CS230800B1 - Water dillutable alkyl dispersed binding agent - Google Patents

Abstract

The invention relates to water-soluble of alkyd based dispersion binder resins, which is particularly useful for the production of paints. The essence of the invention is that the binder consists of 300 and 600 wt. parts salts prepared from nitrogenous bases and alkyd resins modified mono- carboxylic acids having 6 to 24 carbon atoms atoms, 300 to 700 parts by weight of water, t 2 to 35 wt. parts of dryers, 1 to 15 wt. parts of a mixture of surfactants consisting of 2 to 78% wt. fluoride-containing surfactants, 8 to 81% wt. phosphorus-containing surfactants; 70 wt. polyacrylic surfactants, and optionally up to 200 wt. parts of additives from groups of organic solvents agents, antifoams, supplementary agents surfactants, nitrogen bases and regulators viscosity.

Description

The invention relates to a stable water-borne alkyd dispersion binder which is particularly suitable for the preparation of dispersion paints.

Water-borne binders have become increasingly important recently as they significantly address the current problems of paints · First of all they replace scarce and expensive organic solvents, thus also eliminating air pollution during production and especially in paint processing · At the same time significantly reducing the risk of fire and explosion ·

In addition to the well-known and widely distributed water-based binders based on polymer dispersions, such as vinyl acetate, acrylate, styrene acrylate and styrene-butadiene, alkyd dispersion binders are also used to a limited extent (J. Snuparek ml., L. Formanek: Aqueous Dispersions of Synthetic Polymers, SNTL, Prague) 1979). The first alkyd dispersions were made by dispersing conventional alkyd resins in an aqueous ammoniacal casein solution (German Pat. Nos. 551,681 and 5,522,624, French Pat. No. 1,188,139). The dispersions obtained were poorly stable and provided coatings very sensitive to moisture and mold. Improvement has been achieved by the use of other protective colloids such as cellulose ethers and polyvinyl alcohol (U.S. Pat. No. 23,007, U.S. Pat. No. 2,272,057 and 2,308,474), and in particular by the addition of non-ionic emulsifiers, namely ethylene oxide nonylphenol (European Pat. · 2 253, French Pat. No. 1 478 892, German Pat. No. 2 754 141, US Pat. No. 3 440 193). However, these protective colloids and emulsifiers have been used in the art

230,800 high concentrations, thus adversely affecting the resistance of paints to water, atmospheres and environmental influences and sometimes drying speed ·

The present invention is based on the object of the present invention to provide a water-borne alkyd dispersion binder based on oil-based electrolytes, desiccants, surfactants and possibly other additives. The present invention is characterized in that the dispersion binder consists of 300 to 600 wt. parts by weight of salts prepared from nitrogen bases and alkyd resins modified with monocarboxylic acids having 6 to 24 carbon atoms, 300 to 700 wt. 2 to 35 wt. parts of desiccants, in particular cobalt, lead, manganese, zinc, zirconium, calcium and barium octoates and naphthenates, and 1 to 15 parts by weight of a surfactant mixture of 2 to 78% by weight; % surfactants with a fluorine content of 8 to 82 wt. % surfactants containing phosphorus and 10 to 70 wt. polyacrylic surfactants. Optionally, the dispersion binder still contains up to 200 parts by weight of ingredients selected from the group consisting of organic solvents, flow agents, defoamers, additional surfactants, nitrogen bases and viscosity regulators.

A water-borne alkyd dispersion binder has some advantages over known alkyd dispersion binders. For example, it is stable for a long period of time at normal storage temperatures for at least one year. If the dispersion system is stratified, it is not a phase separation but a mixing. reversible sedimentation distribution according to particle size of the dispersion · The excellent stability of the alkyd dispersion binder is mainly due to the particular composition of the surfactant mixtures used, which show strong synergistic dispersion effects. Therefore, they can be added in very small amounts which favorably influence the final properties of the alkyd dispersion binder and the films formed therefrom. Furthermore, it is advantageous that special types of alkyds are not required to prepare the dispersion binder, but can be based on conventional types of alkyd resins otherwise applicable in solvents.

230 800

The basic film forming component of the water-dilutable alkyd dispersion binder of the present invention is alkyd resins. They are known condensation products of polyalcohols (glycerol, pentaerythritol, trimethylolethane, trimethylolpropane) with polycarboxylic acids or their anhydrides (phthalic anhydride, tetrahydrophthalic anhydride, isophthalic and adipic acid, maleic anhydride, trimellitic anhydride). They are modified by natural drying oils (wood, linseed, oiticic, perilla, ricinine, fish, light), semi-dry (soybean, tallum, sunflower, cotton) and non-drying (coconut, olive, castor, fatty or fatty acids) or their fatty acids synthetic fatty acids. Such modifying components are aliphatic monocarboxylic acid _t containing 6-24 carbon atoms. The oil length of the alkyds used ranges from 40 to 70% by weight. In view of the stability of the alkyd dispersions, it is also advantageous to add aromatic monocarboxylic acids, in particular benzoic acid and its derivatives (toluyl, p-tert-butylbenzoic, salicylic).

Said alkyd resins having an acid number of 5 to 25 mg KOH / g are neutralized with volatile inorganic and / or organic nitrogen bases. Ammonia and primary, secondary and tertiary monoamines or polyamines are most commonly used, such as ethylamine, diethylamine, triethylamine, tripropylamine, monoethanolamine, diethanolamine, triethanolamine and N-dimethylethanolamine. Nitrogen bases are usually added in an amount of 0.1 to 3% by weight, thereby forming partially water-dispersible ammonium or amine salts of alkyds.

According to the invention, a mixture of surfactants in an amount of 1 to 15% by weight is added to disperse said alkyd salts. parts which account for 300 to 600 wt. parts of alkyd salts. The surfactant mixture consists primarily of 2 to 78 wt. of fluorine-containing surfactants.

These form derivatives of fluorocarbons, mainly salts of fluorinated alkylcarboxylic and alkylsulfonic acids, hereinafter

230 800 fluorinated alkylalkanols and alkylalkylamines, optionally ethylene oxide. Depending on the surfactant groups present, anionic, cationic or non-ionic types are used. Highly effective anionic surfactants form water-soluble alkali salts, e.g., potassium salts of heptadecafluoro-1-octanesulfonic acid or N-ethyl-1- (heptadecafluorooctyl) sulfones 1, aminoacetic acid.

The second component of the surfactant mixture comprises 8 to 82 wt. phosphorus-containing surfactants. The most important are the water-soluble salts of monoester and diesters of phosphoric acid and monovalent aliphatic alcohols having 11 to 18 carbon atoms (lauryl alcohol, cetyl alcohol, stearyl alcohol). These alcohols may also be alkoxylated (ethoxylated) to various degrees and may contain 1 to 12 ethoxy groups. The same inorganic and / or organic nitrogenous bases already mentioned for the formation of alkyd resin salts or also alkali metal hydroxides are used to neutralize the alkyl phosphates.

The third component of the surfactant mixture is 10 to 70 wt. polyacrylic surfactants. These are linear homopolymers of (meth) acrylic acid or their amides, and in particular copolymers thereof with (meth) acrylic esters, styrene, vinyl acetate and other vinyl or allylic monomers. The carboxylic polymers are neutralized with the aforementioned inorganic and / or organic nitrogen bases or alkali metal hydroxides. Water-soluble acrylic polymers or salts thereof are excellent thickeners whose efficiency increases with increasing relative molecular weight and carboxyl group content.

Another essential component of the water-borne alkyd dispersion binder of the present invention is desiccants which catalytically accelerate the drying of the binder in air. Possible salts of the divalent metals of organic acids with a higher molecular weight are most often suitable. These are, in particular, octoates, oleate, resinates and naphthenates of cobalt, lead, manganese, zinc, zirconium, calcium and barium. They are added in an amount of 2 to 35 wt. parts to 300 to 600 wt. Parts indicated5

230,800 alkyd resin salts · Usually used as solutions of desiccant mixtures in xylene or glycol ethers. The stability of drying solutions in an aqueous medium can be increased by the addition of benzoic acid.

The optional water-borne alkyd dispersion binder additives of the present invention include up to 200 wt. parts of other additives which favorably influence its properties. These are organic solvents and flow agents (xylene, white spirit, alcohols, glycoletheig; glycol ether esters), antifoams (silicones, higher aliphatic alcohols, mixtures of esters and hydrocarbons), supplementary surfactants (non-ionic emulsifiers such as ethoxylated alkylphenols, aliphatic alcohols, acids and others) viscosity regulators (cellulose ethers, polyvinyl alcohol, polyvinylpyrrolidone and the like) and the aforementioned inorganic and / or organic bases, which, according to purpose, are contained in the cell in the oil or aqueous dispersion base.

Water forms a dispersion medium in which the alkyd resin salt and other additives are dispersed. Water dispersed, demineralized or deionized is usually used for dispersion. It should not contain polyvalent metal ions, which otherwise can form insoluble salts with alkyds or even surfactants and thus coagulate the dispersion. According to the present invention, 300 to 600 wt. parts of alkyd resin salts add 300 to 700 wt. parts of water.

The water-dilutable alkyd dispersion binder of the invention can be prepared by any known method using conventional dispersing devices, e.g., so-called dissolveres. Dispersion binders having a particle size of not more than 10 [mu] m are thus obtained, which are particularly suitable for the production of dispersion paints, printing and marking inks and various other applications.

The invention is further illustrated by the following non-limiting examples. The parts and percentages are by weight.

Characteristics of used surfactants:

230 800

Surfactants containing fluorine:

Type A: the potassium salt of 1-heptadecafluoro oktoansulfonové type B: trifluoroacetic acid potassium salt type C: the potassium salt of N-eth.yl-K ^T - £ (] ieptedekafluoroktyl) sulfonyljaminooctové

Phosphorus-containing surfactants:

type I: triethylamine salt and technical mixtures of monoesters and diesters of phosphoric acid with triethoxylated lauryl alcohol type II: potassium salt of monoesters of phosphoric acid with a mixture of aliphatic monovalent alcohols containing 10 to 18 carbon atoms

Polyacrylic surfactants:

type A: triethylamine salt of methacrylic acid copolymer, ethyl acrylate, styrene and diallyl phthalate type B: triethylamine salt of methacrylic acid copolymer, ethyl acrylate and 2-hydroxyethyl acrylate

Example 1

A water-dilutable alkyd dispersion binder based on a long linen-oil alkyd component of the wt. parts

Linseed oil modified triethylamine and alkyd salt, oil length 65 (acid number of the starting alkyd 15 mg KOH / g) 300

Condensed water

Dryers 3

230 600 of which: cobalt naphthenate 1 part lead naphthenate 2 parts

Surfactant mixture of which: fluorine-containing surfactant A 5% phosphorus-containing surfactant I 75% polyacrylate surfactant type A 20%

Nitrogen base (triethylamine) for pH adjustment Xylene

Total

000

Properties: Particle size 2 to 6 µm, pH 8.5, stored for 1 year without phase separation.

Example 2

Water-borne alkyd dispersion binder based on medium-brown alkyds modified with linseed and soybean oil and benzoic acid.

Mass components. parts

Mixed salt of triethylamine and triethanolamine (weight ratio 3: 1) and alkyds modified with linseed and soybean oil and benzoic acid with an oily adduct of 58 (acid-

3 starting alkyds 10 mg KOH / g) 450 Demineralized water 515 Dryers 12 of which: cobalt octoate 1.3 part lead octoate ’ 7.3 part zinc octoate 3.4 part

Smws surfactants

230 800 of which: fluorine-containing surfactant type B 2% fluorine-containing surfactant type C 8% phosphorus-containing surfactant type II 50% polyacrylate surfactant type B 40% Nitrogen base (triethylamine) for pH adjustment 2

Xylene 2

Ethylene glycol monobutyl ether 10

Supplementary surfactant - ethoxylated nonylphenol (HLB 10.5) 1

Defoamer 1 of which: Extract gasoline 0.95 parts ethanol alcohol 0.05 parts

Total 1,000

Properties: dispersion particle size 2 to 4 µm (sporadically 6 µm), pH 9.0, stability for 13 months without phase separation.

Example 3

Water-borne alkyd dispersion binder based on mixtures of short and long alkyd.

Mass components

Tripropylamine salt with a mixture of soybean oil and p.ter.-butylbenzoic acid modified with an oil length of 40 (25 mg KOH / g of the starting alkyd) and a 65-oleic oil of lineage 65 (8 mg KOH / g of the starting alkyd) in wt. 1: 3 ratio

520

230 800

Surface water (filtered)

Drying agents 14 of which: manganese naphthenate 6 parts barium naphthenate 3 parts lead naphthenate 5 parts

Surfactant mixture 15 of which: fluorine-containing surfactant type C 35% phosphorus-containing surfactant type I 30% polyacrylate surfactant 3 35%

Nitrogen base (36% ammonium hydroxide) to adjust pH 2

Influencing agent - poly-2-ethylhexyl acrylate (0n3OOO) 1 Ethoxylated nonylphenol supplemental surfactant (HLB 11,5) 1

Xylene 15

Total

000

Properties: dispersion particle size 2 to 5 yum (sporadically 8 yum), pH 9.3, dispersion shelf life without phase separation for more than 1 year.

Example 4

Water-borne alkyd dispersion binder based on mixtures of short ricinine and safflower alkyd.

Mass components. parts

A salt of tripropylamine and a mixture of acid-modified alkyd dehydrated castor oil with an oil length of 40 (acid value of the starting alkyd of 20 mg'KOH / g) and a safflower modified oil of an oil length of 45 (acid number of the starting alkyde of 15 mg KOH / g) in mass » 1: 3 ratio

480

230 800

Water demineralized 475 Dryers 12 of which: zirconium naphthenate 2 parts cobalt naphthenate 6 parts lead naphthenate 4 parts Mixture of surfactants 13 of which: fluorine-containing surfactant type C 80% phosphorus-containing surfactant type II 10 % polyacrylate surfactant type A 10 % Nitrogen base (tripropylamine) for pH adjustment 2 Xylene 15 Dec White spirit 2 Supplemental surfactant - ethoxylated nonylphenol (HLB 11.0) 1 C e 1 to em 1 000

Properties: dispersion size 2 to 4 yum, pH 9.0, stable up to 1 year without phase separation.

Claims (1)

Water-based alkyd dispersion binder based on oil. alkyd, desiccant, surfactant and optionally other additives, characterized in that it consists of 300 to 600 wt. parts by weight of salts prepared from nitrogen bases and alkyd resins modified with monocarboxylic acids having 6 to 24 carbon atoms, 300 to 700 wt. 2 to 35 wt. 1 to 15 wt. % of a surfactant mixture comprising 2 to 78 wt. surfactants containing fluorine, 8 to 82 wt. % surfactants containing phosphorus and 10 to 70 wt. % polyacrylic surfactants, and optionally up to 200 wt. parts of ingredients from the group consisting of organic solvents, flow agents, defoamers, additional surfactants, nitrogen bases and viscosity regulators.