Moisture-cured hot-melt adhesives having at least one silane group-containing polyurethane prepolymer

FIELD: chemistry.

SUBSTANCE: invention relates to moisture-cured hot-melt adhesives. Disclosed is a moisture-cured hot-melt adhesive composition containing at least one silane group-containing polyurethane prepolymer of formula (I), where R1 is an n-valent organic radical of prepolymer P, which is obtained from at least one polyol and at least one polyisocyanate and has at least n isocyanate groups, followed by removal of the n isocyanate groups; R2 is a C1-C10 alkyl group; R3 is a linear or branched C1-C10 alkylene group; X is a hydrolysable radical OR4, wherein R4 is a C1-C10 alkyl group which can contain 1 or 2 oxygen atoms of an ether; a equals 0, 1 or 2; n equals 2 or more; where the prepolymer of formula (I) is obtained from reaction of the polyurethane prepolymer P with a mercaptosilane of formula (II), wherein the prepolymer P is solid at room temperature and does not have an additional silane group, and the composition has longer storage life (viscosity stability) in uncured form. Disclosed also is a method for adhesive binding of substrates using the disclosed adhesive composition and an article obtained using the adhesive.

EFFECT: disclosed adhesive compositions do not form bubbles neither when heated nor during curing and have stable viscosity at high temperatures.

20 cl, 7 tbl

 

The technical field of the invention

The invention relates to the field of moisture curing hot melt adhesives.

Prior art

Hot-melt adhesives (hot melt) are known adhesives. Adhesives of this kind are free from solvents, adhesives that are solid at room temperature and which are aimed at causing melt and in the form of a melt is applied to contact the substrate. Unlike the so-called Caloplaca adhesives (Talalaev), which are pasty adhesives and applied at slightly elevated temperatures up to typically 60°C, application of hot melt adhesives occurs when the temperature is 85°C or higher. Upon cooling, the adhesive has hardened. Traditional hot-melt adhesives are not reactive adhesives, and therefore, when heated again they are softened or melted and are therefore unsuitable for use at elevated temperatures. In addition, traditional hot-melt adhesives often have a tendency to deform at temperatures much below the softening point (cold stream).

In the case of so-called reactive hot-melt adhesives these shortcomings to a large extent eliminated by introducing into the polymer structure of reaction is-able groups, which lead to crosslinking. It is proved that as reactive groups suitable are isocyanate groups. The first result of the cooling is in the development of early strength, which is normal for hot-melt adhesives. Therefore, the polymers are sewn through the interaction of isocyanate groups due to moisture. As a result of this stitching, adhesives of this type can be applied even at elevated temperature.

Reactive polyurethane hot-melt adhesives of this type are known, for example, from EP-A-0244608 or US 5155180 or EP-A-1036103, and they are widely used commercially.

The lack of moisture curing hot melt adhesives containing isocyanate groups, is that in many cases they lead to the rapid formation of bubbles, namely elevated levels of moisture and/or temperature. Bubbles of this type, however, are undesirable, especially when the data of the adhesive connection is obvious, of this type, which often occurs, for example, when used in the package.

Containing silane groups polyurethanes for some time used as a moisture curing adhesives and sealants. These contain silane groups of the polyurethanes contain silane groups as reactive groups and usually the floor which are stated in the interaction of aminosilanes with polyurethane prepolymers, containing isocyanate groups. Polyurethane adhesives thus obtained are, however, a big disadvantage, namely on prolonged heating, the viscosity of the adhesive can dramatically increase. EP-A-0202491 mentions the hot-melt adhesives based on containing silane groups of the complex polyester, in which the adduct polyol complex of polyester and diisocyanate interacts with the amino - or mercaptoethanol or adduct amino - or mercaptoethane diisocyanate and interacts with the polyol complex polyester. EP-A-0371370 discloses a hot-melt adhesives, which are additionally stitched under the influence of moisture and contain end alkoxysilane and/or NCO groups. EP-A-0371370 further disclosed that these end alkoxysilane group you can enter through mercaptoethane or through a series of aminosilanes. Neither EP-A-0371370 or EP-A-0202491 no distinction between aminosilane and mercaptoethane for the purpose of introducing functional groups to the polymer.

The polymers thus obtained are, however, a big disadvantage, namely on prolonged heating their viscosity may increase very sharply.

The increase in viscosity at elevated temperatures is largely unfavorable, especially for applications in which the adhesive holds a relatively long period of time at a temperature applications. what these applications often happen, for example, in industrial production.

The invention

Therefore, the aim of the present invention is to obtain a moisture curing hot melt adhesives, which lead to no formation of bubbles during heating and curing, nor to a sharp increase in viscosity during long-term storage at the temperature of application.

Surprisingly discovered that this objective can be achieved by using the moisture curing hot melt adhesive compositions according to claim 1 of the claims.

The compositions are suitable for adhesive connection of transparent materials, more particularly for bonding glass and window glass or translucent packaging. Composition otverzhdajutsja without bubbles and surprisingly have a very good shelf life (stability of viscosity) even at high temperatures.

Additionally it is found that through the use of mercaptoethanol formula (II) may be obtained containing silane groups of the polyurethane prepolymers of the polyurethane prepolymers containing isocyanate groups, which are able to achieve significant improvements in the shelf life (stability of viscosity) of the hot-melt adhesives at high temperatures. Additionally clarified that the application containing silane groups of the polyurethane prepolymers of the formula (I) in the hot melt ADH is the Ziva leads to an improvement in the shelf life (stability of viscosity) moisture curing hot melt adhesives at high temperatures.

Additional aspects of the invention are way adhesive connection 11 claims, as well as the product obtained in this way on 17 claims.

Additional variants of the embodiments are the target subject of the dependent claims.

Description of the preferred options accomplishments

The invention relates to a moisture curing hot-melt adhesive composition that includes at least one containing silane group of the polyurethane prepolymer of the formula (I)

where

R1is an n-valent organic radical of the prepolymer P, which is obtained from at least one polyol and at least one MDI and has at least n isocyanate groups, with the subsequent removal of the n isocyanate groups;

R2is an alkyl group having from 1 to 10 atoms;

R3is a linear or branched alkalinous group having from 1 to 10 atoms;

X is a hydrolyzable radical;

and has a value of 0, 1 or 2;

n has a value of 2 or more,

the prepolymer P is a solid at room temperature and has no additional a silanol group.

The prefix “poly” in the names of substances, such as “polyol” or “Paul the isocyanate”, in this document indicates that this substance is formally molecule contains more than one functional group, which is found in its name.

The term “silane group” in the present document defines a group that is joined to an organic radical through the silicon atom, which is hydrolyzable, it has from one to three hydrolyzable radicals. The hydrolysis of a silanol group, such as, for example, by contact with atmospheric moisture, accompanied by the formation of silanol groups (Si-OH) and the subsequent reaction of the condensation of silanol groups by the formation of siloxane groups (Si-O-Si).

The term “silane” defines organic compounds with low molecular weight, which carry at least one silane group. The term “containing silane group” defines a connection, more specifically polymers, which contain silane groups.

Radicals, which meant “hydrolyzable radicals are those radicals at a silanol group, which the hydrolysis reaction is replaced by the water completely from the silicon atom, where they formally replaced by a hydroxyl group. Thanks hydrolysis to the hydrolyzable moiety attached proton to obtain compounds with a low molecular weight, which can show what I organic or inorganic.

Hydrolyzable radicals X in containing silane group of the polyurethane prepolymer of the formula (I) are exactly those which are customary in the chemistry of silicon, more specifically those which are selected from the group consisting of formulas (X-1), (X-2), (X-3) (X-4) (X-5) (X-6) (X-7) (X-8).

where R' and R” independently of one another are alkyl or aryl, and R4is an alkyl group having 1 to 10 C atoms, which optionally contain 1 or 2 oxygen atoms simple ether, and more specifically is an alkyl group having from 1 to 4 atoms C. Particularly preferably hydrolyzable radical X is an alkoxy group OR4.

In one specific embodiment, two alkoxygroup-OR4can be alkalinous deoxyribo-OR5O-, which with the silicon atom forms a ring with five or six elements, and R5is alkalinous group having from 2 to 10, preferably 2 or 3 atom C.

It is important that the prepolymer P did not possess additional a silanol group. It is important that he had no wilanowie groups of this type that appear when aminosilane interacts with the NCO group in the prepolymer R.

Silane names in functional groups as prefixes, such as, for example, “aminosilane Il is “mercaptomerin”, determine the silanes, which have a functional group on the organic radical as Deputy.

It is shown that it is preferable, if R3is propylene.

Preferably hydrolyzable radical X represents-O-methyl, -O-ethyl or O-isopropyl, preferably-O-methyl.

Found that it is preferable if the corresponding atom of silicon has three hydrolyzable radicals in the containing silane group of the polyurethane prepolymer of the formula (I), i.e. for a value of 0 is preferred.

The prepolymer P get at least one polyol and at least one MDI.

The preferred polyols are polyols ethers, polyol esters and polycarbonate polyols.

Suitable polyol ethers, also called polyols of polyoxyalkylene are such polyols, which are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2 - or 2,3-butilenica, tetrahydrofuran or mixtures thereof, optionally polymerized with the aid of starter (initiating) molecule possessing two or more active hydrogen atoms, such as, for example, a molecule of water, ammonia or compounds having two or more HE or NH groups such as, for example, 1,2-ethanediol, 1,2 - or 1,3-propane the IOL, neopentylglycol, diethylene glycol, triethylene glycol, the isomeric dipropyleneglycol and dipropyleneglycol, isomeric butandiol, pentandiol, hexandiol, heptanediol, octanediol, nonanediol, decanediol, undemandingly, 1,3 - and 1,4-cyclohexanedimethanol, bisphenol a, hydrogenated bisphenol a, 1,1,1-trimethyloctane, 1,1,1-trimethylolpropane, glycerol, aniline, and mixtures of the aforementioned compounds. It is possible to apply not only the polyols of polyoxyalkylene, which have a low degree of unsaturation (measured according to ASTM D-2849-69 and expressed in milliequivalent unsaturation per gram of polyol (mEq/g)), obtained, for example, by using compounds that are called double complex catalysts cyanide metals (DMC catalysts), as well as the polyols of polyoxyalkylene with a higher degree of unsaturation obtained, for example, with the aid of anionic catalysts such as NaOH, KOH or alkoxides of alkali metals.

Particularly suitable polyether polyols are diols of polyoxyalkylene or trioli of polyoxyalkylene, more preferably diols of polyoxyethylene or trioli of polyoxyethylene.

Particularly suitable diols are polyoxyalkylene or trioli of polyoxyalkylene having a degree of unsaturation of less than 0.02 mEq/g and having a molecular weight online is rule from 1,000 to 30,000 g/mol, as well as diols and trioli of polyoxypropylene having a molecular weight of from 400 to 8000 g/mol.

Also particularly suitable are those that are known as diols or trioli of polyoxypropylene “with limit SW band” (with limit ethylene oxide). The latter are special polyols of polyoxypropylene and polyoxyethylene obtained, for example, when exposed to pure polyols of polyoxypropylene after the introduction of polypropylene group of ethylene oxide for the introduction of CNS group, and having the primary hydroxyl groups. Under 'molecular weight' or 'molar mass' is understood in this document always average molecular mass Mn.

The most suitable polyether polyols are diols having unsaturation lower than 0.02 mEq/g, having a molecular weight in the range from 7000 to 30000, more specifically between 10000 and 25000 g/mol. Polyethers of this type are sold, for example, under the trade name Acclaim® by the company Bayer.

Suitable polyol polyesters are more specifically those that are derived from dibasic to trekhosnovnykh, preferably dibasic alcohols, such as, for example, 1,2-ethanediol, diethylene glycol, 1,2-propandiol, dipropyleneglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl icol, glycerol, 1,1,1-trimethylolpropane or mixtures of the aforementioned alcohols with organic dicarboxylic acids or their anhydrides or esters, such as, for example, succinic acid, glutaric acid, adipic acid, cork acid, sabotinova acid, dodecadienol acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and hexahydrophthalic acid or mixtures of the aforementioned acids and polyols and polyesters formed from lactones such as, for example, ε-caprolactone.

Particularly suitable polyols and polyester polyols are polyesters formed from adipic acid, sabatinovka acid or dodecadienol acid as dicarboxylic acid, and from hexanediol or neopentyl glycol as dibasic alcohol. The polyol polyesters preferably have a molecular weight of from 1500 to 15000 g/mol, more specifically from 1500 to 8000 g/mol, preferably from 2000 to 5500 g/mol.

Particularly suitable crystalline or partially crystalline polyol polyesters are polyesters of adipic acid and hexanediol and polyesters dodecadienol acid and hexanediol.

Suitable polycarbonate polyols are polyols takoh the type which are obtained during the interaction, for example, the above-mentioned alcohols - alcohols, which are used for the synthesis of polyol polyesters with diallylmalonate, dellcorporate or phosgene.

The preferred polyols are diols, more particularly polyether diols, diols polyesters and polycarbonate diols.

Particularly preferred polyols are diols polyesters, more particularly a mixture of amorphous diol complex polyester and a crystalline or partially crystalline diol complex polyester.

The polyisocyanate contains two or more NCO groups, and this document describes in each case, low molecular weight compounds having molecular weights below 1000 g/mol.

Examples of polyisocyanates are aromatic polyisocyanates such as 2,4 - and 2,6-colorvision (TDI) and any desired mixtures of these isomers, 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanate and any desired mixtures of these isomers (MDI), mixtures of MDI and MDI homologs (polymeric MDI or PMDI), 1,3 - and 1,4-delete the entry, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatobutane (TODI), oligomers and polymers of the above-mentioned diisocyanate and any desired mixtures the above-mentioned isocyanates. Particularly preferred aromatic polyisocyanates are MDI and DI.

Additional examples of such polyisocyanates are aliphatic and cycloaliphatic polyisocyanates such as 1,6-hexamethylenediisocyanate (HDI), 2-methylpentanediol-1,5-diisocyanate, 2,2,4 - and 2,4,4-trimethyl-1,6-hexamethylenediisocyanate (TMDI), 1,12-dodecyltrimethoxysilane, cyclohexane-1,3 - and -1,4-diisocyanate and any desired mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl (i.e. isophorondiisocyanate or IPDI), perhydro-2,4'- and -4,4'-diphenylmethanediisocyanate (HMDI), 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), m - and p-xylylenediisocyanate (m - and p - XDI), m - and p-tetramethyl-1,3 - and -1,4-xylylenediisocyanate (m - and p - TMXDI).

To obtain compositions resistant to light compositions, it is preferable to use aliphatic and cycloaliphatic polyisocyanates.

Preferably the polyisocyanate is a diisocyanate having a molecular weight less than 400 g/mol.

The prepolymer P get in a known manner directly from polyisocyanates and polyols or manual process type adduction, also known as reaction growth of the chain.

It is important that the prepolymers R had a free isocyanate groups and were solid at room temperature. The number of isocyanate groups to a large extent depends on the desired final properties of the cured adhesive. In one preferred variant is nThe implementation of the polyurethane prepolymer obtained when the interaction of at least one MDI and at least one polyol, preferably one amorphous polyol complex polyester and a single crystalline polyol complex polyester, with a stoichiometric excess of isocyanate groups.

The prepolymer P has a molecular weight of preferably more than 2000 g/mol, more specifically the molecular weight between 2000 and 50000 g/mol, preferably one of between 4000 and 30000 g/mol. In addition, the prepolymer P has n isocyanate groups. Depending on the functionality used polyols and polyisocyanates, n takes a value of 2 or more. The predominant is, if n has a value from 2 to 4. In one preferred embodiment, n equals 2. For professionals it is clear that the applied polyols and polyisocyanates are typically mixtures with different functionalities. In other words, for example technical “diol” in fact, on the one hand, contains monooly and diol so that the average functionality was not equal to 2, and Vice versa, less than 2. On the other hand, technical diols can also include additives triolo so that the average functionality was not equal to 2, and Vice versa, more than 2.

Receipt containing silane group of the polyurethane prepolymer of the formula (I) is accomplished preferably through the interaction of the prepolymer P, as described above, with Mercat is a silane of the formula (II)

HS-R3Si(X)(3-a)(R2)a(II)

where the radicals have the definitions and advantages already described for formula (I).

Examples of suitable mercaptoethanol are mercaptoacetyltriglycine, mercaptoacetyltriglycine, mercaptoacetyltriglycine, mercaptoacetyltriglycine, 3-mercaptopropionylglycine, 3-mercaptopropionate, 3-mercaptopropionylglycine, 3 mercaptopropionate(1,2-Ethylenedioxy)silane, 3-mercaptopropionate(1,2-Propylenediamine)silane, 3-mercaptopropionate(1,2-Propylenediamine)silane, 3-mercaptopropionylglycine, 3-mercaptopropionylglycine, 3-mercapto-2-methylpropionitrile, 4-mercapto-3,3-dimethylethoxysilane.

The preferred mercaptoethane are 3-mercaptopropionylglycine and 3-mercaptopropionate, more specifically 3-mercaptopropionylglycine.

The interaction of the prepolymer P containing isocyanate groups, with mercaptoethanol is known.

Depending on the number of used mercaptoethane all isocyanate groups of the prepolymer P face interaction or remain unreacted isocyanate groups. In the first case, mercaptomerin applied stoichiometric or sverhtehnologichny, and obrazu the Xia containing silane groups of the polyurethane prepolymer of the formula (I), which does not contain isocyanate groups, in other words, all of the n isocyanate groups of the prepolymer P consumed in the interaction. In the second case, mercaptomerin used in stoichiometric insufficient, and is formed containing silane groups of the polyurethane prepolymer of the formula (I), which, along with wilanowie groups also contains isocyanate groups, in other words, not all of the n isocyanate groups of the prepolymer P consumed in the interaction.

For certain applications it may be technically advantageous to containing silane groups of the polyurethane prepolymer of the formula (I) still had the isocyanate groups.

For Toxicological reasons, it is advantageous to contain silane groups of the polyurethane prepolymer of the formula (I) did not possess any isocyanate groups.

Containing silane groups of the polyurethane prepolymer of the formula (I) preferably has no isocyanate groups.

Moisture curing hot-melt adhesive composition may include optional additives, such as plasticizers, fillers, adhesion promoters, UV absorbers, UV stabilizers or depletability, antioxidants, flame retardants, optical brighteners, catalysts, colored pigments or dyes. Suitable catalysts is the tsya such that catalyze the hydrolysis and/or stitching Milanovich groups. Such catalysts include, for example, titanates, connection organology, such as dilaurate dibutylamine and deacetylation dibutylamine, organic bismuth compounds or complexes of bismuth compounds containing amino groups, such as, for example, 1,4-diazo-bicyclo[2.2.2]octane or a simple 2,2'-disorganizational ether.

In one preferred embodiment, the hot melt adhesive composition does not contain carbon black. Carbon black is often added as a filler, especially in polyurethane chemistry, more specifically in the case of traditional one-component polyurethane adhesives or in the case of one-component polyurethane Talalaev to improve the mechanical properties of the adhesive, and also for giving adhesives consistency of low viscosity. In an additional preferred embodiment, the adhesive does not contain inorganic fillers. This is because fitness is filled with technical carbon adhesive is not satisfactory for those applications where the aesthetics of adhesive connections are classified as important and in which at least one of the associated substrate is transparent or translucent. In a preferred embodiment, domestic the hot-melt adhesive composition without carbon black and accordingly without inorganic fillers, such applications, however, are possible without adverse effect on the mechanical properties or application.

For moisture curing hot-melt adhesive, it is important that the adhesive was capable of melting, in other words, so that when the temperature of the deposition he had a satisfactorily low viscosity, which allows the application and that upon cooling it quickly hardened, so that the adhesive is able to quickly focus before you are finished with the crosslinking reaction with atmospheric moisture. It is found that moisture curing hot-melt adhesive composition is at a temperature of 150°C, a viscosity of less than 100,000 MPa·s, preferably less than 50,000 MPa·s, and 70°C has a viscosity of more than 20000 MPa·s, preferably more than 50,000 MPa·S.

Containing silane groups of the polyurethane prepolymer of the formula (I) can also be mixed with other polyurethane prepolymers, which provide improved shelf life (stability of viscosity) at elevated temperature moisture curing hot-melt adhesive obtained in this way.

The influence of moisture or water, more specifically, atmospheric moisture, hydrolyzable radicals containing silane groups of the prepolymer of the formula (I) are subjected to hydrolysis, and this leads to the binding.

The invention is an optional method includes adhesive mounting substrate S1 to a substrate S2, includes stages:

i) heating the moisture curing hot melt adhesive compositions of the type described above, to a temperature between 85°C and 200°C., more particularly between 120°C and 160°C;

ii) applying the heated moisture curing hot melt adhesive composition to a substrate S1;

iii) bringing into contact caused moisture curing hot-melt adhesive composition with a second substrate S2;

moreover, the second substrate S2 consists of the same material as the substrate S1 or different material.

By stage iii) is then usually followed by stage iv) chemical curing moisture curing hot-melt adhesive composition with atmospheric moisture. The specialist understands that, depending on the system used and the temperature and reactivity of the adhesive reaction of cross-linking and, therefore, chemical curing may begin immediately at the time of application. The main part of the staple, and, consequently, in a more narrow sense of the term chemical curing, however, occurs after application.

If necessary, the substrates S1 and/or S2 can be pre-processed before applying hot-melt adhesive composition. Such pre-processing includes the processes of physical and/or chemical cleaning and activation, and examples are grinding, packetwin the I treatment, cleansing brushes, treatment by corona discharge, the treatment with plasma processing flames, etching or the like, or treatment with cleaners or solvents, or the application of the adhesion promoter, the solution of the adhesion promoter or primer tools.

The substrates S1 and S2 can be composed of various materials. Suitable properties of plastics, organic materials such as leather, cloth, paper, wood, resin bonded materials based on wood, a composite material of resin and textiles, glass, porcelain, ceramics, and metals and metal alloys, preferably painted or powder coated metals and alloys of metals.

Suitable plastics are polyvinyl chloride (PVC), copolymers of Acrylonitrile, butadiene and styrene (ABS), SMC (molded sheets composites), polycarbonate (PC), polyamide (PA), polyesters (PE), Polyoxymethylene (RUM), polyolefins (PO), more specifically, polyethylene (PE) or polypropylene (PP), preferably PE or PP with the surface treated by plasma, corona or flame.

Preferred materials for the substrates S1 and S2 are transparent materials, more specifically, a transparent polymer films. Other preferred transparent material is glass, more specifically in the form of glass.

Moisture curing thermop the avco adhesive composition is used in industrial manufacturing operations.

Moisture curing hot-melt adhesive composition is suitable for adhesive connections, in which the location of the connection is visible. Thus, on the one hand, is suitable for adhesive attachment of the glass, especially in the vehicle structure and design of the glasses. On the other hand, is suitable for adhesive attachment translucent packaging.

The adhesive cures essentially without bubbles. The usual thickness of the adhesive bonds is 10 micrometers or more. The preferred thickness of the links is between 10 micrometers and 1000 micrometers, in particular between 80 micrometers and 500 micrometers. Found that bubbles are not formed even in fastening the layer thickness of more than 80 micromeres.

A method of adhesive bonding is widely used in the products. Such products are, on the one hand, the products of the industries of transport, furniture or textiles. As the transportation industry preferred automotive industry.

Conventional products are components for automobile interiors, such as the inner roof lining, sun visors, toolbars, side door panels, shelves for packages and the like, materials made of wood fiber for showers and bathrooms, a foil for decorative accessories, film meme the RAS with textile materials, such as cotton fabric, polyester film in sewing products or textile materials with a foam finishing cars.

On the other hand, such materials find application in the packaging and this product includes translucent packaging.

An additional aspect of the present invention is the use of mercaptoethanol the above formula (II) for the modification of polyurethane prepolymers containing isocyanate groups, with the aim of improving the shelf life (stability of viscosity) is not cured containing silane groups of the hot-melt adhesive.

HS-R3-Si(X)(3-a)(R2)a(II)

where the radicals have the preferences and advantages already described for formula (I).

The preferred mercaptoethane are 3-mercaptopropionylglycine and 3-mercaptopropionate, more specifically 3-mercaptopropionylglycine.

Accordingly, it is possible, using mercaptoethane formula (II), to obtain containing silane groups of the polyurethane prepolymers of the polyurethane prepolymers containing isocyanate groups, whereby the shelf life (stability of viscosity) of the hot-melt adhesives at high temperatures can be greatly improved, preferably compared to appropriate ejstvujuschij containing silane groups polyurethane prepolymers, obtained from aminosilanes and polyurethane prepolymers containing isocyanate groups. In addition, it is found that the application containing silane groups of the polyurethane prepolymers of the formula (I) in hot-melt adhesives leads to improved shelf life (stability of viscosity) moisture curing hot melt adhesives at high temperatures.

An additional aspect of the present invention is the use of containing silane groups of the polyurethane prepolymer of the formula (I), as already described above, in hot-melt adhesives to improve the shelf life (stability of viscosity) is not cured adhesive.

Found that the hot-melt adhesive based on containing silane groups of the polyurethane prepolymers of the formula (I) has at elevated temperatures, much better stability of viscosity than the adhesive of the prior art, which is based on containing silane groups of the polyurethane prepolymers obtained from aminosilanes, and polyurethane prepolymers containing isocyanate groups. In accordance with the phenomenon of increase in viscosity with storage time at high temperature, which corresponds more specifically, the temperature of application, usually at a storage temperature between 120°C and 160°C, it is not increased or p is increased only much slower and/or less, and refers in this document to the term “shelf life” or “stability viscosity”.

Furthermore, in addition to the lack of bubbles and improved stability viscosity, determined that UV stability, more yellowing, moisture curing hot-melt adhesive compositions can be largely reduced by using cycloaliphatic polyisocyanates upon receipt of the prepolymer P or containing silane groups of the polyurethane prepolymer of the formula (I).

Examples

In the text below, the applied substance and abbreviations used in table 1.

Table 1
Abbreviations used
A3-mercaptopropionylglycine
A3-aminopropyltrimethoxysilane
A1170bis(3-triethoxysilylpropyl)Amin
TMSDEEdiethyl-N-(3-triethoxysilylpropyl)aminosuccinic
TESDEEdiethyl-N-(3-triethoxysilylpropyl)aminosuccinic
MDI4,4'-diphenylmethanediisocyanate (MDI)
H-MDIperhydro-2,4'- and -4,4'-diphenylmethane Socionet

Getting prepolymers P

The prepolymerP1

1:1 (mass:mass) of the mixture of polyesters Dynacoll® 7150 (Degussa) and Dynacoll® 7250 (Degussa) were loaded into a 1-liter reaction vessel with a non-stick coating and 4-throat cover with ground glass joints. It was melted in an oil bath with temperature control at 120-125°C for 4 hours

The thus obtained liquid mixture of polyols was obezvozhivani under high vacuum with stirring for one hour while maintaining the temperature.

Then MDI in a molar ratio of NCO/OH = 2:1, was added to the polyol in the reaction vessel, and the interaction was performed with stirring for 2 hours while maintaining the temperature. Thus obtained prepolymerP1had a NCO content equal to 2.2%, and a viscosity equal to 15500 MPa·s at 130°C.

The prepolymerP2

The prepolymerP2received a similar way asP1except that forP2a mixture of polyesters has been replaced by a stoichiometric polyether polyol Desmophen® 4028 BD (Bayer). Thus obtained prepolymerP2had a NCO content equal 2,05%, and a viscosity equal to 1875 MPa·s (10 revolutions per minute) at 70°C.

Receipt containing silane groups of the polyurethane prepolymers

The above prepolymerP1and thereforeP2mixed with with otvetstvennym the silane, used stoichiometric (one silane interacts with one NCO group)as seen in table 2, and 0.2 wt.% dilaurate dibutyrate (DBTL) as a catalyst in relation to the prepolymer, and after an interaction time of 1 h, the mixture was placed in tubes or cartridges. It guaranteed storage in the absence of moisture.

Table 2
Song
Ref. 1Ref. 2Ref. 3Ref. 412Ref. 5
The silaneATMSDEETESDEEAAATMSDEE
The prepolymerP1P1P1P1P1P2P2

It is found that in the course of obtaining comparative example Ref. 1 were subjected to gelation. All other composition which can be obtained without gelation.

Shelf life (stability of viscosity)

The viscosity measurement was performed continuously at the corresponding temperature.

To measure the shelf life (stability of viscosity) viscosity η [MPa·s] the respective compositions was measured by remata (viscometer) (Brookfield, Thermosel, spindle 27, shear rate 1 min-1after storage time Tswhen the appropriate temperature So

Table 3
Stability of viscosity at different temperatures
Reference 2Reference 41
T[°C]120140160120140160120140160
η
Ts=2 hours1000025001200was not measured177006000107300385007300
Ts=4 h8000220090000was not measured186009100110300390007600
Ts=6 h70002200immeasurablewas not measured2000092000113300398008100
Ts=8 h65002600immeasurablewas not measured21600immeasurable11630040300 8600
Ts=12 h610020200immeasurablewas not measured26700immeasurable122300of 41,6009300
Ts=12 h6200immeasurableimmeasurablewas not measured40700immeasurable1320004360010000

Table 4
Stability viscosity at 160°C
Ref. 2Ref. 3Ref. 512
T[°C]160160160160160
η
Ts=2 hours12008003007300600
Ts=4 h90000270070076001200
Ts=4.5 himmeasurable43300100081001200
Ts=6 himmeasurableimmeasurable270081001000
Ts=8 himmeasurableimmeasurable164008600600
Ts=9 himmeasurableimmeasurable414008800600
Ts =12 himmeasurableimmeasurablenot measurable9300700
Ts=18 himmeasurableimmeasurablenot measurable10000800

Table 5
Long-term stability of the viscosity of the composition 1 at a storage temperature limit of 160°C
Ts=2 hoursTs=4 hTs=6 hTs=8 hTs=12 hTs=18 hTs=24 hTs=48 hTs=72 hTs=90 h
η73007600810086009300100001050013200 1740020700

Results tables 3-5 show that compositions 1 and 2 differ with respect to a reference examples extraordinarily improved stability during storage. Even at 160°C, the viscosity increase is small even after a long storage time, whereas the reference examples have already experienced such an intense salustiano that more of them could not be measured.

Blisters

To determine the bubble samples were obtained along the lines of obtaining test samples to determine the hardness shore A. In this case, the hot adhesive was injected at a temperature of approximately 140°C in a Teflon ring (2 mm thick). The adhesive is extruded to a thickness by weight of 5 kg) and cooled. The cooled adhesive was subsequently removed from the mold and was utverjdali at 20°C and 55% humidity.

Blistering conducted a visual assessment.

Reference used for the reactive hot-melt adhesive was prepolymer P1.

Table 6
Bubbles
1without the formation of bubbles
2without the formation of bubbles
P1intensive formation of bubbles

Mechanical properties

The ultimate tensile strength

In the method based on DIN 53504 rectangular samples of size 2×12 cm was cut out from utverzhdenii film composition 1 with a thickness of 500 μm. These samples were crushed in a dynamometer (Zwick Z 020) and stretched at a rate of 100 mm/min. Measured parameter was the maximum tensile stress that a given sample.

Tensile strength shear

The ultimate strength in shear of composition 1 was measured by a method based on DIN EN 1465 on the dynamometer from Zwick (Z 020) at a test speed of 100 mm/min Two prototypes of the corresponding substrate was bonded barrier 12×25 mm, the adhesive layer thickness 2 mm) and tested.

The mechanical results of composition 1 are collected in table 7.

Table 7
The mechanical results of the composition 1
Conditional tensile strength27,3±2,1 MPa
Tensile strength shear
Beech5.9 MPa (extract wood fiber)
ABS4.5 MPa
Polycarbonate3,7 MPa

1. Moisture curing hot-melt adhesive composition that includes at least one containing silane group of the polyurethane prepolymer of the formula (I)

where R1is an n-valent organic radical of the prepolymer P, which is obtained from at least one polyol and at least one MDI and has at least n isocyanate groups with the subsequent removal of the n isocyanate groups;
R2is an alkyl group having from 1 to 10 atoms;
R3is a linear or branched alkalinous group having from 1 to 10 atoms;
X is a hydrolyzable radical OR4and R4is an alkyl group having 1 to 10 C atoms, which optionally contains 1 or 2 oxygen atom simple ether;
and has the value 0, 1 or 2;
n has a value of 2 or more;
where the prepolymer of the formula (I) obtained by the interaction of the polyurethane prepolymer P has at least n lantime groups, mercaptoethanol formula (II)

the prepolymer P is a solid at room temperature and does not have additional a silanol group, and the composition has an improved shelf life (stability of viscosity in the uncured form.

2. Moisture curing hot-melt adhesive composition according to claim 1, characterized in that at a temperature equal to 150°C., the composition has a viscosity less than 100,000 MPa·s, preferably less than 50,000 MPa·s, and at a temperature equal to 70°C., the composition has a viscosity of more than 20000 MPa·s, preferably more than 50,000 MPa·S.

3. Moisture curing hot-melt adhesive composition according to claim 1 or 2, characterized in that X is stands, ethyl or isopropyl, preferably the stands.

4. Moisture curing hot-melt adhesive composition according to claim 1 or 2, wherein a has a value of 0.

5. Moisture curing hot-melt adhesive composition according to claim 1 or 2, characterized in that the polyol is diola, preferably diola of ester, and the polyisocyanate is a diisocyanate having a molecular weight of less than 400 g/mol.

6. Moisture curing hot-melt adhesive composition according to claim 1 or 2, characterized in that the containing silane group of the polyurethane prepolymer of the formula (I) has no isocyanate groups.

7. Moisture curing hot-melt adhesive composition according to claim 1 or 2, wherein R3is propylene.

8. A method of adhesive bonding a substrate S1 to a substrate S2, which with a stage in yourself:
i) heating the moisture curing hot-melt adhesive composition according to any one of claims 1 to 9 to a temperature between 85°C and 200°C, preferably between 120°C and 160°C;
ii) applying the heated moisture curing hot-melt adhesive composition pas substrate S1;
in) bringing into contact caused moisture curing hot-melt adhesive composition with a second substrate S2;
moreover, the second substrate S2 consists of the same material as the substrate S1 or different material.

9. The method according to claim 8, characterized in that for stage iii) should stage iv) chemical curing atmospheric moisture moisture curing hot-melt adhesive composition.

10. The method according to claim 8, characterized in that at least one of the substrates, S1 or S2, is a transparent material, preferably a transparent polymer film.

11. The method according to claim 9, characterized in that at least one of the substrates, S1 or S2, is a transparent material, preferably a transparent polymer film.

12. The method according to any one of p-11, characterized in that at least one of the substrates, S1 or S2, is glass, preferably in the form of glass.

13. The method according to any one of p-11, characterized in that the adhesive binding occurs in the industrial operations of receiving the product.

14. The method according to l is the Boma one of PP-11, characterized in that the thickness of the adhesive layer is from 10 μm to 1000 μm, preferably from 80 μm to 500 μm.

15. Product bonded adhesive binding method according to any one of PP-14.

16. The product according to item 15, wherein the product is a translucent package.

17. The product according to item 15, wherein the product is a product used in the field of transport, furniture or textiles.

18. The use of mercaptoethanol formula (II) for the modification of polyurethane prepolymers containing isocyanate groups, with the aim of improving the shelf life (stability of viscosity in the uncured state, the hot-melt adhesive containing a silane group

where R2is an alkyl group having from 1 to 10 atoms;
R3is a linear or branched alkalinous group having from 1 to 10 atoms, preferably propylene; and
X is a hydrolyzable radical OR4and R4is an alkyl group having 1 to 10 C atoms, which optionally contains 1 or 2 oxygen atoms simple ether;
and has the value 0, 1 or 2, preferably 0.

19. Use p, wherein X is a OR4where R4is an alkyl group having 1 to 10 C atoms, which optionally contains 1 or 2 atom is oxygen simple ester, and preferably is stands, ethyl or isopropyl, more preferably the stands.

20. Application containing silane groups of the polyurethane prepolymer of the formula (I)as described in any one of claims 1 to 9, in hot-melt adhesives to improve the shelf life (stability of viscosity) uncured hot-melt adhesive, where the prepolymer has the following formula (I)

where R1is an n-valent organic radical of the prepolymer P, which is obtained from at least one polyol and at least one MDI and has at least n isocyanate groups with the subsequent removal of the n isocyanate groups;
R2is an alkyl group having from 1 to 10 atoms;
R3is a linear or branched alkalinous group having from 1 to 10 atoms;
X is a hydrolyzable radical OR4and R4is an alkyl group having 1 to 10 C atoms, which optionally contains 1 or 2 oxygen atoms simple ether;
and has the value 0, 1 or 2;
n has a value of 2 or more.



 

Same patents:

FIELD: chemistry.

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 di- or higher polyisocyanate components, and D) a mixture (D) of primary and/or secondary monoamine compounds D1) and primary and/or secondary diamine compounds D2), wherein at least one of the components (D1) and/or (D2) contains sulphonate groups, wherein the average amine functionality of the mixture (D) is 1.65-1.95, and the equivalent ratio of NCO groups in the NCO prepolymer and total number of amine and hydroxyl groups of the mixture (D) 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 thermal stability.

14 cl, 10 ex, 1 tbl

FIELD: chemistry.

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

FIELD: chemistry.

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

FIELD: chemistry.

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

FIELD: chemistry.

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

FIELD: chemistry.

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.

3 tbl

FIELD: transport.

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

FIELD: chemistry.

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

FIELD: chemistry.

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

Gluing method // 2451040

FIELD: chemistry.

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

FIELD: chemistry.

SUBSTANCE: invention relates to a curable sealing resin composition. The curable composition contains at least one anhydride-functionalised polymer in amount of 30-60 wt %, a polyol in amount of 10-25 wt %, an epoxide-functionalised polymer, oligomer or monomer in amount of 15-40 wt %, a urethane polyol-functionalised compound selected from a group consisting of urethane diol, polyurethane diol and combination thereof in amount of 5-15 wt % and a catalyst with respect to total weight of the resin. The resin composition can be cured at room temperature. Components used to prepare and cure the resin composition can be provided in form of two or more parts.

EFFECT: hydrolytic stability, high hardness, flexibility and low cost of production of the sealing resin which can be used to restore insulation and/or for environmental protection of cable joints, sealed articles etc.

13 cl, 4 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to production of polymer composite materials - sealants, adhesive sealants and coatings based on moisture-curable urethane siloxane liquid rubber and can be used in car and transport engineering, shipbuilding, refrigeration engineering and in the construction industry. The polymer composition consists of the following, wt %: urethane siloxane liquid rubber - 10-25, plasticiser - 10-25, calcium carbonate filler - 40-65, titanium dioxide and/or zinc oxide - 0-5, antioxidant - 0.2-0.8, thixotropic agent - 0-5, drying agent - 0.5-0.8. Calcium carbonate is selected from a group of fractions with a different degree of dispersion or combinations thereof, wherein the combination of each fraction according to particle size is at least 4-10 times greater or less than the previous or next on dispersion. The curing agent used in the composition is in form of tertiary amines selected from trialkylamine, dialkylarylamine and/or diazobicycloalkane. The adhesion promoter is an organo-functional alkoxy silane with primary and/or secondary amine groups. In another version, the composition contains a curing agent in form of tin dibutyl dilaurate and an adhesion promoter with a balanced ratio thereof.

EFFECT: invention improves technological parameters, operational characteristics of the composition, provides reliable adhesion to different materials and enables wide range control of the curing time of the composition while saving raw materials and other materials.

5 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to polyurethane compositions for producing holographic media which contain (A) one or more polyisocyanates, (B) one or more block copolymers which react with isocyanate, (C) one or more compounds having groups which, during actinic exposure, react with ethylenically unsaturated compounds with polymerisation, (D) optionally one or more free-radical stabilisers and (E) one or more photoinitiators. Topographic media obtained from such polyurethane compositions are also described.

EFFECT: obtaining polyurethane systems having excellent compatibility of the polyurethane polymer matrix with radiation-curable olefinically unsaturated monomers in the composition, and have considerably higher transparency.

13 cl, 3 tbl

FIELD: chemistry.

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

FIELD: chemistry.

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.

3 tbl

FIELD: chemistry.

SUBSTANCE: magnetodielectric material contains a polyurethane prepolymer and magnetically soft filler containing iron particles in amount of 60-65% of the weight of the material and silicon dioxide particles in amount of 1-4% of the weight of the material.

EFFECT: invention increases setting time of the starting composition when producing the material and reduces the probability of conglomeration of metal particles.

3 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: microporous polyurethane elastomers are obtained from a reaction mixture which contains water as a foaming agent and an auxiliary ingredient selected from one or more of the following compounds: 1,2-trans-dichloroethylene, propyl propionate, one or more hydrocarbons having boiling point from 100 to 250°C and flash point higher than 30°C. The microporous polyurethanes have shrinkage characteristics similar to those of polyurethanes foamed with R-134a. Despite the presence of the auxiliary ingredient, the prescribed polyol component in many cases has flash point higher than 65°C and is classified as non-inflammable according to ISO 1523.

EFFECT: invention enables to replace R-134a with water without requiring different forms.

8 cl, 6 tbl, 9 ex

FIELD: chemistry.

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

FIELD: chemistry.

SUBSTANCE: polymer mixture consists of thermoplastic polyurethane (TPP) and a modified impact resistant methylmethacrylate polymer. Said impact-resistant methylmethacrylate polymer is modified with an impact resistant modifier with a "nucleus/shell/shell" structure. The first shell contains 80-98 wt % repeating (meth)acrylate monomers and 2-20 wt % styrene monomers of a defined formula (1). The second shell contains 50-100 wt % repeating alkylmethacrylate units, having 1-20 carbon atoms, 0-40 wt % repeating alkylacrylate units, 0-10 wt % styrene monomers of formula (1). The nucleus contains 50-99 wt % alkylmethacrylate repeating units having 1-20 carbon atoms, 0-40 wt % alkylacrylate repeating units having 1-20 carbon atoms, 0.1-2.0 wt % cross-linking repeating units and 0-8.0 wt % styrene monomers of formula (1).

EFFECT: polymer mixture is used to obtain moulded articles with high light transmission and high impact resistance at above-zero and subzero temperatures.

9 cl, 1 tbl, 2 ex

FIELD: machine-building industry.

SUBSTANCE: invention relates to the method of encapsulating o-rings manufacture for installing them between parts and units of internal combustion engines, between flange connections in chemical industry, for finishing, noise-insulating and thermal insulating panels. The method provides for grinding cork wastes to 0.5-5.0 mm. The cork wastes are mixed up with binding material based on a mixture of urethane and butadiene-acrylo-nitric rubber taken in a weight ratio 10-90:10-90. After rubber mixing with binding material, the mixture is moulded at 143-151°C and 3-10 MPa during 20-60 min. Then it is exposed at room temperature during one day. The sheets of the material are then slit and needed items are cut out. Wastes from cork, shoe and prosthetic and orthopedic production, wastes from finishing, noise and thermal insulating production, proper substandard wastes, flash chipping wastes are used as grinded cork wastes which are taken separately or in any ratios between each other.

EFFECT: invention allows for increasing reliability of o-rings and obtaining multifunctional material.

5 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: aqueous dispersion contains the following structural components: (A) 10-40 wt % of one or more aliphatic polyisocyanate compounds; (B) 40-70 wt % of at least one polyhydroxy compound having molecular weight Mn ranging from 400 g/mol to 8000 g/mol; (C) 19-49 wt % of a non-ionically hydrophilising monofunctional polyoxyalkylene ether which contains only one hydroxyl or amino group and 50-100 wt % of structural components derived from ethylene oxide, and having molecular weight Mn ranging from 1200 g/mol to 3000 g/mol; (D) 0.5-10 wt % of at least one polyamine compound having molecular weight Mn ranging from 32 g/mol to 400 g/mol and functionality greater than or equal to 1; (E) 0.5-10 wt % of a polyhydroxy compound having molecular weight Mn ranging from 62 g/mol to 320 g/mol and functionality greater than or equal to 1; and (F) 0-10 wt % of auxiliary substances and additives; wherein the sum of said structural components (A) through (F) equals 100 wt %.

EFFECT: obtaining novel aqueous polyurethane carbamide dispersions which have sufficiently high storage stability.

6 cl, 9 ex, 2 tbl

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