Water dispersions of glues

FIELD: chemistry.

SUBSTANCE: water dispersion contains polyurethane dispersion and water dispersion of silicon dioxide. Polyurethane dispersion has the average size particle of polyurethane polymer in the range from 60 to 350 nm. The water dispersion of silicon dioxide has SiO2 particles diametre from 20 to 400 nm. Polymer dispersions are used as glues for gluing of any substrates same or different type.

EFFECT: high initial thermal durability of glue joints.

9 cl, 15 ex, 6 tbl

 

The invention relates to aqueous dispersions of polymers based on polyurethane, the method of their production and their use.

Adhesives based on polyurethanes are basically solvent adhesives are applied to both of the joined substrate and dries. By subsequent connections of both substrates under pressure at room temperature or after thermoactivation get bonded structure with high initial strength directly after the connection process.

For reasons of ecology there is an increasing need for suitable aqueous dispersions of adhesives, which can be recycled in the appropriate aqueous adhesive composition. Such systems have the disadvantage: after evaporation of water the initial thermal strength immediately after the connection process is markedly lower than that of adhesives containing solvents, despite preliminary thermoactivation dry adhesive film.

To the present time it is known the use of the products of silicic acid for various purposes. While solid SiO2products commonly used to control rheological properties, as well as fillers or adsorbents, silicic acid sols are often used as binders of various inorganic materials, in which the quality of the polishing material for semiconductors or as a flocculant in chemical reactions, proceeding in a colloidal state. For example, in EP-A 0332928 described the use of polychloroprene latexes in the presence of colloidal solution of silicic acid as an impregnating layer in the manufacture of fire protection. In FR-A 2341537 and FR-A 2210699 described pyrogenic silicic acid in combination with a polychloroprene latex for the manufacture of fire-resistant finishes foam or to improve the quality of bitumen and in JP-A 06256738 they are described in combination with the copolymers chloroprednisone acid.

At the heart of this invention lies task is to provide aqueous compositions of the adhesives that after the application of bonding two substrates and compounds have high initial thermal strength, especially after thermoactivation.

Was discovered the amazing fact that due to the appropriate combination of polyurethane dispersions and aqueous dispersions of silicon dioxide can be obtained adhesives which, after the compounds have high initial thermal resistance.

The subject of this invention are aqueous dispersions of polymers containing

a) at least one polyurethane dispersion with an average particle diameter of from 60 to 350 nm, preferably from 20 to 80 nm, and

b) at least one dispersion of silicon dioxide with a particle diameter of SiO2from 20 to 400 nm, preferably from 30 to 100 nm, most pre is respectfully from 40 to 80 nm.

Used in this invention, the polyurethane dispersion (a) containing polyurethane (A), which are the reaction products of the following components:

A1) polyisocyanates,

A2) polymeric polyols and/or polyamines with an average molecular weight of from 400 to 8000,

A3) optionally, alcohols with one or more hydroxyl groups, amines with one or more amino groups or aminoalcohols with molecular weight up to 400,

and at least one compound selected from the

A4) compounds which have at least one ionic or potentially ionic group or

A5) hydrophilizing deionno connections.

Potentially ionic group in the sense of the present invention is a group which is capable of forming an ionic group.

Preferably the polyurethanes (A) are obtained from 7-45 wt.% A1), 50-91% wt. A2), 0-15 wt.% A5), 0-12 wt.% ionic or potentially ionic compounds A4), and, if necessary, 0-30 wt.% compounds A3), and the sum of A4) and A5) is 0.1-27 wt.%, and the sum of all components is 100 wt.%.

Especially preferably the polyurethanes (A) are obtained from 10-30 wt.% A1), 65-90 wt.% A2), 0-10 wt.% A5), 3-9 wt.% ionic or potentially ionic compounds A4), and, if necessary, 0-10 wt.% compounds A3), and the sum of A4) and A5) is 0.1-19 wt.%, and the sum of all components is 100 wt.%.

p> Most preferably the polyurethanes (A) are obtained from 8-27 wt.% A1), 65-85 wt.% A2), 0-8 wt.% A5), 3-8 wt.% ionic or potentially ionic compounds A4), and, if necessary, 0-8 wt.% compounds A3), and the sum of A4) and A5) is 0.1 to 16 wt.%, and the sum of all components is 100 wt.%.

Suitable polyisocyanates (A1) are aromatic, analiticheskie, aliphatic and/or cycloaliphatic polyisocyanates. You can also use mixtures of such polyisocyanates. Examples of suitable polyisocyanates are butylanisole, hexamethylenediisocyanate (HDI), isophoronediisocyanate (IPDI), 2,2,4 and/or 2,4,4-trimethylhexamethylenediamine, the isomeric bis(4,4'-isocyanatophenyl)methanes or their mixtures of any isomeric composition, isocyanatomethyl-1,8-octadienal, 1,4-cyclohexanedimethanol, 1,4-delete the entry, 2,4 - and/or 2,6-tolylenediisocyanate, 1,5-naphthylenediisocyanate, 2,4'- or 4,4'-diphenylmethanediisocyanate, triphenylmethane-4,4',4"-triisocyanate or their derivatives with urethane, which, allophanate, biuret, uretdione, iminoimidazolidine structure and mixtures thereof. Preferred are hexamethylenediisocyanate, isophoronediisocyanate and isomeric bis(4,4'-isocyanatophenyl)methanes and mixtures thereof.

Preferably it is only an aliphatic and/or cycloaliphatic polyisocyanate is x or mixtures of the polyisocyanates mentioned type. The most preferred source components (A1) are polyisocyanates or mixtures of polyisocyanates based hexamethylenediisocyanate (HDI), isophoronediisocyanate (IPDI) and/or 4,4'-diisocyanatohexane.

Further, as polyisocyanates (A1) suitable any, obtained by modifying simple aliphatic, cycloaliphatic, alifaticheskih and/or aromatic diisocyanates, synthesized from at least two diisocyanates, polyisocyanates with uretdione, which, urethane, allophanate, biuret, iminoimidazolidine and/or oxidization structure, such as, for example, described in the journal J.Prakt. Chem, 1994, 336, str-200.

Suitable polymeric polyols and polyamine (A2) have IT-functionality of at least 1.5 to 4, such as, for example, polyacrylates, polyesters, polylactones, polyethers, polycarbonates, complex politicalparty, Polyacetals, polyolefins and polysiloxanes. Preferred are polyols with a molecular weight of from 600 to 2500 and IT is a functionality of from 2 to 3.

Suitable polycarbonates with hydroxyl groups, obtained by reaction of the derivatives of carbonic acid, for example, diphenylcarbonate, dimethylcarbonate or phosgene with dialami. As this type of suitable diols, such as ethylene glycol, 1,2 - and 1,3-propandiol is s, 1,3 - and 1,4-butandiol, 1,6-hexanediol, 1,8-octandiol, neopentylglycol, 1,4-bishydroxycoumarin, 2-methyl-1,3-propandiol, 2,2,4-trimethylpentanediol-1,3, dipropyleneglycol, polypropyleneglycol, dibutylamino, polietilenglikoli, bisphenol a, tetrabromobisphenol And and modified with lactones diols. Preferably the diol component contains 40-100 wt.% hexanediol, preferably 1,6-hexanediol and/or derivatives hexandiol, particularly preferred diols such that, together with integral HE-groups are groups of simple or complex ester, for example, the products obtained by the interaction of 1 mole of hexanediol at least 1 mole, preferably 1-2 moles, caprolactone in DE-A 1770245 or etherification of hexanediol himself before the formation of di - or tridecylalcohol. Obtaining such derivatives are known, for example, from DE-A 1570540. Can be used also described in DE-A 3717060 simple politicalbetting.

Hydroxypolycarboxylic should preferably have a linear structure. However, if necessary, they can be branched by incorporation of polyfunctional components, in particular low molecular weight polyhydric alcohols. For example, suitable glycerin, trimethylolpropane, hexanetriol-1,2,6, butanetriol-1,2,4, trimethylolpropane, pentaerythritol, hinit, lures and sorbitol, methyl shall lycosid, 1,3,4,6-digitalasset.

As a simple suitable polyether polyols are known in polyurethane chemistry polyethers of polytetramethylene, which can be obtained, for example, by polymerization of tetrahydrofuran by cationic disclosure cycle.

In addition, appropriate simple polyether polyols are, for example, polyesters derived from some source compounds and styrene oxide, propylene oxide, butilenica or epichlorohydrin, especially propylene oxide.

As a complex suitable polyether polyols are, for example, the known reaction products of polyhydric, preferably diatomic and, if necessary, addition of trivalent alcohols with polybasic, preferably dibasic dicarboxylic acids. Instead of free polycarboxylic acids to obtain polyesters can also be used the corresponding anhydrides of polycarboxylic acids or the corresponding esters of polycarboxylic acids and lower alcohols or their mixtures. Polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic and, when necessary, may have halogen atoms as substituents and/or be unsaturated.

Components (A3) are suitable for completion of the circuit polyurethane prepolymer. For this is suitable monofunctional alcohols and amines. The preferred monosperma are aliphatic monosperma with the number of carbon atoms from 1 to 18, such as ethanol, n-butanol, monobutyl ether of ethylene glycol, 2-ethylhexanol, 1-octanol, 1-dodecanol or 1-hexadecanol. Preferred monoamines are aliphatic monoamines, such as, for example, diethylamine, dibutylamine, ethanolamine, N-methylethanolamine or N,N-diethanolamine and amines Jeffamin® M-series (firm Huntsman Corp. Europe, Belgium) or oxides and polypropyleneoxide with amino groups.

Also the components (A3) are polyols, AMINOPHENYL or polyamine with molecular weight less than 400, which in large quantities is described in the literature.

Preferred components (A3) are, for example:

a) arcangioli and-triodes, such as ethanediol, 1,2 - and 1,3-propandiol, 1,4 - and 2,3-butandiol, 1,5-pentanediol, 1,3-dimethylpropanoyl, 1,6-hexanediol, neopentylglycol, 1,4-cyclohexanedimethanol, 2-methyl-1,3-propandiol, 2-ethyl-2-buypropecia, trimethylpentanediol, isomers provisions diethylacetamide, 1,2 - and 1,4-cyclohexanediol, hydrogenated bisphenol a [2,2-bis(4-hydroxycyclohexyl)propane], 2,2-dimethyl-3-hydroxypropionic ether of 2,2-dimethyl-3-hydroxypropionic acid, trimethylacetyl, trimethylolpropane or glycerin,

b) simple afortiori, such as diethyleneglycol, triethylene glycol, tetraethylene the ol, dipropyleneglycol, tripropyleneglycol, 1,3-butyleneglycol or simple dihydroxyethyl ether of hydroquinone,

in complex afortiori General formulas (I) and (II)

in which

R means alkalinity or Allenby balance with the number of carbon atoms from 1 to 10, preferably from 2 to 6,

x=2-6 and

Y=3-5,

such as, for example,

δ-hydroxybutanoic ether ε-hydroxypropranolol acid, ω-hydroxyhexyloxy ether γ-hydroxybutiric acid, β-hydroxyethyloxy ester of adipic acid and bis-β-hydroxyethyloxy ester of terephthalic acid and

d) di - and polyamine, such as 1,2-diaminoethane, 1,3-diaminopropane, 1,6-diaminohexane, 1,3 - and 1,4-phenylenediamine, 4,4'-diphenylmethylene, isophorondiamine, mixture of isomers of 2,2,4 - and 2,4,4-trimethylhexamethylenediamine, 2-methylpentylamine, Diethylenetriamine, 1,3 - and 1,4-xylylenediamine, α,α,α',α'-tetramethyl-1,3 - and -1,4-xylylenediamine, 4,4-diaminodicyclohexylmethane, oxides or polypropyleneoxide with amino groups, which are available under the name Jeffamin® D-series (firm Huntsman Corp.Europe, Belgium), Diethylenetriamine, Triethylenetetramine. As diamines in the sense of the invention is also suitable hydrazine, hydrazinehydrate and substituted hydrazines such as, for example, N-methylhydrazine, N,N'-dimethylhydrazine and their homologues, as well as dihydrate the s adipic, β-methyldienolone, sebacinales, gerasimovoj and terephthalic acids, semicarbazides, such as, for example, hydrazide β-semicarbazide acid (for example, described in DE-A 1770 591), semicarbazidediacetic esters, such as, for example, 2-semicarbazidediacetic ester (for example, described in DE-A 1918504), or also aminosalicylate compounds such as, for example, β-aminoethylethanolamine (for example, described in DE-A 1902931).

Component (A4) contains ionic groups, which can be cationic or anionic. Acting as dispersing agents, cationic or anionic compounds are those compounds which contain, for example, sulfonate, ammonium, postname, carboxylate, sulphonate, phosphonate groups or groups which can be converted into the above groups by salt formation (potentially ionic groups), and can be incorporated into macromolecules using reactive to isocyanate groups. Preferably suitable reactive to the isocyanate groups are hydroxyl or amino group.

Suitable ionic or potentially ionic compounds (A4) are mono - and dihydroxycinnamate acid, mono - and diaminocarbenes acid, mono - and dihydroxyacetone acid, mono - and diaminotoluene acid, and is also mono - and dihydroxyacetone acids or mono - and diaminooctane acids and their salts, such as dimethylolpropionic acid, dimethylaniline acid, hydroxypivalic acid, N-(2-amino-ethyl)-β-alanine, 2-(2-amino-ethylamino)-econsultation, 1,2 - or 1,3-Propylenediamine-β-ethylsulfonyl, ethylendiamine or butylsulfonyl, malic, citric, glycolic, lactic acid, glycine, alanine, taurine, lysine, 3,5-diaminobenzoic acid, the product of the merger of isophorondiisocyanate (IPDI) and acrylic acid (EP-A 0916647, example 1) and its alkali metal salts and/or ammonium salt; the product of the merger of sodium bisulfite to butene-2-dilu-1,4, simple polyethersulfone, propoxycarbonyl product fitting 2-butandiol and NaHSO3for example, described in DE-A 2446440 (p.5-9, formula I-III), and translated into cationic groups of structural elements, such as N-methyldiethanolamine, as hydrophilic structural components. Preferred ionic or potentially ionic compounds are compounds that have a carboxyl or carboxylate and/or sulphonate groups and/or ammonium groups. Particularly preferred ionic compounds are those compounds which contain carboxyl and/or sulphonate groups as ionic or potentially ionic groups, such as the salts of N-(2-amino-ethyl)-β-alanine, 2-(2-amino-ethylamino)-econsultation the s or the product of the joining of IPDI and acrylic acid (EP-A 0916647, example 1) and dimethylolpropionic acid.

Preferred hydrotribromide deionno compounds (A5) are, for example, a simple polyoxyalkylene esters, which contain at least one hydroxyl group or one amino group. These polyethers contain from 30 wt.% to 100 wt.% ethylenoxide structural links. Suitable polyethers of linear structure with a functionality of between 1 and 3, and compounds of General formula (III)

in which

R1and R2mean independently from each other, respectively divalent aliphatic, cycloaliphatic or aromatic residue with the number of carbon atoms from 1 to 18, which may be interrupted by oxygen atom and/or nitrogen, and

R3polietilenoksidnoy balance with CNS group at the end.

Hydrotribromide deionno compounds are, for example, monatomic simple polyalkyleneglycol containing in the molecule an average of 5 to 70, preferably from 7 to 55 ethylenoxide links that get known method by alkoxysilane suitable starting compounds (for example, Ullmanns Encyclopädie der technischen Chemie, Izd-vo Chemie, 4th edition, t, p.31-38).

Suitable parent compounds are, for example, saturated monosperma, such as methanol, ethanol, n-PR is panel, ISO-propanol, n-butanol, ISO-butanol, sec.-butanol, the isomeric pentanol, hexanol, octanol and nonanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, diclohexal, isomeric methylcyclohexanols or hydroxymethylcellulose, 3-ethyl-3-hydroxyethyloxy or tetrahidrofurfurilestera alcohol, monoalkyl ethers of diethylene glycol such as, for example, monobutyl ether of diethylene glycol, unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol or oleic alcohol, aromatic alcohols such as phenol, the isomeric Cresols or methoxyphenols, analiticheskie alcohols such as benzyl alcohol, anise alcohol or cinnamic alcohol, secondary monoamines such as dimethylamine, diethylamine, dipropylamine, Diisopropylamine, dibutylamine, bis(2-ethylhexyl)-amine, N-methyl - and N-ethylcyclohexylamine or dicyclohexylamine, and also heterocyclic secondary amines such as morpholine, pyrrolidine, piperidine or 1H-pyrazole. Preferred parent compounds are saturated monosperma. It is most preferable as the initial connection is monobutyl ether of diethylene glycol. Suitable for reaction alkoxysilane acceleratedly are ethylene oxide and propylene oxide, which can be used in the reaction of alkoxysilane in any serial is a major or also in a mixture.

In the case of simple polyalkyleneglycol we are talking either about the individual polyethylenepolyamine or mixed polyalkyleneglycols, acceleratedly structural units which are not less than 30 mol.%, preferably not less than 40 mol.%, from ethylenoxide links. Preferred nonionic compounds are monofunctional mixed polyalkyleneglycols with not less than 40 mol.% ethyleneoxide units and a maximum of 60 mol.% propylenoxide links.

To obtain the polyurethane (A) is preferably a combination of non-ionic (A4) and ion (A5) hydrophilicity funds. Particularly preferred combinations of nonionic and anionic hydrophilizing funds.

Obtaining an aqueous polyurethane (A) can be performed in one or several stages in a homogeneous phase or in several stages partly dispersed phase. After fully or partially implemented polyaddition stage dispersing, emulsifying or dissolving. In conclusion, if necessary, is carried out subsequent polyprionidae or modification in the dispersed phase.

To obtain an aqueous polyurethane (A) can be applied to all of the known methods such as a method using an emulsifier under conditions of shear, AC is a tone way, way of getting through prepolymer, a method of melt emulsification, kamiminami way or the way of spontaneous dispersion of solid substances or derivatives of these methods. An overview of these methods is contained in the book Houben-Weyl "Methods der organischen Chemie" (Methods of organic chemistry) (supplementary volume to the fourth edition, the, H.BartI J.Falbe, Stuttgart, new York, Thieme publishing house, 1987, str-1682). Preferred is a method of emulsification of the melt and the acetone method. The most preferred acetone method.

Usually, to obtain polyurethane prepolymer in the reactor is placed all the components (A2)-(A5) or part of component (A2)-(A5), which do not have a primary or secondary amino groups, and the polyisocyanate (A1) and, if necessary, diluted with solvent, miscible with water but inert towards isocyanate groups, but preferably without solvent, is heated to a temperature, preferably lying in the range from 50 to 120°.

Suitable solvents are acetone, butanone, tetrahydrofuran, dioxane, acetonitrile, dimethyl ether of dipropyleneglycol and 1-methyl-2-pyrrolidone, which can be added not only at the beginning of the retrieval process, but, if necessary, partially and later. Preferred acetone and butanone. It is possible to carry out the reaction under normal or elevated pressure, for example, above the temperature of the boiling point at normal pressure of the solvent, for example acetone.

Further, to accelerate the reactions of addition of the isocyanate is possible to use known catalysts, such as, for example, triethylamine, 1,4-diazabicyclo-[2,2,2]-octane, oxide dibutylamine, octoate tin or dibutyltindilaurate, bis(2-ethylhexanoate) tin, or other ORGANOMETALLIC compounds, or add them later. The preferred dibutyltindilaurate.

Then added not added to the beginning of the reaction components (A1), (A2), optionally (A3) and (A4) and/or (A5), which do not have a primary or secondary amino groups. Upon receipt of polyurethane prepolymers, the ratio of the number of substances with isocyanate groups to the number of substances with groups reactive to isocyanate groups is from 0.90 to 3, preferably from 0.95 to 2.5, most preferably of 1.05 to 2.0. The interaction of components (A1)-(A5) in the calculation of the total number of reactive toward isocyanate groups part (A2)-(A5), which do not contain primary or secondary amino groups, is partially or completely, but preferably completely. The degree of transformation is usually controlled by tracking the content of NCO-groups in the reaction mixture. This can be used as spectroscopic measurements, for example, as the spectra in the infrared and near-infrared ranges, determination of the refractive index, that is, and chemical analyses, such as titration, the samples. Polyurethane prepolymers which contain free isocyanate groups, get in bulk or in solution.

After obtaining the polyurethane prepolymers or during retrieval of (A1) and (A2)-(A5), if it is not implemented in the original molecules, there is a partial or complete salt formation groups acting as anion and/or cation dispersing groups. In the case of anionic groups are used bases, such as ammonia, carbonate or bicarbonate of ammonium, trimethylamine, triethylamine, tributylamine, diisopropylethylamine, dimethylethanolamine, diethylethanolamine, triethanolamine, potassium hydroxide or sodium carbonate, the preferred triethylamine, triethanolamine, dimethylethanolamine or diisopropylethylamine. The number of bases is from 50 to 100%, preferably from 60 to 90% of the number of agents with anionic groups. In the case of cationic groups are dimethyl ether sulfuric acid or succinic acid. If you are only deionno hydrophilisation compounds (A5) with groups of ethers, stage neutralization is omitted. Neutralization can also be carried out simultaneously with the dispersion, wherein the dispersion water already contains a neutralizing agent.

Possible anionic components are (A2), (A3) and (A4), to the which, if necessary, can interact remaining isocyanate groups. Such elongation of the chain can occur either in the solvent prior to dispersion during dispersion, or in water after dispersion. If (A4) is used amine component, the elongation of the chain is preferably carried out before dispersing.

An amine component (A2), (A3) or (A4) can be added to the reaction mixture diluted with an organic solvent and/or water. Preferably used 70-95 wt.% solvent and/or water. If you have multiple amine component, the interaction with them can occur in any sequence or simultaneously by adding the mixture.

With the aim of obtaining polyurethane dispersion (A) polyurethane prepolymers, optionally, with a strong shift, for example, by vigorously stirring or using a jet disperser, to be paid either in the water dispersion or the water mixed with the prepolymers. Then, if it hasn't happened in a homogeneous phase, may be followed by the increase in molar mass due to the reaction still available, if necessary, isocyanate groups with the components (A2), (A3). The amount used polyamine (A2), (A3) depends on the remaining, unreacted isocyanate groups. In aimogasta with polyamine (A2), (A3) is preferably 50-100%, most preferably 75-95% of the number of isocyanate groups.

If necessary, an organic solvent, it is possible to drive away. The dispersion contains 10-70 wt.%, preferably 25-65 wt.% and most preferably 30-60 wt.% solid.

The polyurethane dispersions according to the invention can be used separately or together with known binders, auxiliary substances and additives, in particular a light stabilizers such as UV absorbers and sterically difficult amines, antioxidants, fillers, and lacquer auxiliary substances, such as additives that prevent sedimentation, defoamers and/or wetting, to contribute to a spill, reactive diluents, plasticizers, catalysts, auxiliary solvents and/or thickeners and additives, such as, for example, dispersions, pigments, dyes or matting tools. In particular, without problems possible combinations with polyurethane dispersions or polyacrylate dispersions, which may also contain hydroxyl groups. Additives may be added to the polyurethane dispersions. according to the invention immediately before processing. However, it is also possible for at least part of the additive to be added before dispersion of the binder or binder mixture/speciate the ü, or during dispersion. The choice and dosage of these substances that can be added as separate components and/or with a total mixture known to the expert.

Aqueous dispersion of silicon dioxide has long been known. They have different structure depending on the retrieval process.

Suitable dispersion of silicon dioxide (b) according to this invention can be obtained based Sol of silicic acid, silica gel, pyrogenic silicic acid or precipitated silicic acid or mixtures thereof.

Silicic acid sols are colloidal solutions of amorphous silicon dioxide in water, also called colloidal solution of silicon dioxide, but more briefly referred to as a colloidal solution of silicic acid. When this silicon dioxide exists in the form of nearly spherical particles with hydroxyl groups on the surface. Typically, the diameter of the colloidal particles is from 1 to 200 nm, and correlated with the particle size of the specific BET-surface (determined by the method G.N.Sears, Analytical Chemistry, 1956, 28, No. 12, 1981-1983) is from 15 to 2000 m2/year Surface of particles of SiO2has the charge, which is compensated by a corresponding counterion, entered into a colloidal solution for stabilization. Stabilised alkaline sols silicic acids have a pH value of from 7 to 11.5 and as alkalizing products contain, for example, Bolshie number of Na 2O, K2O, Li2O, ammonia, organic nitrogen-containing bases, tetraalkylammonium or aluminates of alkali metals or ammonium. Silicic acid sols as palustrine colloidal solutions can also be weakly acidic. Next, by applying to the surface of the Al2(OH)5CL can be prepared cation adjustable silicic acid sols. The concentration of solids in the ash is from 5 to 60 wt.% SiO2.

The process of obtaining colloidal solution of silicic acid mainly passes through the stages of obessessive liquid glass using ion exchange, regulation and stabilization, respectively, of the desired particle size SiO2(or distribution of particles of SiO2size), setting the corresponding desired

the concentration of SiO2and, if necessary, implementation of surface modification of the particles of SiO2for example, with Al2(OH)5CL. In none of these stages of the process the particles of SiO2do not lose the colloidal state of dissolution. This explains the presence of discrete primary particles with high efficiency as a binder.

Under the silica understand colloidal shaped and unshaped silicic acid with consistency from elastic to rigid porous structure from more loose to dense. Silicic acid exist in the form vysokokoncentrirovannym polysilicon acids. On the surface are siloxane and/or silanol group. Get the silica from the liquid glass by interaction with mineral acids.

Next, it is necessary to distinguish pyrogenic silicic acid or precipitated silicic acid. In the case of precipitated silicic acid to the existing water are added liquid glass and acid, such as H2SO4. The formation of colloidal primary particles, which glomerida during subsequent reactions and grow together in agglomerates. The primary particles of these silicic acid, existing in the form of a solid, crosslinked in the secondary agglomerates.

Pyrogenic silicic acid can be obtained by flame hydrolysis or by using the method of electric arc. The predominant method for the synthesis of pyrogenic silicic acid is flame hydrolysis, in which tetrachloride decomposes in an oxygen-hydrogen flame. The resulting silicic acid is rentgenoamorfnogo. Pyrogenic silicic acid on its almost not containing the surface of the pores are noticeably smaller IT groups compared with precipitated silicic acids. Pyrogenic silicic acid, obtained by flame hydrolysis, have a specific surface area of from 50 to 600 m2/g (DIN 66131) and the size of the primary particles of 5 to 50 nm; the silicon KIS is the notes, obtained by the method of electric arc, have a specific surface area of from 25 to 300 m2/g (DIN 66131) and the size of the primary particles of 5 to 500 nm.

Other data about the synthesis and properties of silicic acid in solid form can be found, for example, in the book K..Büchel, H.-H. Moretto, P. Woditsch "Industrielle Anorganische Chemie" ("Industrial inorganic chemistry", Wiley VCH, 1999, Chapter 5.8.

If used according to this invention the polymer dispersions used as a dedicated solid raw materials SiO2such as , for example, pyrogenic or precipitated silicic acid, it is converted into water SiO2-dispersion by dispersing.

To obtain dispersions of silicon dioxide using modern dispersing agents, preferably those which are suitable for creating high shear rates, such as the device "Ultratorrax and disk dissolver.

Preferably used such water dispersion of silicon dioxide particles of SiO2which have dimensions of from 20 to 400 nm, particularly preferably from 30 to 100 nm and most preferably from 40 to 80 nm. If you use a precipitated silicic acid, with the purpose of grinding particles being subjected to grinding.

Preferred polymer dispersions according to the invention are those in which the particles of SiO2dispersion dioc the IDA silicon b) exist as separate unstitched primary particles.

It is also preferred that the particles of SiO2have surface hydroxyl groups.

Most preferably as aqueous dispersions of silica sols are used silicic acid.

To obtain polymer dispersions according to the invention the ratio between the amounts of individual components is chosen so that the resulting dispersion contains from 30 to 60 wt.%, dispersed polymer, and the content of the polyurethane dispersion (a) is from 55 to 99 wt.% and content of the dispersion of silicon dioxide (b) from 1 to 45 wt.%, while the percentage data relate to the weight of non-volatile components and sum up to 100 wt.%.

The polymer dispersions according to the invention preferably contain from 70 to 98 wt.% polyurethane dispersions (a) and from 2 to 30 wt.% dispersion Sol of silicic acid (b), particularly preferred are mixtures of 80-93% wt. dispersion (a) and (7-20 wt.% dispersion (b), and percentage data relate to the weight of non-volatile components and sum up to 100 wt.%.

The polyurethane dispersion may optionally contain other dispersions, such as, for example, polyacrylate, polyvinylidenechloride, polybutadiene, polyvinyl acetate, polychloroprene or Starovoitova dispersion in an amount up to 30 wt.%.

In polymer var is siyah according to this invention, if necessary, contains other auxiliary means for adhesives and additives. For example, can be added fillers such as quartz flour, quartz sand, heavy spar, calcium carbonate, chalk, dolomite or talc, optionally, together with wetting, for example, polyphosphates such as sodium hexametaphosphate, naphthalenesulfonate, ammonium or sodium salts of polyacrylic acids and fillers are added in an amount of from 10 to 60 wt.%, preferably from 20 to 50 wt.%, and wetting in the amount of from 0.2 to 0.6 wt.%, all additives in the calculation of the non-volatile components.

Other suitable auxiliary means, for example, are used in quantities of from 0.01 to 1 wt.% in the calculation of the non-volatile components of the organic thickeners such as cellulose derivatives, alginates, starch, starch derivatives, polyurethane thickeners or polyacrylic acid, or used in quantities of from 0.05 to 5 wt.% in the calculation of the non-volatile components inorganic thickeners, such as bentonites.

For conservation to the adhesive compositions according to this invention can also be added fungicides. They are used in quantities of from 0.02 to 1 wt.% in the calculation of the non-volatile components. Suitable fungicides include, for example, derivatives of phenol and Cresols or olovoorganichyesikh the e connection.

If necessary, the polymer dispersion according to the invention can also be added giving the adhesiveness of the resin, such as, for example, unmodified and modified natural resins, such as esters of colophony, hydrocarbon resins or synthetic resins, such as phthalate resin in dispersed form (see, for example, in the book R.Jordan, R.Hinterwaldner "Klebharze" publishing house Hinterwaldner, Munich, 1994, p.75-115). The preferred dispersion alkylphenolic and terpenophenolic resins with a softening temperature above 70°C, most preferably above 100°C.

It is also possible to use organic solvents, such as, for example, toluene, acetone, xylene, butyl acetate, methyl ethyl ketone, ethyl acetate, dioxane or mixtures thereof, or plasticizers, for example, on the basis of adipates, phthalates or phosphates in an amount of from 0.5 to 10 weight. parts per non-volatile components.

Another object of the invention is a method of obtaining a polymer dispersions according to the invention, characterized in that the polyurethane dispersion (a) is mixed with a dispersion of silicon dioxide (b) and, if necessary, add conventional adhesive AIDS and additives.

The preferred method of obtaining the polymer dispersions according to this invention differs in that the first polyurethane dispersion (a) with eshivot with an adhesive auxiliary and additives, and during mixing or after it add the Sol of silicic acid (b).

The application of adhesives can be carried out in the usual way, for example, by brush, squeegee, pouring, spraying, rolling or dipping. Drying the adhesive film may occur at room temperature or elevated to 220°C temperatures.

The adhesive composition can be applied as onecomponent or the normal way when using hardeners.

The polymer dispersions according to the invention can be used as adhesives, for example, for bonding any substrates of the same or different type, such as wood, paper, plastics, textiles, leather, rubber, or inorganic materials such as ceramics, pottery, glass or cement.

Examples 1.1. Used substances

Bayer AG, Leverkusen, Germany
Table 1
Polyurethane dispersions
VarianceProductSupplied formProvider
AndDispercoll® U 5340%dispersion of aliphatic hydroxyl-containing complex politicalarena; particle diameter of 100 nm minimum temperature of activation: 45-55°C, pH 6,0-9,0
BDispercoll® U 5450%dispersion of aliphatic hydroxyl-containing complex politicalarena; particle diameter 200 nm minimum temperature of activation: 45-55°C, pH 6,0-9,0Bayer AG Leverkusen, Germany

Table 2
Silicon dioxide
ProductProviderSupplied formType
Dispercoll® S 5005Bayer AG, Leverkusen, GermanyDispersion Sol of silicic acid, 50%, BET 50 m2/g, pH 9, the particle Size of 50 nmKieselsol (Sol of silicic acid)
Dispercoll® S 3030Bayer AG, Leverkusen, GermanyDispersion Sol of silicic acid, 30%, WET 300 m2/g, pH 10, the particle Size of 9 nmKieselsol (Sol of silicic acid)

The hardener
Table 3
ProductFunctionManufacturer
Desmodur® DNAliphatic isocyanate hardener based on HDI*)the viscosity of 1250±300 mPas, the NCO content 21,8±0,5%Bayer AG, Leverkusen, Germany
*)at 90.77% wt. polymer hydrophilizing of HDI trimer (hexamethylenediisocyanate) Desmodur® N3600
4,78% wt. internal emulsifier obtained by the interaction of the monofunctional alcohol with a mixture of ethylene oxide/propylene oxide, hydroxyl number 40

1.2. Measurement methods

1.2.1 Determination of resistance to delamination on soft PVC after shock activation

The tests were carried out according to EN 1392. Two of the tested sample soft PVC (30% dioctylphthalate) of size 100×30 mm, which has roughness using abrasive paper (grit 80), was applied by brush variance with the two sides on rough surfaces and at room temperature were dried for 60 minutes. Then the samples were subjected to shock activation: the bonding surfaces were irradiated for 10 seconds, the IR emitter firms Funk (Schock-Aktiviergerät 2000) (device for shock activation). When the adhesive film is heated to the tempo of the atmospheric temperature on the surface of 90±2°C. Bonding occurs immediately after thermoactivation coated with adhesive test samples, in which the activated surface stacked on top of each other and pressed in the press (60 seconds; 4 bar). The test gap occurs at room temperature on a standard tensile testing machine. Defined values of the strength immediately after bonding and after 3 days. The samples kept at 23°C and 50%relative humidity.

1.2.2 Determination of the initial thermal strength (AWT) sklee beech wood/PVC

Materials:

- Tested sample from beech wood 50×150×4 mm

list of PVC (Renolit 32052096 Strukton; firm Worms, Germany) Desmodur® DN

Adhesive application:

- adhesive single component using a squeegee, 200 µm

The time of drying:

- At least 3 hours after application of the adhesive at room temperature

The pressing conditions:

10 seconds when the junction temperature of 77°C and a pressure of 4 bar

Test conditions in a drying Cabinet

chamber dryer air circulation 80°C, load 2.5 kg

Implementation:

The adhesive is applied, single component, using a squeegee (200 μm) on the test sample of the wood. The sheet is cut so that after three clinching edge total length is 12 see Later, 3 hours after application of glue wooden subject obraztsovaya with the sheet when the junction temperature of 77°C and 4 bar eff. pressure 10 seconds on membrane press.

Immediately after that United the sample is placed in a drying Cabinet for 3 min without load and then load 2.5 kg for 5 minutes. For this test a sample of wood is suspended in a drying Cabinet and to him to secure folded three times the sheet is attached terminal connection with the cargo. After a time the goods immediately removed and layered composition is released. Measured section of exfoliation and is specified in [mm/min].

1.3 Obtain adhesive compositions

To obtain the compositions of the polyurethane dispersion is placed in a chemical glass. With stirring, is added to silicon dioxide. For two-component bonding 100 weight parts of the dispersion is homogenized with 3 weight parts of emulsifiable isocyanate hardener for at least 2 minutes. This mixture can be used for approximately 2 hours.

Table 4
Song
ProductRecipe (data in parts by weight)
1234 56
Polyurethane dispersion
And100100100100100100
B
The type of silicon dioxide
Dispercoll® S 5005-26--32,5-
Dispercoll® S 3030-43- 54,1

1.4 Results

1.4.1. Determination of resistance to delamination on soft PVC

Table 5
The resistance to peeling of soft PVC
Example No.Composition No.Desmodur DN [part]Resistance to peeling immediately [n/mm]Resistance to peeling after 3 days [n/mm]
1*1-5,010,2
2*133,5the 10.1
32-6,19,5
4235,29,5
5*3-1,01,0
6*/td> 330,92,3
7*4-6,18,9
8*435,58,7
95-5,5of 5.4
1053of 5.47,0
11*6-1,40,2
12*631,60,8
*comparative example

As can be seen from table 5, the addition Dispercoll® S 5005 entails invariably the same high level of strength as polyurethane dispersions that are not included in the composition. Composition with Dispercoll® S 3030 is a characteristic ear is the determination of the resistance to peeling of the soft PVC.

1.4.2 Determination of the initial thermal and mechanical strength sklee beech wood/PVC

Table 6
The initial thermal strength
Example No.Composition No.The initial thermal strength [mm/min]
13*49,8
1451,9
15*6the peeling
*comparative example

As can be seen from table 6, the addition Dispercoll® S 5005 is a characteristic improvement of the initial thermal strength as compared with polyurethane dispersions that are not included in the composition. Composition with Dispercoll® S 3030 leads to a complete lifting of the tested samples.

1. The use of aqueous dispersions of polymers containing
a) polyurethane dispersion with an average particle size of from 60 to 350 nm, and
b) the aqueous dispersion of silicon dioxide with a particle diameter of SiO2from 20 to 400 nm
to obtain adhesives.

2. The use according to claim 1 characterized in, that used particles of SiO2have a diameter of from 30 to 100 nm.

3. The use according to claim 1, characterized in that the particles of SiO2have a diameter of from 40 to 80 nm.

4. The use according to any one of claims 1 to 3, characterized in that the aqueous dispersion of silica (b) is an aqueous colloidal solution of silicic acid.

5. The use according to any one of claims 1 to 3, characterized in that the particles of SiO2have surface hydroxyl groups.

6. The use according to any one of claims 1 to 3, characterized in that the particles of SiO2exist as separate unstitched primary particles.

7. The use according to claim 6, characterized in that the aqueous dispersion of silica (b) is an aqueous colloidal solution of silicic acid.

8. The use according to claim 6, characterized in that the particles of SiO2have surface hydroxyl groups.

9. The use of claim 8, characterized in that the aqueous dispersion of silica (b) is an aqueous colloidal solution of silicic acid.



 

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