Dispersion adhesives ii
SUBSTANCE: present invention relates to an aqueous polyurethane-polyurethane-urea dispersion which is used as a starting adhesive material in dispersion adhesives, as well as a method of producing such a dispersion, use thereof, adhesive compositions containing said dispersion and adhesive composite materials. The aqueous polyurethane-polyurethane-urea dispersion is composed of: A) one or more di- or higher functional polyols, having average molecular weight of 400-5000 Da, B) optionally one or more di- or higher functional polyol components, having molecular weight of 62-399 Da, C) one or more compounds which are monofunctional when reacting with a polyisocyanate and which have ethylene oxide content of at least 50 wt % and molecular weight of at least 400 Da, D) one or more di- or higher polyisocyanate components, and E) a mixture (E) of primary and/or secondary monoamine compounds E1) and primary and/or secondary diamine compounds E2), wherein at least one of the components (E1) and/or (E2) contains sulphonate groups, wherein the average amine functionality of the mixture (E) is 1.65-1.98, and the equivalent ratio of NCO groups in the NCO prepolymer and the total number of amine and hydroxyl groups of the mixture (E) which react with the isocyanate is equal to 1.04-1.9.
EFFECT: obtaining stable aqueous dispersions of adhesives without the need to use an emulsifying agent, films from which have improved initial thermal stability and high final heat stability.
14 cl, 4 ex, 1 tbl
The invention relates to aqueous dispersions of adhesives based on aqueous polyurethane-poliuretanovykh dispersions, method for their production and use dispersion adhesives in the manufacture of adhesive composites.
Obtaining an aqueous polyurethane-poliuretanovykh dispersions is known. When using such dispersions as adhesives for joining substrates commonly used method of thermal activation. In this method, the dispersion is applied to the substrate and, when the water is completely evaporated, the adhesive layer is activated by heating, for example, using an infrared emitter, and is translated into a viscous state. The temperature at which the adhesive film becomes sticky, is called the activation temperature. Usually you want as low as possible temperature activation, since at high temperatures the activation required unprofitable high energy costs, as well as manual Assembly becomes difficult to implement.
Adhesives based on aqueous polyurethane-poliuretanovykh dispersions that are suitable for use according to the method of thermal activation, as described in application for U.S. patent US-A 4870129. According to this technical description, through the use of special mixtures of diisocyanates possible to obtain an aqueous polyurethane-poliuretanovym the e dispersion by acetone technology, and the films obtained in this manner can easily be activated at temperatures from 40° to 80°C.
Similarly, in European patent application EP-A 0304718 describes how to obtain an aqueous polyurethane-poliuretanovykh dispersions, allowing to produce films that can be easily activated. This is achieved through the use of special amino compounds as chain-extending agents. The amino compounds are primary and/or secondary monoaminooxidase, optionally in a mixture with primary and/or secondary diaminododecane having an average functionality on the amino group of from 1 to 1.9. The equivalent ratio of NCO groups in the NCO-prepolymer and the total number of hydrogen atoms active towards isocyanates is from 0.5:1 to 0.98:1. Preferably used a mixture of diamino - and monoaminooxidase.
In the German patent application DE-A 2551094 describes polyurethanes, which can dispergirujutsja in water and contain side chains of the polyether-polyalkylated, and ionic groups (sulphonate, carboxylate or ammonium group) and which can also be used, inter alia, as adhesives.
The main disadvantage of these dispersion adhesives described in the prior art, is their lack of initial heat is stoikosti. In addition, they find insufficient the final heat in the case of one-component adhesive connection, the term "single component" in the context of this invention means that the additional polyisocyanate compound is not added as a component of polymer crosslinking to use.
Another method to obtain an aqueous polyurethane-poliuretanovykh dispersions which are suitable as adhesive, in particular, in accordance with the method of thermal activation, as proposed in the German patent application DE-A 10152405. In this Datasheet aqueous polyurethane-poliuretanovye dispersion can be obtained by using a special complex of polyether polyols containing an aromatic methylsulfonate group. Films made of them by removing water, can easily be activated at temperatures from 50 to 60°C. However, these polyesters containing aromatic methylsulfonate group, can be obtained only with difficulty, or are very expensive due to containing methylsulfonate or sulfopropyl dicarboxylic acids, which must be used as the starting materials.
In the German patent application DE-A 102004023768 reported another method for production of polyurethane-poliuretanovykh dispersions, which prigodin is as adhesives, having a good initial resistance. However, the content of 7.5 wt.% additional emulsifier adversely affect the possible use of these adhesives, as this is the reason for the high hydrophilicity and the sensitivity of the products to the water. In addition, adhesion and bond strength can adversely impacts of migration chemically not related emulsifier.
Thus, an object of the present invention to provide a dispersion adhesives based on polyurethane-poliuretanovykh dispersions obtained without using an emulsifier, which can be obtained by evaporation of the water or remove it in another way (for example, water absorption by the substrate, which itself is absorbent, or auxiliary absorbent agent), films that have improved the initial resistance and improved high end heat resistance in comparison with the already known issues prior art.
So, unexpectedly, it was found that aqueous polyurethane-polyurea dispersions, described below, which are obtained without using an emulsifier, suitable as a source of adhesive material, and that thermally activated film obtained from them by evaporation of water or remove it another way, have the Ulu is high initial resistance and improved high end heat resistance in comparison with the already known issues prior art. The dispersions according to the invention are stable by themselves and do not need any additional emulsifiers.
Thus, the present invention provides aqueous polyurethane-poliuretanovye dispersion-based
A) one or more di - or more functional polyol(s)having average molecular weight of from 400 to 5000 daltons,
B) optionally one or more di - or more highly functional Paleologo component(s)having a molecular weight of from 62 to 399 daltons,
C) one or more compound(s), monofunctional in the case of the polyaddition reaction of isocyanates and which have a content of ethylene oxide is at least 50 wt.% and a molecular weight of at least 400 daltons,
D) one or more di - or polyisocyanate component(s), and
E) a mixture of (E) primary and/or secondary monoaminooxidase E1) and primary and/or secondary diaminododecane E2), characterized in that at least one of the components E1 and/or E2) containing sulfonate and/or carboxylate group, and an average amine functionality of the mixture (E) is from 1.65 to 1.98, and the equivalent ratio of NCO groups in the NCO-prepolymer and the overall quantities of reacting with isocyanate, amino and hydroxyl groups in the mixture (E) is from 1.04 to 1.9.
Suitable di - or more is highly functional polyols (A) are compounds having at least two hydrogen atoms, reactive towards isocyanates, as well as the average molecular weight of from 400 to 5000 daltons. Examples of suitable structural components are polyethers, polyesters, polycarbonates, polylactones or polyamides. Preferred polyols (A) contain from 2 to 4, particularly preferably 2 to 3 hydroxyl groups. Also suitable are mixtures of various compounds of this type.
As a complex polyether polyols should be considered, in particular, the linear complex polyetherdiol or also often weakly branched complex polyether polyols, which can be synthesized by known methods from aliphatic, cycloaliphatic or aromatic di - or polycarboxylic acids, such as, for example, succinic acid, methylestra acid, glutaric acid, adipic acid, Emelyanova acid, cork acid, azelaic acid, sabotinova acid, nonindigenous acid, decanedicarbonitrile acid, terephthalic acid, isophthalic acid, o-phthalic acid, tetrahydrophtalic acid, hexahydrophthalic acid, cyclohexanecarbonyl acid, maleic acid, fumaric acid, malonic acid or trimellitate acid, and acid anhydrides, such as o-phthalic anhydride, tremell the starting anhydride, succinic anhydride, or mixtures thereof with polyhydric alcohols, such as, for example, ethanediol, di-, tri-, tetraethylene glycol, 1,2-propandiol, di-, tri-, tetrapropylene, 1,3-propandiol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propandiol, 1,4-dihydrocyclopenta, 1,4-dimethylcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol or their mixtures, if necessary, with the joint use of more highly functional polyols, such as trimethylolpropane, glycerol or pentaerythritol. Suitable polyhydric alcohols to produce complex polyether polyols are undoubtedly well as cycloaliphatic and/or aromatic di - and polyhydroxylated connection. Instead of free polycarboxylic acid to produce polyesters can also use the corresponding polycarboxylic anhydrides of the acids or the corresponding esters of the lower alcohols and polycarboxylic acids or mixtures thereof.
Of course, complex polyether polyols can also be homopolymers or copolymers of lactones, which are preferably obtained by adding lactones or mixtures of lactones, such as butyrolactone, ε-caprolactone and/or methyl-ε-caprolacton, to the corresponding di - and/or more highly functional molecules of the original substances, such as, for example, mn is gatonye alcohols with low molecular weight, mentioned above as a lengthening chain of components for complex polyether polyols. Preferred are the corresponding polymers of ε-caprolactone.
Special preference is given predominantly linear complex polyether polyols, which as structural elements contain adipic acid and 1,4-butanediol and/or 1,6 hexanediol, and/or 2,2-dimethyl-1,3-propandiol.
Polycarbonates containing hydroxyl groups are also taken into consideration as polyhydroxylated components, for example, those which can be obtained by reaction of diols, such as 1,4-butanediol and/or 1,6-hexanediol with dellcorporate, such as, for example, diphenylcarbonate, diallylmalonate, such as, for example, dimethylcarbonate, or phosgene. Hydrolytic stability of the dispersion adhesives according to the invention can be improved by at least partial use of polycarbonates containing hydroxyl groups.
Preferred polycarbonates obtained by the reaction of 1,6-hexandiol with dimethylcarbonate.
Suitable as a simple polyether polyols can be, for example, polyaddition products of styrene oxide, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin, as well as the products of mixed accession and previousauthorisation, as well as simple polyether polyols obtained by condensation of polyhydric alcohols or their mixtures, and simple polyether polyols obtained by alkoxysilane polyhydric alcohols, amines and aminoalcohols. Simple polyether polyols suitable as a lengthening chain of components A)are homopolymers, mixed polymers and graft polymers of propylene oxide and ethylene oxide, which can be obtained by adding the above-mentioned epoxides to dilam or trilam low molecular weight mentioned above as structural elements for complex polyether polyols or more highly available, high performance polyols with low molecular weight, such as, for example, pentaerythritol or sugar, or water.
Particularly preferred di - or more highly functional polyols (A) are complex polyether polyols, polylactones or polycarbonates, most preferred are complex polyether polyols of the above-mentioned type.
As a component for chain elongation In the appropriate components of the di - or more functional polyol having a molecular weight of from 62 to 399 daltons, such as, for example, polyethers, polyesters, polycarbonates, polylactones or polyamides, provided that they have a molecular weight of from 62 to 399 daltons.
Other suitable components of Vlada polyatomic, in particular, diatomic alcohols referred to in paragraph (A) to obtain a complex of polyether polyols, as well as complex polyetherdiol with low molecular weight, such as, for example, a complex bis-(hydroxyethyloxy) ester of adipic acid or short-chained products of Homo - and mixed accession of ethylene oxide or propylene oxide to an aromatic dilam as starting compounds. Examples of aromatic diols that can be used as starting components for the short-chained homopolymers or mixed polymers of ethylene oxide or propylene oxide are, for example, 1,4-, 1,3-, 1,2-dihydroxybenzene or 2,2-bis-(4-hydroxyphenyl)propane (bisphenol a).
The compounds exhibiting monofunctionality within the polyaddition reaction of isocyanates and having a content of ethylene oxide is at least 50 wt.%, and a molecular weight of at least 400 daltons, suitable as component C). Compound (C) is a hydrophilic component to attach chains containing terminal hydrophilic ethylenoxide structural units of the Formula (I)
R denotes a monovalent hydrocarbon radical containing from 1 to 12 carbon atoms, preferably unsubstituted alkyl radical containing from 1 to 4 carbon atoms,
X represents the Wallpaper polyalkyleneglycol chain, containing from 5 to 90, preferably from 20 to 70 chain elements that contain at least 51%, preferably at least 65% ethylenoxide structural units and which may contain, in addition to ethylenoxide structural units, structural units of propylene oxide, butilenica or styrene oxide, among the structural units propylenoxide structural units are preferred, and
Y/Y' represents an oxygen atom or-NR'-, where R' corresponds to R in accordance with its definition or hydrogen atoms.
Getting monofunctional hydrophilic components is carried out similarly to the method described in German patent applications DE-a 2314512 or DE-A 2314513 or in patent applications U.S. US-A 3,905,929 or US-A 3,920,598 by alkoxysilane monofunctional starting compound, such as, for example, methanol, ethanol, isopropanol, n-butanol or N-methylbutylamine, by means of ethylene oxide and, if necessary, additional accelerated, such as, for example, propylene oxide.
Preferred components C) are mixed polymers of ethylene oxide with propylene oxide in which the weight percent of ethylene oxide is greater than 50%, particularly preferably from 65 to 89%. In a preferred embodiment of the invention as component (C) used soy is inane with a molecular weight of at least 400 daltons, preferably from 1000 to 4500 daltons, particularly preferably from 1500 to 3500 daltons, and most preferably from 2000 to 2500 daltons.
Suitable as component D) are any organic compounds containing at least two free isocyanate groups in one molecule. The advantage of using preferred diisocyanates Y(NCO)2in which Y represents the divalent aliphatic hydrocarbon radical containing from 4 to 12 carbon atoms, a divalent cycloaliphatic hydrocarbon radical containing from 6 to 15 carbon atoms, divalent aromatic hydrocarbon radical containing from 6 to 15 carbon atoms or a divalent arylaliphatic hydrocarbon radical containing from 7 to 15 carbon atoms. Examples of such preferred to use diisocyanates are tetramethyldisilane, methylphenyldichlorosilane, hexamethylenediisocyanate, dodecyltrimethoxysilane, 1,4-diisocyanatohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl, 4,4'-diisocyanatohexane, 4,4'-diisocyanato-2,2'-dicyclohexylmethane, 1,4-diisocyanates, 2,4-diisocyanate, 2,6-diisocyanate, 4,4'-diisocyanatobutane, 2,2'- and 2,4'-diisocyanatobutane, tetramethylcyclopentadienyl, p-xylylenediisocyanate, p-isopropylidene Socionet, as well as mixtures of these compounds.
Of course, you can also used proportionally more highly functional polyisocyanates known directly in polyurethane chemistry, or, also, modified polyisocyanates, known in themselves, for example, polyisocyanates containing carbodiimide groups, allophanate group, which groups, urethane groups and/or biuret groups.
The preferred diisocyanates D) are aliphatic and arylaliphatic the diisocyanates, such as hexamethylenediisocyanate, 1,4-diisocyanatohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane, 4,4'-diisocyanatohexane or 4,4'-diisocyanato-2,2'-dicyclohexylurea, as well as mixtures of these compounds.
Particularly preferred components D) are a mixture of hexamethylenediisocyanate and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl.
The polymer, which are based dispersion according to the invention contains an ionic or potentially ionic groups to hydrophilization, which can be either cationic, and anionic in nature. Preferred are the sulfate and carboxylate groups. As a variant, can also be used by groups that can be converted into the above-mentioned ionic groups by salt formation (potentially IO the groups). The hydrophilic group introduced into the polymer by means of components E1 and/or E2).
Suitable for lengthening chains of component (E) is a mixture of primary and/or secondary monoaminooxidase E1), as well as primary and/or secondary diaminododecane E2), in which at least one of the components E1 and/or E2) has sulfoxylate and/or carboxyl groups.
Examples E1) are aliphatic and/or alicyclic primary and/or secondary monoamines such as ethylamine, diethylamine, isomeric propyl - and butylamine, higher linear aliphatic monoamines and cycloaliphatic monoamines, such as cyclohexylamine. Additional examples E1) are aminoalcohols, in other words, compounds which contain in the molecule of the amino and hydroxyl groups, such as, for example, ethanolamine, N-methylethanolamine, diethanolamine and 2-propanolamine. Other examples E1) are monoaminooxidase, which, in addition, have sulfoxylate and/or carboxyl groups, such as, for example, taurine, glycine or alanine. Of course, you can also use a combination of several monoaminooxidase E1).
Preferred to extend the circuit components E1) are diethylamine, ethanolamine or diethanolamine. Particularly preferred components for chain elongation E1) are ethanolamine or diet elamin.
Examples E2) are 1,2-amandemen, 1,6-hexamethylenediamine were, 1-amino-3,3,5-trimethyl-5-aminomethylation (ISOPHORONEDIAMINE), piperazine, 1,4-diaminocyclohexane or bis-(4-aminocyclohexane)methane. Also suitable are dehydrated adipic acid, hydrazine or hydrazinehydrate. Polyamine, such as Diethylenetriamine, can also be used as a component for chain elongation E2) instead of diaminododecane.
Other examples E2) are aminoalcohols, in other words, compounds which contain in the molecule of the amino and hydroxyl groups, such as, for example, 1,3-diamino-2-propanol, N-(2-hydroxyethyl)Ethylenediamine, or N,N-bis(2-hydroxyethyl)Ethylenediamine.
Compounds E2), which can also be used, are diaminododecane, which additionally contain sulphonate and/or carboxylate groups, such as, for example, sodium or potassium salts of N-(2-amino-ethyl)-2-aminoethanesulfonic acid, N-(3-aminopropyl)-2-aminoethanesulfonic acid, N-(3-aminopropyl)-3-aminopropiophenone acid, N-(2-amino-ethyl)-3-aminopropiophenone acid or similar carboxylic acids. Is also possible to use mixtures of several diaminododecane E2).
Preferred components for chain elongation E2) are 1,2-amandemen, 1,6-hexamethylenediamine were, 1-amino-3,3,5-trimethyl-5-aminomethyl the cyclohexane (ISOPHORONEDIAMINE), piperazine, N-(2-hydroxyethyl)Ethylenediamine, N,N-bis(2-hydroxyethyl)Ethylenediamine, sodium salt N-(2-amino-ethyl)-2-aminoethanesulfonic acid or sodium salt of N-(2-amino-ethyl)-2-aminoethanethiol acid.
Particularly preferred components for chain elongation E2) are N-(2-hydroxyethyl)Ethylenediamine, or the sodium salt of N-(2-amino-ethyl)-2-aminoethanesulfonic acid.
Average amine functionality of the mixture (E) has a value of from 1.65 to 1.98, preferably from about 1.75 to 1.98, particularly preferably from 1,78 up to 1,95.
The equivalent ratio of NCO groups in the NCO-prepolymer and the total number of reactive isocyanate amino and hydroxyl groups in the mixture (E) has a value of from 1.04 to 1.9, preferably from 1.08 to 1.85, most preferably from 1.11 to 1.8.
A mixture of (E) preferably contains monoaminooxidase E1), diaminododecane E2)having a hydroxyl group, and diaminododecane E2)having sulphonate or carboxylate groups. Particularly preferably, if a mixture of (E) contains monolinoleate E1), diaminopurine E2) and diaminobenzidine E2)having sulphonate groups. Most preferably, if a mixture of (E) contains diethanolamine, N-(2-hydroxyethyl)Ethylenediamine and sodium salt of N-(2-amino-ethyl)-2-aminoethanesulfonic acid.
The content of ionic groups is from 10 to 600 mmol / kg of solid substances is STV, preferably from 20 to 300 mmol, particularly preferably from 30 to 150 mmol / kg of solids.
The present invention additionally provide a method of obtaining an aqueous polyurethane-poliuretanovykh dispersions according to the invention, characterized in that in the first stage, some or all of the components A), B), C) and D), optionally in the presence of a solvent which can be mixed with water, but is inert towards isocyanate groups, are placed in a reactor and heated to temperatures in the range from 50 to 120°C., and then dosed any of the components A), B), C) or D), which was not added at the beginning of the reaction in the second step is the elongation chain with a mixture of (E) at temperatures from 15 to 60°C, as well as before, during or after extension of the chain is transferred to the aqueous phase, and optionally used solvent is removed.
Obtaining an aqueous polyurethane-polyurea dispersions according to the invention can be implemented in one or more stages in a homogeneous phase or, in the case of multi-stage reaction, partly in the dispersed phase. When polyprionidae was carried out partially or completely, there are steps of dispersing, emulsifying or dissolving. Then, if necessary, is further polyprionidae or modification dispersed in the AZE. For this receipt, you can use all the methods known from the issues of the prior art. Preferably used acetone technology.
Suitable solvents are, for example, acetone, butanone, tetrahydrofuran, dioxane, acetonitrile, dimethyl simple broadcast dipropyleneglycol and 1-methyl-2-pyrrolidone, preferably butanone or acetone, especially preferred is acetone. Solvents can be added not only at the beginning of the retrieval process, but also, if necessary, partially and later. The reaction can be conducted at normal pressure or at elevated pressure.
To obtain a prepolymer of a number of individual components a) to D)are such that the isocyanate number is from 1.05 to 2.5, preferably from 1.1 to 1.5. The isocyanate content in the prepolymers is from 0.3 to 3%, preferably from 0.7 to 1.5%, particularly preferably from 0.9 to 1.5%.
Use from 50 to 96 mass parts, preferably from 75 to 96 mass parts component (A), from 0 to 10 mass parts, preferably from 0 to 5 mass parts of component B), from 0.1 to 10 mass parts, preferably from 0.5 to 5 mass parts, particularly preferably from 0.8 to 3.5 mass parts of the component (C), and from 3 to 30 mass parts, preferably from 5 to 18 mass parts component (D) when is slowiy, that the sum of the components is 100.
The reaction of components A), b) and C) with component (D) is partially or completely, but preferably completely, taking into account the total number of reactive isocyanate groups. The degree of conversion in the reaction is usually controlled by monitoring the NCO content in the reaction mixture. With this purpose it is possible to perform both spectroscopic measurements, for example, an infrared or near-infrared spectrum to determine the refractive index, and also to carry out chemical tests, such as titration of samples.
In order to accelerate the reaction of the accession of the isocyanate, it is possible to use well-known specialist of the conventional catalysts for accelerating the reaction of NCO groups with HE-groups. Examples are triethylamine, 1,4-diazabicyclo-[2,2,2]-octane, oxide dibutylamine, diktat tin or dilaurate dibutylamine, bis(2-ethylhexanoate) tin, or other metal-organic compounds.
Elongation chain with a mixture of (E) can be performed before dispersion during dispersion or after dispersion. Preferably the elongation of the chain is carried out before dispersing.
Elongation of the chain is carried out at temperatures from 15 to 60°C., preferably from 25 to 55°C., particularly preferably from 40 to 50°C.
The expression "lengthening chain" within this image the program also includes the reaction of monoaminooxidase E1), which by reason of its monofunctionality act as agents of chain breakage and lead, therefore, not to increase, and to decrease the molecular weight. This is also true, in particular, for aminoalcohols E1), because their hydroxyl groups in the selected temperature range does not react with isocyanate groups or react only very slightly.
Component (E) can be added to the reaction mixture diluted in organic solvents and/or water. The amino compounds E1) and E2) can be added one by one in any desired sequence or simultaneously by adding them to the mixture.
With the purpose of preparation of the dispersions according to the invention, the prepolymer, optionally with strong shearing, such as, for example, intensive mixing, or introduced into the dispersing water or, conversely, the dispersing water is added to the prepolymer. You can then make the process of chain elongation, if it was not carried out in homogeneous phase.
After dispersion of the organic solvent that was used when necessary, for example, acetone is removed by distillation.
According to the invention, the method preferably does not use additional emulsifiers.
The solids content in the dispersion is from 10 to 70 wt.%, preferably about the 25 to 60 wt.% and particularly preferably from 35 to 60 wt.%.
Dispersion adhesives according to the invention can be used by themselves or with binders, auxiliary substances and additives known in the technology of coatings and adhesives, in particular, emulsifiers or light stabilizers, such as absorbers of UV radiation or spatial-employed amines (compounds type HALS), as well as antioxidants, fillers or auxiliary means, for example, by preventing the deposition, defoamers and/or hydration treatment, additives to improve the fluidity, active diluents, plasticizers, catalysts, auxiliary solvents and/or thickeners, and additives, such as, for example, pigments, dyes or matting agent. You can also add increase the stickiness of resin.
Additives can be added to the applied layer system according to the invention, immediately before processing. However, it is also possible to add at least some of the additives before, during or after dispersion of the binder.
This invention also provides adhesive compositions containing the polyurethane-poliuretanovye dispersion according to the invention and polyisocyanate compounds having in the molecule at least two isocyanate groups. The polymeric agents with whom ivci can be added before use (two-component (2K) processing). In this case, the preferred polyisocyanate compounds which can emulgirovanija in the water. This is, for example, compounds described in European patent application EP-A 0206059, German patent applications DE-A 3112117 or DE-A 10024624. Polyisocyanate compounds are used in quantities of from 0.1 to 20 wt.%, preferably from 0.5 to 10 wt.%, particularly preferably from 1.5 to 6 wt.%, in terms of the aqueous dispersion.
Films prepared from aqueous polyurethane-poliuretanovykh dispersions according to the invention, are low activation temperatures in the range of from 40° to 80°C, a very good initial resistance ≤2 mm/min, preferably ≤1.5 mm/min, and a high final temperature ≥90°C, preferably ≥100°C, particularly preferably ≥110°C. in Addition, they exhibit excellent adhesion to a very wide range of substrates, such as wood, leather, textiles, various grades of polyvinyl chloride (rigid plasticized PVC), rubber or polietilenimin.
Adhesive compositions containing dispersions according to the invention, suitable for bonding any desired substrates, such as paper, cardboard, wood, textile, metal, leather or mineral materials. Adhesive compositions according to the invention is suitable in particular for bonding rubber materials, such to the to, for example, natural and synthetic rubber, various synthetic materials such as polyurethane, polyvinyl acetate, polyvinyl chloride, particularly plasticized polyvinyl chloride. Particularly preferable to use them for gluing soles made from these materials, preferably based on polyvinyl chloride, particularly preferably plasticized polyvinyl chloride, or based on polyethyleneamine or polyurethane panretin, to the upper part of shoes made of natural or artificial leather. Adhesive compositions according to the invention is also particularly suitable for bonding films based on plasticized polyvinyl chloride or PVC to wood.
Adhesive compositions according to the invention are also suitable for use as primers.
This invention also provides adhesive compositions containing substrates connected by means of adhesion using the polyurethane-poliuretanovykh dispersions according to the invention.
Adhesive compositions according to the invention are processed is known in the adhesive technologies methods with technology compliance aqueous dispersion adhesives.
The invention is explained in detail below by means of examples.
The initial heat and final heat shall be possible to define the following methods:
A) Determining an initial heat
The measurement of the initial heat is conducted in the form of a one-component system (without an agent, polymer crosslinking).
Study material/study sample
a) Film Renolit (32052096 Strukton; firm Renolit AG, 67547 worms / Germany)
Dimensions: 50×300×0.2 mm
b) Beech wood (planed)
Dimensions: 50×140×4 mm
Bonding and measurement
The test is carried out not earlier than 14 days after preparation of the dispersion adhesive. It is applied on the prototype wood using a doctor blade with a gap of 200 μm. The bonding area is 50×110 mm drying Time of the applied adhesive is at least 3 hours at room temperature. Then two of the test sample are put against each other and connect in 10 seconds at a temperature of 77°C with a pressure of 4 bar. Immediately after this test sample thermostatic for 3 minutes at 80°C without load, and then perpendicular to the adhesive connection, put a load of 2.5 kg for 5 minutes at 80°C (peeling angle of 180°). The amount by which exfoliate the connection, measured in millimeters. Initial resistance point in mm/min.
C) Determining the final heat
One-component adhesive system (1K): the adhesive agent-polymer crosslinking
Two-component adhesive system (2K): DHESIVE with emulsifiable isocyanate agent polymer crosslinking
3 parts of Desmodur® DN 100 parts of adhesive intensively stirred until homogenization.
Recommended hitch: 25 g of adhesive and 0.75 g agent polymer crosslinking.
Study material/study sample
a) Hard cover PVC film (Benelitfolie, firms Benecke-Kaliko AG, Hannover / Germany)
Dimensions: 50×210×0.4 mm
b) Beech wood (planed), room size: 50×140×4 mm
Bonding and measurement
One-component adhesive dispersion (1K) or a mixture of the adhesive dispersion with isocyanate agent polymer crosslinking (2K) is applied on the prototype beech wood with a brush. The bonding area is 50×110 mm After drying for 30 minutes at room temperature on top of the first layer, the second adhesive layer, and then drying for 60 minutes at room temperature. Then two of the test sample are put against each other and connect in 10 seconds at a temperature of 90°C with a pressure of 4 bar.
After keeping the prototypes for 3 days at room temperature, to prototyping put a load of 0.5 kg at an angle of 180° relative to adhesive bonding. The initial temperature is 50°C after 60 minutes the temperature increases by 10°C per hour up to a maximum of 120°C. In each case, the measured temperature at which the adhesive connection is fully disconnect is applied.
The materials used
|Complex polyester I:||1,4-buttondialleradapter with a hydroxyl number = 50|
|Complex polyester II:||complex polyetherdiol of 1,6-hexandiol, neopentyl glycol and adipic acid with a hydroxyl number = 66|
|Simple polyester I:||mono-functional copolymer of ethylene oxide and propylene oxide-based n-butanol|
|the content of ethylene oxide 84%, with a hydroxyl number = 25|
|Desmodur® H:||1,6-hexamethylenediisocyanate (Bayer MaterialScience AG, Leverkusen/Germany)|
|Desmodur® I:||isophorondiisocyanate (Bayer MaterialScience AG, Leverkusen/Germany)|
|Desmodur® DN:||hydrophilic aliphatic polyisocyanate on the basis of hexamethylenediisocyanate (Bayer MaterialScience AG, Leverkusen/Germany)|
Example 1 (according to the invention):
A mixture of 450 g of a complex of the polyester I, 42,51 g complex polyester II and 5.58 g of polyether I dehydrate for 1 hour at a temperature of 110°C and pressure of 15 MB the R. At 60°C add 2.25 g of 1,4-butanediol, 37,82 g of Desmodur® H, and then 24,99 g Desmodur® I. the Mixture was stirred at 80°C as long as there is a constant isocyanate content of 1.13% (which corresponds to 6.39 g NCO or 0.15 mol NCO). The reaction mixture is dissolved in 778 g of acetone while cooling to 50°C. the Solution to 5.57 g of sodium salt of N-(2-amino-ethyl)-2-aminoethanesulfonic acid (0,029 mol), 0,89 g diethanolamine (0,009 mol) and 1.14 g of N-(2-hydroxyethyl)Ethylenediamine (to 0.011 mol) in 55 g of water is added to the homogeneous solution under vigorous stirring. After 30 minutes to prepare a dispersion by adding 530 g of water. After distillation of the acetone is obtained solvent free aqueous polyurethane-polyurea dispersion with a solids content 40,1% of the mass. and an average particle size of the dispersed phase, determined by laser correlation, 175 nm.
Average amine functionality: 1,82
NCO-groups(amino groups+hydroxyl group)=0,15/(0,089+0,029)=1,27
Example 2 (according to the invention):
A mixture of 585 g of a complex of the polyester I, 55,26 g complex polyester II and of 21.75 g of polyether I dehydrate for 1 hour at a temperature of 110°C and pressure of 15 mbar. At 60°C type of 2.93 g of 1,4-butanediol, 49,16 g of Desmodur® H, and then 32,49 g Desmodur® I. the Mixture was stirred at 80°C as long as there is a constant isocyanate content of 1.16% (which corresponds to 8,66 g NCO or 0,206 mol NCO). actionnow mixture is dissolved in 1031 g of acetone, while cooling to 50°C. a Solution of 7.24 g of sodium salt of N-(2-amino-ethyl)-2-aminoethanesulfonic acid (0,029 mol), of 0.48 g of diethanolamine (0,005 mol) and 1.48 g of N-(2-hydroxyethyl)Ethylenediamine (0.014 mol) in 67 g of water is added to the homogeneous solution under vigorous stirring. After 30 minutes to prepare a dispersion by adding 1087 g of water. After distillation of the acetone is obtained solvent free aqueous polyurethane-polyurea dispersion with a solids content of 40.3% of the mass. and an average particle size of the dispersed phase, determined by laser correlation, 141 nm.
Average amine functionality: 1,90
NCO-groups(amino groups+hydroxyl group)=0,206/(0,091+0,024)=1,79
Example 3 (according to the invention):
A mixture of 450 g of a complex of the polyester I and 15 g of polyether I dehydrate for 1 hour at a temperature of 110°C and pressure of 15 mbar. At 60°C add 30,24 g of Desmodur® H and 19,98 g Desmodur® I. the Mixture was stirred at 80°C as long as there is a constant isocyanate content of 0.98% (equivalent of 5.05 g NCO or 0,120 mol NCO). The reaction mixture is dissolved in 773 g of acetone while cooling to 50°C. a Solution of 5.85 g of sodium salt of N-(2-amino-ethyl)-2-aminoethanesulfonic acid (0,031 mol), 0,42 g diethanolamine (0,004 mol) and of 1.11 g of N-(2-hydroxyethyl)Ethylenediamine (to 0.011 mol) in 73 g of water is added to a homogeneous solution with vigorous stirring Over 30 minutes to prepare a dispersion by adding 730 g of water. After distillation of the acetone is obtained solvent free aqueous polyurethane-polyurea dispersion with a solids content 40,1% of the mass. and an average particle size of the dispersed phase, determined by laser correlation, 151 nm.
Average amine functionality: 1,91
Example 4 (for comparison):
A mixture of 450 g of a complex of the polyester I, 42.5 g of a complex of the polyester II and 9.00 g of polyether I dehydrate for 1 hour at a temperature of 110°C and pressure of 15 mbar. At 60°C add 2.25 g of 1,4-butanediol, 37,81 g of Desmodur® H, and then 24,98 g Desmodur® I. the Mixture was stirred at 80°C as long as there is a constant isocyanate content of 1.02% (which corresponds 5,78 g NCO or was 0.138 mol NCO). The reaction mixture is dissolved in 782 g of acetone while cooling to 50°C. a Solution of 6.25 g of sodium salt of N-(2-amino-ethyl)-2-aminoethanesulfonic acid (0,033 mol), 1.24 g ethanolamine (0.012 mol) and of 1.23 g of N-(2-hydroxyethyl)Ethylenediamine (0.012 mol) in 85 g of water is added to the homogeneous solution under vigorous stirring. After 30 minutes to prepare a dispersion by adding 504 g of water. After distillation of the acetone is obtained solvent free aqueous polyurethane-polyurea dispersion with a solids content of 49.9% wt. and an average particle size of the dispersed phase, identified through the laser correlation, 196 nm.
Average amine functionality: 1,79
NCO-groups(amino groups+hydroxyl group)=0,138/(0,102+0,036)=1,00
|The measurement of the initial heat resistance and thermal stability|
|The initial resistance, [mm/min]||thermal stability of one-component systems (1K), [°C]||The stability of two-component system (2K), [°C]|
|Example 1 according to the invention||1,2||110||120|
|Example 2 according to the invention||0,6||110||120|
|Example 3 according to the invention||0,4||>120||>120|
|Example 4 for comparison||9,8||90||>120|
The films of Examples 1 to 3 obtained from the aqueous polyurethane-poliuretanovykh dispersions according to the invention, differ in FOSS is the provision of an Example for comparison, very good initial resistance from 0.4 to 1.2 mm/min and high temperature resistance ≥110°C.
1. Aqueous polyurethane-poliuretanoviy dispersion used as a source of adhesive material in a dispersion adhesives based on
A) one or more di - or more functional polyol(s)having average molecular weight of 400 to 5000 daltons,
B) optionally one or more di - or more highly functional polianovich component(s)having a molecular weight of 62 to 399 daltons,
C) one or more compounds, monofunctional in the case of the polyaddition reaction of isocyanates and which have a content of ethylene oxide is at least 50 wt.% and a molecular weight of at least 400 daltons,
D) one or more di - or polyisocyanate component(s)and
E) a mixture of (E) primary and/or secondary monoaminooxidase E1) and primary and/or secondary diaminododecane E2),
characterized in that at least one of the components E1 and/or E2) containing sulfonate groups, with an average amine functionality of the mixture (E) is 1.65 ÷ 1,98, and the equivalent ratio of NCO groups in the NCO-prepolymer and the overall quantities of reacting with isocyanate, amino and hydroxyl groups in the mixture (E) is the 1.04 ÷ 1,9.
2. Aqueous polyurethane-poliuretanoviy dispersion according to claim 1, otlichayas the same time, which component D) is a mixture of hexamethylenediisocyanate and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl.
3. Aqueous polyurethane-poliuretanoviy dispersion according to claim 1, characterized in that the component E1) represents diethylamine, ethanolamine or diethanolamine.
4. Aqueous polyurethane-poliuretanoviy dispersion according to claim 1, characterized in that the component E2) is a 1,2-amandemen, 1,6-hexamethylenediamine were, 1-amino-3,3,5-trimethyl-5-aminomethylation (ISOPHORONEDIAMINE), piperazine, N-(2-hydroxyethyl)Ethylenediamine, N,N-bis(2-hydroxyethyl)Ethylenediamine, or the sodium salt of N-(2-amino-ethyl)-2-aminoethanesulfonic acid.
5. The way to obtain an aqueous polyurethane-poliuretanovykh dispersions according to claim 1, characterized in that in the first stage, some or all of the components A), B), C) and D), optionally in the presence of a solvent which can be mixed with water, but is inert towards isocyanate groups, are placed in a reactor and heated to temperatures in the range of 50 ÷ 120°C, and then dispense any of the components A), B), C) or D), which was not added at the beginning of the reaction in the second stage carry out chain elongation a mixture of (E) at temperatures of 15 ÷ 60°C, while, before, during or after the chain elongation produce translation in the aqueous phase, and optionally used solvent in Aleut.
6. The method according to claim 5, characterized in that upon receipt of the prepolymer of the number of individual components a) to D), such that is achieved isocyanate number of from 1.05 to 2.5.
7. The method according to claim 5, characterized in that the isocyanate content in the prepolymers is 0.3 ÷ 3,0%.
8. The method according to claim 5, characterized in that no added emulsifiers.
9. Adhesive compositions containing the aqueous polyurethane-poliuretanovye dispersion according to claim 1, and polyisocyanate compounds containing in the molecule at least two isocyanate groups.
10. The use of aqueous polyurethane-poliuretanovykh dispersions according to claim 1 when receiving the adhesive composite materials.
11. The use of claim 10, wherein the adhesive composite materials as the substrate contain rubber and/or synthetic materials.
12. The use of claim 10, wherein the adhesive composite materials include Shoe soles and Shoe tops.
13. The use of claim 10, wherein the adhesive composite materials include films and wood.
14. Adhesive composite materials containing substrates together using adhesion to aqueous polyurethane-poliuritanovymi dispersions according to claim 1.
SUBSTANCE: adhesive composition contains a polyfunctional isocyanate, polyether polyol and a catalyst. The catalyst consists of at least one organic compound of iron and at least one chelating ligand. The multicomponent adhesive composition is prepared in form of at least two inter-reacting chemical components. One of the at least two inter-reacting chemical components contains a polyfunctional isocyanate and a catalyst, and the other contains polyether polyol. The multicomponent adhesive composition is used to produce articles from bound lignocellulose composite based on a lignocellulose substrate, especially for making oriented fibre panels.
EFFECT: invention enables to obtain articles using filler with high moisture content, which are structured at low pressing temperatures without reducing efficiency of the press.
4 tbl, 1 ex, 17 cl
SUBSTANCE: moisture-curable and biodegradable adhesive which contains a reaction product of: (a) an isocyanate component having an average functionality of at least 2, the isocyanate component being selected from a group consisting of lysine diisocyanate and derivatives thereof, lysine triisocyanate and derivatives thereof, and combinations thereof; (b) an active hydrogen component having an average functionality greater than 2.1, the active hydrogen component containing a component with a hydroxyl functional group; and (c) an ionic salt component having an average hydroxyl or amino functionality, or combination thereof, of at least 1, selected from a group consisting of ammonium salts, halides, sulphonates, phosphonates, carboxylates and combinations thereof.
EFFECT: obtaining a moisture-curable and biodegradable adhesive.
18 cl, 1 dwg, 17 ex
SUBSTANCE: adhesive polyurethane composition consists of a prime coat and polyurethane adhesive, comprising urethane rubber and ethyl acetate, applied on its surface. The prime coat consists of a solution of polyurethane thermoplastic elastomer with ethyl acetate in ratio: polyurethane thermoplastic elastomer 10-18 wt % and ethyl acetate - the balance. The polyurethane adhesive contains a solution of polyurethane thermoplastic elastomer and a mixture of polar organic solvents consisting of ethyl acetate and methylene chloride, with the following ratio of components: polyurethane thermoplastic elastomer 17-27 wt %; methylene chloride 7-10 wt % and ethyl acetate - the balance. The polyurethane adhesive can contain perchlorovinyl resin as a target additive in amount of 0-10% to the total weight of the adhesive.
EFFECT: low cost and improved adhesion properties of the adhesive composition and cohesion strength characteristics of the adhesive joints.
2 cl, 2 tbl
SUBSTANCE: composition contains the following in pts.wt: 100 bifunctional prepolymer with terminal isocyanate groups, 10.6-12.8 - 3,3'-dichloro-4,4'-diaminodiphenylmethane, 15.9-19.2 dioctylsebacate, 1.2-1.4 - 1,4-butanediol, 0.31-0.35 - para-phenylenediamine and 0.015-0.030 - Agidol 51,52,53 (mixture of 2-dimethylaminomethylphenol, 4-dimethylaminophenol, 2,6-bis (dimethylaminomethyl)phenol, 2,4-bis-(dimethylaminomethyl)phenol,2,4,6-tris-dimethylaminomethyl)phenol.
EFFECT: obtaining a fixing composition which, after prolonged storage, retains strength and adhesion parameters vital for operation of charges of antitank grenades at both high and low temperatures, and also prevents accidental exposure to substances which are harmful to health of personnel, in cases of technical faults and emergencies.
SUBSTANCE: invention relates to method for covering light airplanes with polyester sheathing fabric, as well as to dispersive hot-gluing glue and its application for covering. For covering, polyester sheathing fabric with longitudinal shrinkage of 7% and transversal shrinkage of 5% at 160-180°C is used. In the process of covering light airplanes and/or their parts consisting of frame system, sheathing fabric in the area of its overhangs and frame parts is covered by dispersive hot-gluing glue and wrapped around longeron part of frame so that when connection between sheathing fabric and frame produced by glue is destructed the fabric could be held on frame carcass. Dispersive hot-gluing glue contains 80-88% of adhesive, 12-15% of hardener and 0.15-0.3% thickener, and the glue is polymerised at temperatures >40°C. The hardener contains 54-60% of solvent, 0.35-0.5% of naphthalensulfonic acid sodium salt-based stabiliser, 0.25-0.35% of propoxylated spirit-based emulsifier, 1.7-1.9% of polyetheramines-based hardener, 37-41% of polyisocyanate.
EFFECT: reliability and durability of light airplanes and/or their parts covering.
15 cl, 3 dwg
SUBSTANCE: invention relates to aldimines of formula (I)
where A does not contain active hydrogen and a primary amine group, or together with R7 denotes a (n+2)-valent hydrocarbon radical containing 3-20 carbon atoms and, if necessary, at least one heteroatom in form of oxygen of an ether group or nitrogen or a tertiary amine group; n equals 1, 2, 3 or 4; m equals 0,1, 2, 3 or 4; R1 and R2 each denotes a univalent hydrocarbon residue with 1-12 carbon atoms or together denote a divalent hydrocarbon radical which is part of a carbocyclic ring with 5-8 carbon atoms; R3 denotes H or alkyl; R4 and R5 independently denote CH3 or a univalent aliphatic radical containing 2-12 carbon atoms and optionally hydroxy groups; X denotes O, S, N-R6, or N-R7, where R6 denotes a univalent hydrocarbon radical containing 1-20 carbon atoms and having at least one hydroxy group; as well as curable compositions containing such aldimines and use of said compositions.
EFFECT: obtaining novel aldimines which can be used as curing agents in curable compositions.
22 cl, 18 ex, 6 tbl
SUBSTANCE: present invention relates to a polyisocyanurate based adhesive which is obtained by reacting an organic polyisocyanate with a compound containing hydrogen atoms which are reactive towards isocyanate, in the presence of a trimerisation catalyst. The organic polyisocyanate is a polymer or prepolymer polyisocyanate, and content of the soft block in the adhesive ranges from 40 to 60 wt %. A reaction mixture for producing said adhesive is also described.
EFFECT: obtaining an adhesive capable of withstanding high maximum stress, having extremely fast setting and having a good and strong bond with the base, as well as high thermal stability, resistance to salty water and creep.
9 cl, 4 ex, 6 tbl
SUBSTANCE: method involves applying a UV curable adhesive resin composition, containing a photolatent base, onto at least one transparent surface of at least one of a first and a second substrate. The substrates are then brought together so that said adhesive composition lies in between. The adhesive composition is then exposed to actinic radiation for curing. The UV curable adhesive is a OH/NCO system or SH/NCO system. In another version of the gluing method, the first and second substrates are brought together after exposing the adhesive composition in between to actinic radiation.
EFFECT: disclosed gluing method enables faster curing of the adhesive.
5 cl, 10 tbl, 6 ex
SUBSTANCE: composition contains one or more urethane prepolymers, having isocyanate residues, one or more compounds which catalyse the reaction of isocyanate residues with water or a compound which contains active hydrogen and one or more alpha-hydrocarbyl silane compounds. The urethane propolymer additionally contains a silane functional group. The composition additionally contains a compound or a polymer, containing silane residues. The composition additionally contains one or more compounds which catalyse silanol condensation. The composition is deposited onto the surface of glass or plastic with a coating or onto the surface of a substrate to obtain a sealant, then brought into contact and the composition is then hardened. The composition is placed between the glass or plastic with coating and the substrate. The sealing composition is used for binding an unprimed surface with a coating, such as a window lintel with glass with a transparent plastic, coated with an abrasive-resistant coating or with glass or plastic with a coating, additionally coated with glass cement, such as ceramic or organic glass cement.
EFFECT: improved composition properties.
10 cl, 2 ex
SUBSTANCE: invention relates to a method of producing dispersions of blocked polyurethane prepolymers, use of dispersions obtained using said method to produce coating agents, adhesive substances and sealants and elastomers, said application products themselves, as well as substrates provided with coating agents. The method involves the following: I) a blocked polyurethane prepolymer is obtained first by reacting a) 100 equivalent % of at least one polyisocyanate with b) 50-90 equivalent %, in terms of isocyanate reactive groups, of a thermally split blocking agent, c) 5-45 equivalent %, in terms of isocyanate reactive groups, monohydroxycarboxylic acid as a hydrophilic agent and d) 0-25 equivalent %, in terms of isocyanate reactive groups, of polyhydroxycarboxylic acid as a hydrophilic agent and e) 0-15 equivalent %, in terms of isocyanate reactive groups, of at least one, in terms of isocyanate reactive groups, di- or polyfunctional component of a chain extender with molecular weight from 32 to 350 g/mol, where i) this takes place using (partially) water-miscible organic solvents which are inert to NCO-groups and have boiling point lower than 120°C (at 1013 mbar), ii) and they are used in such an amount that the polyurethane prepolymer contained in the reaction solution after complete conversion ranges from 70 to 98 wt %. Further, II) the polyurethane prepolymer solution obtained at step (I) is dispersed in water, where before, during or after dispersion, deprotonation of carboxylic acid groups with a base takes place at least partially, and then III) if needed, the contained organic solvent is completely removed during dispersion via distillation.
EFFECT: obtaining polyurethane dispersions which are stable during storage, endow said products of their application with good optical properties, high resistance to chemical reagents and pendulum hardness.
13 cl, 10 ex, 1 tbl
SUBSTANCE: invention relates to compositions based on silane-functional polymers, which are suitable for adhesive binding, sealing and coating porous substrates. The composition contains at least one silane-functional polymer, at least one organosilane and at least one organotitanate. The silane-functional polymer is a silane-functional polyurethane polymer or can be obtained through hydrosilylation of polymers, having terminal double bonds. The organosilane contains at least one sulphur atom. The organotitanate has ligands bound to a titanium atom through an oxygen-titanium bond. The ligands are selected from a group consisting of an alkoxy group, a sulphate group, a carboxylate group, a dialkylphosphate group and an acetylacetonate group. Content of the organotitanate in the composition is between 0.1 and 10 wt %. Content of the organosilane in the composition is between 0.1 and 7 wt %. The composition also contains at least one filler, content of which is between 10 and 70 wt %. The composition is used for binding, sealing and coating substrates made from concrete, mortar, brick, tiles, plaster, natural stone such as granite or marble, glass, glass-ceramic, metal or metal alloy, wood, plastic and lacquer.
EFFECT: obtained article, which is bound, sealed or coated using the composition, is a building structure, more specifically a building or civil construction structure; the composition guarantees efficient adhesion to a substrate even after storage in the presence of water.
17 cl, 1 tbl
SUBSTANCE: invention relates to making adhesives based on phenoformaldehyde resin, used in wood-working industry when making chaff plates. An adhesive is described, which contains phenol-formaldehyde resin SFZ-3014 and a modifier - butanol-1 in amount of 1.5-2.5 pts. wt per 100 pts. wt of liquid resin.
EFFECT: adhesive provides for uniform resin formation by boon particles and improved physical and mechanical properties of the chaff plates.
1 cl, 1 dwg, 2 tbl, 7 ex
SUBSTANCE: invention relates to making adhesives based on carbamide-formaldehyde resins, used in wood-working industry when making chaff plates. An adhesive is described, which contains carbamide-formaldehyde resin, acid hardener and modifier - butanol-1 in amount of 1-2 pts. wt per 100 pts. wt of the liquid resin.
EFFECT: adhesive provides for uniform resin formation by boon particles when making chaff plates and improved physical and mechanical properties of the end product.
1 cl, 1 dwg, 2 tbl, 5 ex
FIELD: polymerization processes.
SUBSTANCE: invention relates to two-component composition used to initiate curing of one or more polymerizable monomers that are cured when affected by free radicals, which composition consists of organoborane-amino complex and an isocyanate capable of destroying organoborane-amino complex, wherein equivalent ratio of amine nitrogen atoms to boron atoms ranges from more than 4.0:1 to 20.0:1. In another embodiment of invention, subject of invention is two-component composition for use as sealing materials, coatings, primers for modifying polymer surfaces, and as molded resins, which composition consists of component 1: organoborane-amino complex wherein ratio of amine nitrogen atoms to boron atoms ranges from more than 4.0:1 to 20.0:1; component 2: one or more monomers, oligomers, or polymers having olefinic instauration, which are able of being subjected to free-radical polymerization; and effective amount of an isocyanate, which can initiate dissociation of complex to free borane for initiation of polymerization of one or more monomers, oligomers, or polymers having olefinic instauration, provided that complex dissociation initiator is stored separately from complex until initiation of polymerization becomes desirable. Such compositions are handling safe, i.e. they are not self-inflammable, stable at or near ambient temperature and so they do not initiate polymerization at or near ambient temperature in absence of complex dissociation initiator. Polymerized composition show good cohesion and adhesion strength. Described are polymerizable composition polymerization process, method of gluing two or more substrates using polymerizable composition; method of modifying polymer surface having low surface energy using polymerizable composition, as well as coating and laminate containing polymerizable composition.
EFFECT: enlarged resource of polymerizable compositions and expanded application areas thereof.
10 cl, 2 dwg, 4 tbl
FIELD: mechanical rubber goods, automotive industry, adhesive composition based on chlorine-containing rubber.
SUBSTANCE: claimed composition contains chlorinated natural rubber, aromatic dinitroazo compound, epoxy resin, fillers, and antioxidants. Said composition is characterized in that it contains 2,3-dichlorobutadiene-1,3/chloroprene copolymer as polymeric carrier and additionally phenol-formaldehyde resins of phenol- and resole-type, wetting agent and mixture of xylene or toluene with methylethylketone as solvent.
EFFECT: universal composition with increased adhesive resistance.
SUBSTANCE: present invention relates to a double-component coating composition (2C), as well as a coated article, a method of making a coated article and use of material which contains a phosphorus-containing polyol as a fireproof material in the disclosed composition. The composition contains: (a) first component containing isocyanate, wherein said isocyanate contains a prepolymer having isocyanate functional groups formed from a reaction mixture containing isocyanate and a material containing a phosphorus-containing polyol with the equivalent ratio of isocyanate groups to hydroxyl groups greater than 1 and the phosphorus-containing polyol which acts as fireproof material is (i) a product of reaction of the source phosphorus-containing polyol, selected from polyphosphate polyols, polyphosphite polyols, polyphosphonate polyols and mixtures thereof and compounds having epoxy functional groups; or (and) a product of reaction of a phosphorus-containing acid, a compound having epoxy functional groups and, optionally, a phosphorus-containing polyol; and (b) a second component containing a polyamine, wherein the first and second components are stored separately and form polyurea after mixing and the composition further contains an additional fireproof material which is added to the first and/or second component and is selected from graphite, halogenated phosphates, phosphates without a halogen, tris(2-chloropropyl)phosphate, tris(2,3-dibromopropyl)phosphate, tris(1,3-dichloropropyl)phosphate, diammonium phosphate, powdered or pyrogenic silicon dioxide, sheet silicates, aluminium hydroxide, bromated fire-retardants, halogenated aromatic compounds, antimony oxide, aluminium oxide trihydrate, metal borates, zinc borate, barium metaborate pentahydrate, ester phosphates, polyvinyl chloride, melamine cyanurate, melamine phosphates, polymelamine phosphates, melamine pyrophosphates, polylmelamine pyrophosphates, melamine borate, other melamine derivatives and mixtures of compounds.
EFFECT: obtaining a double-component coating composition, having improved fire-resistance and heat-resistance.
12 cl, 7 ex, 1 tbl
SUBSTANCE: present invention relates to hydroxyl containing polyester polyurethane dispersions for producing lacquer, coatings and adhesive materials. The dispersions contain products of reacting (a) at least one, at least bifunctional polyol, (b) at least one (potentially) ionic compound with at least one acid group and at least one group capable of reacting with isocyanates and selected from di-, tri- or mono-oxycarboxylic acids, (c) at least one acid anhydride and (d) at least one, at least bifunctional polyisocyanate component. Also described are methods of producing said dispersions and coating agents containing said dispersions.
EFFECT: easy and cheap production of hydroxyl containing polyester polyurethane dispersions which enable to obtain coatings having excellent optical properties and flow, low susceptibility to pitting, good resistance to solvents and controlled relationship between hardness and elasticity.
SUBSTANCE: invention relates to a method of producing a polymer-modified polyol, where olamine reacts with organic polyisocyanate in the presence of a polyol and at least one catalyst which is a metal salt of an organic acid, where the olamine reacts, at least preferably polyfunctionally, with isocyanate, where said catalyst or at least one said catalyst is a metal salt of an organic acid which does not have a metal-carbon bond, and where viscosity of the polymer-modified polyol is at least 2250 mP when measured at 25°C using a Brookfield viscosimeter or is compatible with a Brookfield viscosimeter system. The invention also describes versions of the method of producing a polymer-modified polyol, where the catalyst has the formula M(O.CO.R.CH3)2, where M is a metal, R is a carbon chain with 6-20 carbon atoms, wherein the chain is straight or branched with side functional OH groups, and/or with or without double bonds, and where the catalyst is a metal salt of a fat monohydroxy acid, respectively. Described also is a polymer-modified polyol produced using the disclosed methods, a method of producing polyurethane foam plastic (foamed polyurethane) using such a polyol and elastic polyurethane foam plastic (elastic foamed polyurethane) produced using said method.
EFFECT: use of metal-carboxylate catalysts when producing polymer-modified polyols, which results in stability of the obtained polyols, stability of foamed products from such polyols, as well as solving the environmental problem.
27 cl, 16 ex, 8 tbl, 3 dwg
SUBSTANCE: present invention relates to radiation-curable compositions, as well as a coating containing said composition for protecting metal substrates from corrosion. The composition consists of radiation-curable urethane(meth)acrylate with OH number ≥ 10 mg KOH/g, a monofunctional, radiation-curable reactive diluent, an acidic adhesion promoter, a photoinitiator, a multifunctional reactive diluent, radiation-curable resins and other inert additives. The adhesion booster used is phosphoric or phosphonic acid or products of their conversion with functionalised acrylates.
EFFECT: radiation-curable compositions, having good corrosion-protective properties for metal substrates, which are elastic and capable of being well moulded.
15 cl, 2 tbl, 5 ex
FIELD: industrial chemistry.
SUBSTANCE: present invention refers to a pulverizable system based on polyurethane that is applicable for production of the bottom layer for polyurethane formed parts that contains a polyol component (A) and an isocyanate component (B) and does not contain amine catalysts. The polyol component (A) contains: (a1) at least one compound that goes into reaction with isocyanate, (a2) at least one agent that is able to prolong the reactive chain with at least two groups that are able to go into reaction with isocyanate; at least one group that is able to go into reaction with isocyanate is represented by a free primary group NH2-, and (a3) at least one metallic catalyst and (a4) if necessary, other additives. The invention also refers to the way of production of the polyurethane bottom layer for formed parts, to the bottom layer that is manufactured in such a way and to application of this bottom layer in production of seats, control panel, remote controls, pockets and boxes or parts of the internal or external automobile siding.
EFFECT: production of the bottom layer for formed parts from the polyurethane-based pulverizable system that is characterized by low emanation of low-boiling components and condensing components, improved mechanical properties, in particular by breaking strength rupture limit, extensibility and breaking strength tearing limit as well as a small amount of time necessary for extraction from the mould if compared with the residency in an opened position.
20 cl, 4 tbl