and raise the temperature. Water produced by the reaction is removed by azeotropic reflux with xylene. The temperature is raised to 190°C over about 2 hours from the start of refluxing, stirring and dehydration are continued until the acid value equivalent to carboxylic acid reaches 145, and the mixture is cooled to 140°C. Next, the temperature of the reaction solution was maintained at 140° C., and 314 parts of “Cardilla E10” (Versatellite glycidyl ester manufactured by Shell) was added dropwise over 30 minutes, followed by stirring for 2 hours to complete the reaction. The obtained polyester resin had an acid value of 59, a hydroxyl value of 90, and an M value of 1054. Reference Example 3 Same method as in Reference Example 1 except that 340 parts of β-hydroxyethylaminodiethanesulfonic acid, 94 parts of neopentyglycol, 340 parts of azazelaic acid, and 226 parts of "Cardilla H10" were used as reaction components. According to the following conditions, a polyester resin having an acid value of 62, a hydroxyl value of 62, and M908 is obtained. Reference Example 4 85 parts of dehydrated castor oil, 63 parts of coconut oil, and 53 parts of trimethylolpropane were charged into a 2-kolben equipped with a stirrer, nitrogen inlet tube, temperature control accelerator, condenser, and decanter, and the temperature was brought to a boil under a nitrogen atmosphere. 240℃
After stirring for 30 minutes, the methanol tolerance became infinite. The temperature of the contents is 150℃
725 parts of phthalic anhydride, 343 parts of diethylene glycol, 43 parts of trimethylolpropane, 375 parts of N,N-bis-(2-hydroxyethyl)aminoethanesulfonic acid, and 45 parts of xylene.
I prepared a section. Stirring was started again, and while the temperature was gradually raised, the generated water was removed by azeotropic reflux with xylene. Bring the temperature to 240℃ for about 2 hours,
Furthermore, stirring and dehydration were continued at the same temperature until the acid value equivalent to carboxylic acid reached 8, and the reaction was completed.
The obtained polyester resin had an oil length of 10, an acid value of 66, a hydroxyl value of 100, and an M of 800. Reference example 5 1 equipped with a stirrer, cooler, and temperature control device
A reaction vessel was charged with 306 parts of deionized water, 30 parts of the polyester resin obtained in Reference Example 2, and 3 parts of dimethylethanolamine, and dissolved while stirring while maintaining the temperature at 80°C.
1 part dissolved in 45 parts deionized water and 4.3 parts diethanolamine is added. Next, 72 parts of methyl methacrylate, 96 parts of n-butyl acrylate,
A mixture of 72 parts of styrene and 30 parts of 2-hydroxyethyl acrylate is added dropwise over 60 minutes. After the dropwise addition, 1.5 parts of azobiscyanovaleric acid dissolved in 15 parts of deionized water and 1.4 parts of diethanolamine was added, and stirring was continued at 80°C for 60 minutes. ),
An acrylic resin emulsion with a particle size of 0.135μ is obtained. When this emulsion was passed through a 400-mesh wire mesh, the amount of aggregates that did not pass through was less than 0.2% (ratio to the emulsion produced), and the amount of aggregates formed was extremely small. Example 1 In 100 parts of the emulsion produced in Reference Example 5, 11 parts of hexamethoxymethylolmelamine (trade name "Cymel 303" manufactured by American Cyamide) was dissolved in 5.5 parts of ethylene glycol monobutyl ether and 5.5 parts of deionized water. A thermosetting coating composition is prepared by gradually adding an aminoplast resin solution with stirring using a lab mixer. When the above composition was applied to a steel plate to a dry film thickness of approximately 20 μm and heat-cured at 100°C, 120°C, 140°C, or 160°C for 30 minutes, a transparent coating film was obtained. . The coating film was extracted with acetone for 4 hours using a Soxhlet extractor, and the results are shown in Table 2. The gloss, hardness and 1 hour immersion in boiling deionized water of the coatings cured at 140°C are shown in Table 1. Comparative Example 1 Resin Emulsion In the same reaction vessel as in Reference Example 1, 248 parts of neopentyl glycol, 224 parts of azelaic acid, and phthalic anhydride were added.
176 parts, trimellitic anhydride 114 parts and xylene
Prepare 40 parts and raise the temperature. Water produced by the reaction is removed by azeotropic reflux with xylene. The temperature is raised to 190°C over 2 hours from the start of reflux, stirring and dehydration are continued until the acid value reaches 150, and the mixture is cooled to 140°C. Next, 238 parts of "Carjiura E10" was dripped in 30 minutes.
After that, stirring was continued for 2 hours to complete the reaction. The obtained polyester resin has an acid value of 48 and a hydroxyl value
140, it was M1191. Next, in the emulsion production method of Reference Example 5, the same method and conditions were followed except that 30 parts of the above-mentioned polyester resin not containing an aminosulfonic acid type zwitterionic group was used in place of the polyester resin of Reference Example 2. 41% non-volatile content, PH7, viscosity
An emulsion with a particle diameter of 0.221μ and a content of 9.1% that did not pass through a 400-mesh wire mesh was obtained at 28 cps. Coating Composition Using the above emulsion, a thermosetting coating composition was prepared using the same method and conditions as in Example 1,
Each test was conducted. The results are shown in Table 1.

【table】

【table】

Claims (1)

[Scope of Claims] 1. A coating composition comprising as a main component an acrylic resin emulsion comprising a polymer of α,β-unsaturated monomers emulsified and stabilized in an aqueous medium with an emulsifier, The formula in the molecule as, [In the formula, A represents a C ₁ to C ₆ linear or branched alkylene group, phenylene group, or substituted phenylene group. ] A coating composition characterized in that it uses a polyester resin having an aminosulfonic acid type zwitterionic group. 2. The coating composition according to item 1 above, which contains a melamine resin as another component.