SE191780C1 - - Google Patents

Description

CLASS INTERNATIONAL SWEDISH C 08 f39 b: 22/06 C 09 d22 g: 2/01 PATENT AND REGISTRATION AGENCY Ans. 9857/1955 was received on 2/11 1955, published on 10/2 1964 WR GRACE & Co., CAMBRIDGE, MASS., USA , NG Tompkins and A Urjil Priority issued on 30 December 1954 (USA) Polyvinyl acetate is one of the more useful thermoplastic resins. Especially in emulsion form, it acts highly film-forming, adhering and joining. Due to this, polyvinyl acetate emulsions have been widely used as carriers for aqueous paint pigments.

As carriers for water-based larger ones, polyvinyl acetate emulsions have been found to have many benefits, hi. a. light color and good color stability, good stability to oxygen and ultraviolet light, which results in good durability when used outdoors, self-priming properties on porous surfaces, moderate cost, excellent resistance to grease and oil in the formed films and membranes, shape for good adhesion to de fiesta substrates, good permeability to moist angels, which prevents blistering and flaking, as well as good emulsion stability opa. made of acidic materials or polyvalent ions.

However, in order to be used as a colorant, polyvinyl acetate emulsions must first be mixed with a plasticizer. The grinding agent achieves the necessary flexibility and ductility of what would otherwise be a hard and shoe film or film. In addition, the plasticizer facilitates the film-forming process, probably due to its emollient effect on the resin particles. From 5 to 15% or more of a phthalate acid ester such as dibutyl phthalate is usually required, depending on the resin content of the emulsion.

The fact that a plasticizer must be used as part of the carrier in a nig based on a polyvinyl acetate emulsion is both an advantage and a serious disadvantage. On the one hand, by using different plasticizers in varying amounts to a certain extent, a color developer can provide a barber which corresponds to his special requirements. Now, however, in such a case, the film-forming material is a physical mixture of two materials, the polyvinyl acetate resin and the plasticizer. Like all such mixtures, this mixture can be separated by such physical processes as evaporation, separation of the constituents or leaching. This is a significant, potentially cold response in terms of durability and ability to withstand the influence of the weather on thin membranes. The separation and loss of the plasticizer over a period of time and exposure to the action of the wadding can make the skin appear. In addition, the use of an organic, liquid plasticizer as part of the carrier in an emulsion paint has sometimes resulted in color durations when organic pigments are used, depending on the possibility of rinsing between the water and plasticizer phases.

Polyvinyl acetate further has the disadvantage in common with many other water-insoluble polymers that membranes and roof layers formed from polyvinyl acetate emulsions under normal drying conditions are quite sensitive to water. The obvious reason for this water sensitivity is that the water-sensitive materials required for the formation of a stable emulsion of the polymer remain in the dried film or roofing layer and tend to re-emit the same emulsion.

The present invention relates to a composition lamped as a carrier in aqueous grinding larvae, whereby these imperfections are overcome.

According to the invention, the composition in combination comprises an aqueous dispersion of a copolymer prepared by emulsion polymerization of vinyl acetate and a diester of butene-2-diacid-1,4 and an aliphatic alcohol selected from the group comprising ethanol, butanol, isopropanol, 1,4 -dimethyl-1-butanol and 2-ethyl-1-hexanol, said monomeric ingredients being present in the proportions 82, to 62.5 parts by weight of acetate and 17.5 to 32.5 parts by weight of the diester and from to 17 parts by weight, per 100 parts by weight of the copolymer, on the one hand a glycol, substituted glycol or a glycol derivative selected from the group comprising hexylene glycol, 3-chloro-1,2-propanediol, 2- (fl-butoxyethoxy) ethanol, -butoxyethanol acetate, dipropylene glycol and diethylene glycol monoethyl ether.

The modal effect is achieved when the ratio between the vinyl acetate monomer and the diester is 77 to 23. The ranges ph each side are at this maximum but the critical range yields useful products, which exhibit a surprisingly good wear-flake or abrasion resistance, which is' Mgt Over de varden , which usually occur in paints based on polyvinyl acetate base. It could be expected that as the membranes became softer, the half-strength against water scrubbing would decrease. As is clear from the data in the table below and from the corresponding diagrams in the accompanying drawing, there is such a tendency, with the exception of the area where the copolymer contains between 17 II, and 32% of the diester, and consequently 82 1/2 more 67 V,% vinyl acetate, in which range the water scrubbing strength of the copolymer Or strongly & ad.

Table I Water scrubbing strength divided into number of types of Gardner machine.

% Hexylene glycol predation assumed A 70 Vinyl- p2,5,010,0 Number of strokes A 100 50 870 4740 6790 93 50 320 3020 8490 85 50 430 2710 5790 77 50 1610 4890 7650 70 50 450 2220 7090 62.5 50 270 1060 2076 55 50 260 1280 2090 - The values in this table are recovered as follows. Membranes of the unpigmented emulsion, with about 50% solids in each case, were applied to a cleaned glass sheet using a Baker / ran instant at a gap of about 0.05 frame. The membrane was dried (lame at room temperature for a period of between 16 and hours. This gay result in a dry membrane with a thickness of about it. This thin membrane was chosen in the spirit to speed up the test. Gardner Straight Line Washability Machine using a standard brush with a Chinese pig bristle, weighing 0.45 kg. ph sample, said that this hails moist all the time.

In each case, the test was continued until the membrane was enlarged. The results are expressed in terms of the Gardner machine and represent the needle number of several experiments in each case.

In Table I, in cases where magnification Or is given at 50 beats, the magnification actually occurred at slightly less than 50 beats and was due to ph. re-emulsification of the membrane. In all other cases, f OrstrOrelsen was due. wear of the membrane and the sample was terminated as soon as any part of the membrane was completely bare.

The above samples were prepared as follows: In each case, the following solution was prepared - Ammonhun persulf at 0.3 gram Natthunbicarbonate 0.18 »Sodium sulfo succinic acid dioctyl ester (Aerosol OT) 0.1 Polyvinyl alcohol 4.0 Water 78.0 solution was then added under vigorous stirring to 100 grams of monomer or monomer mixture as follows: Pray A 100 vinyl acetate »B 93 vinyl acetate 7 dibutyl maleate C 85 vinyl acetate dibutyl maleate» D 77 vinyl acetate 23 dibutyl maleate E 70 vinyl acetate dibutyl maleate » »G 55 vinyl acetate dibutylarealate The resulting water emulsion was then transferred to a reaction flask equipped with a stirred stirrer, a thermometer and a reflux condenser. The reaction mixture in the flask was then heated with stirring to a temperature of 67-68 ° C and heated at this temperature until the polymerization reaction started. As the polymerization reaction continued, the temperature was allowed to rise to about 75-80 ° C at a very slow rate, and the reaction was subsequently maintained at this temperature. The reaction was continued until it was practically terminated and stopped only when the residual monomer content was determined by titration to be less than 1%. The emulsion was then cooled to room temperature and a sufficient amount of sodium bicarbonate was added to adjust the pH to the range between 4.5 and 7.0.

A sufficient quantity of a solution of equal parts by weight of hexylene glycol and water was added to parts of each of the samples with stirring, to obtain a concentration of hexylene glycol in% by weight of the total amount of solid emulsion constituents of 2.5, 5.0 and 10, G resp. It has been found that the hexylene glycol solution can also be added to the polymerization mixture as a portion of the water required for the preparation of the emulsion, without any disadvantages but with the advantage that the resulting final emulsion has a higher total solids content. constituents.

Potassium persulphate, sodium persulphate and hydrogen peroxide can be used instead of ammonium persulphate as reaction catalyst with equally good results. The concentration of available oxygen, based on the weight of the monomer, is suitably between 0.01 and 1.0%.

In place of sodium sulfosuccinic acid dioxyl ester, thorn wetting agents can be used in many of the sodium salts of alkyl sulfonates, the esters of the sodium salts of alkyl sulfonates, sulfates of higher alcohols, ethylene oxide condensation products of alkylphenols or polyethylene glycols of fatty acids.

The polyvinyl alcohol used as emulsifier is a hydrolyzed polyvinyl acetate prepared by hydrolysis of a polyvinyl acetate having a viscosity of between 7 and 100 centipois as a molar solution in benzene to a residual acetate content of 1 to 25%. The appropriate concentration of such an Egger emulsifier is in the range between 3 and 7% by weight of the monomer.

Unlike the malein content, the amount of hexylene glycol is not particularly critical. At less than 5% hexylene glycol by weight of the copolymer, the effect becomes too small to be of any particular importance. As the quantity of hexylene glycol is increased, the drying time progressively decreases for membranes and tack layers formed by copolymer emulsions. Above about 17% hexylene glycol .. the content of the drying time becomes excessively long and the membrane or the roofing layer remains sticky for a long time.

In addition to hexylene glycol, the following glycols, substituted glycols or glycol derivatives have been found to be useful in increasing the water resistance of the films; 3-chloro-1,2-propanediol; diethylene glycol monobutyl ether (2- (13-butoxyethyl) ethanol); ethylene glycol monobutyl ether acetate (2-butoxyethanol acetate); diethylene glycol monoethyl ether (2- (η-ethoxyethoxy) ethanol) and dipropylene glycol. During the flirting operations listed in Table I and using the copolymer emulsion comprising 77% vinyl acetate and 23% dibutyl maleate with the addition of 5% of the solidification additive, the following results were obtained: Table II.

Additive Type 3-chloro-1,2-propanediol 2900 Diethylene glycol monobutyl ether 5160 Ethylene glycol monobutyl ether acetate Diethylene glycol monoethyl ether 34 Dipropylene glycol 57 In addition to dibutyl maleate (di-1-butylbutene diacid ester), the following maleic esters have been found to be satisfactory; diisopropyl maleate (diisopropylbutene diacid ester); di (methylamyl) maleate (di-1,4-dimethyl-1-butylbutenedioic acid ester) and di-2-ethylhexyl maleate (di-2-ethylhexylbutenedioic acid ester). In a foaming resistance test under the same conditions as those given in Table I and using an emulsion of the copolymer with 77% vinyl acetate and 23% of the indicated maleate ester with the addition of 10% hexylene glycol, the following results were obtained: Table III.

Ester Type Diethyl maleate 97 Diisopropyl maleate 7270 Di (methylamyl) maleate 15090 Di-2-ethylhexyl maleate 56 In the description, the term «maleate» is used throughout for simplicity instead of the more correct term «butenedioic acid ester». The term is intended to include both the cisform (maleate) and the transform (fumarate). In comparative tests using a pure maleate ester, the corresponding pure fumarate ester and the corresponding ester consisting of a mixture of maleate and fumarate, no clear difference was found.47) These emulsions are particularly useful in the preparation of water-based paints. They have been used with great success as barers for such larger for both indoor and outdoor use. Such Niger can be characterized by lasting flexibility, as the bar does not lose its plasticizer content or be subjected to oxidation. As an example of such permanent flexibility, three larger ones with identical composition were prepared except that two were based on an externally softened polyvinyl acetate emulsion and the third was based on the copolymer emulsion preferred above. These larger ones were applied in equal file thicknesses to sheet metal panels, which were then Milos at a temperature of 60 ° C for eight days in a circulating air oven. The panels were then cooled to room temperature and bent 90 ° over a spindle 13 mm thick. The membranes of the two colors, which were based on externally plasticized polyvinyl acetate, cracked during this test, while the color film based on the copolymer emulsion remained undamaged.

Another special advantage of Adana colors Or, is that they have a significantly improved solidification shape at low temperatures. Even at temperatures where color membranes based on externally softened polyvinyl acetate emulsions do not solidify, color films based on copolymer emulsions exhibit good solidification.

This can be shown by feeding the mirror reflection of color membranes. Samples were prepared by placing membranes of Niger on a water-based basis on plasterboard panels at a low temperature and drying these membranes at the low temperature in a storage barn with circulating air and a relative humidity of 50% or less. Prior to the test, the paints, test panels and brushes used in the application of the paints were stored in the chamber long enough to ensure that their temperature was at night equilibrium. After the membranes had dried, the samples were allowed to warm to room temperature and a layer of semi-gloss cradle was applied. After this layer had dried, the mirror reflection for each sample was measured with a Hunter reflectometer according to the method set forth in the Journal of Research of the National Bureau of Standards, No. 25, p. 582-618, November 1940. The reflection lesson is a mat on the solidification of the primer layer of water-based paint. Reflection of, for example, a layer of semi-gloss paint applied to an unfounded rim is less than 0.7, which is the smallest reading on the reflectometer.

With larger produced at a temperature of 21 ° C, the reflection was usually about the same, with a reading of between 5.2 and 5.6. The greatest variation in reflection occurred in samples prepared at a temperature of 10 ° C. At this temperature gay a color with a pure polyvinyl acetate emulsion bearing a reading of 0.7, while larger with a 77-23 copolymer of vinyl acetate and dibutyl maleate gay readings of, 2.4 with 5% hexylene glycol, 3.7 with 10% hexylene glycol and 4.8 with 17% hexylene glycol.

In addition, larger based on the copolymer Rutile titanium dioxide 275 kg Diatomaceous earth 70 »Phenylmercuryborate 0.1» Polyvinyl acetate 10% Display in water Water-soluble soy lecithin Surfactant 4 »Water Water 7 Preferred copolymer emulsion 4% - 4% Viscose emulsion. laming in water 7 Water 25 »Water and / or methyl-cellulose solution for adjusting the viscosity 59 a sufficient degree of moisture permeability to allow the passage of moisture which would otherwise vam. trapped and cause blisters or flaking. To show this, two identical stair panels were used. One of these was painted with an oil-based primer followed by two coats of the usual, oil-based paint according to the manufacturer's record recommendations. The second panel was painted with two coats of a paint based on the preferred copolymer emulsion. The two panels were then sealed with sealant at the open sides of a 20 liter square jug and the unpainted backs were subjected to a temperature of 50 to 60 ° C and a relative humidity of 100% for 48 hours. The oil-painted stair panel showed strong blistering where the trapped moisture could not escape. The stair panel, which was sewn with the color based on the copolymer emulsion, remained completely unaffected.

The particular color used in both of the above samples was prepared according to the following composition: These ingredients are mixed to form a paste, which is suitably stirred in a paste mixer. Mix thoroughly.

After this has been thoroughly mixed, the pasta is allowed to pass through a high-speed stone grinder. About one. roller mill was used, some or all of the last water additive should be added after grinding. With the paste in a diluent tank, these ingredients are then added and mixed. 17 »Resin ethylene oxide 2» Water Bacteriostatic agent 8i Preferred copolymer emulsion 4 »Water and / or methylcellulose for viscosity adjustment» Total 1168 kg These copolymer emulsions appear to be compatible with all the blend ingredients commonly used in water-based compositions precautionary measures other than those usually observed at OmrOr in pasta mixers, then grind in a stone mill with Mgt speed. Roller can be used if part of the water was added afterwards.

Rich, but avoid foaming.

Stir and adjust the viscosity. OmrOr thoroughly. manufacture of paints using externally plasticized polyvinyl acetate as a bar. Calcium-based titanium pigments should be avoided because, although they do not make the emulsion unstable, they make the film more water-sensitive. Its auton - boron lithopone is used with caution and only after careful testing, since color produced by such an emulsion is usually slightly acidic.

The preferred emulsion is also advantageous in lumnite and Portland cement paste or paints. Used as an additive in place of some of the normally used water, the copolymer emulsion greatly increases the adhesive properties of slender pastes and paints and dilates a significant reduction in the total amount of water required, while improving the plasticity. Unlike pastes and larger containing ordinary polyvinyl acetate emulsion, pastes and paints containing the copolymer emulsion are water repellent..and able to withstand continuous immersion in water without softening or dissolving.

As the binder in the following composition has been found to be very satisfactory: Weight parts Cement100 Copolymer emulsion20 (solid constituents) Water20- When applying a new layer of mortar or concrete on old mortar or concrete, the surface should be cleaned of oil, grease, loose material and other materials. . The clean surface is then moistened with water and the binder paste, which Or mixed to a consistency similarly rather thick, with brush paste printable color, is spread over the surface. This is conveniently done by means of a brush with rigid bristles or a rigid broom, in the spirit of working the paste into the irregularities of the surface. The new mortar or concrete is suitably applied immediately and in the usual way. It has been found that the strength of the bond obtained is about twice as great when the new mortar or concrete is applied without the bonding layer -Oate dryness, as the strength obtained when the bonding layer is allowed to dry. In hada cases Or the strength of the bond by means of the binder paste is usually greater On the strength of saval the new as the old mortar or concrete. Advantageous results are obtained Oven, if a final Unpinning is desired, by using a very spattered layer of binder paste as surface plaster.

The copolymer emulsion also provides some unusual properties of cement paints. A typical, tin-satisfying cement paint has the following composition: Weight parts Copolymer emulsion5 (solid constituents) Cement Water - sufficient to achieve a measurable consistency.

The properties of such a color are surprising. Its adhesion to jam and steel Or so, that metal plate with two layers of this gig can bops 90 ° without the color cracking or flaking ay. The color Or Oven is exceptionally resistant to rust and can be used without application. ay. thank-you layers on metal, even corroded metal, which thank-you layers are durable and prevent the cracking of or continued corrosion of the metal. Steel plates ground with this cement paint showed no rust even after 1224 hours of exposure in an Atlas Weatherometer. These cement paints, which are also particularly effective in the presence of acidic or other types of corrosive water and protect steel structures which are subject to the influence of weather and the corrosive industry, are much more likely than conventional anti-corrosion paints.

Where normal weathering occurs, ordinary Portland cement (A.ST11 / type 1) is used. Where the quenched metal Or is exposed to seawater, acidic water, salt coating, acidic industrial vapors, etc., »Lumnito should be used, which Or a cement with a high aluminum content. In cases where the material is to a lesser extent exposed to acid- or sulphate-containing water, Portland cement with a low C3A content (ASTM type 2) can be used. Where the material Or is exposed to a higher degree of action and «Lumnite» or similar cement with a high alumina content joke is available, Portland cement with a very low C3A content can be used (as well as modified ASTM type 3). Of course, if the color Or is important, white Portland cement can be used for light colors and colored cement or light pigments for special colors.

The cement paint can be applied either with a brush or with a sprayer. As the color thickens, it is important that no more color is mixed at once on what goes on during Indian 30 minutes and an hour.

The cement paint can be applied to all kinds of materials. In the case of metal surfaces, it is only necessary to remove pink flakes and rust, and if so, oil and grease membranes and oil-based paint layers. In the case of masonry surfaces or other moisture-absorbing surfaces, the surface should be exposed to water before the paint is applied, in order to ensure proper hydration of the cement content of the paint. However, it is not necessary to treat the cement paint with a water spray or with cloths or the like.

Claims (6)

Patent claims: A composition lamped as a carrier in aqueous paints and comprising in combination an aqueous dispersion of a copolymer prepared by emulsion polymerization of vinyl acetate and a diester of butene-2-diacid-1,4 and an aliphatic alcohol maid frail of the group comprising ethanol , butanol, isopropanol, 1,4-dimethyl-1-butanol and 2-ethyl-1-hexanol, said monomeric ingredients being present in the proportions 82.5 to 62.5 parts by weight of vinyl acetate and 17.5 to 32.5 parts by weight of the diester and from 5,01,17 parts by weight, per 100 parts by weight of the 6 copolymer, on the one hand a glycol, substituted glycol or a glycol derivative selected from the group comprising hexylene glycol, 3-chloro-1,2-propanediol, 2- (3- butoxyethoxy) -ethanol, 2-butoxyethanol acetate, dipropylene glycol and diethylene glycol monoethyl ether. 2. A composition according to claim 1, characterized in that the diester consists of the di-1-butyl ester of the butene di-acid. 3. A composition according to claim 2, characterized in that the glycol is hexylene glycol. 4. A composition according to claims 1-3, characterized in that the copolymer is prepared by emulsion polymerization of about 77 parts by weight of vinyl acetate and about 23 parts by weight of the di-1-butyl ester of the butenedioic acid. A water-based paint containing, as such, the composition of claim 1. Water-based paint according to patent claim 5 containing hydraulic cement. Request Publications: U.S. Patent Nos. 2,188 27 2.