JPH0325445B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing an oil-free polyester having a specific zwitterionic group in its molecule. [Prior art] Regarding hydroxyl group-containing amphoteric ionic compounds, the formula [In the formula, R ₁ is a C ₁ to C ₂₀ alkyl group having at least one hydroxyl group, R ₂ and R ₃ are each the same or different and are a hydrogen atom, a C ₁ to C ₂₀ alkyl group, and at least one an alkyl group having hydroxyl groups and/or sulfonic acid groups, and A represents a C ₁ -C ₆ straight-chain or branched alkylene group. ] The hydroxyl group-containing aminosulfonic acid type zwitterionic compound represented by the following exists as a mixture of tautomers as shown in the following formula. In addition, the ion form differs depending on the environmental conditions. For example, due to changes in PH make a change. Therefore, by controlling the environmental conditions, different reactivity, surface activity, electrochemical properties, etc. can be expressed. For example, amino resin and alkyd resin or acrylic resin,
Acid and
It functions as a base catalyst or as a surfactant such as an emulsifier or a dispersant. By the way, such aminosulfonic acid type zwitterionic compounds (especially those with low molecular weight) are soluble only in water or limited polar solvents (e.g. dimethyl sulfoxide), but are sparingly soluble in many organic solvents and are used as solvents in the coating industry. It was not miscible with the mold resin composition, and the above-mentioned function expression was restricted. [Problems to be Solved by the Invention] The present inventors have conducted intensive research in order to improve the solubility of the above-mentioned hydroxyl group-containing aminosulfonic acid type zwitterionic compound in various organic solvents and to fully exhibit its excellent functions. As a result of progress,
By using the amphoteric ionic compound as an alcohol component and converting it into a resin by esterifying it with a normal acid component, the formula: [In the formula, A has the same meaning as above. ] A novel oil-free polyester having an aminosulfonic acid type zwitterionic group shown in the molecule is obtained, and furthermore, such polyester exhibits the above-mentioned good solubility and also has good miscibility with solvent-based resin compositions. In particular, the inventors have discovered that the amphoteric ionic group can fully exhibit the above-mentioned reaction catalytic function and surfactant function in solvent-based paints, leading to the completion of the present invention. [Means for Solving the Problems] That is, the gist of the present invention is to use the above-mentioned hydroxyl group-containing aminosulfonic acid type zwitterionic compound (hereinafter simply referred to as zwitterionic compound) as the alcohol component in the reaction components in all reaction components. Medium 0.05-50%
(wt%, hereinafter the same), the amphoteric ionic compound, polybasic acid compound, and polyhydric alcohol and/or oxirane compound are reacted, and the above aminosulfonic acid type amphoteric ionic group (hereinafter simply referred to as The present invention relates to a method for producing an oil-free polyester, which is characterized by obtaining an oil-free polyester having a zwitterionic group (abbreviated as zwitterionic group). The method for producing oil-free polyester of the present invention is characterized by using the above-mentioned amphoteric ionic compound in a specific ratio as the alcohol component in the reaction component, and in addition to the raw material components and reaction conditions and method of ordinary oil-free polyester. may be adopted. Such usual reaction conditions and methods are described, for example, in "Introduction to Synthetic Resins for Paints" by Kyozo Kitaoka (published by Kobunshi Kankai on May 25, 1974, pp. 92-127), or by DH Solomon, John Willey and・The Chemistry of Organic Film Formers by Sun (pp. 75-87)
1967). That is, using a the above-mentioned amphoteric ionic compound, b a polybasic acid compound, and c a polyhydric alcohol and/or d an oxirane compound as reaction components, these are esterified in an appropriate solvent according to the procedure described in Examples below. The oil-free polyester of the present invention is produced by reaction and, if necessary, transesterification. 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 (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-methyl ethyl) aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(2-hydroxypropyl)aminomethanesulfonic acid and its N-alkyl substituted products and 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 substituents, 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 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-5,5-dimethyl-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 product and N,N-dialkyl substituted product, N-(1-hydroxymethyl-3 -hydroxypropyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(1-(γ-hydroxypropyl)-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted products substituents and N,N-dialkyl substituents, N-(1,1-
Bis(hydroxymethyl)-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl- and N,N-dialkyl-substituted products, N-
(2,2-bis(hydroxymethyl)-3-hydroxypropyl)aminomethanesulfonic acid and its N
-alkyl substituted product and N,N-dialkyl substituted product, N,N-bis(2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted product (N-methyl-N,N-bis(2-hydroxyethyl) ) Betaine ammoniomethane sulfonate, 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-bis(hydroxymethyl)-2-hydroxyethyl)aminomethanesulfonic acid and its N
-alkyl substituted product, N,N-bis(2,3-dihydroxypropyl)aminomethanesulfonic acid and its N-alkyl substituted product, N,N-bis(1-(hydroxymethyl)-2-hydroxyethyl)aminomethane Sulfonic acid and its N-alkyl substituted product,
N,N-bis-(1,1-hydroxymethyl)-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 product (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-
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 products, 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-hydroxyethyl)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- 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 and N,N-dialkyl substituted products, N-(1-hydroxymethyl-2-methyl-2-hydroxyethyl)
Aminoethanesulfonic acid and its N-alkyl 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 and N,N-dialkyl substituted products, N-(1,
1-bis(hydroxymethyl)-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N
-(2,2-bis(hydroxymethyl)-3-hydroxypropyl)aminoethanesulfonic acid and its N-alkyl- and N,N-dialkyl-substituted products, N,N-bis(2-hydroxyethyl)aminoethane Sulfonic acid and its N-alkyl substituted product (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 substituted product, N,N-bis(2,3-dihydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted product, N,N-bis-(1-(hydroxymethyl)-2-hydroxyethyl)amino Ethanesulfonic acid and its N-alkyl substituted products,
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-hydroxyethyl)}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 substitution and N,N-dialkyl substituted product, 3-{N-(2-hydroxypropyl)}aminopropanesulfonic acid-
(1) and its N-alkyl substituted product and N,N-dialkyl substituted product, 3-{N-(3-hydroxypropyl)}aminopropanesulfonic acid-(1) and its N-
Alkyl substituted product and N,N-dialkyl substituted product, 3-{N-(2-propyl-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N
-Alkyl substituted product and N,N-dialkyl substituted product, 3-{N-(2-methyl-2-ethyl-2-hydroxyethyl)}aminopropanesulfonic acid-
(1) and its N-alkyl- 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 product, 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 and N,N-dialkyl substituted products, 3-{N-(1,2 -diisopropyl-
2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted products 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 product body and N,
N-dialkyl substituted product, 3-{N-(1-hydroxymethyl-2-methyl-2-hydroxyethyl)}
Aminopropanesulfonic acid-(1) and its N-alkyl- and N,N-dialkyl-substituted products, 3-
{N-(1-hydroxymethyl-3-hydroxypropyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted products and N,N-dialkyl substituted products, 3-{N-(1-(γ- hydroxypropyl)
-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted products and N,
N-dialkyl substituted product, 3-{N-(1,1-bis(hydroxymethyl)-2-hydroxyethyl)}
Aminopropanesulfonic acid-(1) and its N-alkyl- and N,N-dialkyl-substituted products, 3-
{N-(2,2-bis(hydroxymethyl)-3-
hydroxypropyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted products and N,N-
Dialkyl substituted product, 3-{N,N-bis(2-hydroxyethyl)}aminopropanesulfonic acid-
(1) and its N-alkyl substituted product (3-{N-methylN,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)} -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(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 substituted product, 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)imino Diethanesulfonic acid, N-(2-hydroxypropyl)iminodiethanesulfonic acid, N-(2,3-dihydroxypropyl)iminodiethanesulfonic acid, N
-(1,1-bis(hydroxymethyl)-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, etc., and one or more of these may be used. The amount used is 0.05 to 50 of the total reaction components.
%, preferably in the range of 0.5 to 30%.
If it is less than 0.05%, the reactivity, surface activity, and electrochemical properties of the oil-free polyester of the present invention will not be sufficiently expressed, and if it exceeds 50%, the viscosity of the oil-free polyester of the present invention will tend to increase. , storage stability deteriorates. Such amphoteric ionic compounds may be used as they are or as salts with basic substances (eg ammonia, organic amines, alkali metals). Furthermore, when calculating the addition of this amphoteric ionic compound to the oil-free polyester of the present invention, the compound may be calculated as an alcohol component. That is, if the total number of hydroxyl groups contained in one molecule is one, then 1
alcohol, in the case of 2 alcohol, dihydric alcohol, 3
In the case of 1, it is calculated as trihydric alcohol, and in the case of n, it is calculated as n-hydric alcohol. As a method for synthesizing the above-mentioned amphoteric ionic compound, a conventional method may be employed, and examples thereof include the following reaction method. The polybasic acid compound is a polycarboxylic acid having two or more carboxyl groups or an anhydride thereof, such as adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecyldicarboxylic acid, phthalic anhydride, isophthalic acid, Terephthalic acid, succinic anhydride, tetrahydrophthalic anhydride,
Examples include hemicic anhydride, trimetic anhydride, pyromellitic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, and hectonic anhydride, and one or more of these may be used. The amount to be used may be normally selected within the range of 2 to 90% of the total reaction components. 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. The amount to be used may be normally selected within the range of 2 to 90% of the total reaction components. Examples of the oxirane compound 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. The amount to be used may be normally selected within the range of 2 to 90% of the total reaction components. [Function] The typical schematic structure of the oil-free polyester obtained as described above is classified as follows based on the alcohol valence of the amphoteric ionic compound. (However, 〓〓 represents a resin molecule with an ester bond chain.) In this way, since such oil-free polyester has the amphoteric ionic group in its molecule,
It has reactivity, surface activity, electrochemical properties, and has good solubility in various organic solvents, such as alkyd resin varnish, acrylic resin varnish,
It has excellent miscibility with solvent-based resin compositions such as melamine resin varnish, and can sufficiently exhibit the above-mentioned reaction catalyst function and surfactant function even in these applications. The molecular weight of the oil-free polyester is not particularly limited, but when used in paint applications, M = 10,000 or less is suitable. [Effects of the Invention] As described above, the oil-free polyester of the present invention is characterized in that it has an amphoteric ionic group in its structure. Therefore, when this is used as a coating resin, the coating film formed by the coating composition has the characteristics of ordinary oil-free polyester (such as hardness, flexibility, weather resistance, and stain resistance). In addition to the antistatic properties derived from the amphoteric ionic group, it can have antistatic properties derived from the amphoteric ionic group. [Example] Next, the present invention will be specifically explained with reference to Examples and Reference Examples. Example 1 191 parts of hydroxyethyl taurine (parts by weight, the same applies hereinafter), 140 parts of ethylene glycol, 170 parts of triethylene glycol, and adipic acid were placed in a two-colben equipped with a stirrer, a nitrogen inlet tube, a temperature control device, a condenser, and a decanter. 331 parts, phthalic acid 168
1 part and 40 parts of xylene 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 after the start of reflux.
The reaction was completed by continuing stirring and dehydration until the acid value equivalent to carboxylic acid became 10 or less. The resulting oil-free polyester has an acid value of 79 and a hydroxyl value of
97, it was M708. Example 2 139 parts of hydroxyethyl taurine, 110 parts of trimethylolpropane, 121 parts of phthalic anhydride, and azelaic acid were added to a two-colben equipped with a stirrer, a nitrogen inlet tube, a temperature control device, a condenser, and a decanter.
Add 308 parts and 27 parts of xylene 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 after the start of reflux.
Continue stirring and dehydration until the acid value equivalent to carboxylic acid reaches 145, and then cool to 140°C. Next, the temperature of the reaction solution was maintained at 140°C, and the “AOE
-X24'' (α-olefin oxide manufactured by Daicel) was added dropwise over 30 minutes, and stirring was continued for 2 hours to complete the reaction. The obtained oil-free polyester has an acid value of 57, a hydroxyl value of 105, and an M
It was 1040. Example 3 Using the raw materials shown in Table 1 and following the same method and conditions as in Example 1, an oil-free polyester having the special values shown in the table is obtained. Examples 4 to 9 Using the raw materials shown in Table 1 and following the same method and conditions as in Example 2, oil-free polyesters having the special values shown in the table are obtained. Reference Example 1 9 parts of various solvents were added to 1 part of the oil-free polyester obtained in Examples 1 to 9, and the mixture was heated to 50-50% in a test tube.
After heating to 80°C, the solvent solubility of the polyester was examined while maintaining the temperature at 25°C. The solubility was determined based on the following criteria, and the results are shown in Table 1 (for comparison, the results for two zwitterionic compounds are also shown). 〇: Uniformly dissolved. Δ: Slight turbidity. ×: Phase separation or significant turbidity. Comparative Examples 1 and 2 Same as Reference Example 1 except that N-octylaminoethanesulfonic acid or N-(β-hydroxycetyl)aminoethanesulfonic acid was used instead of the oil-free polyester obtained in Examples 1 to 9. The solvent solubility was investigated. The results are shown in Table 1.

【table】

【table】

[Table] Reference Example 2 The oil-free polyester obtained in Examples 4 and 7, "Betsukosol 1323" (coconut oil-modified alkyd resin manufactured by DIC, oil length 32%), "Betsucolyte M6402"
-50” (oil-free alkyd resin manufactured by DIC)
Or "Super Beth Carmine J-820-60"
(butylated melamine resin manufactured by DIC Corporation) at a ratio of 1:1, and the miscibility of the polyester with the solvent-based resin composition was examined. Miscibility was evaluated based on the following criteria, and the results are shown in Table 2. ○: Mixed uniformly. Δ: Slightly cloudy. ×: Phase separation or significant turbidity. Comparative Examples 3 and 4 Miscibility with a solvent-based resin composition was determined in the same manner as in Reference Example 2, except that the zwitterionic compound of Comparative Example 1 or 2 was used in place of the oil-free polyester obtained in Examples 4 and 7. Examined. The results are shown in Table 2.

[Table] Comparative Example 5 Same method as in Example 4 except that 65 parts of neopentyl glycol was used in place of 134 parts of bishydroxyethyl taurine in the raw material formulation of Example 4 (total amount of neopentyl glycol was 195 parts). According to the conditions, oil-free polyester is obtained. This polyester had an acid value of 31 and an M of 1040. Reference Example 3 Two types of varnishes were prepared by mixing 10 parts of the oil-free polyester of Example 4 or Comparative Example 5 with 1 part of dimethylethanolamine and 190 parts of toluene. Each varnish was applied with a #30 bar coater to a polypropylene plate that had been thoroughly degreased and washed with toluene solvent, dried at 100°C for 30 minutes, and stored in a desiccator containing a silica gel desiccant for 3 hours. After that, we tested the antistatic properties of each polypropylene plate.
Using a static honest meter (manufactured by Shishido Shokai), evaluation was made based on the half-life of charge band decay after applying 10 KV for 1 minute. In the case of Example 4, the half-life was 9 seconds, indicating excellent antistatic properties. However, in the case of Comparative Example 5, the half-life was 100 seconds or more and the effect was low.

Claims (1)

[Claims] 1. As the alcohol component in the reaction components, the formula [In the formula, R ₁ is a C ₁ to C ₂₀ alkyl group having at least one hydroxyl group, R ₂ and R ₃ are each the same or different and are a hydrogen atom, a C ₁ to C ₂₀ alkyl group, and at least one an alkyl group having hydroxyl groups and/or sulfonic acid groups, and A represents a C ₁ -C ₆ straight-chain or branched alkylene group. ] Using a hydroxyl group-containing aminosulfonic acid type zwitterionic compound represented by 0.05 to 50% by weight of the total reaction components, the zwitterionic compound, polybasic acid compound, and polyhydric alcohol and/or oxirane compound are reacted. and the formula in the molecule, [In the formula, A has the same meaning as above. ] A method for producing an oil-free polyester, which comprises obtaining an oil-free polyester having an aminosulfonic acid type zwitterionic group.