JPS6219219B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the use of polyester resins having aminosulfonic acid type zwitterionic groups, more specifically,
The present invention relates to an emulsifier made of the polyester resin.

The present inventors have created a new polyester resin (alkyd type, oil-free type) having a specific zwitterionic group, and have already applied for a patent for this (Japanese Patent Application No. 110865-1983, ―56048
issue).

Such polyester resin has the formula, [In the formula, A represents a C ₁ to C ₆ linear or branched alkylene group, phenylene group, or substituted phenylene group. ] Those having an aminosulfonic acid type zwitterionic group shown in the following, especially oil-free systems have good solubility in various organic solvents and are also excellent in miscibility with solvent-based resin compositions, and have an aminosulfonic acid type zwitterionic group. It is said to be useful because it fully exhibits its reaction catalytic function and surfactant function.

As a result of intensive research into the uses of such polyester resins, the present inventors found that when emulsifying and dispersing water-insoluble or sparingly soluble substances in water,
It was discovered that a uniform and stable emulsion could be obtained by using the above polyester resin as an emulsifier,
The present invention has now been completed.

That is, the gist of the present invention resides in a polymer emulsifier characterized by containing the above-mentioned polyester resin as a main component.

The above-mentioned polyester resin used in the present invention has, as an alcohol component in its reaction components,
formula, [In the formula, R ₁ is a C ₁ to C ₂₀ alkyl group that has at least one hydroxyl group and may contain -O- or -COO- in the molecular group, R ₂ and
R ₃ is the same or different and hydrogen atom, C _1
-C20 alkyl group, alkyl group or cyclic group having at least one hydroxyl group and/or sulfonic acid group, and A have the same meaning as above. ] Except for using the hydroxyl group-containing aminosulfonic acid type zwitterionic compound (hereinafter simply referred to as zwitterionic compound), it may be produced by adopting the raw materials and reaction conditions/methods of ordinary polyester resins. Specifically, it can be produced by subjecting the reaction components to an esterification reaction and, if necessary, a transesterification reaction, in a suitable solvent according to the procedure described in Reference Examples described later.

In addition, specific examples of the reaction components of the polyester resin and their usage amounts are as follows.

Oil-free system a Zwitterionic compound 0.05-50% (wt%, the same applies hereinafter), preferably 0.5-30%, b Polybasic acid compound 2-90%, if necessary c Polyhydric alcohol 0-90% and/ or d oxirane compound 0-90%.

Alkyd-based a zwitterionic compound 0.05-30%, preferably
0.1-20%, b polybasic acid compound 2-90%, c polyhydric alcohol 2-90%, d fatty acid and/or oil 1-80%.

Examples of the above-mentioned amphoteric ionic compound include N-
(2-hydroxyethyl)aminosulfonic 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) and N,N-dialkyl substituted products (N,N-dimethyl-N-(2-hydroxyethyl)ammoniomethanesulfonic acid betaine, N,N'-diethyl-N
-(2-Hydroxyethyl)ammoniomethanesulfonic acid betaine, N-methyl-N-dodecyl-
N-(2-hydroxyethyl)ammoniomethanesulfonic acid betaine, etc.), N-(2-hydroxy-1-methylethyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N -(2-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 product, N-(2-propyl-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, N
-(2-methyl-2-ethyl-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-
(1,2-dimethyl-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(1,
1,2,2-tetramethyl-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N'dialkyl substituted products, N-
(1-Methyl-5,5-dimethyl-5-hydroxypentyl)aminomethanesulfonic acid and its N-
Alkyl substituted product and N,N-dialkyl substituted product, N-(1,2-diisopropyl-2-hydroxyethyl)aminomethanesulfonic 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 products, N-(1-hydroxymethyl-2-methyl-2-hydroxyethyl)
Aminomethanesulfonic acid and its N-alkyl and N,N-dialkyl substituted products, N-(1-
Hydroxymethyl-3-hydroxypropyl)aminomethanesulfonic acid and its N-alkyl- and N,N-dialkyl-substituted products, N-(1-
(γ-Hydroxypropyl)-2-hydroxyethyl)aminomethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, 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 substituted products and N,N-dialkyl substituted products, 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 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(hydroxyethyl)-2-hydroxyethyl)aminomethanesulfonic acid and Its N-alkyl substituent, N,N
-bis(2,3-dihydroxypropyl)aminomethanesulfonic acid and its N-alkyl substituted product,
N,N-bis-(1-hydroxyethyl)-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)aminoethanesulfonic acid, N- Ethyl-N-(2-hydroxyethyl)aminoethanesulfonic acid, N-isopropyl-N-(2-hydroxyethyl)aminoethanesulfonic acid, N-(2-ethylhexyl)-N-
(2-hydroxyethyl)aminoethanesulfonic acid, N-decyl-N-(2-hydroxyethyl)
Aminoethanesulfonic acid, N-stearyl-N-
(2-hydroxyethyl)aminoethanesulfonic acid, etc.) and N,N-dialkyl substituted products (N,
N-dimethyl-N-(2-hydroxyethyl)ammonioethanesulfonic acid betaine, N,N-diethyl-N-(2-hydroxyethyl)ammonioethanesulfonic acid betaine, N-methyl-N-
dodecyl-N-(2-hydroxyethyl)ammonioethanesulfonic acid betaine, etc.), N-(2-hydroxyethyl),
-Hydroxy-1-methylethyl)aminoethanesulfonic acid and its N-alkyl substituted products and N,
N-dialkyl substituted product, N-(2-hydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, N
-(3-hydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted products and N,N-
Dialkyl substituted product, N-(2-propyl-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, N-(2-methyl-2-ethyl-2-hydroxy ethyl)aminoethanesulfonic acid and its N
-Alkyl substituted product and N,N-dialkyl substituted product, N-(1,2-dimethyl-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, N-
(1,1,2,2-tetramethyl-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products,
N-(1-methyl-5,5-dimethyl-5-hydroxypentyl)aminoethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(1,2-diisopropyl-2-hydroxy ethyl)aminoethanesulfonic acid and its N
-alkyl substituted product and N,N-dialkyl substituted product, N-(2,3-dihydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, N-(1-hydroxymethyl -2-hydroxyethyl) aminoethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(1-hydroxymethyl-2-methyl-2-hydroxyethyl)
Aminoethanesulfonic acid and its N-alkyl substituted products and N,N-dialkyl substituted products, N-(1-
Hydroxymethyl-3-hydroxypropyl)aminoethanesulfonic acid and its N-alkyl- and N,N-dialkyl-substituted products, N-(1-
(γ-hydroxypropyl)-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product and N,N-dialkyl substituted product, 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 substituted products and N,N-dialkyl substituted products, N,N-bis(2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted products (N -Methyl-N,N-bis(2-hydroxyethyl)ammonioethanesulfonic acid betaine, N-ethyl-N,N-bis(2-hydroxyethyl)ammonioethanesulfonic acid betaine, N-butyl-N,N -bis(2-hydroxyethyl)ammonioethanesulfonic acid betaine,
N-dodecyl-N,N-bis(2-hydroxyethyl)ammonioethanesulfonic acid betaine, N
-stearyl-N,N-bis(2-hydroxyethyl)ammonioethanesulfonic acid betaine, etc.), N-(2-hydroxyethyl)-N-(2
-Hydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted product, N,N-bis(2-
hydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted product, N,N-bis(4-hydroxybutyl)aminoethanesulfonic acid and its N-alkyl substituted product, N-(2-hydroxyethyl)-N-( 1,1-bis(hydroxymethyl)
-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product, N-(3-hydroxypropyl)-N-(1,1-bis(hydroxymethyl)-2-hydroxyethyl)aminoethanesulfonic acid and Its N-alkyl substituent, N,N
-bis(2,3-dihydroxypropyl)aminoethanesulfonic acid and its N-alkyl substituted product,
N,N-bis-(1-(hydroxymethyl)-2
-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product, N,N-bis-(1,
1-(bishydroxymethyl)-2-hydroxyethyl)aminoethanesulfonic acid and its N-alkyl substituted product, N,N,N-tris-(2-hydroxyethyl)ammonioethanesulfonic acid betaine, N,N- Bis(2-hydroxyethyl)-N
-(3-Hydroxypropyl)ammonioethanesulfonic acid betaine, N,N,N-tris(3-
hydroxypropyl)ammonioethanesulfonic acid betaine, 3-{N-(2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted product (3-{N-methyl-N-(2- 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 substituted product 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 products and N,N-dialkyl substituted products, 3-{N-(2-
propyl-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted products and N,N-dialkyl substituted products, 3-{N-(2
-Methyl-2-ethyl-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-
Alkyl substituted product and N,N-dialkyl substituted product, 3-{N-(1,2-dimethyl-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted product and N,N- Dialkyl substituted product, 3-{N-(1,1,2,2-tetramethyl-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted product and N,N-dialkyl substituted product , 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 substituted products and N,N-dialkyl substituted products, 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 and N ，
N-dialkyl substituted product, 3-{N-(1-hydroxymethyl-2-methyl-2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-
Alkyl substituted product and N,N-dialkyl substituted product, 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)}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 product and N,N-dialkyl substituted product, 3-
{N,N-bis(2-hydroxyethyl)}aminopropanesulfonic acid-(1) and its N-alkyl substituted product (3-{N-methyl-N,N-bis(2-hydroxyethyl)}ammonio Propanesulfonic 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-(1) and its N-alkyl substituted product, 3-
{N-(2-hydroxyethyl)-N-(1,1
-bis(hydroxyethyl)-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 substitution body, 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 that 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-hydroxyethylpropyl)}ammoniopropanesulfonic acid-(1) Betaine, 5-{N-(2-hydroxyethyl)}aminopentanesulfonic acid -(1) and its N-alkyl substituted product (5-{N-methyl-N-(2-hydroxyethyl)}aminopentanesulfonic acid-(1), 5-
{N-ethyl-N-(2-hydroxyethyl)}aminopentanesulfonic acid-(1), 5-{N-isopropyl-N-(2-hydroxyethyl)}aminopentanesulfonic acid-(1), 5- {N-(2-ethylhexyl)-N-(2-hydroxyethyl)}
Aminopentanesulfonic acid (1), 5-{N-decyl-N-(2-hydroxyethyl)} Aminopentanesulfonic acid (1), 5-{N-stearyl-N
-(2-hydroxyethyl)}aminopentanesulfonic acid-(1), etc.) and N,N-dialkyl substituted products (5-{N,N-dimethyl-N-(2-hydroxyethyl)}ammoniopentanesulfonic acid -(1)Betaine, 5-{N,N-diethyl-N-
(2-Hydroxyethyl)ammoniopentanesulfonic acid-(1) betaine, 5-{N-methyl-N-
dodecyl-N-(2-hydroxyethyl)}ammoniopentanesulfonic acid-(1) betaine, etc.),
5-{N,N-bis-(2-hydroxyethyl)}aminopentanesulfonic acid-(1) and its N-
Alkyl substituted product (5-{N-methyl-N,N-bis(2-hydroxyethyl)}ammoniopentanesulfonic acid-(1) betaine, 5-{N-ethyl-
N,N-bis(2-hydroxyethyl)}ammoniopentanesulfonic acid-(1)betaine, 5-{N
-Butyl-N,N-bis(2-hydroxyethyl)}ammoniopentanesulfonic acid-(1)betaine, 5-{N-dodecyl-N,N-bis(2-hydroxyethyl)}ammoniopentanesulfonic acid -(1)Betaine, 5-{N-stearyl-N,N
-bis(2-hydroxyethyl)}ammoniopentanesulfonic acid-(1)betaine, etc.), 5-
{N,N,N-tris-(2-hydroxyethyl)}ammoniopentanesulfonic acid-(1) betaine, N-(2-hydroxyethyl)iminodiethanesulfonic acid, N-(2-hydroxypropyl)imino Diethanesulfonic 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, N-(2-hydroxyethyl)orthanylic acid,
N-(2-hydroxyethyl)methanilic acid, N-
(2-hydroxyethyl)sulfanilic acid, N,
Examples include N-bis-(2-hydroxyethyl)orthanilic acid, N,N-bis-(2-hydroxyethyl)methanilic acid, N,N-bis-(2-hydroxyethyl)sulfanilic acid, and these 1 The species or species are provided for use. Such amphoteric ionic compounds may be used as they are or as a salt with a basic substance (eg, ammonia, amine, alkali metal).

Examples of the polybasic acid compounds include adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecyldicarboxylic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, tetrahydrophthalic anhydride, hymic anhydride, trimellitic acid, pyromellitic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride,
Examples include hectic anhydride, and one or more of these may be used.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexanediol,
Diethylene glycol, dipropylene glycol, neopentyl glycol, triethylene glycol, hydrogenated bisphenol, glycerin, trimethylolethane, trimethylolpropane,
Examples include pentaerythritol, and one of these
Use one species or two or more species.

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.

Examples of the above-mentioned fatty acids include soybean oil fatty acids, linseed oil fatty acids, safflower oil fatty acids, tall oil fatty acids, coconut oil fatty acids, dehydrated castor oil fatty acids, tung oil fatty acids, synthetic fatty acids, and in place of or in combination with such fatty acids. Examples of the above-mentioned oils include castor oil, coconut oil, linseed oil, palm kernel oil, safflower oil, soybean oil, tung oil, dehydrated castor oil, etc., and one or more of each can be used. .

The polymer emulsifier according to the present invention is composed of a polyester resin obtained as described above, and particularly has an acid value of 30 to 150, preferably 40 to 150, and a number average molecular weight (hereinafter referred to as M) of 500. ~5000,
Preferably, it should be set in the range of 700 to 3000. By adjusting the balance between the molecular weight and the hydrophilic functional groups in this manner, various properties such as foaming properties, emulsifying and dispersing properties as an emulsifier are improved. Further, the polyester resin may be used in a state in which at least 30 or more of its acid groups are neutralized with ammonia, an amine (preferably a tertiary amine), or an alkali metal. Such a neutralized state improves solubility in water.

Such an emulsifier is a novel polysoap type emulsifier, and is capable of stably emulsifying polymer particles, for example.

In addition, as conventional polymer emulsifiers, there are known ones that are mainly composed of unsaturated polyesters obtained by the esterification reaction of long-chain unsaturated dibasic acids and dihydric alcohols (Japanese Patent Laid-Open No. 126290/1983). ), but this does not have the reaction catalytic function of the zwitterionic group as in the present invention.

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

Reference Example 1 In a two-colben equipped with a stirrer, nitrogen inlet tube, temperature control device, condenser, and decanter, 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. 331 parts, phthalic anhydride
Charge 168 parts and 40 parts of xylene and raise the temperature.
Water produced by the reaction is removed by azeotropic reflux with xylene. The temperature is increased over approximately 2 hours from the start of reflux.
The temperature was raised to 190°C, and stirring and dehydration were continued until the acid value equivalent to carboxylic acid became 10 or less to complete the reaction. The resulting polyester resin has an acid value of 79 and a hydroxyl value.
79, M708.

Reference Example 2 134 parts of bishydroxyethyl taurine, 130 parts of neopentyl glycol, 236 parts of azelaic acid, 186 parts of phthalic anhydride, and 27 parts of xylene were added to a 2-colben equipped with a stirrer, a nitrogen inlet tube, a temperature control device, 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 is raised to 190°C over about 2 hours from the start of refluxing, stirring and dehydration are continued until the acid value equivalent to carboxylic acid reaches 145, and the mixture is cooled to 140°C.

Next, while maintaining the temperature of the reaction solution at 140° C., 314 parts of “Cardilla E10” (Versatellite glycidyl ester manufactured by Shell) was added dropwise over 30 minutes, and stirring was continued for 2 hours to complete the reaction. The obtained polyester resin has an acid value of 59, a hydroxyl value of 90, and an M
It was 1054.

Reference Example 3 Same method and conditions as in Reference Example 1 except that 340 parts of β-hydroxyethylaminodiethanesulfonic acid, 94 parts of neopentyl glycol, 340 parts of azelaic acid, and 226 parts of "Cardilla E10" were used as reaction components. Accordingly, a polyester resin having an acid value of 62, a hydroxyl value of 62, and M908 is obtained.

Reference Example 4 85 parts of dehydrated castor oil, 63 parts of coconut oil, and 53 parts of trimethylolpropane were charged into a 2-kolben equipped with a stirrer, nitrogen inlet tube, temperature control device, condenser, and decanter, and the temperature was brought to 240°C under a nitrogen atmosphere. ℃
After stirring for 30 minutes, the methanol tolerance became infinite. The temperature of the contents is 150℃
725 parts of phthalic anhydride, 343 parts of diethylene glycol, 43 parts of trimethylolpropane, 375 parts of N,N-bis-(2-hydroxyethyl)aminoethanesulfonic acid, and 45 parts of xylene.
I prepared a section. Stirring was started again, and while the temperature was gradually raised, the generated water was removed by azeotropic reflux with xylene. Bring the temperature to 240℃ for about 2 hours,
Furthermore, stirring and dehydration were continued at the same temperature until the acid value equivalent to carboxylic acid reached 8, and the reaction was completed.
The obtained polyester resin had an oil length of 10, an acid value of 66, a hydroxyl value of 100, and an M of 800.

Example 1 In a container equipped with a stirrer and a temperature control device, 100 parts of paraffin wax with a melting point of 70 to 90°C and 10 parts of the polyester resin of Reference Example 1 were charged, and the temperature was adjusted to 120°C.
Stir and mix to make a homogeneous solution. This is the temperature
Pour into 300 parts of deionized water containing 1 part of dimethylethanolamine at 90°C with vigorous stirring. The solution immediately becomes cloudy. The mixture is cooled to obtain a white emulsion with good stability.

Example 2 In a container equipped with a stirrer and a temperature control device, 144.2 parts of butyl cellosolve was charged, the temperature was maintained at 120°C, and while stirring was continued, 10.5 parts of acrylic acid and 2-
68.1 parts of hydroxyethyl acrylate, 396 parts of methyl methacrylate, and n-butyl acrylate
A solution of 5 parts of azobisisobutyronitrile dissolved in 225.8 parts and 123.6 parts of styrene was charged, and stirring was continued for 2 hours. The resulting acrylic resin M6300
The acid value was 11.7.

This resin solution was maintained at a temperature of 100°C, and 400 parts of the polyester resin of Reference Example 2 was added thereto to form a homogeneous solution. This is poured into 1675 parts of a deionized water solution containing 40 parts of dimethylethanolamine at a temperature of 70° C. with vigorous stirring. The solution immediately becomes cloudy. The mixture is cooled to obtain a white emulsion with good stability. The viscosity of this emulsion is
It was 32000cps.

Example 3 In a container equipped with a stirrer and a temperature control device, short oil alkyd resin-tall oil fatty acid modified alkyd resin (“R-1730 resin” manufactured by Nippon Paint Co., Ltd., oil length 40
%, acid value 3.8, hydroxyl value 124, M1420), 22 parts of xylene, and 40 parts of the polyester resin of Reference Example 2, and the temperature was maintained at 80°C while stirring. Add 5 parts of dimethylethanolamine to this and add 450 parts of deionized water dropwise over 60 minutes. It becomes cloudy during dripping with deionized water. The mixture is cooled to obtain a white emulsion with good stability.
The viscosity of this emulsion was 21000 cps (25°C).

Example 4 Oil-free alkyd resin (“R” manufactured by Nippon Paint Co., Ltd.) was placed in a container equipped with a stirrer and a temperature control device.
-4304 resin, acid value 8.9, hydroxyl value 85, M1960)
200 parts of xylol, 22 parts of xylene, and 10 parts of the polyester resin of Reference Example 3 were added, and the temperature was raised while stirring.
Hold at 80°C. 450 parts of deionized water containing 3 parts of dimethylethanolamine are added dropwise. It becomes cloudy while the amine aqueous solution is added dropwise. The mixture is cooled to obtain a white emulsion with good stability. The viscosity of this emulsion was 15,000 cps (25°C).

Example 5 In Example 3, 50 parts of the polyester resin of Reference Example 4 and 5 parts of the polyester resin of Reference Example 4 and 5 parts of dimethylethanolamine were used instead of 40 parts of the polyester resin of Reference Example 2 and 5 parts of dimethylethanolamine.
A white emulsion is obtained using the same formulation and method except that 4.3 parts of 28% aqueous ammonia is used. The viscosity of this emulsion was 19500 cps (25°C).

Comparative Example 1 248 parts of neopentyl glycol, 224 parts of azelaic acid,
176 parts of phthalic anhydride, 114 parts of trimellitic anhydride and 40 parts of xylene are charged, and the temperature is raised. Water produced by the reaction is removed by azeotropic reflux with xylene. The temperature was raised to 190°C over 2 hours from the start of reflux, and stirring and dehydration were continued until the acid value reached 150.
Cool to ℃.

Next, while maintaining the temperature of the reaction solution at 140° C., 238 parts of “Cardilla E10” was added dropwise over 30 minutes, and stirring was continued for 2 hours to complete the reaction. The obtained polyester resin had an acid value of 48, a hydroxyl value of 140, and an M of 1191.

A white emulsion is obtained using the above polyester resin and following the same method and conditions as in Example 2. In this white emulsion, significant phase separation was observed after one week of aging, and the dispersion stability was poor. On the other hand, the emulsion of Example 2 remained stable even when left under the same conditions.

Claims (1)

[Claims] 1 Formula in the molecule, [In the formula, A represents a C ₁ to C ₆ linear or branched alkylene group, phenylene group, or substituted phenylene group. ] A polymer emulsifier characterized by mainly comprising a polyester resin having an aminosulfonic acid type amphoteric ionic group. 2. The emulsifier according to item 1 above, wherein the polyester resin has an acid value of 30 to 150 and a number average molecular weight of 500 to 5,000. 3. The emulsifier according to item 1 above, wherein at least 30 or more of the acid groups in the polyester resin are neutralized with ammonia, amine or alkali metal.