CS217718B1 - Rubber pulp based elastic materials - Google Patents

Abstract

The invention relates to and contributes to the elimination of low adhesion of flexible coatings to absorbent substrates. This is achieved by using 5 to 500 parts by weight of dry matter of polymers or copolymers of olefinic and/or olefinic monomers, or mixtures of these polymers and copolymers, in the form of aqueous dispersions, or in a mixture with water-dilutable dispersions or solutions of polymers and reactive resins, with at least one of the above components containing reactive functional groups, in particular carboxyl, hydroxyl, amine, amide, methyl, alkoxy, alkoxymethylamide, epoxy, mercaptan. Furthermore, the mass contains up to 100 parts by weight of rubber crumb, 0.01 to 5 parts by weight of catalysts based on ammonium salts of inorganic or organic acids, or these acids themselves, and 0.01 to 10 parts by weight of accelerators and hardeners. These flexible materials can be applied as flooring for sports purposes, factory halls, roofing, joint sealants and adhesives.

Description

FIELD OF THE INVENTION The invention relates to rubber crumb-based resins in which water-dilutable and / or water-soluble polymers or reactive resins are used as binders. These compositions are characterized by good adhesion to absorbent substrates and are particularly suitable as floor coverings, sports ground coatings, roof coverings and the like.

Rubber crumbs obtained from old tires or other rubber products by grinding, grinding at low temperatures, tablecloths, etc. are an interesting raw material, which is not yet fully utilized. One application is the application as a filler in the preparation of various materials and sealants. The crushed rubber particles are bonded to a rigid resilient mass by various kinds of binders, e.g. polyurethane (US Pat. 3,869,421, US AO 460,285, Fr. Pat. 2,333,087), Asphalt (US Pat. 95,984, US Pat. No. 4 085 078), polyvinyl chloride and other polymers (NSR Pat. 2 515 871 jap. Pat. 5 2066 561), Polymer dispersions (GDR Pat. 126 485, fr, Pat. 2 301 636, British Pat. 1 498 297 No. 5,304,723) and rubber (U.S. Pat. No. 4,082,888, Irish Pat. 2,355,974). These materials can be processed either by cold casting or by pressing at a higher temperature.

The use of aqueous dispersions of polymers and copolymers of vinyl or olefinic monomers as fillers for the preparation of rubble materials in the presence of pigments, fillers, dyes, plasticizers, etc. is disclosed in German Patent 2,750,903. The polymers and copolymers of vinyl or olefin monomers used in dispersions are non-reactive substances which after loose water connect loose components of matter. The properties of the resulting films are greatly influenced by the composition of the polymers or copolymers. The resulting compositions are highly elastic, having an elasticity that exceeds the elasticity of the binder itself, but have a relatively low adhesion to the substrate and low resistance to solvents and chemicals.

The aforementioned disadvantages are overcome by the present invention, which are based on rubber pulp resins bonded with water-dilutable and / or water-soluble polymers and / or reactive resins in the presence of hardeners, fillers, pigments, dyes and other additives. The essence is that the elastic masses consist of 100 masses. 5 to 500 wt. parts of dry polymers of polymers of copolymers of vinyl and / or olefinic monomers, preferably acrylic and methacrylic acid, styrene and butadiene, or mixtures of these polymers and copolymers, in the form of aqueous dispersions or mixtures with water-dilutable dispersions or solutions of polymers and reactive resins, especially epoxyester , alkyd, polyester, epoxy, polyurethane, ureaomelamino-, guanamino-, phenol-formaldehyde condensates, wherein at least one of the polymers or copolymers and / or reactive resins used contains reactive functional groups, in particular carboxyl, hydroxyl, amine, amide, methylol, alkoxymethyl, from alkoxymethylamide, epoxy, mercaptan, from 0.01 to 5 wt. % of parts of catalysts of condensation crosslinking reactions based on ammonium salts of inorganic or organic acids or of these acids themselves, preferably ammonium sulfate, phosphoric acid and p-toluenesulfonic acid, and 0.01 to 10 wt. parts of accelerators and hardeners, preferably piperidine, triethanolamine, diethylenetriamine, tris-dimethylaminomethylphenol, tertiary amine salts and transition element salts and organic acids, in particular cobalt naphthenate, dialkylsalicylic acid chromate and titanium and zirconium oleate.

The advantage of the present invention is a considerable improvement in the drying rate of the mass and its toughness, and an increase in resistance to solvents and chemicals. Furthermore, the elastic masses are characterized by low abrasion and high adhesion to absorbent substrates.

Rubber rubble is obtained in many ways, for example by shredding used tires free of metal parts at low temperatures, or by grinding tires in vulcanizing plants, by abrasion of rubber parts in consumer plants, etc.

Depending on the method of preparation and the type of rubber, the pulp has different particle shape and size, different surface quality and hardness according to the content of the vulcanizing agent and fillers. The grits obtained by crushing or grinding the tire treads have a relatively small surface and are highly elastic and have a particle size of from 0.5 to 5 mm. They give the materials high elasticity and abrasion resistance. The resulting masses shrink relatively little during curing. In contrast, the abrasive rubber pulp is fine with a particle size of 0.05 to 1 mm. It has a large surface area and a higher binder content is required for perfect bonding of the individual particles. For this reason, the resulting compositions are soft, have higher abrasion and higher shrinkage during curing.

Disperse binders used to prepare resilient compositions are polymers and copolymers prepared by emulsion polymerization and copolymerization of unsaturated monomers such as esters of acrylic acid, methacrylic acid, vinyl esters of organic acids, styrene and its derivatives, divinylbenzene, vinyl acetate and vinylpropionate, acrylonitrile, butadiene, butadiene, butadiene, butadiene, and mixtures of all these monomers. Furthermore, they are copolymers which contain, in addition to said unsaturated monomers, unsaturated monomers with reactive functional groups, such as acrylic and methacrylic acid, acrylamide, methacrylamide.

N-isobutoxymethyl acrylamide, N-methylolacrylamide, hydroxyethyl methacrylate, N-alko217718 xymethylmethylmethacrylamide, maleic and fumaric acid and its esters, vinyl lactam, N-vinylpyrrolidone.

Further, they are dispersions of alkyd, epoxyester resins containing unsaturated fatty acids, which dry by air polymerization. Among the polycondensation reactive resins are aqueous or aqueous alcoholic solutions of urea-, melamino-, guanamine-, phenol-, cresol-, xylenol-formaldehyde resins, water-soluble or water-dilutable epoxy resins, such as polyglycidyl ethers of aliphatic alcohols, tetrahydrofuryl glycols. water-dispersible bisphenol A-based epoxy resins, such as Bisphenol A-bisglycidyl ether, higher molecular weight bisphenol A epoxy resins dissolved in organic solvents, and unsaturated polyester resins dissolved in reactive monomers such as styrene, in esters of acrylic and methacrylic acids and the like

Various types of catalysts, accelerators and hardeners are used to accelerate the curing reactions. Of the acid catalysts that accelerate the esterification, etherification and pre-amination reactions, the ammonium salts of inorganic or organic acids, such as ammonium chloride, ammonium sulfate, ammonium phosphate, or the acids themselves, such as phosphoric, oxalic, citric, are used. organic sulfoacids such as p-toluenesulfonic acid. For example, triethanolamine, benzyldimethylamine, tris-dimethylaminomethylphenol, piperidine, polyalkylene polyamines can be used as accelerators and hardeners for the reactions of epoxy groups, double bonds in polymers and monomers. Furthermore, salts of organic acids with transition elements such as chromium salt of dialkylsalicylic acid, cobalt naphthenate, titanium and zirconium oleate may be used.

A wide variety of substances applied in the coating industry can be used as fillers, pigments and dyes. The silicates include feldspar, kaolin, mica, wolastonite, asbestos, slate, fused quartz, basalt.

The oxides include silicon, titanium, lead, ferric and ferrous oxides, zinc and antimony. The sulphides are cadmium and zinc sulphides. Of the sulphates, for example, barium sulphate and of the carbonates are limestone and chalk. Furthermore, there are chromates, powder metals, graphite. Of the organic pigments, carbon black, phthalocyanines, azo pigments, and the like are used. Of the organic pigments, azo dyes, phthalocyanine dyes, anthraquinone dyes, triphenylmethane dyes, etc. are used.

If desired, plasticizers of conventional types such as dibutyl phthalate, tricresyl phosphate, polyalkylene oxide and other additives used to control the evaporation and coalescence of aqueous dispersions such as ethylene glycol, white spirit and the like may be added to the compositions as desired.

The preparation of said compositions is very simple, they can be produced by mixing all the components at once in any mixing device, such as in a concrete mixer. For more complex mixtures, premixtures of aqueous dispersions with pigments, fillers, or colorants can be prepared first and then the rubber pulp added at a later stage. The pigments or dyes may be added in the form of aqueous pastes or dispersions.

These materials can be used for the preparation of flexible coatings, flooring, thicker layers for sports purposes, such as floor coverings in gyms, basketball, handball courts, tennis, playgrounds, floors in factory halls, garages, farm buildings for housing cattle, for covering roofing, for application to the bottom of car bodies, as grout, spray materials, sealants for construction, adhesives, etc.

Composition of copolymers used in the form of aqueous dispersions in the following application examples:

A - aqueous dispersion of styrene butyl acryloate, N-1-butoxymethylacrylamide, methacrylamide and acrylic acid copolymers in a weight ratio of 27:

: 59: 3: 10: 1 containing 45% dry matter;

B - an aqueous dispersion of butadiene, styrene copolymers in a weight ratio of 70:30 containing 20% dry matter;

C - an aqueous dispersion of copolymers of butyl acrylate, acrylonitrile, ethylene glycol dimethacrylate and N-methylolacrylamide in a weight ratio of 80: 5: 10: 4 containing 45% dry matter,

D - an aqueous dispersion of copolymers of butyl acrylate, styrene, N-isobutoxymethyl acrylamide and methacrylic acid in a weight ratio of 68: 25: 3: 4 containing 45% dry matter;

E - an aqueous dispersion of copolymers of vinyl acetate, 2-ethylhexyl acrylate in a weight ratio of 70:30 containing 50% solids;

F - aqueous dispersion of copolymers of vinyl acetate, vinyl esters of acids from propylene trimers in a weight ratio of 55:

45 containing 45% dry matter;

G - an aqueous dispersion of epoxy ester resin prepared by esterifying an epoxy resin based on bisphenol A with soybean oil fatty acids followed by dispersion in water containing 50% dry matter;

H - aqueous dispersion of copolymers of methyl methacrylate, ethyl acrylate, methacrylamide and N-methylolacrylamide in a weight ratio of 45: 47: 5: 3 containing 45 why. dry matter;

CH-aqueous dispersion of copolymers of ethyl acrylate and acrylic acid in a weight ratio of 90:10 containing 45% dry matter;

I - an aqueous dispersion of a copolymer of butyl acrylate, acrylonitrile, hydroxyethyl methacrylate and methacrylic acid in a weight ratio of 70: 10: 8: 2 containing 40% solids;

J - an aqueous dispersion of a butyl acrylate, butyl methacrylate and acrylic acid copolymer in a weight ratio of 15: 82: 3 containing 50% dry matter;

K - aqueous dispersion of a copolymer of ethyl acrylate, methyl acrylate and hydroxypropyl acrylate in a weight ratio of 55: 40: 5 containing 45% solids.

Examples of use:

Example 1 a d 1

100 wt. parts of rubber pulp having a particle size of 0.5 to 5 mm obtained by treading the treads of old tires was mixed with 20 wt. parts of microasbestos and this mixture was mixed with 35 wt. parts of aqueous dispersion C and 45 wt. 10 parts by weight of aqueous dispersion B were added to this mixture with stirring. parts by weight of an aqueous solution of urea-formaldehyde resin containing 50% dry matter and 0.3 wt. parts of ammonium sulfate as curing catalyst. The mixture was thoroughly mixed and applied at a temperature of 15-25 ° C in a layer approximately 1 cm thick on the concrete substrate. After application, the mass was compressed and left at normal temperature for 3 days. The resulting layer is strong and flexible and can serve as a flexible coating of concrete floors for sporting purposes. After 7 days, an additional mass of approximately 1 cm can be applied to this layer, which will bond very well to the backing to form a flexible coating having a high layer elasticity. The material has a high adhesion to the substrate and is resistant to weathering at alternating temperatures.

Example 2

100 wt. parts of rubber crumb having a particle size of 0.1 to 1 mm obtained by crushing old tires at low temperatures was mixed in a mixer with a mixture of 20 wt. 5 parts by weight of the aqueous dispersion C and 5 parts by weight of the aqueous urea-formaldehyde resin solution mentioned in Example 1; parts of p-toluenesulfonic acid. The obtained mass was applied to a concrete substrate in a layer approximately 0.6 mm thick and left for 7 days at ambient temperature after compaction. The obtained layer was hard elastic, very well adhering to the substrate. It was used as a coating of concrete floors in farm buildings with stable cattle.

Example 3

100 wt. parts of rubber pulp obtained by abrasion of colored soles of particle size

0.05-0.5 mm was mixed with 3 wt. parts of the aerosol and in a mixer were mixed with an aqueous dispersion prepared by dispersing 25 wt. parts of an aqueous dispersion Dal wt. % of bisphenol A-based low molecular weight epoxy resin containing about 0.5 epoxy equivalents per 100 g and 0.1 tris-dimethylaminomethylphenol. The obtained mass was applied in a thickness of 0.4 cm on the concrete treasure and after curing for 5 days at normal temperature it served as a flexible flooring in the factory hall. Excellent adhesion to the substrate was achieved and the obtained material had good anti-slip properties.

Example 4

100 wt. parts of the rubble of Example 1 were mixed with 5 wt. parts of green pigment based on chromium oxide and with 10 wt. parts of cork pulp. This mixture was added to the mixer and 30 wt. parts of aqueous dispersion E and 10 wt. parts of aqueous dispersion B and finally 5 wt. parts by weight of an aqueous solution of melamine formaldehyde resin of 40% dry matter and 0.3 wt. parts of ammonium chloride. After thorough mixing, a green colored mass was obtained, which was applied and used as the mass in Example 1. This mass did not lose color or elasticity and adhesion even after prolonged exposure to weather.

Example 5 wt. parts by weight of 0.1 to 0.5 mm particle size of rubber pulp obtained by rubbing the rubber rollers were mixed with 5 wt. parts of fine sand, 5 wt. parts of brown-red iron oxide and 10 wt. parts of finely ground diatomaceous earth. This mixture was mixed with a 40 wt. parts of aqueous dispersion F and 8 wt. parts by weight of aqueous dispersion G and finally 0.5 wt. % of a 50% solution of cobalt naphthenate in xylene. The obtained fine mass was used as a gravel mass on an absorbent substrate. It is hard elastic and can be smoothed to a smooth surface. It can also be used as a topsheet for the compositions of Examples 1, 2, 3, 4.

Example 6

100 wt. parts of the rubble used in Example 1 were mixed with 30 wt. parts by weight of aqueous dispersion B and 40 wt. parts by weight of aqueous dispersion A with the addition of 0.5 wt. parts of secondary ammonium phosphate and 5 wt. parts of a 20% aqueous dispersion of a yellow organic pigment based on 2-nitro-4-methylaniline and acetoacetanilide (e.g. Yelow 1 azopigment). Said composition can be used as a permanently elastic elastic coating for the preparation of light athletic tracks.

Example 7 wt. parts of rubber pulp having a particle size of 1 to 5 mm and 60 wt. parts of rubber pulp having a particle size of 0.1 to 1 mm were mixed with a mixture containing 25 wt. parts by weight of aqueous dispersion H, 10 wt. parts by weight of aqueous dispersion CH, 2 wt. parts by weight of blue organic phthalocyanine pigment, 7 wt. parts of titanium white and 0.05 wt. parts of chromic chelate of salicylic acid. The material obtained after application and compression was used as a flexible jointing putty in the construction industry.

Example 8 wt. parts of rubber pulp having a particle size of 0.05 to 0.5 mm and 5 wt. ruby-type titanium white, 15 wt. parts of diatomaceous earth, 5 wt. parts of yellow ferric oxide were mixed with 25 wt. parts of the aqueous dispersion J and with 20 wt. parts of aqueous dispersion I with the addition of 5 wt. parts of tricresyl phosphate, 4 wt. parts of antimony trioxide and 4 wt. 40 parts by weight of an aqueous solution of phenol-formaldehyde resin having a dry weight of 40. Finally, 0.2 wt. parts of phosphoric acid. The obtained mass was applied as a protective layer on roofing with limited flammability.

Example 9 wt. parts by weight of the rubble with a particle size of 0.1 to 1 mm, 10 wt. 30 parts by weight of silica drift were mixed with 30 wt. parts of the aqueous dispersion K and 40 wt. parts by weight of an asphalt slurry having a dry matter content of 60% / 0.5 wt. parts of furfuryl alcohol and 1 wt. % phosphoric acid. The composition was used as a flexible sealant for the protection of automobile bodies.

Example 10 wt. parts of fine rubble are added to a mixture of aqueous dispersions containing 40 wt. parts of dispersion B, 30 wt. parts of dispersion F are added and after mixing 20 wt. parts of paste containing 15 wt. parts of microasbestos, 4.8 wt. After thorough mixing, a medium viscous mass is obtained which can be used as an adhesive flexible interlayer between concrete, wood, cork and rubber plates in the preparation, eg in parts of guanamin-formaldehyde resin (50% aqueous solution) and 0.05 parts by weight of oxalic acid. artificial surfaces for sports halls.

They did

100 wt. parts by weight of the rubble with a particle size of 0.1 to 5 mm, 150 wt. parts of fine sand, 20 wt. parts of microasbestos and 15 wt. parts of yellow iron oxide are mixed with 60 wt. parts of the aqueous dispersion J, with 600 wt. parts by weight of an aqueous dispersion of a low molecular weight epoxy resin in water (50% dry matter), with 200 wt. parts by weight of an alcoholic fatty acid amide amide solution (60% dry matter) and 8 wt. tertiary amine accelerator parts. The resulting material can be used for surface treatment of concrete floors. The resulting films are very tough, resistant to chemicals, with low abrasion.

Example 12

100 wt. parts of yellow rubber pulp having a particle size below 0.1 mm and 5 wt. parts of the organic pigment of Example 6 were mixed with 30 wt. parts of aqueous dispersion Has 150 wt. parts of an alcoholic solution of phenyl urea-formaldehyde condensate (dry matter 60%). This mixture was allowed to wipe in a ball mill and 5 wt. parts of an 80% solution of oxalic acid in ethanol. The resulting coating composition can be used to prepare flexible coatings for absorbent substrates.

Claims (1)

Flexible rubber base materials bonded with water-dilutable and / or water-soluble polymers and / or reactive resins in the presence of hardeners, fillers, pigments, dyes and additives are characterized in that they consist of 100 wt. 5 to 500 wt. parts by weight of the polymer or copolymer of vinyl and / or olefinic monomers, preferably acrylic and methacrylic acid derivatives, styrene and butadiene, or mixtures of these polymers and copolymers, in the form of aqueous dispersions or mixtures with water-dilutable dispersions or solutions of polymers and reactive resins, in particular epoxyester, alkyd, polyester, epoxy, polyurethane, ureaomelamino, guanamine, phenol-formaldehyde condensates, wherein at least one of the polymers or co-polymers used and / or reactive resins contains reactive functional groups, in particular carboxylic, hydroxyl, amine, amide, methylol %, alkoxymethyl, alkoxymethylamide, epoxy, mercaptan, further from 0.01 to 5 wt. % by weight of parts of catalysts of condensation crosslinking reactions based on ammonium salts of inorganic acids or these acids themselves, preferably ammonium sulfate, phosphoric acid and p-toluenesulfonic acid, and 0.01 to 10 wt. parts of accelerators and hardeners, preferably piperidine, triethanolamine, diethylenetriamine, tris-dimethylaminomethylphenol, salts of tertiary amines and salts of transition elements and organic acids, in particular cobalt naphthenate, dialkylsalicylic acid chromate and titanium and zirconium oleate.