JPH02630A - Alkyd resin - Google Patents

Abstract

PURPOSE:To obtain an alkyd resin having an amphoteric ion, which can exhibit reactivity and surface activity differing according to the conditions of the environment and is useful for a coating composition, etc., by using a specified OH group-containing amphoteric compound as an alcohol component of the reactants. CONSTITUTION:An alkyd resin having an amphoteric group of formula II is obtained by using 0.05-30wt.%, based on the total reactant, OH group-containing amphoteric compound of formula I [wherein R1 is a 1-20 C alkyl having at least one OH group; R2-3 are each H, a 1-20 C alkyl or an alkyl or a cyclic group having at least one OH group and/or SO3H group; and A is a 1-6 C alkylene or a (substituted) phenylene group], e.g., N,N-bis-(2-hydroxyethyl) aminoethanesulfonic acid, as at least one alcohol component of the reactants and adopting starting materials, reaction conditions and systems of a usual alkyd resin as other conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel alkyd resin and a method for producing the same.

Introducing ionic functional groups into a polymer compound has a significant effect on the physical and chemical properties of the polymer compound.

Moreover, when such an ionic functional group is incorporated into a polymer compound rather than when used as a low-molecular compound, its properties appear more emphasized or complex. For this reason, research on polymeric compounds containing ionic functional groups has been actively conducted in recent years. There is increasing interest in polymer compounds having zwitterionic groups that exhibit chemical and biochemical properties.

An object of the present invention is to provide a novel alkyd resin having the above-mentioned amphoteric ionic group and a method for producing the same.

That is, the gist of the present invention is, firstly, that a resin molecule has the formula: c, where A represents a Cl-Cm linear or branched alkylene group, a phenylene group, or a substituted phenylene group.

Second, as one of the alcohol components in the reaction components, an alkyd resin characterized by having a zwitterionic group represented by the formula: [wherein R1 has at least one hydroxyl group] C20 alkyl group, R2 and R1 are the same or different and each represent a hydrogen atom, a Cl-02° alkyl group, an alkyl group or a cyclic group having at least one hydroxyl group and/or sulfonic acid group;
has the same meaning as above. ] 0.05 to 30% (wt%) of the total reaction components
, hereinafter the same) to obtain the above-mentioned alkyd resin.

The novel alkyd resin of the present invention has the above formula [I
] It is an alkyd resin having an amphoteric ionic group. Among the zwitterionic groups represented by the above formula [I], especially N
Those having at least one hydrogen atom as a substituent on an atom exist as a mixture of the following tautomers.

Moreover, the above-mentioned amphoteric ionic group changes its ionic form depending on the environment. For example, due to pH change, pH decreases.
Makes a large change in pH. Therefore, by controlling the environmental conditions, different reactivity, surface activity, electrochemical properties, etc. can be expressed.

In the method for producing the alkyd resin of the present invention, a hydroxyl group-containing reionizable compound represented by the above formula [I[] is added as one of the alcohol components in the reaction components to 0% of the total reaction components.
．． It is characterized in that it is used at a concentration of 0.05 to 30%, preferably 0.1 to 20%, and in other respects, ordinary alkyd resin raw materials and reaction conditions and methods may be employed. Such usual reaction conditions and methods include, for example, Kyozo Kitaoka, "Introduction to Synthetic Resins for Paints J" (published by Kobunshi Kankakai, May 25, 1974, pp. 92-127);

H. Solomon, Joan Wiley & Son, “
The Chemistry of Organic Film 7
The procedure is carried out according to the content described in "Omars" (pp. 75-87, 1967). That is, as reaction components, a, polyhydric alcohol, b, polybasic acid compound, C1 fatty acid and/or oil, and d, the above-mentioned hydroxyl group-containing reionizable compound are used, and these are carried out in an appropriate solvent as described below. The alkyd resin of the present invention is produced by carrying out an esterification reaction and, if necessary, a transesterification reaction, according to the same procedure as in the examples. In addition, in the alkyd resin of the present invention, as long as the reaction component d is used,
Also included are alkyd resins modified with various resins, such as rosin-modified alkyd resins, phenol-modified alkyd resins, epoxy-modified alkyd resins, vinyl-modified alkyd resins, isocyanate-modified alkyd resins, and silicon-modified alkyd resins.

The above-mentioned polyhydric alcohol may be one that is normally used as a raw material for alkyd resin, such as ethylene glycol, fluoropylene glycol, 1,3-butylene glycol, 1,6-hegylene glycol, diethylene glycol, dipropylene glycol, neo Pentyl glycol, triethyl glycol, 2,2-dimethyl-3
-Hydroxypropyl-2,2-dimethyl-3-hydroxypropione-1, hydrogenated bisphenol A1 bisphenol dihydroxypropyl ether, glycerin, trimethylolethane, trimethylolpropane, trishydroxymethylaminomethane, pentaerydrift , dipentaerythritol, etc., and these 1
The species or species are provided for use. The amount to be used is not particularly limited, but it should normally be selected within the range of 2 to 90% of the total reaction components.

The above-mentioned polybasic acid compound may be one commonly used as a raw material for alginic acid, such as phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid,
Azelaic acid, sebacic acid, tetrahydroheptalic anhydride, hegizahydrophthalic anhydride, tetrabromo heptalbutyric anhydride, tetrachlorophthalic anhydride, hetonic anhydride, himic anhydride, maleic anhydride, fumaric acid, itaconic acid,
Examples include trimellitic anhydride, methylcyclohegisene i-ricarboxylic anhydride, pyromellitic anhydride, and one or more of these may be used. The amount used is not particularly limited, but it should normally be selected within the range of 2 to 90% of the total reaction components.

The fatty acids in Reaction Component C may be ordinary ones, such as soybean oil fatty acids, linseed oil fatty acids, safflower oil fatty acids, 1-l oil fatty acids, coconut oil fatty acids, dehydrated castor oil fatty acids, and tungsten oil fatty acids. Oil fatty acids, synthetic fatty acids, etc.41
．． , or in place of such fatty acids, the oils to be used in conjunction with 17 may include conventional oils such as castor oil, coconut oil, linseed oil,
Examples include palm kernel oil, safflower oil, soybean oil, tung oil, dehydrated castor oil, and one or more of each.
Use the second one. The amount of reaction component C to be used is not particularly limited, but it is usually selected within the range of 1 to 80% of the total reaction components.

At 1° with the hydroxyl group-containing amphoteric compound,
For example, 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-ethylhegicyl)-N(2-hydroxyethyl)aminomethanesulfonic acid hydronic acid, N-decyl-N-(2-hydroxyethyl)aminomethanesulfonic acid, N-stearyl-N-(2hydroxyethyl)aminomethanesulfonic acid, etc.) and N
, N-dialkyl substituted product (N,N-dimethyl-N-
(2-Hydroxyethyl)ammoniomethanesulfonic acid betaine, N,N-jedyl N-(2-hydroxyethyl)ammoniomethanesulfonic acid betaine, N-methyl-N-dodecyl-N-(2-hydroxyethyl)ammoni betaine omethanesulfonate, etc.), N-(2-hydroxy-1-methylethyl)aminomethanesulfonic acid and its N-argyl substituted products and N,N-dialkyl substituted products, N-(2-hydroxypropyl)aminomethane Sulfonic acids and their N-alkyl substituted products and N.

N-dialkyl substituted product, N-(3-human Y-cogicibrovir)aminomethanesulfonic acid and its tri-alkyl substituted product and N,N-dialkyl substituted product, N-(2-propyl-2-hydroxyethyl)aminomethane N-alkyl-substituted and N,N-dialkyl-substituted sulfonic acids; N-dialkyl substituted product, 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-
Argyl substituted product B and N,N-dialkyl substituted product, N-
(1-Methyl-5,5-dimethyl-5-hydroxypentyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(1,2-diisopropyl-2-hydroxyethyl) Aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(2,3-dihydroxypropyl)
Aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(1-hydroxymethyl-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl products Substituted product, N-(1-hydroxymethyl-2-methyl-2-
hydroxyethyl)aminomethanesulfonic acid and its N-
Alkyl substituents and N,N-dialkyl substituents, N-
(1-hydroxymethyl-3-hydroxypropynolyaminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(1-(γ-hydroxypropyl)-2-hydroxyethyl)aminomethane Sulfonic 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 product and N, N-dialkyl substituted product, N-(2゜2-bis(hydroxymethyl)-3-hydroxypropyl)aminomethanesulfonic acid and its N-
Alkyl substituents and N,N-dialkyl substituents, N.

N-bis(2-hydroxyethyl)aminomethanesulfonic 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-hydroxybutynolyaminomethanesulfone) Acid and its N-alkyl substituted product, N-(2- and droxyethyl)-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-
(l-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 product (N-methyl-N-(2-hydroxyethyl)aminoethanesulfone L N-ethyl-N-(2-hydroxyethyl)aminoethanesulfonic acid, N -isopropyl-N-(2-hydroxyethyl)
Aminoethanesulfonic acid, N-(2-ethylhexyl)
-N-(2-hydroxyethyl)aminoethanesulfone M, N-decyl-N-(2-hydroxyethyl)aminoethanesulfone L N-stearyl-N-(2-hydroxyethyl)aminoethanesulfonic acid, etc.) and N ,
N-dialkyl substituted product (N, N-dimethyl-N-(2-
hydroxyethyl) ammonioethanesulfonic acid hetain, 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-(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 products and N,N-dialkyl substituted products, 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-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl- and N,N-dialkyl-substituted products, N-(2,3-dihydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituents and N,N-dialkyl substituents, N-(
1-hydroxymethyl-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted products and N,
N-dialkyl substituted product, 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 substituents and N,N-dialkyl substituents, 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 product, N-(2,2-bis(hydroxymethyl)-3-hydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, 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 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-
(1.1-(bishydroxymethyl)-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product, N,N,N-1-lis-(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))aminopropanesulfone a-(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-fN, N-diethyl-N-(2-hydroxyethyl))ammoniopropanesulfonic acid-(1) betaine, 3-(N-methyl-N-dodecyl-N-(2-hydroxyethyl))ammonio Propanesulfonic 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 product and N,N-dialkyl substituted product, 3-(N-(2-propyl-2- and droxyethyl))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 products, 3-(N-(1
, 1,2,2-tetramethyl-2-hydroxyethyl)
) Aminopropanesulfone li&-(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 product and N,N-dialkyl substituted product,
3-(N-(1,2 diisopropyl-2-hydroxyethyl))aminopropanesulfonic acid-(1) and its N-
Alkyl substituents and N,N-dialkyl substituents, 3-
(N-(2,3-dihydroxypropyl))aminopropanesulfonic acid-(1) and its N-alkyl substituted products and N,N-dialkyl substituted products, 3-(N-(1-hydroxymethyl-2-hydroxy ethyl)) aminopropane sulfone 1l-(1) and its N-alkyl substituted products and N,N-dialkyl substituted products, 3-(N-(1-hydroxymethyl-2-methyl-2-hydroxyethyl))aminopropane Sulfonic 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 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))aminopropanesulfone fi-(1) and its N-alkyl substituted product and N,N-dialkyl substituted product, 3-( N-(
2,2-bis(hydroxymethyl)-3-hydroxypropyl))aminopropanesulfonic acid-(1) and its N
-alkyl substituents and N,N-dialkyl substituents, 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))ammoni Opropanesulfonic 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), 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゜l)
-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=(l-(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 substituent, 3-(N.

N,N-1-lis=(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-IN-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-(2hydroxyethyl))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))aminopentanesulfone [1-(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))ammoniopentanesulfone a-(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)ammoniopentanesulfone fl-(1) Betaine, N-(2-hydroxyethyl)iminodiethanesulfonic acid, N-(2-
hydroxypropyl)iminodiethanesulfonic acid, N-
(2,3-dihydroxypropyl)iminodiethanesulfonic acid, N-(1゜l-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, N-(2-hydroxyethyl)
Ortanilic acid, N-(2-hydroxyethyl)methanilic acid, N-(2-hydroxyethyl)sulfanilic acid, N
, N-bis-(2-hydroxyethyl)orthanylic acid,
NlN-bis(2-hydroxyethyl)methanilic acid%N
+N-bis-(2-hydroxyethyl)sulfanilic acid, etc., and one or more of these may be used. The amount used is selected in the range of 0.05 to 30%, preferably 0.1 to 20% of the total reaction components. 0.05%
If it is less than 30%, the reactivity, surface activity, and electrochemical properties of the alkyd resin of the present invention will not be sufficiently expressed; and if it exceeds 30%, the viscosity of the alkyd resin of the present invention will tend to increase, making storage difficult. Stability deteriorates. Such a hydroxyl group-containing reionizable compound may be used as it is or as a salt with a basic substance (eg, ammonia, organic amine, alkali metal). Furthermore, when calculating the addition of this amphoteric compound to the alkyd resin of the present invention, the compound may be calculated as an alcohol component. That is, if the total number of hydroxyl groups in one molecule is one, it is a monohydric alcohol, and if there are two, it is a dihydric alcohol.
In the case of 3, it is calculated as trihydric alcohol, and in the case of n, it is calculated as zero hydric alcohol.

A typical structural example of the alkyd resin of the present invention, calculated as such a mono- to trihydric alcohol, is as follows when modeled around the amphoteric ionic group of the above formula [I].

(However, represents a resin molecule having an ester bond chain.) In case of monovalent case In case of divalent case A conventional method may be adopted as a method for synthesizing the above-mentioned hydroxyl group-containing reionizable compound, for example, the following reaction method. can be mentioned.

I? .

R, -NH + CH, O + hydrogen sulfite (BH3O3:B
is HalL NH4, etc.) → R1-N CH2-5O3B → R+ N CH2CH2S03BH (b) R1-old H+HO-CHICH, -5o,
B→Rr N CH2CH25O3Bp+ (c) R1-^H+CH2-CH-5O,R(R:
Alkyl group) → R, -N-CH2CH2-5O3R →
Rt-N-CH2CH2-3OsH0R, -N'''-
CH2CH2So? R, -NH+propanesultone→Rr N CH2CH2CH25OsHp.

iV) Rr N A 5O3B + RsXr? .

V) HN A 5O3B +R' CH2CHCH2N2 The alkyd resin of the present invention exhibits good pigment dispersibility, shortens the dispersion time and reduces the viscosity of the adjusted pigment paste compared to ordinary alkyd resins that do not have zwitterionic groups. This also contributes to the formation of a colored coating film with good color tone.

The coating composition containing the alkyd resin of the present invention has the alkyd resin as a main component, and if necessary, conventional organic or inorganic coloring pigments, extender pigments, antirust pigments, and other additives. (fillers, extenders, thickeners, etc.), and further mix appropriate amounts of surface conditioners, dryers, organic solvents, etc.
Prepared by dispersion mixing at room temperature. A coating film is formed by applying such a composition to an object to be coated in a conventional manner to a film thickness of 5 to 500 μm, and then drying at room temperature.

Of course, this composition can be dried by baking instead of or in addition to drying at room temperature.

The thermosetting resin composition has the alkyd resin and aminoplast resin as main components.

The above-mentioned aminoplast resin may be a usual one, for example, one or more of melamine resin, guanamine resin, urea resin, etc. can be used as it is or, if necessary, dissolved in an organic solvent for convenient use. Just offer it. The amount of such aminoplast resin used is not particularly limited, but is usually 5 to 10 parts per 100 parts of the above alkyd resin.
0 parts, preferably in the range of 7 to 90 parts. If the amount is less than 5 parts, a sufficient crosslinked film will not be formed, resulting in unsatisfied solvent resistance and chemical resistance, and if it exceeds 100 parts, the formed film will tend to become too brittle.

The above-mentioned alkyd resin and aminoplast resin or a solution thereof are blended in a predetermined ratio and mixed with stirring at room temperature to prepare a desired resin composition. In such a resin composition, the amphoteric ionic group in the alkyd bulking agent effectively causes a crosslinking reaction with the aminoplast resin, and also promotes the crosslinking reaction between the carpoxyl group or hydroxyl group in the alkyd resin and the aminoplast resin. It has an effect. For this reason, baking drying for film formation does not require conditions such as high temperatures and long periods of time as with compositions using ordinary alkyd resins, but mild conditions such as 30 seconds to 120 minutes at a temperature of 70 to 220°C are used. It's okay to be. Further, under the baking conditions of the same temperature and time, a three-dimensional film in which the crosslinking reaction has progressed more can be obtained compared to the above-mentioned ordinary composition. In this way, the resin composition forms a highly durable film by thermosetting while contributing to saving energy resources. That is, it can be widely used as a raw material for thermosetting molding processing, and is particularly useful for use in bake-drying paint compositions, and in this case, the type of material to be coated can be metal, wood, paper thread, or plastic. It becomes possible to apply it widely.

The above-mentioned bake-drying paint composition may contain conventional organic or inorganic coloring pigments, extender pigments, anti-rust pigments, and other additives (fillers, extenders, thickeners, etc.) in the resin composition. ), and further mixed with an appropriate amount of at least one of a surface conditioner, an organic solvent, etc., and is prepared by dispersing and mixing at room temperature. The composition is applied to the object to be coated to a film thickness of 5 to 500 mm by a conventional method.
By painting with μ and then baking drying, the appearance,
A three-dimensional coating film with good durability is formed. In particular, when using various pigments, mix an appropriate amount of the alkyd resin of the present invention, the pigment, and an organic solvent as necessary, disperse and mix at room temperature, and then add the remaining alkyd resin of the present invention, aminoplast resin, and other additives. The coating composition can also be prepared by mixing and stirring the following.

This coating composition has the same low-temperature baking effect without impairing the reaction accelerating effect seen in the resin composition described above.

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

Example 1 (First stage reaction) 994 parts of linseed oil, 188 parts of pentaerythritol, and 15 parts of lead naphthenate were charged into a 2ρ Kolben equipped with a stirrer, a nitrogen inlet tube, a temperature control device, a condenser, and a decanter. Temperature 240°C under nitrogen atmosphere
When the mixture was stirred for 30 minutes, the methanol tolerance became infinite. (Second stage reaction) The temperature of the contents is 1
The temperature was lowered to 50°C, stirring was stopped, and 321 parts of phthalic anhydride and N
, 5.5 parts of N-bis-(2-hydroxyethyl)aminomethanesulfonic acid and 45 parts of xylene were charged. Stirring was started again, and while the temperature was gradually raised, the generated water was removed by azeotropic reflux with xylene. The temperature was raised to 240° C. over about 2 hours, and stirring and dehydration were continued at the same temperature until the acid value equivalent to carboxylic acid reached 8 to complete the reaction. The obtained resin had an oil length of 65, an acid value of 85, a hydroxyl value of 50, and a number average molecular weight (CMn) of 1,800. This resin was diluted with xylene to obtain an alkyd varnish with a nonvolatile content of 70%.

The viscosity of this varnish is Z on a Gardner viscometer.

Examples 2 to 9 and Comparative Examples 1 to 2 Alkyd resin varnishes shown in Table 1 were obtained in the same manner as in Example 1, except that the raw materials shown in Table 1 were used in the amounts shown in Table 1.

(continuation) Note) Abbreviations in the table are as follows.

HOCH2CH2 \ SO: Soybean oil / HO-CH2CH2 N-CH2CH2-3o3H DCO: Dehydrated castor oil Y○: Coconut oil L○: Linseed oil PE: Pentaerythritol TMP: l-limethylolpropane IAN: Phthalic anhydride IPA: Isophthalic acid ADA: Adipic acid EG: Ethylene glycol DEG Nidiethylene glycol Among the amphoteric compounds of *, ■: N-(2,3-dihydroxypropyl)aminopropanesulfonic acid.

■: N-(1,1-bis-(hydroxymethyl)-2
-hydroxyethyl)aminoethanesulfone H20H HOCHz-CNHCH2CH25OsHH20H ■: N,N,N-tris-(2-hydroxyethyl)
Betaine ammoniopropanesulfonate.

HOCH, CH.

■: N-(2,3-dihydroxypropyl)-N-octylaminoethanesulfonic acid.

CH2-CH-CH2-NH-CH2CH2CH, -3
o, HOHOH ■: N,N-bis-(2-hydroxyethyl)aminoethanesulfonic acid.

■: N-(3-hydroxypropyl)-N-(1,1
-bis-(hydroxymethyl)-2-hydroxyethyl)aminoethanesulfonic acid.

HOCH2CHICH2 \ / HOCH! Example 1O In a 2a Kolben equipped with a stirrer, nitrogen inlet tube, temperature control device, condenser, and decanter, 81 parts of dehydrated castor oil fatty acid, 59 parts of coconut oil fatty acid, 121 parts of trimethylolpropane, 715% of phthalic anhydride, Diethylene glycol 481%, N-methyl-N-(1-hydroxymethyl-2-hydroxyethyl)aminomethanesulfonic acid 80%
1 part and 45 parts of xylene were added, and the temperature was raised to 24 parts while stirring.
Raised to 0°C. The reaction was continued while the produced water was removed by azeotropic reflux with xylene, and the reaction was terminated when the acid value equivalent to the carboxylic acid reached 8. The obtained resin has an oil length l
The O1 acid value was 22.5, the hydroxyl value was 100, and the Mn was 800. This resin was diluted with xylene to obtain an alkyd varnish with a non-volatile content of 60%. The viscosity of this varnish was Z.

Examples 11-14 and Comparative Example 3 Example IO except that the raw materials in Table 2 were used in the amounts shown in Table 2.
The alkyd resin varnish shown in Table 2 was obtained in the same manner as above.

Note: In the table, DCOFA represents dehydrated castor oil fatty acid, YFA represents coconut oil fatty acid, and for other abbreviations, see the notes to Table 1 above.

Further, among the amphoteric compounds marked with *, (1): N,N-dimethyl-N-(2- and droxyethyl)ammoniopropanesulfonate hetain.

r■.

CH.

■: N-(2-hydroxyethyl)iminodiethanesulfonic acid.

＼ CHxCHt 503H Reference Example 1 158 parts of the alkyd resin face obtained in Example 2, 8° 5 parts of butylated melamine resin varnish (Super Beckamine G-821-60J, manufactured by Dainippon Ink Co., Ltd.), and petroleum solvent (Tonen Co., Ltd.) A thermosetting resin composition was prepared by stirring and mixing 100 parts of "Tsurupets-100J" (manufactured by Sekiyu Co., Ltd.) at room temperature using a lab mixer.
Paint it to 0μ and heat it to 100°C! 1120℃, 1
A transparent coating film was obtained by heat curing at a temperature of 40°C and 160°C for 20 minutes, respectively. This coating film was extracted with acetone for 4 hours using a Soxhlet extractor, and the result was 68% for the 100°C cured film, 88% for the 120°C cured film, 92% for the 140°C cured film, and 96% for the 160°C cured film. % remained.

Reference Example 2 Instead of using the alkyd resin varnish obtained in Example 2, 117 parts of the alkyd resin varnish obtained in Example 3 was used, and "Reference Example 1 except that 50 parts of Super Beckamine G-821-60J was used. A thermosetting resin composition was prepared in the same manner as above.This composition was coated on a tin plate to a dry film thickness of 40 mm.
It was coated to give a transparent coating film. The pencil hardness of this product was H and the crosslinking density was 2.08XIO-3 mol/C.

Comparative Example 4 A transparent coating film was obtained in the same manner as in Reference Example 2, except that the alkyd resin varnish obtained in Comparative Example 2 was used instead of the alkyd resin varnish obtained in Example 3. The pencil hardness of this product is HB and the crosslink density is l.

22XlO-'mol/cry''.

Reference Example 3 Instead of using the alkyd resin varnish obtained in Example 2, Examples 4, 5.6.8, 9, 10.11.12, 13 were used.
．． 133 parts of the resin obtained in Example 14 (133 parts of the resin obtained in Example 8)
14 parts), [Super Beckamine G-821-60
Various transparent coating films were obtained in the same manner as in Reference Example 1 except that 33 parts of J were used and the thermosetting temperature was 120°C. The residual content after acetone extraction using a Soxhlet extractor was 87% or more.

Reference Example 4.5 and Comparative Example 5 To 50 parts of the alkyd resin varnish obtained in Example 1.7 and Comparative Example 1, 27 parts of titanium oxide pigment ("Tie Bake R-820J" manufactured by Mihara Sangyo Co., Ltd.) and calcium carbonate pigment were added. (
"Heavy Charcoal" manufactured by Maruo Calcium Co., Ltd.) 10 parts, lead naphthenate 0
．． 3 parts and 8 parts of an aliphatic hydrocarbon mixed solvent (Nippon Oil Co., Ltd. "Tokutsuru"), and paint conditioner 3
A white paint composition was obtained by dispersion for 0 minutes. This material was coated on a steel plate to a dry film thickness of 40 μm, and the properties when dried at room temperature are shown in Table 3.

Table 3 Note: “Image sharpness” was determined visually.

Reference Example 6 225 parts of the alkyd resin varnish obtained in Example 3 was added with an anthraquinone red pigment (Ciba Co., Ltd. "Chromophthane Red A").
3BJ), 132 parts of xylene, and 53 parts of ethylene glycol monobutyl ether were added and mixed and dispersed for 2 hours using a paint conditioner to obtain a red pigment dispersion paste with coarse particles of 5 μm.

28 parts of the above pigment dispersion paste, 40 parts of the alkyd resin varnish obtained in Example 3 and "Super Beckamine G-821-
Add 28 parts of 60J while stirring with a lab mixer,
A red thermosetting coating composition was obtained by mixing for a minute.

The above coating composition was applied onto a steel plate previously coated with an alkyd-melamine type intermediate coating paint (rOTO-7784 manufactured by Nippon Paint Co., Ltd.) so that the dry film thickness was 40 μm.
Bake dry by placing in a baking oven set at ℃ for 20 minutes,
A red coating was obtained.

For comparison purposes, the alkyd resin varnish obtained in Comparative Example 2 was used instead of the alkyd resin varnish obtained in Example 3, and the red pigment dispersion paste and paint were prepared in the same manner except that the mixing and dispersion in a paint conditioner was carried out for 3 hours. A composition and a baked coating were obtained.

Table 4 shows the properties of the paste, coating composition, and coating film.

Table 4 Note) Viscosity was measured at 25°C using a Brookfield viscometer (H type).

V2: Viscosity when the number of rotations is 2r, p, m v2゜Viscosity when the number of rotations is 2Q r, p, m TI: V,
/V.

Gloss was measured using a 60° gloss meter.

Water resistance is determined by the appearance of the coating film after immersion in 40°C warm water for 15 days.

HCQ resistance was determined by the appearance of the coating after placing a glass cylinder on the coated plate, adding approximately 1 cc of 1N hydrochloric acid, and leaving it in an atmosphere at a temperature of 55°C for 1 hour.

Reference Example 7 70 parts of the alkyd resin varnish obtained in Example 12 was added with a perylene red pigment (“Pariogen Maroon 40” manufactured by BASF).
20J) 47 copies, “Tsurupets-100” 69 copies, n-
14 parts of butanol was added and mixed and dispersed using a paint conditioner for 2 hours to obtain a red pigment paste with coarse particles of 5 μm.

28 parts of the above pigment paste, 40 parts of the alkyd resin varnish obtained in Example 12 and "Super Beckamine G-821-6"
28 parts of 0J was added while stirring with a lab mixer and mixed for 20 minutes to obtain a red thermosetting coating composition.

The above coating composition was coated with rOTo-778J in advance.
; Paint on a steel plate so that the dry film thickness is 40μ,
It was baked and dried by placing it in a baking oven set at 40°C for 20 minutes to obtain a red coating film.

For comparison purposes, the alkyd resin varnish obtained in Comparative Example 3 was used instead of the alkyd resin varnish obtained in Example 12,
A red pigment paste, a paint composition, and a baked paint film were obtained in the same manner except that mixing and dispersion in a paint conditioner was carried out for 3 hours.

Table 5 shows the properties of the above coating composition and coating film.

Table 5 Patent applicant: Nippon Paint Co., Ltd. Representative patent attorney: 1 person, Aohaku Sogai

Claims (1)

[Claims] 1. Formula in the resin molecule: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] [In the formula, A is a C_1 to C_6 linear or branched alkylene group, phenylene group, or substituted Represents a phenylene group. ] An alkyd resin characterized by having a zwitterionic group represented by the following. 2. As one of the alcohol components in the reaction components, the formula: ▲Mathematical formula, chemical formula, table, etc.▼ [II] [In the formula, R_1 is an alkyl group of C_1 to C_2_0 having at least one hydroxyl group, 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_6 linear or branched alkylene group, phenylene group or substituted phenylene group. ] A hydroxyl group-containing amphoteric compound represented by 0.05 to 30% by weight of the total reaction components is used, and the resin molecule contains the formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] [In the formula , A has the same meaning as above] A method for producing an alkyd resin, which comprises obtaining an alkyd resin having an amphoteric ionic group.