DD258918A3 - BITUMENOUS ELASTOMER MODIFIED MIXTURE FOR BUILDING PROTECTION PURPOSES - Google Patents

Abstract

The invention relates to an aging-resistant bitumen-containing elastomer-modified mixture for building protection purposes of bitumen emulsions with solids emulsifier, Elastomerlatex, mineral fillers and vulcanizing agents. The mixture according to the invention consists of 50 to 90 parts by weight of a bitumen emulsion with a clay emulsifier, 0.1 to 1.5 parts by weight of a mixture of a cold and a hot vulcanization accelerator, 0.1 to 1.5 parts by weight of ground or colloidal Sulfur, 10 to 40 parts by weight of a styrene-butadiene latex, 0.01 to 0.5 parts by weight of an organic stabilizer and 0.5 to 15 parts by weight of ground or fibrous fillers.

Description

Field of application of the invention

The invention relates to an aging-resistant bituminous elastomer-modified mixture with high elasticity for building protection purposes of bitumen emulsions with Feststoffemulgator, Elastomerlatex, mineral fillers and vulcanizing agents for the execution of seamless roof and sealing coverings.

Characteristic of the known technical solutions

In bituminous building protection, bitumen emulsions and their mixtures with piast and elast dispersions have been increasingly used for several years. These products have the advantage of cold workability, toxicological safety and incombustibility. The content of water, which serves as a liquefying agent instead of the usual organic solvents, favorable economic effects are achieved.

These positive characteristics led to a number of developments of products, methods of application and types of applications.

Mixtures of bitumen emulsions of the most varied types with elastomer dispersions, in particular with styrene-butadiene latices, are known. For thickening of the products, preference is given to using organic thixotropic agents which are effective in the alkaline range which is preferably used. Furthermore, it is common to mineral substances such as stone flours, kaolin, glass fibers, glass chaff, mineral wool, asbestos fibers, nonwovens u. Ä. Add substances, hydraulically acting binders such as cement, gypsum, lime, ashes, as well as organic fillers such as plastic fibers, animal hair, plastic and Elastabfälle. The resulting emulsion mixtures are applied by various methods of application by brushing, spraying, filling on surfaces to be protected, in particular, the roof seal occupies a preferred position. However, the well-known materials seal off structures in the underground area, hydraulic structures and agricultural containers, canals and buildings. To improve and speed up the drying process, various solutions are offered, such as the addition of water-binding substances, flocculent salts, such as calcium chloride or copper sulfate, or by the simultaneous spraying of cationic bitumen emulsion with anionic rubber latex, wherein the emulsions mutually flocculate. The use of cationic emulsions is recommended in some cases, as higher adhesion is achieved in conjunction with glass and minerals. However, all solutions described here have the disadvantage that they are hardly stretchable, especially at temperatures below -5 ⁰ C. So it is especially at high temperature drop in relatively short time intervals to cracks and distortions especially at heavily loaded roof coatings. Another disadvantage of the described products, which are produced from emulsions or dispersions, is the low resistance to the influence of water. This causes swelling phenomena lead to the reduction of mechanical strength and to

Separation phenomena. Furthermore, the layers are sensitive to water shortly after application for a very long time. Particularly thick applied gaskets require setting times of more than 2 weeks. During this time, occurring rain can lead to rinsing or destruction.

Compounds of bitumen and elastomers with additions of vulcanizing agents such as sulfur, zinc oxide and vulcanization accelerators are offered to reduce these disadvantages. The vulcanization proceeds at temperatures around 130 ⁰ C.

Emulsion-based mixtures with vulcanizing agents are not known for the required application. For the production of sports field coverings mixtures of bituminous emulsion rubber latex, cold vulcanization accelerators, rubber waste and cement are recommended. The resulting layers of at least 3cm thickness are not usable in the roof area.

These layers are not resistant to aging, are not impermeable to water and tend to embrittle due to the influence of sunlight (UV radiation). Furthermore, a decrease in the strength of water exposure, caused by a relatively high swelling capacity, recorded.

Object of the invention

The aim of the invention is a cold-processable mixture based on aqueous emulsions and dispersions of bitumen and elastomers, which is producible and cold processable in variable viscosity, which dries and sets quickly and then a sealing layer with high elasticity even at low temperatures, high aging resistance and forms high resistance without loss of strength to water. The bitumen mixture is intended to be used for sealing roofs and structures in underground installation space.

Explanation of the essence of the invention

The invention has for its object to develop a mixture of stable bitumen emulsions, elast dispersions, mineral fillers and vulcanization additives, which dries quickly even in high layer thicknesses and in the dried state has a high elasticity, aging stable and waterproof and thus for the sealing of Roofs and structures with high loads is suitable.

According to the invention, the object is achieved by a bituminous elastomer-modified mixture comprising 50 to 90 parts by weight of a 45 to 60% bitumen emulsion with a Tonemulgator and 50 to 350mVal / 100g clay zinc ions and which has a pH of 9 to 13, 0 , 1 to 1.5 parts by mass of a mixture of a cold and a hot vulcanization accelerator in the ratio of 3: 1 to 1: 3.0.1 to 1.5 parts by mass of ground or colloidal sulfur, 10 to 40 parts by mass of a 35 to 55 % styrene-butadiene latex having a styrene content of 20 to 35% by mass and an anionic emulsifier system based on fatty acids and alkylarylsulfonates, 0.01 to 0.5 part by weight of an organic stabilizer of alkoxylated alkylphenols, alcohols or amines having alkoxylation numbers of 3 to 10 and 0.5 to 15 parts by mass of a milled or fibrous filler. 0.05 to 1.5 parts by weight of an aqueous dispersion of a polyacrylate or a dispersion of a copolymer of butadiene-styrene-methacrylic acid which thickening in an alkaline medium may be added to the mixture.

The cold vulcanization accelerator is a sodium dithiocarbamate, the hot vulcanization accelerator either an Zin dithiocarbamate or a thiuram compound, e.g. B. Tetramethylthiuramdisulfid.

The organic stabilizer is an alkoxylated alkylphenol having an alkyl group of 7 to 12 carbon atoms and / or an alkoxylated chain alcohol or an alkoxylated chain monoamine having 10 to 20C atoms. The alkoxy groups are preferably ethoxy groups.

The filler is kaolin or stone meal and / or asbestos or asbestos fibers or organic fibers such as textile waste

or animal hair. , ,

The thixotropic agent which thickening in the alkaline medium is an aqueous dispersion of a polyacrylate or of a copolymer of butadiene-styrene-methacrylic acid. The proposed mixture makes it possible to achieve an easily processible building protection material which has all the required properties. The mixtures in the specified formulation limits are adjustable from medium to pasty consistency.

Higher viscosities can be achieved especially by an increased use of zinc ions in the bitumen emulsion, by increasing the proportion of fillers and especially by using the thixotropic agent, but also by lowering the content of organic stabilizers.

The variation of the consistency is particularly advantageous for the wide range of applications. Thus, with very high-viscosity mixtures in a process step thick layers can be achieved up to 10 mm thickness. The mixture according to the invention is cold-processable at outside temperatures of at least 5 ° C. On the one hand, it is storage- and transport-stable on the one hand in closed containers for a long period of time, on the other hand, however, a rapid drying out and setting of the layer is surprisingly achieved over known emulsion mixtures.

In this case, the vulcanization process already begins during drying out, that is already when the main amount of water is still present in the applied layer.

Depending on the prevailing outside temperature, the applied layers are already hardened after a short time so that an onset of rain no longer causes rinsing. This is all the more surprising because otherwise both bitumen emulsions with a Tonemulgator, and rubber latexes with emulsifier based on fatty acids and alkylarylsulfonic acids are stable and bind only after evaporation of more than 90% of the existing emulsion water

start and become waterproof. -

The vulcanization is known to be effected by sulfur and organic vulcanization accelerators. The likewise necessary proportion of zinc oxide is not necessary in the mixture according to the invention. The zinc ions are already contained in the bitumen emulsion with Tonemulgator as a firmly bound component. Due to the simultaneous presence of a cold vulcanization accelerator next to that of a hot vulcanization accelerator, the vulcanization can be instantaneous, as well

begin at temperatures as low as 5 ⁰ C and then continue in the course of storage of the layer. The 2nd phase of the vulcanization process then takes over the Heißvulkanistionsbeschleuniger. The reaction is finished with complete incorporation of the available sulfur. The course of the reaction can be observed from the values of elongation at break and tensile strength. The reaction is ended when the maximum values for both parameters are reached at the same time. This occurs when stored at 20 ⁰ C in a closed room after about 6 months. At higher temperatures and under the action of sunlight, the reaction process is significantly accelerated. A fully reacted layer of the mixture according to the invention combines the positive properties of the bitumen, such as aging resistance to UV radiation or oxygen and water resistance with those of a rubber, such as high elongation and recovery. Surprisingly, even at temperatures down to -20 ° C even high strains of over 50% are achieved, although the proportion of the rubber from the rubber latex is only 10 to 40% in the total mixture. Even with a content of vulcanized rubber of only 10 to 15% by mass, still distinct elastic properties are obtained.

The applied and dried layers of the mixture according to the invention are very s + abil against UV radiation. As a result, these layers are advantageous for the execution of roof coatings or such sealing measures in which the sealing layer remains unprotected against the weather. In the case of short-term aging tests, it was possible to demonstrate that, for example, a mixture according to the invention containing 20% by weight of a 50% butadiene-styrene latex after the end of vulcanization has an aging stability of more than 8 years without loss of elastic properties. In the corresponding short-term weathering on a Gardner wheel according to TGL 25788/01, only a decrease in elongation at break of originally 250 to 216%, ie 13.6%, and an increase in tensile strength from 0.81 to 0.88 N / mm ² , thus determined by 8.6%. On the other hand, in a rubber tested in the same short-term aging test, a standard mixture of 10 parts by weight of butadiene-styrene rubber containing 24% of styrene, 2.2 parts by mass of sulfur, 1.3 parts by mass of thiumram disulfide, 7.5 parts by weight of ZnO, 45 parts by mass of carbon black, the decrease in elongation at break from the original 1050% to 350%, ie 200%, and the decrease in tensile strength from 19.8 N / mm ² to 14.9 N / mm ² , So 32.9%. '

The cured and vulcanized layers, which are prepared from the mixture according to the invention are also surprisingly stable to continuous load of water, while otherwise swell sealing layers of known emulsion mixtures with continuous exposure to water, absorb a high proportion of water and lose strength. In hydraulic structures themselves it comes to the detachment of these layers. Thus, e.g. a layer consisting of a mixture according to the invention of 70 parts by weight of bitumen emulsion, 0.4 parts by weight of a mixture of Na dithiocarbamate and tetramethylthiumram disulfide in the ratio 1: 1,0,5Ma. parts of sulfur, 20 parts by mass of butadiene -Styren latex, 0.2Ma parts ethoxylated nonylphenol, 10 parts by weight of kaolin and 0.06 parts by weight of a polyacrylate dispersion was prepared, with a water storage of 56 days, only 2.1 Ma .-% water on.

The tensile strength of 0.81 N / mm ² and the elongation at break of 250% change only by 1.2 or 3.2%. Due to the illustrated positive properties, the mixture according to the invention is outstandingly suitable for the execution of seamless liquid coatings on roofs of any slope area, for insulating roofs with high tensile stress due to high temperature loads, for sealing layers in the underground space, for hydraulic structures and similar sealing measures.

Ausfiihrungsbeispiele

1. In a stirrer are mixed successively:

70 parts by mass of a 52% bitumen emulsion with a clay emulsifier and 250 meq / 100 g of zinc ion, the

pH is 11, 0.4 parts by mass of a mixture of Na-diethyl-dithiocarbamate and tetra-thiuram-disulfide in the quantitative ratio

of 1: 1, wherein the Na-diethyl dithiocarbamate is present in a 37% aqueous solution, 0.5 parts by mass of ground sulfur, 20 parts by mass of a 50% butadiene-styrene latex with a styrene content in the copolymer of 25% and one

Content of ethoxylated nonylphenol as stabilizer of 5%, 0.2 part by weight of ethoxylated nonylphenol with an alkoxylation number of 6, 10 parts by weight of kaolin in ground form.

The mixture is of thick to pasty consistency and has the following properties:

Quasi-viscosity,

Shear rate in the rotational viscometer

145.8s " ¹ '51OcP

pH 10

Resistance to rinsing after 5 hours

no rinsing at 20 ^° C. '-

The film produced from this mixture has, after a 6-month storage at 2O ⁰ C the following properties: tensile strength at 20 ⁰ C

(200 mm / min) after 4h 0.81 N / mm ' Elongation at break at 2O ⁰ C. after 24 h 250 mm Tensile strength at -15X 2.45 N / mm ² Elongation at -15X Aging group AI 97% Resilience after 100% 95% Elongation at 2O ⁰ C 99% Resistance to aging after 8 weeks short-term test Increase the tensile strength (20X) 0.88 N / mm ² Decrease in elongation at break 216mm Water absorption after 56d storage 2.1% thereafter, tensile strength (20 ⁰ C) 0.80 N / mm ² then elongation at break 242 mm

2. Analogously to Example 1, mixtures are prepared according to the following composition (data in parts by weight)

Mixture No. 1 23 4 5 6 7 8 910

Bitumen emulsion with clay

emulsifier with 50 mVal

Zn / 100gTon 80 70 - - - - - _ _ -

Bitumen emulsion with toner emulsion

gator with 10OmVaI

Zn / 100g clay - - 75 65 - - - - - -

Bitumen emulsion with toner emulsion

gator with 30OmVaI

Zn / 100 g clay

Na-dimethyl-dithiocarbamate

Zn-dimethyl dithiocarbamate

Tetramethyl thiuram disulfide

ground sulfur

Butadiene-styrene latex

Ethoxylated nonylphenol

(EO = 6) · j

Ethoxylated allyl alcohol. j

(EO = 8) - - - - 0.4 - - - 0.25 - j

Ethoxylated alkylamine i

(EO = 4) _____ o, 45 - - - 0.3 j

Kaolin 12 14 12 14 - 8 10 10 10 10 j

Asbestos flour with fiber content - - - - 5 - - - - -

Animal hair - - - - - 6 - - - 5 y

Textile fibers - - -. - - - - - - 1 ]

Polyacrylate dispersion 0.5 1.0 - - - - - - - - j

Butadiene-styrene-methacrylic-j

Acid dispersion - - 0.5 0.7 - - - - - - j

The mixtures and the layers produced therefrom have the following properties after a storage time of 6 months:

- - - 80 75 70 65 60 55 0.1 0.1 0.2 0.2 0.2 '0.3 0.2 0.3 0.5 1.0 0.1 - 0.2 - 0.3 0.3 0.2 - - - 0.2 - 0.3 - - - 0.1 0.9 0.4 0.2 0.4 0.2 0.4 0.5 0.3 0.5 0.6 0.7 1.0 15 25 15 25 10 15 20 25 30 35 0.4 0.3 0.3 0.2 0.2 0.2 .

Mixture no. cP 1 2 3 4 CJL 38 6 55 7 0.88 8th 0.80 9 10 Quasi-viscosity (145.8 s ~ ¹ ) 142 145 155 160 10 10 510 479 225 168 PH value 9 12 9 12 10 10 10 10 Resistance to unwinding at H 6.5 4.5 20 ° C after N / mm ² 5.5 6.5 5 6 0.68 0.72 5 6 7 8th Tensile strength 2OX % 0.4 0.75 0.5 0.85 221 240 0.81 0.80 0.85 0.81 Elongation at break 20 ° C N / mm ² 145 310 183 412 1.81 , 2.12 250 295 320 410 Tensile strength -15 ⁰ C % 2.5 2.1 1.9 2.0 65 80 2.45 2.65 3.41 2.10 Elongation at break -15 ⁰ C 45 92 58 110 97 95 88 63 Stiffness after 100% % 85 93 Elongation at 2O ⁰ C after 4 h % 60 71 65 78 87 98 95 96 96 97 Elongation at 2O ⁰ C after 24 h 69 74 71 80 99 98 98 99 Resistance to aging after Alles Al / Il 8 week trial aging group N / mm ² Alles Al / Il Alles Al / Il 0.59 0.66 al al Al / Il Alles -Thereafter tensile strength 0.5 0.85 0.7 0.95 0.78 0.70

Wt .-% 4.1 3.1 2.4 1.9 3.4 2.5 2.1 2.7 2.9 4.4 N / mm ² 0.41 0.71 0.48 0.84 0.50 0.65 0.80 0.71 0.79 0.69 % 140 299 185 401- 189 201 242 280 310 328

Mixture No. 1 2 3 4 5 6 7 8 9

- thereafter elongation at break% 90 250 142 305 200 215 216 240 288 Water absorption after 56 d water storage

- then tensile strength -then elongation at break

3. In contrast, has a known mixture of bitumen emulsion, butadiene-styrene latex, filler, such as animal hair and viscosity-regulating additives the properties in column 1, while in column 2, a mixture according to the invention, which is similar to that in Example 1.

1

Resistance to unwinding at 20 ⁰ C in hours elongation at break at 20 ⁰ C Elongation at break at-15 ⁰ C resilience after 25% elongation at 20 ⁰ C after 24 hours aging resistance after 8 weeks testing, then elongation at break decrease water uptake after 56Tagen wt .-% after elongation at break loss

12 5 50 300 2 90 1 ' 100 75 14 3.5 21 58 5

Claims (5)

1. Bitumen-containing elastomer-modified mixture for building protection purposes of bitumen emulsions with solid emulsifier, Elastomerlatex, mineral fillers and vulcanizing agents, characterized by 50 to 90 parts by mass of a 45 to 60% bitumen emulsion with a Tonemulgator and 50 to 350mVal / 100g clay zinc ions with a pH From 9 to 13, 0.1 to 1.5 Ma. Parts of a mixture of a cold and a hot vulcanization accelerator in the proportion of 3: 1 to 1: 3.0.1 to 1.5 parts by mass of ground or colloidal Sulfur, 10 to 40 parts by mass of a 35 to 55% styrene-butadiene latex having a styrene content of 20 to 35% by mass and an anionic emulsifier system based on fatty acids and alkylarylsulfonates, 0.01 to 0.5 Ma. Parts of an organic stabilizer from alkoxylated alkylphenols, alcohols or amines with alkoxylation numbers from 3 to 10 and 0.5 to 15 Ma.-parts of ground or fibrous fillers. 2. Bituminous, elastomer-modified mixture according to item 1, characterized by an addition of 0.05 to 1.5 parts by weight of an aqueous medium thickening aqueous dispersion of a polyacrylate or a dispersion of a copolymer of butadiene-styrene-methacrylic acid. 3. Bituminous, elastomer-modified mixture according to item 1 and 2, characterized in that the Kaltvercannisationsbeschleuniger a sodium dithiocarbamate and the Heißvulkanisationsbeschleuniger a zinc dithiocarbamate and / or a Thiuramdisulfid. 4. Bituminous, elastomer-modified mixture and point 1 and 2, characterized in that the organic stabilizing agent is an alkoxylated alkylphenol having an alkyl group of 7 to 12 carbon atoms and / or an alkoxylated chain alcohol or an alkoxylated chain monoamine having 10 to 20C- Atoms and that the alkoxy groups are preferably ethoxy groups. 5. Bituminous, elastomer-modified mixture according to item 1 and 2, characterized in that the fillers are kaolin or flour and / or asbestos or asbestos fibers or organic fibers, such as textile waste or animal hair.