Polyacrylate connecting the sealing composition in the form of a pasty mass
This invention relates to polyacrylate docking sealing composition consisting of copolymers of acrylate with a number of carbon atoms in the alcohol fragment from two to eight and Acrylonitrile as binders fatty substances, as a plasticizer and fillers and/or pigments, auxiliaries and water. As fatty substances it preferably contains methyl ether of apocrisiarius acid as the preferred acrylate co monomer copolymer contains butyl acrylate. This composition exhibits high elasticity. Consequently, it is especially suitable for substrates with different coefficients of thermal expansion. 2 C.p. f-crystals, 3 tables.
The invention relates to sealing compositions, in particular polyacrylate connecting the sealant composition of the copolymers and Acrylonitrile.
In the international application WO 96/06897 describes the composition of homopolynucleotides and methyl ether of apocrisiarius acid (see page 21, example 4). Such compositions are particularly suitable to obtain a paste-like seals, namely the expansion sealing SOS the Noi application WO 97/07173 sealing the connecting part, containing butyl acrylate/styrene copolymers, methyl ether of apocrisiarius acid, clay, titanium dioxide, ammonia, wetting agent. The ability to return to the initial state makes these materials 22% when the test sample is stretched by 100%, is retained in this position at room temperature for 24 hours and then for 1 h his relaxation. E-100 module, a measure of the elongation/tension at 100% elongation) is when applied on concrete - 0,04, tree - 0,05, PVC - 0.015 and aluminum - 0,06 N/mm2.
Known compounds as a hub sealing mass can be used at low requirements to the core components, however, cannot be regarded as plastoelastic and certainly not as flexible docking sealant compositions. For these purposes, the following conditions are necessary: the ability to return to its original state should be more than 40 or more than 70% according to IVD-instruction No. 2. Measurements are carried out according to the standards ISO 7389, method B or DIN 52458.
The objective of the invention is to develop high-quality docking sealing compound, the cat is used in the construction of priming surfaces without application of a primer.
The problem is solved, we offer polyacrylate docking sealing composition in the form of a pasty mass containing the following components:
A) from 10 to 60 wt.% copolymers of acrylate with a number of carbon atoms in the alcohol fragment from two to eight and Acrylonitrile as binders
B) from 0.2 to 15 wt.% fatty substances as a plasticizer,
B) from 20 to 70 wt.% fillers and/or pigments,
D) from 0.3 to 5 wt.% auxiliary substances and
D) from 5 to 20 wt.% water.
Docking sealant turns into a pasty condition, if the maximum extrusion speed does not exceed 6000 g/min and preferably is in the range from 500 to 4000 g/min measured temperature is 23°C. the Measurements are carried out in accordance with ISO 9048.
Under the copolymers of acrylate and Acrylonitrile mean copolymers that contain at least one acrylate and Acrylonitrile as comonomers. The proportion of Acrylonitrile is preferably from 2 to 15 wt.%, in particular from 4 to 8 wt.%. The proportion of the acrylate is preferably from 85 to 98 wt.%, in particular from 90 to 98 wt.%. Separate from the butyl acrylate. Instead of butyl acrylate can be used also other esters of acrylic acid with the number of carbon atoms in the alcohol fragment from two to eight, preferably two to four.
The above copolymer may also contain small amounts of other comonomers to achieve special effects. To improve the adhesion serve, for example, olefinic unsaturated, hydrolyzable silicon compounds, such as vinyltriethoxysilane, at the same time as alkoxygroup are methoxy, ethoxy, methoxyphenyl, ethoxyphenyl-and methoxypropionitrile ether or ethoxypropionitrile ether. To regulate the yield strength can be used by regulators, such as water-soluble monomers and acrylic acid, of methacrylic kislota, acrylamide, methacrylamide, N-methylolacrylamide or N-methylolmethacrylamide.
The dispersions can contain monomers that cause chemical cross-linking of the polymer, therefore, is necessary or whether the dispersion of the reactive fragments for knitting or introduction through their excipients. This can be, for example, compounds with a single primelkavshiesya by hydrolysis, for example glycidylmethacrylate or glycidylmethacrylate.
The above copolymers is mainly obtained by the emulsion polymerization.
Under "fatty substance" is understood fatty acids, fatty alcohols and their derivatives. In General, if the molecular weight exceeds 100, in particular greater than 200. The upper bound is 20 000, preferably from 300 to 1500. Fatty substances are used in quantities of from 0.2 to 15 wt.%, preferably from 1 to 10 wt.%.
Under "essential fatty acids" mean acid containing one or more carboxyl groups. Carboxyl groups can be associated with saturated, unsaturated, unbranched and branched alkyl radicals with carbon atoms is more than eight, in particular more than twelve. They can along with hydroxyl groups, sulfhydryl groups, -C=C-groups, carboxyl groups, amine groups, anhydrite or epoxypropane also contain fragments of simple or complex esters, halogen atoms, amide, amine, urethane, and urea groups. Preferred, however, such carboxylic acids as natural fatty acids or mixtures thereof, dimeric and trimeric fatty acids. A specific item is multiple double bonds: palmitoleate, oleic, elaidic, Petroselinum, erucic, ricinoleic, hydroxymatairesinol, 12-hydroxystearate, linoleic, linolenic, gadolinia.
As fatty acids can also be applied to the products resulting from the reaction of the Arms of a linear saturated or unsaturated fatty alcohols with subsequent oxidation. As examples can be mentioned: 2-ethylhexanoate acid, 2-mucilaginosa acid, 2-hexyldecanoic acid, 2-decyltetradeceth acid, 2-tetrameristaceae acid, 2-hexadecyl-C20-acid or mixtures thereof. In addition, this series also includes ezoterikova acid, which is a by-product of the dimerization of fatty acids.
Along with natural fatty acids can also be used polyhydroxyalkane fatty acids. They can be obtained, for example, epoxydecane unsaturated fats and oils or fatty acid esters with alcohols, splitting cycle compounds with active hydrogen atom, such as alcohols, amines and carboxylic acids, with subsequent saponification. As starting compounds can be used fats and oils, both vegetable and animal origin, or, if necessary is to be based on the fat or oil feedstock, available, for example, in the reactions of accession, the Diels-alder reaction, interesterification reactions, condensation reactions, immunizations (e.g., with maleic acid anhydride or acrylic acid), and epoxidation. As examples can be mentioned: a) epoxides such unsaturated fatty acids as palmitoleate, oleic, elaidic, Petroselinum, erucic, linoleic, linolenic, gadolinia, b) the interaction products of unsaturated fatty acids with maleic acid, anhydride of maleic acid, methacrylic or acrylic acids, condensation products hydroxycarbonic acids, namely ricinoleic acid or 12-hydroxystearate acid and polyhydroxyalkanoic acids. Not all of the above fatty acids are stable at room temperature. If necessary it is possible therefore suitable for use in accordance with this invention, derivatives of the aforementioned acids as esters or amides.
In a preferred embodiment of the present invention use a fully or partially esterified with one or polyhydric alcohols of the aforementioned fatty acids. The term "spirits" should be understood hydroxyine the hydrocarbons. Along with monohydroxy alcohols these are also known in polyurethane chemistry of low molecular weight extender chain with a hydroxyl group or staplers. Specific examples of low molecular weight compounds are: methanol, ethanol, propanol, butanol, pentanol, decanol, octadecanol, 2-ethylhexanol, 2-octanol, ethylene glycol, propylene glycol, triethyleneglycol, tetraethyleneglycol, 2,3-butyleneglycol, hexamethylene, octamethylene, neopentylglycol, 1,4-bis(hydroxymethyl)cyclohexane, gerberoy alcohol, 2-methyl-1,3-propandiol, hexane-1,2,6-triol, glycerol, trimethylolpropane, trimethylacetyl, pentaerythritol, sorbitol, formic, methylglucoside, butyleneglycol restored to alcohols dimeric and trimeric fatty acids. For the esterification can also be used alcohol-based resin acids from rosin, for example abietinus alcohol.
Instead of the above-mentioned alcohols can be applied also hydroxycobalamin tertiary amines, polyglyceryl or partially hydrolyzed polyvinyl alcohol.
In addition, oligomerization can be added or polycarboxylic hydroxycarbonate acid. As examples may serve the following acids: oxalic, melanosoma, phthalic, isophthalic, terephthalic, hexahydrophthalic, tetrahydrophtalic, dimeric fatty acid, trimeric fatty acid, citric, lactic, tartaric, ricinoleic, 12-hydroxystearate. Preference should be given to adipic acid.
Examples of suitable esters along with partially gidrolizovannykh fats, such as glycerol monostearate, are preferably natural fats and oils from rapeseed (new) and (old), sunflower, soybean, flax, castor, coconut, oil palm (palm and palm kernel oil) and olives, as well as their methyl esters. The preferred fats and oils are, for example, beef tallow, which consists of 67% oleic acid, 2% stearic acid, 1% heptadecanoic acid, 10% saturated acids with carbon chain with the number of carbon atoms from twelve to sixteen, 12 wt.% linoleic acid and 2 wt.% unsaturated acids with the number of carbon atoms is less than 18 or, for example, new oil sunflower, in which about 80% oleic acid, 5% stearic acid, 8% linoleic acid and about 7% palmitic acid. Needless to say that the application can find the corresponding epoxides and products usamade castor oil, partially acetylated castor oil, the products formed by the disclosure of cycles in epoxydecane soy oil by the action of dimeric fatty acids.
In addition, the composition may contain esters of fatty acids and their derivatives obtained by epoxidation. As examples of such esters can be called methyl esters of the acids of soybean oil, methyl esters of acids of linseed oil, methyl esters of acids of castor oil, methyl ether of apocrisiarius acid, 2-ethylhexyloxy ether of apocrisiarius acid. From glycerides preferred triglycerides, such as oil bittercress, linseed oil, soybean oil, castor oil, partially or fully digidrirovannye castor oil, partially acetylated castor oil, epoxydecane soybean oil, epoxydecane linseed oil, epoxydecane rapeseed oil, epoxydecane oil sunflower seed.
Preferably the application of the products formed during the opening of cycles epoxydecane triglycerides of unsaturated fatty acids by nucleophiles. These nucleophiles are alcohols, such as methanol, ethanol, ethylene glycol, glycerin or trimethylolpropane can be carboxylic acid, for example acetic acid, dimer fatty acid, maleic acid, phthalic acid or mixture of fatty acids with the number of carbon atoms from six to thirty-six.
Fats and oils (triglycerides) can be used as in-kind and after thermal and/or oxidative treatment, as well as derivatives obtained by epoxidation of, or accession of maleic anhydride or acrylic acid. Specific examples include: palm oil, petroleum oil, rapeseed oil, cottonseed oil, soybean oil, castor oil, partially or fully digidratirovannogo castor oil, partially acetylated castor oil, sunflower seed oil, linseed oil, varnish, epoxydecane soybean oil, epoxydecane linseed oil, rapeseed oil, coconut oil, palm kernel oil and animal fats.
As derivatives can be used and amides of the above fatty acids. They can be obtained by the interaction with primary and secondary amines or polyamines, for example monoethanolamine, diethanolamine, Ethylenediamine, hexamethylenediamine were, ammonia.
The term "fatty alcohol" includes compounds that ), unsaturated, unbranched or branched alkyl residues with the number of carbon atoms greater than eight, in particular more than twelve. Along with the need for subsequent transformations involving alkalisation sulfhydryl groups, -C=C-groups, carboxyl, amine groups, functional groups, anhydrides of acids or epoxy groups, they can contain other groups, such as functional groups, ethers, esters, halogen atoms, amine, amide, urea and urethane groups. Specific examples relevant to this invention, the fatty alcohols may be: ricinoleic alcohol, 12-hydroxystearates alcohol, alerby alcohol, aracelly alcohol, linalilovy alcohol, arachidonoyl alcohol, gadolinia alcohol, aroroy alcohol, passively alcohol, dimetyl (the product of the hydrogenation of methyl ester of dimer fatty acids).
Perhaps the use of branched alcohols, also known as spirits of the Arms, which are formed by condensation of a linear saturated or unsaturated alcohols. Examples of such alcohols are 2-ethylhexanol, 2-butyloctyl, 2-hexyldecanol, 2-tetradecyltrimethyl, 2-hexadecyl-C20-almetov.
As derivatives of fatty alcohols can be used symmetrical and unsymmetrical ethers and esters with mono - and polycarboxylic acids. As the monocarboxylic acids used formic acid, acetic acid, propionic acid, butyric acid, valeric acid, Caproic acid, enanthic acid, Caprylic acid, pelargonium acid, capric acid, undecanoyl acid, lauric acid, tridecane acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachnid acid, beenbuy acid, lignocellulose acid, arotinolol acid, melissinos acid. Among the polycarboxylic acids include, for example, oxalic, adipic, maleic, tartaric and citric acid. However, as the carboxylic acids can be used and the above-described fatty acids, for example oleic acid olejowego ether. The above examples show that the esters of fatty alcohols and fatty acids are also included in the term "fatty substance".
Fatty alcohols can be used in the form of ethers, especially when it comes to mnogodelnym fatty substance is a fatty acid ester, in particular the methyl ether of apocrisiarius acid. Preferably as a plasticizer use only fatty substances, it is important not to use polyalkyloxy and/or their chemical derivatives with fatty substances. But, in addition, can also be used in addition to the fatty substances of conventional plasticizers.
Used fillers are, on the one hand, to save binders, and on the other hand, increase technical applicability. In the case of connecting the sealant compositions selection of fillers and mixtures thereof has a positive influence on surface adhesion, reduction, adhesion, and mechanical properties of the solidified mass. As fillers and/or pigments are considered: chalk, heavy spar, kaolin, carbon black, gypsum, Aerosil, silica gel, kaolin, talc, graphite, oxides of such metals as aluminum, iron, zinc, titanium, chromium, cobalt, Nickel, manganese and others, if necessary, this can be a mixture of metal oxides, chromates, molybdates, carbonates, silicates, aluminates, sulphates, natural fibers, cellulose, sawdust, phthalocyanines and quartz flour. Preferred fillers and/or pigments javlautsa quantities from 20 to 60 wt.%, considering the total number of docking sealing mass.
Excipients are used depending on the purpose of application to achieve special effects. To excipients include antioxidants, wetting agents and fungicides (for example, isothiazolinone derivatives), preservatives, means for damping foams, film-forming means, deodorants, water, adhesive compositions, solvents, dyes, flame retardants, processing AIDS, resins, substances for improving adhesiveness, viscosity regulators, dispersing means (for example, sodium and ammonium salts of polyacrylic acid), emulsifiers (for example, alkoxyalkanols and sulfosuccinate) and thickeners (e.g., methylcellulose and hydroxytyrosol). These auxiliary substances are added in an amount of from 0.3 to 5 wt.%, preferably from 1 to 2.5 wt.%, considering the total number of docking sealing mass.
In the role of viscosity regulator can be, for example, ethers, cellulose, utverjdenie castor oil and highly dispersed silicic acid, and ionic and nonionic thickeners, such as polyacrylic acid and complex thickeners.
The preferred connecting the sealing composition, corresponding to this invention, includes:
A) from 15 to 60 wt.% copolymers of acrylate with a number of carbon atoms in the alcohol fragment from two to eight and Acrylonitrile as binders
B) from 1 to 10 wt.%, fatty substances as a plasticizer,
B) from 20 to 60 wt.% fillers and/or pigments,
D) from 1 to 2.5 wt.%, auxiliary substances and
D) from 10 to 15 wt.%, water.
Wt.% refer to finish connecting to the sealant composition.
In the General case, corresponding to the invention connecting the sealing composition is prepared from starting compounds, as follows: add the relevant invention plasticizer to binder medium (polymer or polymer dispersion) is carried out as carried out after polymerization or during polymerization or before it. Typically, the composition is prepared so that the binder or dispersion binders have already been prepared, then p through the addition of water is set to the desired viscosity.
The obtained paste dries after application to education plastoelastic or elastic expansion of the seal with the parameters according to DIN 52458.
Docking sealing compounds, corresponding to the present invention have excellent mechanical properties such as elongation, the total deformation, the rate of resistance to tensile at 100% elongation and, first of all, flexibility. Elongation is determined according to ISO 8339, metric - resistance, tensile strength at 100% elongation (ISO 8339, elasticity according to ISO 7389, method B.
Already adding only 0.2 wt.% fatty substances elasticity increases by 37%, adding 1 wt.% increases to 80% and adding 4 wt.% the elasticity reaches 92%. I.e., the elasticity increase is not linear, and leaps in the field of from 0.2 to 1.0 wt.% and then grows only slowly with the further addition of an appropriate present invention plasticizer. Thus, corresponding to this invention connecting sealing compounds are suitable, in particular if the substrates have different elastic properties or different coefficients of thermal expansion.2without the addition of plasticizer to 0.13 N/mm2when 2 wt.% added according to this invention, a plasticizer and to 0.11 N/mm2adding 4 wt.% plasticizer suitable for the invention. Thus, the modulus of elasticity decreases almost linearly.
Thanks corresponding to this invention the combination of binders and plasticizer is possible to obtain high-quality docking sealing compounds while using low-cost original substance. Other advantages are: universal adhesion without primer, stability to environmental influences and aging, small volume shrinkage, high mechanical stability and easy of use.
The invention is further illustrated in Appendix examples.
Example 1 (see tab.A)
(A) the Original substance
a) 30 wt.% copolymer of butyl acrylate and Acrylonitrile, with approximately 6% of Acrylonitrile (Primal 3362, 62% water dispersion),
b) from 0 to 4 wt.% methyl ether of apocrisiarius acid as a plasticizer,
C) 60 wt.% pigment and filler (titanium dioxide TBE auxiliary substances,
d) from 1 to 1.5 wt.% thickeners (cellulose ether, ammonium salt of polyacrylic acid), as auxiliary substances (e) water (balance).
B) Receiving a docking sealant compositions
Mix and homogenize the binder, excipient and a plasticizer. To this mixture is added a filler and/or pigment, intensively mixed in a planetary mixer, remove and place in a plastic cartridge, and then connecting the sealing composition is subjected to technical tests.
C) Test the docking sealant compositions
Connecting the sealing composition is tested in accordance with the applicable standards for connecting the sealant compositions on anodized aluminum (ISO 11600). To do this, use the following standards:
Mechanical stability: ISO 7390.
Easy of use: ISO 9048.
Description clutch/extension: ISO 8339.
The ability to return to original state: ISO 7389.
Corresponding results were obtained also on the concrete.
In the presented table 1 is tificate. The elongation test was 100%. All comparative samples Acronal 3496X (a copolymer of styrene and butyl acrylate content of about 29% styrene, about 60% of butyl acrylate and about 5% of acrylic acid) was detected during the measurement and subsequent storage breaks on the border with the surface of the substrate, and the volume of the seal, resulting in the determination of the ability of a return to the original state it was impossible. Values obtained in accordance with this invention, compositions are given in the column Primal 3362.
Table 2 shows the resistance value of the tensile strength (modulus of rupture and elongation at break).
Thus, the ability to return to its original state for the composition according to this invention is more than 70%, whereas in the comparative example cannot be measured. Elongation at break is also twice; modulus of rupture rises to 50%.
1. Polyacrylate connecting the sealing composition in the form of a pasty mass containing the following components: A) 10-60 wt.% copolymers of acrylate with a number of carbon atoms in the alcohol fragment from two to eight and Acrylonitrile as svaov, G) 0.3-5 wt.% auxiliary substances and D) 5-20 wt.% water.
2. Docking sealant under item 1, characterized in that the acrylate/Acrylonitrile copolymer contains 85-98 wt.% acrylate and 2-15 wt.% Acrylonitrile relative to the total content of comonomers.
3. Docking sealant under item 1 or 2, characterized in that it contains as lipid esters of fatty acids, in particular methyl ether of apocrisiarius acid.
- constructions, which are used outdoors and indoors;
- pipelines, drainage channels and pits;
- chemical equipment (when exposed to diluted mineral acids, alkalis, salts);
- hull, bottoms and wing cars
SUBSTANCE: invention discloses versions of water resistant, pressure sensitive adhesive acrylic polymers having volume-average particle size of at least 250 nm, formed during polymerisation in the presence of a surfactant in an emulsion of a mixture of monomers. Disclosed also are versions of labels having a frontal base and a pressure sensitive adhesive, which is one of the versions of the disclosed water resistant acrylic polymers.
EFFECT: disclosed polymers enable to obtain pressure sensitive acrylic based adhesives, which during coating and drying in form of a film become transparent and resistance to whitening when exposed to water.
44 cl, 1 dwg, 2 tbl, 16 ex