FI66636B - FAERG- OCH LACEMULSION - Google Patents

Description

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Sweden-Sverige (SE) 7510014-9 (71) Berol Kemi AB, S-444 01 Stenungsund 1, Sweden-Sverige (SE) (72) Artur Leif Albert Augustsson, Stenungsund,

Sigurd Haldor Ingemar Ingvarsson, Stenungsund, Sweden-Sweden (SE) (74) Berggren Oy Ab (54) Paint and varnish emulsion - FSrg- and lackemulsion

Many paints consist of a binder of relatively high molecular weight products, which gives them a viscosity that must be diluted with solvents, which are usually organic in nature, for application. The use of organic solvents causes environmental problems and this has led to a general effort to eliminate or at least greatly reduce the proportion of organic solvents in paints. Developments here have followed a number of different guidelines.

Among other things, attempts have been made to use relatively low molecular weight binders which, due to their reasonable viscosity, require little dilution with organic solvents. This method has so far had poor success because it causes a number of disadvantages, including slow drying, run-off problems on vertical or inclined surfaces and too strong penetration into absorbent substrates.

In another method, one or more carboxyl groups are attached to the high molecular weight binders, which, after neutralization with amines or ammonia, allow the binder to be diluted with water to give a soap solution in principle. However, this case requires the presence of an organic co-solvent of the glycol ether or alcohol type or a mixture thereof, in which case the ready-to-apply mixture still contains significant amounts of volatile organic compounds together with less insignificant amounts of volatile amines or ammonia.

To date, the most commercially successful method is to make the binder an emulsion. This method has been particularly common for paints intended for manual application. The binder is usually a polymer based on acrylates, vinyl acetate or a copolymer of these or other monomers. Film formation occurs when separate binder particles merge into a single film as water evaporates from the applied film. A prerequisite for this to happen is that the particles have sufficient binding capacity and that their viscosity in film formation is low enough for complete fusion to occur. The dry film is heat-meltable, which in practice means that if the film-forming temperature is not higher than the operating temperature, a film is obtained which is soft and often smooth.

Alkyds, which are the most common binders, are used in self-oxidatively drying or otherwise curable films. Compared to the above-mentioned polymers, air-drying films in emulsion form have several technical advantages. Due to their relatively low molecular weight and thus their viscosity, they require relatively little dilution with organic solvents. Very good adhesion to most substrates is also obtained and can be pigmented with virtually all commercially available pigments. The application method and drying time can be chosen within a very wide range. The dried film has low heat formability and good resistance properties. After drying, the water-emulsified alkyd can give films having approximately the same properties as films obtained from solutions of organic solvents. To date, however, it has not been possible to properly produce storage-resistant emulsions which, after application, would give glossy films.

It has now proved possible in a simple manner to prepare a binder emulsion for a paint or varnish which contains a self-adhesively drying binder / e.g. alkyd type binder and which is storage-resistant and gives glossy films without the use of large amounts of organic solvents. The emulsion according to the invention is characterized in that it contains as a binder a self-oxidizing drying alkyd having an average molecular weight of 700-15,000 and an average of more than 2.0 self-oxidizing groups per molecule; a nonionic surface active alkylene oxide adduct in an amount of 0.01 to 0.1, preferably 0.03 to 0.07 parts by weight per part by weight of the polymer; a carboxyl group-containing organic compound having at least 6 carbon atoms, wherein at least 15% of the carboxyl groups are neutralized with a monovalent cation in an amount of 0.002 to 0.2 parts by weight per part by weight of the polymer; and 0.6 to 3.5 parts by weight of diluent per part by weight of polymer, wherein at least 85% of the diluent is water.

By surfactant is meant herein that the nonionic alkylene oxide adduct at a concentration of 1% in water at 25 ° C lowers the surface tension to less than 50 dynes / cm.

The binder according to the invention may be an alkyd modified with drying or semi-drying oils, a urethane alkyd and a correspondingly modified epoxy ester, a polymerized drying or semi-drying oil, an ester of unsaturated fatty acids and polyalcohols and a polyurethane modified with an alkyl ether. The binder may also be an alkyd modified by transesterification with a phenolic, maleinate or acrylic resin and / or by copolymerization with e.g. styrene, acrylate or vinyl monomers or by reaction with other reactive substances. Self-oxidizing groups are derived from unsaturated fatty acids, allyl ether compounds or other compounds containing double bonds.

The molecular weight of these alkyds naturally varies widely, but practical experiments have shown that the average molecular weight of the alkyd must be 700-15,000. Preferred alkyds according to the invention are alkyds modified Namely, they have an average molecular weight of 2000 to 10,000. In addition, the binder according to the invention can be combined with smaller amounts, usually not more than 15% by weight, based on the binder according to the invention of non-reactive binders, e.g. resins, esters, maleate petroleum resins. These non-reactive binders are thus not included in the oxidatively drying polymers.

The nonionic surfactant alkylene oxide adduct can be prepared by reacting an organic compound containing a hydrogen atom reactive with an alkylene oxide, ethylene oxide and / or propylene oxide and / or butylene oxide and / or a mixture of these alkylene oxides in one or more steps in a known basic manner. Such compounds are described, for example, in Schwartz and Perry: Surface Active Agents; volume I 1949, and Schwarz, Perry, and Berch: Surface Active Agents; volym II, 1958. The hydrophobic portion of the surfactant may be derived from a fatty alcohol, a synthetic alcohol prepared, e.g., by the oxo or Ziegler process, a mono- or dialkylphenol, a primary or secondary aliphatic amine, or a carboxylic acid. This part of the molecule may advantageously contain an air-drying unsaturation, e.g. in the form of an unsaturated fatty acid. Particularly preferred are alkylene oxide adducts of the general formula

H O

I K

R-C-O (A) nH or R-C-O (A) nH

B

wherein R represents an aliphatic, cycloaliphatic or aromatic group having 7 to 25 carbon atoms, each A represents a group derived from an alkylene oxide having 2 to 4 carbon atoms, and n is a number having an average value of 3 to 20.

The carboxyl group-containing organic compound having at least six carbon atoms, preferably at least ten carbon atoms, may be, for example, a saturated or unsaturated, straight or branched carboxylic acid, . In the latter case, its drying property can be further enhanced by esterifying part of the carboxyl groups of the formed adduct with an allyl ether alcohol, e.g. trimethylolpropane diallyl ether. The carboxyl-containing compound must be in the form of a salt formed with at least 15% of a monovalent cation. Suitable cations are primarily ammonium ion, alkali metal ion or organic nitrogen compound ion. For neutralization, for example, sodium, potassium or lithium hydroxide or ammonia or morpholine, 5,66636 triethylamine, triethanolamine, dimethylaminoethanol and the like amino compounds can be used. Regardless of the structure of the carboxyl-containing compounds, it has proved suitable to add 0.01 to 0.06 moles of neutralized carboxyl groups per 1000 g of the polymer according to the invention.

According to a preferred embodiment of the invention, the emulsion diluent is water. If desired, smaller amounts of organic diluent may be added, in which case the amount should not exceed 15% of the total amount. The amount of organic diluent is preferably adjusted so that, after evaporation from 1 liter of emulsion to be applied, it needs a maximum of 100 m of air to be diluted to a concentration below the applicable hygienic limits. The organic diluents may be, for example, aliphatic and aromatic hydrocarbons having a boiling point between 100 and 200 ° C, Glycol ethers and glycol ether acetates.

In preparing the emulsion according to the invention, in addition to the above-mentioned ingredients, it may also contain additives customary for paints and varnishes, e.g. desiccants, pigments, dyes, anti-skin agents, bactericides, fungicides, UV-absorbing additives, thickeners and effluents and fillers.

The invention is described in more detail below by means of examples.

Example 1

A flask equipped with a stirrer, thermometer, inert gas feeder, reflux condenser and water separator was charged with 1051 g of pine fatty acid, 176 g of pentaerythritol, 112 g of glycerol and 40 g of xylene.

The contents were heated under a nitrogen atmosphere to 220 ° C, which was maintained until the acid number was less than 10 mg KOH / g. After cooling to 180 ° C, 346 g of phthalic anhydride were added. After heating to 230 ° C, the reaction was continued until the final product had an acid number of 11.6 KOH / g and a viscosity at 20 ° C of 7400 mNs / m 2 (90% solution in lacquer-naphtha). Xylene was removed by distillation. To 100 parts by weight of the above-prepared air-drying alkyd having an average molecular weight of 5,000 was added 5 parts by weight of the reaction product of 1 mole of C 1-4 alcohol and 10 moles of ethylene oxide and 1 part by weight of pine fatty acid neutralized with sodium hydroxide. The alkyd mixture was 6,66636 easy to emulsify in water. The emulsion had a particle size of less than 1 μm and was storage stable.

Example 2

To the alkyd prepared in Example 1, petroleum resin (melting point 104 + 5 ° C by the Ring and Ball method) was added in the ratio alkyd: Petro meat resin = 9: 1. To 100 parts by weight of this mixture were added 4 parts by weight of an adduct of 1 mole of C 1-4 fatty acid and 12 moles of ethylene oxide and 5 parts by weight of 1 mole of safflower oil, 2 moles of maleic anhydride and 2 moles of trimethylolpropane diethyl ether. In this reaction product, 35% of the carboxyl groups were neutralized with ammonium hydroxide. The emulsifiable alkyd mixture thus obtained was easy to emulsify in water. The emulsion had a particle size of about 1 μm and lasted for storage.

Example 3 100 parts by weight of the alkyd described in Example 1 were mixed with 4 parts by weight of an adduct containing 1 mole of nonylphenol and 16 moles of ethylene oxide and 4 parts by weight of the product obtained by adding 1 mole of sunflower oil, 1 mole of maleic anhydride and 1 mole of trim. -stylpropane diallyl ether to react with each other in which half of the carboxyl groups of the product are neutralized with triethylamine.

After emulsification of the alkyd mixture, an emulsion was obtained which proved to be stable on storage and had a particle size of less than 1.

Example 4

In the same manner as in Example 1, 948 g of soybean fatty acid, 345 g of pentaerythritol and 50 g of xylene were charged.

The contents of the flask were heated to 220 ° C under an inert gas atmosphere and this temperature was maintained until the acid number was less than 10 mg KOH / g. After cooling to 180 ° C, 406 g of phthalic anhydride were charged and the temperature was raised to 230 ° C. The reaction was continued at this temperature and stopped at such a time that the final product had an acid number of 7.8 mg KOH / g, a viscosity at 20 ° C 2 of 6900 mNs / m (65% solution in lacquer naphtha) and an average molecular weight of about 4500 The xylene was removed by distillation. The auto-oxidatively drying alkyd was cooled to below 100 ° C and 5 parts by weight of an adduct of 1 mole of dinonylphenyl and 16 moles of ethylene oxide and 1 part by weight of soybean fatty acid neutralized with dimethylaminoethanol were added per 100 parts by weight of alkyd. The mixture was stirred until homogeneous and transferred to a dissolver in which the alkyd mixture was emulsified at a circumferential speed of 5 m / sec by adding deposited water heated to 85 ° C in portions. At a dry matter content of about 70% by weight, there was a phase change from a water-in-alkyd emulsion to an alkyd-in-water emulsion. After the phase change, the viscosity of the emulsion decreased significantly as more water was added.

The alkyd emulsion prepared in this way contained 50% by weight of alkyd and had a viscosity at 60 ° C of 60 mNs / m 2. The particle size was 1 μm or less and the emulsion proved to be stable when stored for a longer period of time.

Example 5

A pigment paste was prepared as follows. The dissolver was charged with 12.04 parts by weight of a 2.5% aqueous solution of ethylhydroxyethylcellulose (viscosity at 20 ° C 65,000 mNs / m 2, 2% aqueous solution), 0.23 parts by weight of K4P2O7, 0.27% by weight parts of emulsifier (C 1-20 alcohol + 10 moles of ethylene oxide) and 0.10 parts by weight of antifoam. The mixture was homogenized, the circumferential speed was adjusted to 5 m / sec, and 21.16 parts by weight of rutile-type titanium dioxide was added. The pigment was dispersed for about 20 minutes, after which 12.04 parts by weight of deionized water was added.

32.30 parts by weight of the alkyd mixture prepared in Example 1 were emulsified in the pigment paste by adding the mixture continuously for 10 minutes. Then 0.05% cobalt, 0.06% zinc and 0.2% barium in the form of naphthenate (calculated as metal for alkyd) were added, after which stirring was continued for another 15 min. An additional 0.10 parts by weight of antifoam was added, after which the paint was diluted with deionized water to a dry content of 55% by weight.

The pigment volume concentration of the prepared dye was 14%. The viscosity at 20 ° C was 120 mNs / m 2 at 10,000 ss and 2400 mNs / m 2 at 1 r / s (Brookfield, mixer no. 4). The paint was stable after repeated frost / protection treatment and storage at 50 ° C.

The applied paint was dust dry after 2.5 hours and did not set after 4 hours. According to Gardner 60 °, the gloss was 91 and according to Gardner 20 ° 78. The dry paint layer had a very good adhesion to various substrates. The paint layer did not cure and withstood significant surface loads without permanently deforming to temperatures up to 70 ° C.

Example 6

In the same manner as described in Example 5, a paint was prepared from the alkyd mixture prepared in Example 2. The dry weight content of the paint was 55% and the pigment volume concentration was 14%.

The gloss measured after color application was 87 according to Gardner 60 ° and 61 according to Gardner 20 °.

Example 7 29.50 parts by weight of rutile-type titanium dioxide and 0.10 parts by weight of 2,4,5,6-tetrachloroisophthalonitrile were dispersed in 18.00 parts by weight of an alkyd mixture prepared according to Example 3. To 11.50 parts by weight of the same alkyd mixture were added 0.05% of cobalt, 0.06% of zinc and 0.12% of barium in the form of octoate (calculated as metal of the total amount of alkyd) and 0.10 parts by weight of methyl ethyl ketoxime. The zigzag alkyd mixture was mixed with the pigment paste.

The pigment-alkyd mixture thus obtained was transferred to a dissolver. 34.50 parts by weight of deionized water were added portionwise at a circumferential speed of 5 m / s to give an oil / water emulsion. Finally, 0.27 parts by weight of ethylene oxide adduct (nonylphenyl + 16 moles of ethylene oxide) were mixed with 0.20 parts by weight of antifoam and 4.00 parts by weight of a 2% aqueous solution of ethylhydroxyethylcellulose (viscosity at 20 ° C 65,000 mNs / m 2). ).

The lime produced had a weight-dry matter content of 60% and a pigment volume concentration of 20%.

The viscosity at 20 ° C was 230 mNs / m 2 at 10,000 s ~ ^ and 700 mNs / m 2 at 1 r / s (Brookfield, mixer no. 3). The applied paint was dust dry after 2.5 hours and did not set after 4 hours. Gardner at 60 ° had a gloss of 85 and Gardner at 20 ° had a gloss of 60.

Example 8 12.01 parts by weight of a 2.5% aqueous solution of ethylhydroxyethylcellulose (viscosity at 20 ° C 65,000 mNs / m 2, 2% aqueous solution), 0.23 parts by weight of K4P2O7, 0.27 parts by weight of emulsifier , dinonylphenol + 16 moles of ethylene oxide) and 0.10 parts by weight of antifoam were charged to the dissolver and mixed until the mixture was homogeneous. The circumferential speed was adjusted to 5 m / sec and 20.59 parts by weight of rutile-type titanium dioxide were added. The pigment was dispersed for 20 min, after which 1.00 parts by weight of an organic metal salt containing 1.5% cobalt, 7.0% barium and 2.0% zinc were mixed into the pigment paste. The circumferential speed was reduced to 1 meter / sec and 62.90 parts by weight of the alkyd emulsion described in Example 4 were added. Finally, 0.10 parts by weight of antifoam was mixed.

The emulsion paint thus obtained had a dry matter content of 53.5% and a pigment volume concentration of 14.2%.

The viscosity of the paint at 20 ° C was 110 mNs / m ^ 10,000 s ^ and 2100 mNs / m ^ 1 r / s (Brookfield, mixer no. 4).

The applied paint was dust dry after 1 1/2 hours and did not set after 3.5 hours. According to Gardner 60 °, the gloss was 90 and according to Gardner 20 °, 70. The same gloss values were obtained at both 65% and 40% relative humidity. The gloss resistance was the same as that obtained with paints prepared from solutions of organic solvents in the conventional manner and with an air-drying alkyd acting as a binder.

Claims (13)

66636 10 A paint and varnish emulsion comprising an alkyd, a non-ionic surfactant and water as an essential diluent, characterized in that it contains in combination a) a self-oxidizing drying alkyd having an average molecular weight of 700-15,000 and an average of more than than 2.0 self-oxidizing groups in the molecule, b) 0.01 to 0.1 parts by weight per weight of alkyd of nonionic surfactant alkylene oxide adduct, c) 0.002 to 0.2 parts by weight per weight of alkyd of carboxylic a second organic compound containing at least 6 carbon atoms, wherein the carboxyl groups are neutralized by at least 15% with a monovalent cation, and d) 0.6 to 3.5 parts by weight per part by weight of alkyd of diluent, wherein at least 85% of the diluent is water. Emulsion according to Claim 1, characterized in that the alkyd has an average molecular weight of 2,000 to 10,000. Emulsion according to Claim 1 or 2, characterized in that the self-oxidizing groups of the alkyd are derived essentially from unsaturated fatty acids. Emulsion according to Claims 1 to 3, characterized in that the self-oxidizing groups of the alkyd are derived mainly from allyl ether compounds. Emulsion according to Claims 1 to 4, characterized in that the alkyd is composed essentially of orthophthalic acid or isophthalic acid and at least a divalent hydroxyl compound. Emulsion according to Claims 1 to 5, characterized in that the nonionic surfactant alkylene oxide adduct has the general formula? n RC-O (A) nH or RC-O (A) nH H wherein R represents an aliphatic, cyclool-666636 aliphatic or aromatic group having 7 to 25 carbon atoms, each A represents a group derived from an alkylene oxide having 2 to 4 carbon atoms, and n is a number with an average value of 3-20. Emulsion according to Claims 1 to 6, characterized in that the nonionic surfactant alkylene oxide adduct is from 0.03 to 0.07 parts by weight per part by weight of alkyd. Emulsion according to Claims 1 to 7, characterized in that the carboxyl-containing compound contains at least 10 carbon atoms and is an unsaturated or saturated, straight-chain or branched carboxylic acid. Emulsion according to Claims 1 to 7, characterized in that the carboxyl group-containing compound is a triglyceride of an unsaturated fatty acid having at least one carboxyl group, optionally some of the carboxyl groups being esterified with allyl ether alcohol. Emulsion according to Claims 1 to 9, characterized in that 1000 g of alkyd contain 0.01 to 0.06 mol of neutralized carboxyl groups derived from a carboxyl group-containing organic compound. Emulsion according to Claims 1 to 10, characterized in that the diluent is water. Emulsion according to Claims 1 to 10, characterized in that at most 15% of the diluent is an organic diluent. Emulsion according to Claim 12, characterized in that the organic diluent is a saturated hydrocarbon compound having a boiling point of between 100 and 200 ° C. 66636 12