JPH02138335A - New oil-free polyester and preparation thereof - Google Patents

Abstract

PURPOSE:To improve solubility in an org. solvent, etc., by reacting an amino- sulfonic acid type amphoteric compd. contg. a specified OH group, a polybasic acid compd. and, if necessary, a polyalcohol and/or an oxirane compd. CONSTITUTION:The title polyester with an amino-sulfonic acid type amphoteric group of formula II is obtd. by reacting 0.05-5wt.% OH group-contg. amino- sulfonic acid type amphoteric compd. (a) of formula I [wherein R] is a 1-20C alkyl which has one or more OH groups and may contain -O or -COO- in the molecular group; R2-3 are each H, a 1-20C alkyl, an alkyl contg. one or more OH and/or sulfonic acid groups, a cyclic group; A is a 1-6C linear or branched alkylene or a (substd.)phenylene], 2-90wt.% polybasic acid compd. (b) (e.g., adipic acid) and 0-90wt.% polyhydric alcohol (e.g. ethylene glycol) and/or oxirane compd. (e.g., phenyl glycidyl ether).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel oil-free polyester, more specifically, an oil-free polyester having a specific zwitterionic group in the molecule, and a zwitterionic compound containing a specific hydroxyl group. The present invention relates to a method for producing the above-mentioned polyester, which comprises using as an alcohol component.

[Conventional technology]

Hydroxyl group-containing zwitterionic compounds have the formula, R+N''A5O3e [wherein R3 has at least 61 hydroxyl groups and may contain 10- or 1000- in the molecular group] an alkyl group of CI-CI0, R2 and R3 are the same or different from each other and are a hydrogen atom, an alkyl group of c, xC*, an alkyl group or a cyclic group having at least one hydroxyl group and/or a sulfonic acid group, and A represents a C1 to Co linear or branched alkylene group, phenylene group, or substituted phenylene group.] The hydroxyl group-containing aminosulfonic acid type zwitterionic compound represented by the following formula is a mixture of tautomers as shown in the following formula. It exists as.

In addition, the ion form differs depending on the environmental conditions. For example, a change in I)H causes a small change in pH; Therefore, by controlling the environmental conditions, different reactivity, surface activity, electrochemical properties, etc. can be expressed. For example, it functions as an acid/base catalyst in coating film forming reactions such as amino resins and alkyd resins or acrylic resins, isocyanate groups and polyols, and epoxy resins and amino resins, or functions as surfactants such as emulsifiers and dispersants. do.

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 poorly soluble in many organic solvents and are used in the coating industry. It was not miscible with the solvent-based resin composition, and the above-mentioned function expression was restricted.

[Problem to be solved by the invention]

The present inventors have carried out intensive research to improve the solubility of the above-mentioned hydroxyl group-containing aminosulfonic acid type zwitterionic compound in various organic solvents and to fully demonstrate its excellent functions. An aminosulfonic acid represented by the formula, N"-A-9O3e [wherein A has the same meaning as above] is obtained by using an alcohol component and esterifying it with a normal acid component to form a resin. A novel oil-free polyester having an amphoteric ionic group in the molecule is obtained, and this polyester exhibits the above-mentioned good solubility and also has good miscibility with solvent-based resin compositions, particularly in solvent-based paints. We have discovered that the amphoteric ionic group can fully exhibit the above-mentioned reaction catalyst function and surfactant function, and have completed the present invention.

[Means to solve the problem]

That is, the gist of the present invention is, firstly, an oil-free polyester characterized by having the aminosulfonic acid type zwitterionic group (hereinafter simply referred to as zwitterionic group) in the molecule; and secondly, a reactive component. The above-mentioned hydroxyl group-containing aminosulfonic acid type zwitterionic compound (hereinafter simply referred to as zwitterionic compound) is used as the alcohol component in the total reaction component at 0.05 to 50% (wt%, the same applies hereinafter),
The method for producing an oil-free polyester is characterized in that the oil-free polyester is obtained by reacting this with a polybasic acid compound and, if necessary, a polyhydric alcohol and/or an oxirane compound.

The method for producing the oil-free polyester of the present invention includes:
It is characterized in that the above-mentioned amphoteric ionic compound is used in a specific ratio as the alcohol component in the reaction component, and the raw material components and reaction conditions and methods of ordinary oil-free polyester may be adopted for this. Such usual reaction conditions and methods include, for example, Kyozo Kitaoka, "Introduction to Synthetic Resins for Paints J.
Published by Kobunshi Kankai, May 25, 1974, 92-127
The Chemistry of Organic Film Formers (pp. 75-87, 19
It will be implemented in accordance with the contents described in 1967).

That is, a, the above-mentioned amphoteric ionic compound, b, a polybasic acid compound, and, if necessary, a C1 polyhydric alcohol and/or d, an oxirane compound are used as reaction components, and these are mixed in a suitable solvent in the following example. The oil-free polyester of the present invention is produced by carrying out an esterification reaction and, if necessary, a transesterification reaction, according to the procedure described above.

Examples of the amphoteric ionic compounds include N-(2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted product (N-methyl-N-(2hydroxylethyl)).
Aminomethanesulfonic acid, N-ethyl-N-(2-hydroxyethyl)aminomethanesulfonic acid, N-isopropyl-N-(2hydroxyethyl)aminomethanesulfonic acid, N(2-ethylhexyl)-N-(2-hydro quinethyl) aminomethanesulfonic acid, N-decyl N-(2
-hydroxyethyl)aminomethanesulfonic acid, N-stearyl-N-(2-hydroxyethyl)aminomethanesulfonic acid, etc.) and N,N-dialkyl substituted products (N-hydroxyethyl)aminomethanesulfonic acid, etc.
, N-dimethyl-N-(2hydroxyethyl)ammoniomethanesulfonic acid hetain, N,N-diethyl-N-
(2-hydroxyethyl)ammoniomethanesulfonate hetaine, N-methyl-N-dodecyl-N-(2-hydroxyethyl)ammoniomethanesulfonate betaine, etc.), N-(2-hydroxy-■-methylethyl) Aminomethanesulfonic acid and its N-alkyl substituted products and N
, N-dialkyl substituted product, N-(2-hydroxypropyl)aminomethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, N-(3-hydroxypropyl)aminomethanesulfonic acid and its N -alkyl substituents and N,N-dialkyl substituents, N-(2-
Propyl-2-hydroxyethyl)aminomethanesulfonic acid and its N to N alkyl substituted products and N,N-dialkyl substituted products, N-(2-methyl-2-ethyl-2-hydroxyethyl)aminomethanesulfonic acid and its N -alkyl substituents and N,N-dialkyl substituents, N-(1,2
-dimethyl-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl- and N,N-dialkyl-substituted products, N-(1,l,2.2-tetramethyl-2-
hydroxyethyl)aminomethanesulfonic acid and its N-alkyl-substituted and N,N-dialkyl-substituted products, N-(
1-Methyl-55-dimethyl-5-hydroxypendel)aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(1,2-diisopropyl-2-hydroxyethyl)aminomethanesulfone acid and its N-alkyl substituted product and N,N-dialkyl substituted product, N-(2,3-dihydroxypropyl)aminomethanesulfonic acid and its N-alkyl substituted product and N,
N-dialkyl substituted product, N-(1-hydroxymethyl-
2-Hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted products and N.

N-dialkyl substituted product, N-(1-hydroquinemethyl-
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 substituents and N,N-dialkyl substituents, N-(1
-(γ-hydroxypropyl)-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl- and N,N-dialkyl-substituted products, N-(1,1-bis(
hydroxymethyl)-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N
-dialkyl substituted product, 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 products (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 products, N,N -Bis(2-
droxyprovir) aminomethane sulfonic 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)aminomethanesulfonic acid and its N-alkyl substituted products, N,N-
Bis-(1,l-(bishydroxymethyl)-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted product, N,N,N-tris-(2hydroxyethyl)ammoniomethanesulfonic acid betaine, N,N-bis-(2-hydroxyethyl)-N-(3-hydroxypropyl)ammoniomethanesulfonic acid betaine, N
, N,N-)lis(3-hydroxypropyl)ammoniomethanesulfonic acid betaine, N-(2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product (N-methyl-N-(2-hydroxy ethyl)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 product (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 products body,
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 product and N, N-dialkyl substituted product, N-(2propyl-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product and N.

N-dialkyl substituted product, N-(2-methyl-2edy-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product,
N-(1,2-dimethyl-2hydroxyethyl)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 product and N,N-dialkyl substituted product, 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-2hydroxyethyl)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-hydroquinemethyl-2-hydroxyethyl) Aminoethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, N-(1-hydroxymethyl-2-methyl-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product and N , N-dialkyl substituted product, N-(1-hydroquinomethyl-3-hydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, N-(1-(γ-
hydroxypropyl)-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted products and N,
N-dialkyl substituted product, N-(1,1bis(hydroxymethyl)-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, N-(2,2bis (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 product (N-methyl-N,
N-bis(2-hydroxyethyl)ammonioethanesulfonic acid betaine, N-edyl N, N-bis(2-hydroxyethyl)ammonioethanesulfonic acid betaine,
N-Butyl-N, N-bis(2-hydroquinethyl)ammonioethanesulfonic acid betaine, N-dodenru-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-hydroquinepropyl)-N-(1,1-bis (Hydroxymethyl)-2
= hydroxyedyl) 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)aminoethanesulfonic acid and its N-alkyl substituted product, N,N-bis-(1,I-(bishydroxymethyl)-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product body, 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, 31N-(2-hydroxyethyl))aminopropanesulfonic acid-(rito and its N-alkyl substituted product(1(N-methyl-N-(2-hydroxyethyl) )Aminopropanesulfonic acid-(1), 3-(N-ethyl-N-(2-hydroxyethyl))aminopropanesulfonic acid-(+)
, 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))amino Propanesulfonic acid (1), etc.) and N,N-dialkyl substituted product (3-(NN-dimethyl-N-(2-hydroxyethyl)) ammoniopropanesulfonic acid (1) betaine, 3 -(N,N-diethyl-N-(2-hydroxyethyl))ammoniopropanesulfonic acid = (ribetaine, 3-(N-methyl-
N-dodecyl-N-(2hydroxyethyl))ammoniopropanesulfonic acid-(1) betaine, etc.), 3-(
N-(2-hydroxy-1-methylethyl))aminopropanesulfonic acid = (1) and its N-alkyl substituted product and N.

N-dialkyl substituted product, 3-(N-(2-hydroxypropyl))aminopropanesulfonic acid-(1) and its N
-alkyl substituents and N,N-dialkyl substituents, 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 product and N,N-dialkyl substituted product, 3(N-(2-methyl-2-ethyl-2-hydroxyethyl))aminopropanesulfonic acid-(1)
and its N-alkyl substituted product and its N,N-dialkyl substituted product, 3-(N-(1,2-dimethyl-2-hydroxyethyl))aminopropanesulfonic acid-(1) and its N
-alkyl substituents and N,N-dialkyl substituents, 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-dimedy-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 products and N,N-dialkyl substituted products, 3-(N-(2,3-dihydroxypropyl))
Aminopropanesulfonic acid-(1) and its N-alkyl-substituted product, 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 substituted products 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 products, 3-
(N-(1,l-bis(hydroxymethyl)-2-hydroxyethyl))aminopropanesulfonic acid = (1) and its N-alkyl substituted products and N,N-dialkyl substituted products, 3-(N-( 2,2-bis(hydroxymethyl)-
3-hydroxypropyl)) aminopropanesulfonic acid (1) and its N-alkyl substituted products, N,N-dialkyl substituted products, 3-(N,N-bis(2-hydroxyethyl))aminopropanesulfone 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(4-hydroxybutyl))aminopropanesulfonic acid-〇) 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(hydroxydimethyl)-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-(I-(hydroquinemethyl)-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-(■)betaine, 5iN -(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-(summer)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-medylN, N-bis(2-hydroxyethyl))ammoniopentanesulfonic acid (1) betaine, 5-(N- Ethyl-N,N-bis(2-hydroxyethyl))ammoniopentanesulfone 112-(
+) betaine, 5(N-butyl-N,N-bis(2-hydroxyethyl))ammoniopentanesulfonic acid-(
1) Betaine, 5-(N-dodenruN, N-bis(2)
-hydroxyethyl)) ammoniopentanesulfonic acid (1) betaine, 5-(N-stearyl-N, N-bis(2-hydroquinoethyl))ammoniopentanesulfonic acid (1) betaine, etc.), 5iN, N.

N-tris-(2-hydroxyethyl)ammoniopentanesulfonic acid-(1) betaine, N-(2-hydroxyethyl)iminodiethanesulfonic acid, N-(2-hydroxypropyl)iminodiethanesulfonic acid, N-(
2,3-dihydroxypropyl)iminodiethanesulfonic acid, N-(1°!-bis(hydroxymethyl)-2-
hydroxyethyl)iminodiethanesulfonic acid, N-(
2-hydroxyethyl)iminoethanesulfonic acid propanesulfonic acid, N-(2-hydroquinepropyl)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, N-
Bis-(2-hydroxyethyl)orthanylic acid, N.

N-bis-(2-hydroxyethyl)methanilic acid, N,
Examples include N-bis-(2-hydroxyethyl)sulfanilic acid, and one or more of these may be used. The amount used is selected in the range of 0.05 to 50%, preferably 0.5 to 30% of the total reaction components. 0.05%
If it is less than 50%, 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, making storage difficult. 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, it is a monohydric alcohol, if there are two, it is a dihydric alcohol, and if the total number of hydroxyl groups contained in one molecule is two, it is a dihydric alcohol.
In the case of 1, it is calculated as trihydric alcohol, and in the case of n, it is calculated as 0hydric 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.

Rt N” CH* 5Ose (In case of D:
R2 R, -NH+CH,0+bisulfite (BHSO3:B
is Na, Ni, NH, etc.) -) R, -N-CH2-S 03B t ii) Rt-N” a) 1.-NH+X-CItCHt (X: CLBr, I) 1--→ Rt N CHpCHt- CHpCHt
- In the case of SO8e:
R1 R, -NH+H0 CH, CH, -503B 1--→ Rr N CHt CHt S 03
B=GoR+ N" CHzCHt S03"Summer (Rt NH+CH!=CH5OsR (R: alkyl group) 11 → Rt N CH*'CHt 5OsRR
2 = GoR+ N, Φ-CH*CH* 5O3e■1 iii) R1 Rt-N@ CHtCHtCHz 503e(1)1
14: Rt R, -NH+propanesultone->R' -N -CHffi CHt CH2-5O
3HR chapter = GoR, -NΦ-CHyCHtCHt 503eiv
) R1 R, -N-A-SOsB+RsX 111 → R, -Nψ-A 5Ose+BXR8 111 → Rt N CHpCHt SOaHv
) R4 BΦ +H@OHH Examples of the polybasic acid compounds include adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecyldicarboxylic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, and tetrahydrophthalic anhydride. , hymic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrabromo phthalic anhydride, tetrachlorophthalic anhydride, het acid anhydride, etc., and one or more of these are used. The amount to be used is usually selected within the range of 2 to 90% of the total reaction components.

Examples of the polyhydric alcohols listed above include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexanediol, polyethylene glycol, dipropylene glycol, neopendel glycol,
Examples include triethylene glycol, hydrogenated bisphenol, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol, and one or more of these may be used. The amount to be used may be normally selected within the range of 0 to 90% of the total reaction components.

Examples of the oxirane compound include phenylglycidyl ether, methylglycidyl ether, n-butylglycidyl ether, persatic acid glycidyl ester, and α-olefin oxide, and one or more of these may be used. The amount used may be normally selected within the range of θ to 90% of the total reaction components.

[Effect]

The typical schematic structure of the oil-free polyester obtained as described above is classified by the alcohol valence of the amphoteric ionic compound as follows. (however,
represents a resin molecule with an ester bond chain. ) In the case of monovalent A or A SO3e 5Oae In the case of divalent 5O3e 5O3e S03e 5o3e Thus, since the oil-free polyester has the amphoteric ionic group in the molecule, its reactivity, surface activity, and electrochemical properties Furthermore, it has good solubility in various organic solvents, and has excellent miscibility with solvent-based resin compositions such as alkyd resin varnishes, acrylic resin varnishes, and melamine resin varnishes. It can fully demonstrate its functions and surfactant functions. The molecular weight of the oil-free polyester is not particularly limited, but when used in paint applications, Mn = 10,000 or less is suitable.

〔Effect of the invention〕

When used, for example, in paints, the oil-free polyester of the present invention exhibits the superior properties of ordinary oil-free polyesters, such as high hardness, flexibility, and In addition to excellent weather resistance, stain resistance, and chemical resistance, it is possible to add the characteristic functions of the amphoteric ionic group.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples and Reference Examples.

Example I 191 parts of hydroxyethyl taurine (parts by weight, the same applies hereinafter), 140 parts of ethylene glycol, 170 parts of triethylene glycol, and adipine were added to a 2 g Kolben equipped with a stirrer, nitrogen inlet tube, temperature control device, condenser, and decanter. 331 parts of acid, 168 parts of phthalic acid and 40 parts of xylene
Prepare the ingredients and raise the temperature. Water produced by the reaction is removed by azeotropic reflux with xylene. From the beginning of reflux Dn, the temperature was raised to 190°C over about 2 hours until the acid value equivalent to carboxylic acid was 10.
Stirring and dehydration were continued until the reaction was completed.

The obtained oil-free polyester had an acid value of 79, a hydroxyl value of 79, and an Mn of 708.

Example 2 139 parts of hydroxyethyl taurine, 110 parts of trimethylolpropane, 121 parts of phthalic anhydride, 308 parts of azelaic acid, and 27 parts of xylene were added to a 2 g Kolben equipped with a stirrer, a nitrogen inlet tube, a temperature controller, a condenser, and a decanter. 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 after the start of reflux, and the acid value equivalent to carboxylic acid was 1.
Stirring and dehydration are continued until the temperature reaches 45°C, and then cooled to 140°C.

Next, the temperature of the reaction solution was maintained at 140°C, and the
24J (α-olefin oxide manufactured by Daicel) 3
92 parts were added dropwise over 30 minutes, and stirring was continued for 2 hours to complete the reaction. The resulting oil-free polyester is
The acid value was 57, the hydroxyl value was 1O5, and the Mnf was 040.

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 Oil-free polyesters having the special values shown in the table are obtained using the raw materials shown in the table and according to the same method and conditions as in Example 2.

Reference Example 1 To 1 part of the oil-free polyester obtained in Examples 1 to 9, 9 parts of various solvents were added and heated to 50 to 80°C in a test tube, and then the solvent solubility of the polyester was determined while maintaining the temperature at 25°C. I looked into it. The solubility was determined based on the following criteria, and the results are shown in Table 1 (for comparison, the results for two types of zwitterionic compounds are also shown).

O: Uniformly dissolved.

Δ: Slight turbidity.

×: Phase separation or significant turbidity.

Note *) The abbreviations used in ingredient display are as follows.

Zwitterionic compound HET: Hydroxyethyltaurine HOCHICHIN・Ht CHt CHt S 03
eBHET: Bishydroxyethyltaurine (HOC
HzCH*)tN"HCHtCH*5OseTES:
) Lis(hydroxymethyl)methylaminoethanesulfonic acid (HOCHy)acN" HICH*CHtSOse)
[)ES: Hydroxyethylaminodiethanesulfonic acid HOCH! CHt N (CHt CHt S 03
H) tHSES: β-hydroxycetylaminoethanesulfonic acid CHs(CHt)+5CH(OH)CHtN” HtC
l-1tCH1SO3e Polybasic acid compound ADA: Adivic acid PAn: Phthalic anhydride AZA: Azelaic acid SBA: Sebacic acid TMAn: Trimellitic anhydride polyhydric alcohol EG: Ethylene glycol TEG: Triethylene glycol TMP: Trimethylol pronocent 6 -HDO: 1,6-hexanediol NPG: Neopentyl glycol oxirane compound CaE+or Cardura E1° (manufactured by Shell) (-
satic acid glycidyl ester) AOE-X24: rAOE-X24J (α-olefin oxide manufactured by Daicel Corporation) B G E : r Nissan Eveol BJ (butyl glycidyl ether manufactured by NOF Corporation) Reference Example 2 In Example 4.7 The obtained oil-free polyester, "Betsucosol 1323J (coconut oil modified alkyd resin manufactured by DIC, oil length 32%), [Beracolite M6402-5]
0J (oil-free alkyd resin manufactured by DIC Corporation) or Supervecamine J-820-60J (butylated melamine resin manufactured by DIC Corporation) at a ratio of 1:1, and the above polyester solvent-based resin composition. The miscibility was determined based on the following criteria, and the results are shown in Table 2 (the results of Comparative Example 1.2 are also listed as in Reference Example 1).

O: Uniformly mixed.

Δ: Slightly cloudy.

×: Phase separation or significant turbidity.

Claims (1)

[Claims] 1. There is a formula, ▲numeric formula, chemical formula, table, etc. in the molecule▼ [In the formula, A represents a C_1 to C_8 linear or branched alkylene group, phenylene group, or substituted phenylene group . ] An oil-free polyester characterized by having an aminosulfonic acid type amphoteric ionic group. 2. As the alcohol component in the reaction components, there are formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 must have at least one hydroxyl group and contain -O- or -COO- in the molecular group. There are also C_1 to C_2_0 alkyl groups, R_2 and R_
3 are the same or different from each other and are hydrogen atoms, C_1 to C
_2_0 alkyl group, an alkyl group or cyclic group having at least one hydroxyl group and/or sulfonic acid group, and A represents a C_1 to C_8 linear or branched alkylene group, phenylene group or substituted phenylene group. ] A hydroxyl group-containing aminosulfonic acid type zwitterionic compound represented by is used in an amount of 0.05 to 50% by weight based on the total reaction components, and a polybasic acid compound and, if necessary, a polyhydric alcohol and/or oxirane are used. When reacted with a compound, there are formulas, ▲mathematical formulas, chemical formulas, tables, etc. 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.