DE102008038899A1 - Aqueous polyurethane-polyurethane urea dispersion based on di- or higher-functional polyols, di- or poly-isocyanate components, and mixture of primary and/or secondary mono- or di-amino compounds, useful e.g. to produce rubber materials - Google Patents

Abstract

Aqueous polyurethane-polyurethane urea dispersion (I) based on one or more di- or higher-functional polyols (A) having a mean molecular weight of 400-5000 Daltons, optionally one or more di- or higher-functional polyol components (B) having a molecular weight of 62-399 Daltons, one or more di- or poly-isocyanate components (C), and a mixture (D) of primary and/or secondary monoamino compounds (D1) and primary and/or secondary diamino compounds (D2), is claimed. Aqueous polyurethane-polyurethane urea dispersion (I) based on one or more di- or higher-functional polyols (A) having a mean molecular weight of 400-5000 Daltons, optionally one or more di- or higher-functional polyol components (B) having a molecular weight of 62-399 Daltons, one or more di- or poly-isocyanate components (C), and a mixture (D) of primary and/or secondary monoamino compounds (D1) and primary and/or secondary diamino compounds (D2), where: at least one of components (D1) and/or (D2) carries sulfonate and/or carboxylate groups; the mean amino functionality of (D) is 1.65-1.95; and the equivalent ratio of isocyanate (NCO) groups in the NCO prepolymer to the total amount of isocyanate-reactive amino and hydroxyl groups of (D) is 1.04-1.9, is claimed. Independent claims are included for: (1) the preparation of (I) comprising placing some or all of components (A)-(C), optionally in the presence of a solvent that is miscible with water but inert towards isocyanate groups, in a reactor and heating to 50-120[deg] C and then metering in any constituents of (A)-(C) that are not added at the beginning of the reaction; and carrying out chain extension with the mixture (D) at 15-60[deg] C, and before, during or after the chain extension, converting the mixture into the aqueous phase and optionally removing the solvent; (2) an adhesive compositions comprising (I) and polyisocyanate compounds having at least two isocyanate groups per molecule; and (3) an adhesive composite containing substrates adhesively bonded with (I).

Description

The The invention relates to aqueous dispersion adhesives based on aqueous polyurethane-polyurethaneurea dispersions, a process for their preparation, as well as the use of dispersion adhesives for Production of adhesive composites.

The Preparation of aqueous polyurethane-polyurethaneurea dispersions is known. When using such dispersions for gluing Of substrates is often after the thermal activation process worked. In this case, the dispersion is applied to the substrate and after complete evaporation of the water, the Adhesive layer by heating, z. B. with an infrared radiator, activated and converted into a sticky state. The temperature at which the adhesive film becomes sticky indicates one as activating temperature. In general, one is possible low activation temperature, since at high activation temperatures an unfavorably high energy consumption required and the Manual joining makes it difficult until it becomes impossible.

Adhesives based on aqueous polyurethane-polyurethaneurea dispersions, which are suitable for the application of the thermal activation process, are described in US Pat US Pat. No. 4,870,129 described. Thereafter, by using special mixtures of diisocyanates by the acetone process, aqueous polyurethane-polyurethaneurea dispersions can be obtained and the films obtainable therefrom have a good activatability at 40 ° to 80 ° C.

Likewise describes the EP-A 0 304 718 the preparation of aqueous polyurethane-polyurethaneurea dispersions which enable the production of films with good activatability. This is achieved by the use of special amino compounds as chain extenders. These are primary and / or secondary monoamino compounds, optionally in admixture with primary and / or secondary diamino compounds having an average amino functionality of 1 to 1.9. The equivalent ratio of NCO groups in the NCO prepolymer to the total amount of isocyanate-active hydrogens there is 0.5: 1 to 0.98: 1. Preference is given to using mixtures of di- and monoamino compounds.

In the DE-A 2551094 describes water-dispersible polyurethanes with polyalkylene oxide polyether side chains and with ionic groups (sulfonate, carboxylate or ammonium groups), which are also useful as adhesives.

One significant disadvantage of this described in the prior art Dispersion adhesives is their insufficient initial heat resistance. Moreover, these do not show one-component bonding sufficient heat, with one-component in the frame The present invention means that before the application no additional polyisocyanate compound as crosslinker component is added.

Another way to prepare aqueous polyurethane-polyurethaneurea dispersions, which are suitable as an adhesive, in particular by the thermal activation, discloses the DE-A 101 52 405 , There can be obtained by using special polyester polyols containing aromatic metal sulfonate, aqueous polyurethane-polyurethane urea dispersions. Films made therefrom by removal of the water are readily activatable even at 50 to 60 ° C. However, these polyesters containing aromatic metal sulfonate groups are difficult to obtain or very expensive due to the dicarboxylic acids necessarily containing metal sulfonate or sulfonic acid groups as raw materials.

In the DE-A 10 2004 023 768 discloses another way of producing polyurethane-polyurethane urea dispersions which are useful as adhesives having good initial heat resistance. However, the content of up to 7.5% by weight of an external emulsifier adversely affects the uses of these adhesives because they provide high hydrophilicity and sensitivity of the products to water. In addition, migration effects of the non-chemically bound emulsifier can adversely affect adhesion and bond strength.

The object of the present invention was therefore to provide dispersion adhesives based on emulsifier-free polyurethane-polyurethane urea dispersions, from which by evaporation or other type (eg., Absorbing the water by the inherently absorbent substrate or an absorbent aid) removal of the Water films can be obtained, which have over the prior art improved initial heat resistance and improved high heat resistance feature.

Surprised it has now been found that the emulsifier-free described below prepared aqueous polyurethane-polyurea dispersion is suitable as an adhesive raw material and from this by evaporation or otherwise removing the water obtained thermoactivatable Films about one, compared to the state of the art, improved initial heat resistance and improved high heat level. The inventive Dispersion is stable as such and requires no external Emulsifiers.

• A) einem oder mehreren di- oder höherfunktionellen Polyol/en mit einem mittleren Molekulargewicht von 400 bis 5000 Dalton,
• B) gegebenenfalls einer oder mehreren di- oder höherfunktionellen Polyolkomponente/n mit einem Molekulargewicht von 62 bis 399 Dalton,
• C) einer oder mehreren im Sinne der Isocyanatpolyadditionsreaktion mono-funktionellen Verbindungen mit einem Ethylenoxidgehalt von mindestens 50 Gew.-% und einem Molekulargewicht von mindestens 400 Dalton,
• D) einer oder mehreren Di- oder Polyisocyanatkomponente/n und
• E) einer Mischung E) aus primären und/oder sekundären Monoaminoverbindungen E1) und aus primären und/oder sekundären Diaminoverbindungen E2),

dadurch gekennzeichnet, dass mindestens einer der Komponenten E1) und/oder E2) Sulfonat- und/oder Carboxylatgruppen tragen und die mittlere Aminofunktionalität der Mischung E) zwischen 1,65 und 1,98 beträgt und das Äquivalentverhältnis von NCO-Gruppen im NCO-Prepolymer zur Gesamtmenge der gegenüber Isocyanat reaktiven Amino- und Hydroxylgruppen der Mischung E) zwischen 1,04 und 1,9 liegt.The present invention thus relates to aqueous polyurethane-polyurethaneurea dispersions based on

• A) one or more di- or higher-functional polyol (s) having an average molecular weight of from 400 to 5,000 daltons,
• B) optionally one or more di- or higher-functional polyol component (s) having a molecular weight of 62 to 399 daltons,
• C) one or more monofunctional compounds in the sense of the isocyanate polyaddition reaction having an ethylene oxide content of at least 50% by weight and a molecular weight of at least 400 daltons,
• D) one or more di- or polyisocyanate component / s and
• E) a mixture E) of primary and / or secondary monoamino compounds E1) and of primary and / or secondary diamino compounds E2),

characterized in that at least one of the components E1) and / or E2) carry sulfonate and / or carboxylate groups and the average amino functionality of the mixture E) is between 1.65 and 1.98 and the equivalent ratio of NCO groups in the NCO prepolymer to the total amount of the isocyanate-reactive amino and hydroxyl groups of the mixture E) is between 1.04 and 1.9.

suitable di- or higher-functional polyols A) are compounds with at least two isocyanate-reactive Hydrogen atoms and an average molecular weight of 400 to 5000 daltons. Examples of suitable structural components are polyethers, polyesters, polycarbonates, polylactones or polyamides. Preferred polyols A) have 2 to 4, more preferably 2 to 3 hydroxyl groups on. Also mixtures of various such compounds come into question.

When Polyester polyols are in particular linear polyester diols or also weakly branched polyester polyols, as in known manner from aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids, such as. Amber, methyl amber, Glutaric, adipic, pimelic, cork, azelaic, sebacic, nonandicarboxylic, Decandicarbon, terephthalic, isophthalic, o-phthalic, tetrahydrophthalic, Hexahydrophthalic, cyclohexanedicarboxylic, maleic, fumaric, malonic or Trimellitic acid and acid anhydrides, such as o-phthalic, Trimellitic or succinic anhydride or mixtures thereof with polyhydric alcohols, such as. B. ethanediol, di-, tri-, tetraethylene glycol, 1,2-propanediol, di-, tri-, tetra-propylene glycol, 1,3-propanediol, Butanediol-1,4, butanediol-1,3, butanediol-2,3, pentanediol-1,5, hexanediol-1,6, 2,2-dimethyl-1,3-propanediol, 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, Octanediol-1,8, decanediol-1,10, dodecanediol-1,12 or mixtures thereof, optionally with the concomitant use of higher-functional polyols, such as trimethylolpropane, glycerol or pentaerythritol can be. As polyhydric alcohols for the production Of course, the polyester polyols are also cycloaliphatic and / or aromatic di- and polyhydroxyl compounds in question. In place of the free polycarboxylic acid can also the corresponding polycarboxylic anhydrides or corresponding Polycarboxylic acid esters of lower alcohols or their Mixtures are used to make the polyester.

Of course It may be in the polyester polyols also homopolymers or copolymers of Lactones act, preferably by addition of lactones or Lactone mixtures, such as butyrolactone, ε-caprolactone and / or Methyl ε-caprolactone to the appropriate di- and / or higher functional Starter molecules, such as. B. the above as structural components for polyester polyols, low molecular weight, polyvalent Alcohols are obtained. The corresponding polymers of ε-caprolactone are preferred.

Especially preferred are largely linear polyester polyols, as structural components Adipic acid and 1,4-butanediol and / or 1,6-hexanediol and / or 2,2-dimethyl-1,3-propanediol.

Also, hydroxyl-containing polycarbonates come as polyhydroxyl components into consideration, for. As those obtained by reacting diols such as 1,4-butanediol and / or 1,6-hexanediol with diaryl carbonates, such as. B. diphenyl carbonate, dialkyl carbonates, such as. As dimethyl carbonate or phosgene can be. The at least partial use of hydroxyl-containing polycarbonates, the hydrolysis resistance of the dispersion adhesives of the invention can be improved.

Prefers are polycarbonates prepared by reacting 1,6-hexanediol with dimethyl carbonate were manufactured.

When Polyether polyols are suitable for. B. the polyaddition products of Styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, Butylene oxides, epichlorohydrins, and their mixed addition and grafting products, as well as by condensation of polyhydric alcohols or mixtures same and by alkoxylation of polyhydric alcohols, Amines and amino alcohols obtained polyether polyols. As structural components A) suitable polyether polyols are the homo-, mixed and graft polymers of propylene oxide and ethylene oxide, which by addition said epoxides of low molecular weight di- or triols, as they mentioned above as structural components for polyester polyols or higher functional low molecular weight polyols such as As pentaerythritol or sugar or accessible to water are.

Especially preferred di- or higher-functional polyols A) are polyester polyols, Polylactones or polycarbonates, very particularly preferred are polyester polyols of the above kind.

When Construction component B) are di- or higher functional Polyol components having a molecular weight of 62 to 399 daltons such as polyethers, polyesters, polycarbonates, polylactones or polyamides, as far as they have a molecular weight of 62 to 399 daltons exhibit.

Further suitable components are those under A) for the preparation of the polyester polyols polyhydric, especially dihydric alcohols mentioned as well as continue low molecular weight polyester diols such. B. adipic acid bis (hydroxyethyl) ester or short-chain homo- and mixed addition products started on aromatic diols of ethylene oxide or propylene oxide. Examples of aromatic Diols used as starters for short-chain homopolymers and copolymers of ethylene oxide or propylene oxide can be used z. For example, 1,4-, 1,3-, 1,2-dihydroxybenzene or 2,2-bis (4-hydroxyphenyl) propane (Bisphenol A).

For the purposes of the isocyanate polyaddition monofunctional compounds having an ethylene oxide content of at least 50 wt .-% and a molecular weight of at least 400 daltons, are suitable as the starting component C) in question. Component C) is a hydrophilic synthesis component for incorporation of terminal hydrophilic ethylene oxide units containing chains of the formula (I), H-Y'-XYR (I) in which
R is a monovalent hydrocarbon radical having 1 to 12 carbon atoms, preferably an alkyl radical having 1 to 4 carbon atoms,
X is a polyalkylene oxide chain with 5 to 90, preferably 20 to 70 chain members which consist of at least 51%, preferably at least 65% of ethylene oxide units and which may consist of ethylene oxide units of propylene oxide, Buylenoxid- or styrene oxide units, among the latter units propylene oxide units are preferred, and
Y / Y 'is oxygen or also -NR'-, where R' corresponds to its definition R or hydrogen.

The preparation of the monofunctional, hydrophilic structural components is carried out in analogy to that in the DE-A 23 14 512 or DE-A 23 14 513 or in the US-A 3,905,929 or US-A 3,920,598 described manner by alkoxylation of a monofunctional starter such. For example, methanol, ethanol, i-propanol, n-butanol or N-methyl-butylamine using ethylene oxide and optionally a further alkylene oxide such. For example, propylene oxide.

Prefers as structural components C) are the copolymers of ethylene oxide with propylene oxide having an ethylene oxide mass fraction greater 50%, more preferably from 65 to 89%. In a preferred embodiment are used as synthesis components C) compounds having a molecular weight of at least 400 daltons, preferably from 1000 to 4500 daltons, especially preferably from 1500 to 3500 daltons, and most preferably used from 2000 to 2500 daltons.

As structural components D) any organic compounds are suitable which have at least two free isocyanate groups per molecule. Preference is given to using diisocyanates Y (NCO) ₂ , where Y is a divalent aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a dihydric cycloaliphatic hydrocarbon radical having 6 to 15 carbon atoms, a bivalent aromatic hydrocarbon radical having 6 to 15 carbon atoms or a divalent araliphatic hydrocarbon radical having 7 to 15 carbon atoms. Examples of such preferably used diisocyanates are tetramethylene diisocyanate, methylpentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanato-cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 4,4'-diisocyanato-dicyclohexyl-methane , 4,4'-diisocyanato-dicyclohexylpropane (2,2), 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanato-diphenylmethane, 2,2'- and 2 , 4'-diisocyanatodiphenylmethane, tetramethylxylylene diisocyanate, p-xylylene diisocyanate, p-isopropylidene diisocyanate and mixtures consisting of these compounds.

It is of course also possible in the Polyurethane chemistry per se known higher functional Polyisocyanates or known per se modified, for example Carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups and / or biuret polyisocyanates partially share.

preferred Diisocyanates D) are aliphatic and araliphatic diisocyanates such as hexamethylene diisocyanate, 1,4-diisocyanato-cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 4,4'-diisocyanato-dicyclohexylmethane or 4,4'-diisocyanato-dicyclohexylpropane (2,2) and mixtures consisting of these compounds.

Especially preferred structural components D) are mixtures of hexamethylene diisocyanate and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane.

The underlying the dispersions of the invention Polymer contains ionic or potentially ionic groups for hydrophilization, either cationic or anionic Nature can be. Preferred are sulfonate and carboxylate groups. Alternatively, such groups can also be used which converted by salt formation in the aforementioned ionic groups can be (potentially ionic groups). The hydrophilic ones Groups are via the components E1) and / or E2) in introduced the polymer.

When Building component E) comes a mixture of primary and / or secondary monoamine compounds E1) and from primary and / or secondary diamino compounds E2) in question, wherein at least one of the components E1) and / or E2) sulfonic acid and / or carry carboxyl groups.

Examples for E1) are aliphatic and / or alicyclic primary and / or secondary monoamines such as ethylamine, diethylamine, the isomeric propyl and butylamines, higher linear aliphatic Monoamines and cycloaliphatic monoamines such as cyclohexylamine. Further Examples of E1) are amino alcohols, i. H. Links, containing amino and hydroxyl groups in one molecule, such as For example, ethanolamine, N-methylethanolamine, diethanolamine and 2-propanolamine. Further examples of E1) are monoamino compounds which additionally sulfonic acid and / or carboxyl groups such as taurine, glycine or alanine. Of course also mixtures of several monoamino compounds E1) be used.

preferred Construction components E1) are diethylamine, ethanolamine or diethanolamine. Particularly preferred structural components E1) are ethanolamine or Diethanolamine.

Examples for E2) are 1,2-ethanediamine, 1,6-hexamethylenediamine, 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane (Isophoronediamine), piperazine 1,4-diaminocyclohexane or bis (4-aminocyclohexyl) methane. Farther are adipic dihydrazide, hydrazine or hydrazine hydrate in question. Polyamines such as diethylenetriamine can also be used instead of Diaminoverbindung be used as structural component E2).

Further Examples of E2) are amino alcohols, i. H. Links, containing amino and hydroxyl groups in one molecule, such as For example, 1,3-diamino-2-propanol, N- (2-hydroxyethyl) ethylenediamine or N, N-bis (2-hydroxyethyl) ethylenediamine.

Also suitable compounds E2) are diamino compounds which are additionally Wear sulfonate and / or carboxylate groups, such as the sodium or potassium salts of N- (2-aminoethyl) -2-aminoethanesulfonic acid, N- (3-aminopropyl) -2-aminoethanesulfonic acid, N- (3-aminoproyl) -3-aminopropanesulfonic acid, N- (2-aminoethyl) -3-aminopropanesulfonic acid or analogous carboxylic acids. It can also be mixtures several diamino compounds E2) are used.

Preferred structural components E2) are 1,2-ethanediamine, 1,6-hexamethylenediamine, 1-Ami no-3,3,5-trimethyl-5-aminomethylcyclohexane (isophoronediamine), piperazine, N- (2-hydroxyethyl) ethylenediamine, N, N-bis (2-hydroxyethyl) ethylenediamine, the sodium salt of N- ( 2-aminoethyl) -2-aminoethanesulfonic acid or the sodium salt of N- (2-aminoethyl) -2-aminoethanecarboxylic acid.

Especially preferred structural components E2) are N- (2-hydroxyethyl) ethylenediamine or the sodium salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid.

The average amino functionality of the mixture E) is between 1.65 and 1.98, preferably between 1.75 and 1.98, especially preferably between 1.78 and 1.95.

The equivalent ratio of NCO groups in the NCO prepolymer to the total amount of isocyanate reactive amino and hydroxyl groups of the mixture E) is between 1.04 and 1.9, preferably between 1.08 and 1.85, especially preferably between 1.11 and 1.8.

Prefers contains the mixture E) monoamino compounds E1), diamino compounds E2) with hydroxyl groups and diamino compounds E2) with sulfonate or carboxylate groups. Particularly preferably contains the Mixture E) monoamino alcohols E1), diamino alcohols E2) and diamino compounds E2) with sulfonate groups. Very particularly preferably contains the mixture E) diethanolamine, N- (2-hydroxyethyl) ethylenediamine and the sodium salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid.

Of the Content of ionic groups is between 10 and 600 mmol per kg of solid, preferably between 20 and 300 mmol, especially preferably between 30 and 150 mmol per kg of solid.

object The present invention further provides a process for the production the aqueous polyurethane-polyurethaneurea dispersions according to the invention, characterized in that in a first step, the components A), B), C) and D), optionally in the presence of one with water miscible but isocyanate-inert solvent, submitted in full or in part to a rector and to temperatures be heated in the range of 50 to 120 ° C, then which may not be added at the beginning of the reaction Ingredients A), B), C) or D) are added, in a second Step up the chain extension with the mixture E) Temperatures of 15 to 60 ° C is carried out and before, during or after chain extension the conversion into the aqueous phase takes place and the optionally used solvent Will get removed. Preferably, no solvent is used.

The Preparation of the inventive aqueous Polyurethane-polyurea may be in one or more Stages in homogeneous or multi-stage implementation, partly in Disperse phase can be performed. After complete or partially performed polyaddition takes place Dispersing, emulsifying or dissolving step. In connection If appropriate, another polyaddition or modification takes place in disperse phase. For the production, all, From the prior art known methods are used. Preferably, the acetone method is used.

suitable Solvents are z. Acetone, butanone, tetrahydrofuran, Dioxane, acetonitrile, dipropylene glycol dimethyl ether and 1-methyl-2-pyrrolidone, preferred are butanone or acetone, more preferably acetone. The solvents can not just start the Production, but possibly also in parts later be added. It is possible the reaction under normal pressure or to apply increased pressure.

to Production of the prepolymer are the amounts of the individual components A) to D) such that an isocyanate index of 1.05 to 2.5, preferably from 1.1 to 1.5 results. The isocyanate content of Prepolymers is between 0.3 and 3.0%, preferably between 0.7 and 1.5%, more preferably between 0.9 and 1.5%.

It are 50 to 96 parts by weight, preferably 75 to 96 parts by weight of Component A), 0 to 10 parts by weight, preferably 0 to 5 parts by weight component B), 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, particularly preferably 0.8 to 3.5 parts by weight of component C) and 3 to 30 parts by weight, preferably 5 to 18 parts by weight of the component D) with the requirement that the sum of the components 100 results.

The reaction of components A), B) and C) with D) takes place, based on the total amount of isocyanate-reactive groups, partially or completely, but preferably completely. The degree of conversion is usually monitored by monitoring the NCO content of the reaction mixture. For this purpose, both spectroscopic measurements, z. As infrared or near-infrared spectra, determinations of refraction index as well as chemical analyzes, such as titrations of samples taken.

to Acceleration of the isocyanate addition reaction can be conventional Catalysts, as they are to accelerate the NCO-OH reaction the Those skilled in the art are used. Examples are triethylamine, 1,4-diazabicyclo [2,2,2] octane, dibutyltin oxide, tin dioctoate or Dibutyltin dilaurate, tin bis (2-ethylhexanoate) or other organometallic Links.

The Chain extension with the mixture E) can, before dispersing, during dispersing or after dispersing become. Preferably, the chain extension takes place before Dispersing.

The Chain extension is at temperatures of 15 to 60 ° C carried out, preferably from 25 to 55 ° C, especially preferably from 40 to 50 ° C.

Of the Term chain extension in the context of the present invention also includes the reactions of the monoamino compounds E1), which act as chain terminators due to their monofunctionality and thus not to an increase, but to a decrease in molecular weight to lead. This applies in particular to the amino alcohols E1), since their hydroxyl groups in the selected temperature range not or only to a very small extent with the isocyanate groups react.

The Component E) can with organic solvents and / or diluted with water to be added to the reaction mixture. The addition of the aminic compounds E1) and E2) can successively in in any order or at the same time by adding a mixture respectively.

For the purpose of Preparation of the dispersion of the invention is the prepolymer, optionally under high shear, such as. B. strong stirring, either added to the dispersing water or, conversely, the dispersing water is stirred into the prepolymer. Then, if not in the homogeneous Phase done, the chain extension done.

To the dispersion is the optionally used organic Solvent, for example acetone, distilled off.

In the method according to the invention are preferred no external emulsifiers used.

The Dispersions have a solids content of 10 to 70 Wt .-%, preferably 25 to 60 wt .-% and particularly preferably 35 bis 60% by weight.

The Dispersion adhesives according to the invention can alone or with those in the coating and adhesive technology known binders, excipients and impact substances, in particular Emulsifiers or light stabilizers such as UV absorbers or steric hindered amines (HALS), furthermore antioxidants, fillers or aids, eg. Anti-settling agent, defoaming and / or wetting agents, leveling agents, reactive thinners, Plasticizers, catalysts, auxiliary solvents and / or Thickeners and additives, such as pigments, dyes or matting agents are used. Also sticky Resins ("tackifiers") can be added become.

The Additives can the inventive Coating system can be added immediately before processing. But it is also possible, at least part of the additives before, during or after the dispersion of the binder admit.

Likewise provided by the present invention are adhesive compositions comprising the polyurethane-polyurea-urea dispersions according to the invention and also polyisocyanate compounds having at least two isocyanate groups per molecule. The crosslinkers can be added before use (2K processing). In this case, preference is given to polyisocyanate compounds which are emulsifiable in water. These are z. B. in the EP-A 0 206 059 . DE-A 31 12 117 or DE-A 100 24 624 described compounds. The polyisocyanate compounds are used in an amount of 0.1 to 20 wt .-%, preferably 0.5 to 10 wt .-%, particularly preferably 1.5 to 6 wt .-%, based on the aqueous dispersion.

The films obtained from the aqueous polyurethane-polyurethaneurea dispersions according to the invention are distinguished by low activation temperatures in the range from 40 ° to 80 ° C., very good initial heat resistance of ≦ 2 mm / min, preferably ≦ 1.5 mm / min and high heat levels ≥ 90 ° C, preferably ≥ 100 ° C, more preferably ≥ 110 ° C from. In addition, they show excellent adhesion to a wide variety of substrates such as wood, leather, textiles, different Polyvinylchloridqualitäten (hard, soft PVC), rubber or Polyethylvinylacetat.

The Adhesive compositions containing the invention Dispersions are suitable for the bonding of any substrates such as z. As paper, cardboard, wood, textiles, metal, leather or mineral Materials. Particularly suitable are the inventive Adhesive compositions for bonding rubber materials such. As natural and synthetic rubbers, various plastics such Polyurethanes, polyvinyl acetate, polyvinyl chloride, in particular plasticizer-containing Polyvinyl chloride. Particularly preferred is the use for bonding soles of these materials, preferably based on polyvinyl chloride, especially preferably plasticized polyvinyl chloride or of polyethylvinyl acetate or polyurethane elastomer foam with shoe stems Leather or imitation leather. Furthermore, the adhesive compositions of the invention particularly suitable for bonding films based on polyvinyl chloride or plasticized polyvinyl chloride with wood.

Also for primer applications are the invention Adhesive compositions suitable.

adhesive composites comprising with the polyurethane-polyurethane-urea dispersions according to the invention bonded substrates are also the subject of the present application.

The Processing of the adhesive compositions according to the invention takes place according to the known methods of adhesive technology the processing of aqueous dispersion adhesives.

Examples

below the invention will be explained in more detail with reference to the examples.

The Initial heat resistance and heat levels can be determined by the following methods:

A) Determination of initial heat resistance

The Initial heat resistance test becomes one-component (without crosslinker) performed.

Test material / specimen

• a) Renolite foil (32052096 strukton; rhenolite AG, 67547 Worms / Germany) Dimensions: 50 × 300 × 0.2mm
• b) beechwood (planed) Dimensions: 50 × 140 × 4.0 mm

Bonding and measurement

The Testing takes place at the earliest 14 days after production the adhesive dispersion. This is done with a 200 μm doctor blade applied to the wood test specimen. The adhesive surface is 50 × 110 mm. The flash off time of applied adhesive is at least 3 hours at room temperature. Subsequently, the two specimens are superimposed placed and 10 s at 4 bar pressure at 77 ° C added. Immediately thereafter, the specimen without weight for 3 min at 80 ° C annealed, then 5 min at 80 ° C with 2.5 kg perpendicular to the glue joint (180 ° peel) loaded. Measured is the distance, which solved the bonding has, in millimeters. The initial heat resistance is in mm / min.

B) Determination of the heat level

• 1K adhesive: adhesive without crosslinker
• 2K bond: adhesive with an emulsifiable crosslinker isocyanate
• 3 parts of Desmodur ^® DN per 100 parts of adhesive are thoroughly homogenized.
• Recommended weight: 25 g of adhesive and 0.75 g of crosslinker

Test material / specimen

• a) rigid PVC laminating film (Benelit film, Benecke-Kaliko AG, Hanover / D) Dimensions: 50 × 210 × 0.4 mm
• b) beechwood (planed) Dimensions: 50 × 140 × 4.0 mm

Bonding and measurement

The Adhesive dispersion (1 K) or the mixture of adhesive dispersion and Venetzerisocyanat (2 K) is applied by means of a brush on the Buchenholzprüfkörper applied. The adhesive surface is 50 × 110 mm. After a drying time of 30 minutes at room temperature a second layer of adhesive is applied over the first and then dried at room temperature for 60 minutes. Subsequently, the two specimens are superimposed placed and 10 s at 4 bar pressure and 90 ° C added.

After three days of storage of the specimens at room temperature, the test specimens are loaded with 0.5 kg at an angle of 180 ° to the adhesive joint. Start temperature is 50 ° C, after 60 min the temperature is increased by 10 ° C per hour to a maximum of 120 ° C. In each case, the temperature is measured at which an adhesive bond is completely separated. feedstocks Polyester I: 1,4-butanediol polyadipate diol of OH-Z = 50 Polyester II: Polyester diol from 1,6-hexanediol, neopentyl glycol and adipic acid of OH-Z = 66 Polyether I: monofunctional, n-butanol-started ethylene oxide-propylene oxide copolymer having an ethylene oxide content of 84% of the OH-Z = 25 Desmodur ^® H: Hexamethylene diisocyanate-1.6 (Bayer MaterialScience AG, Leverkusen / D) Desmodur ^® I: Isophorone diisocyanate (Bayer MaterialScience AG, Leverkusen / D) Desmodur ^® DN: hydrophilic, aliphatic polyisocyanate based on hexamethylene diisocyanate (Bayer MaterialScience AG, Leverkusen / D)

Example 1 (according to the invention):

A mixture of 450 g of polyester I, 42.51 g of polyester II and 5.58 g of polyether I are dewatered for 1 hour at 110 ° C. and 15 mbar. At 60 ° C 2.25 g of 1,4-butanediol, 37.82 g of Desmodur ^® H and then 24.99 g of Desmodur ^® I are added. The mixture is stirred at 80 ° C until a constant isocyanate content of 1.13% (corresponding to 6.39 g NCO or 0.15 mol NCO) is reached. The reaction mixture is dissolved in 778 g of acetone and cooled to 50 ° C. To the homogeneous solution is added a solution of 5.57 g of sodium salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid (0.029 mol), 0.89 g of diethanolamine (0.009 mol) and 1.14 g of N- (2-hydroxyethyl ) ethylenediamine (0.011 mol) in 55 g of water with vigorous stirring. After 30 minutes, it is dispersed by adding 530 g of water. After distillative removal of the acetone, a solvent-free, aqueous polyurethane-polyurea dispersion having a solids content of 40.1% by weight and an average particle size of the disperse phase, determined by laser correlation, of 175 nm is obtained.
Average amino functionality: 1.82
NCO groups / (amino + hydroxyl groups) = 0.15 / (0.089 + 0.029) = 1.27

Example 2 (according to the invention):

A mixture of 585 g of polyester I, 55.26 g of polyester II and 21.75 g of polyether I are dehydrated for 1 hour at 110 ° C and 15 mbar. At 60 ° C 2.93 g of 1,4-butanediol, 49.16 g of Desmodur ^® H and then 32.49 g of Desmodur ^® I are added. The mixture is stirred at 80 ° C until a constant isocyanate content of 1.16% (corresponding to 8.66 g NCO or 0.206 mol NCO) is reached. The reaction mixture is dissolved in 1031 g of acetone and cooled to 50 ° C. Into the homogeneous solution is added a solution of 7.24 g of sodium salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid (0.029 mol), 0.48 g of diethanolamine (0.005 mol) and 1.48 g of N- (2-hydroxyethyl ) ethylenediamine (0.014 mol) in 67 g of water with vigorous stirring. After 30 minutes, it is dispersed by adding 1087 g of water. After distillative removal of the acetone, a solvent-free, aqueous polyurethane-polyurea dispersion having a solids content of 40.3% by weight and an average particle size of the disperse phase, determined by laser correlation, of 141 nm is obtained.
Average amino functionality: 1.90
NCO groups / (amino + hydroxyl groups) = 0.206 / (0.091 + 0.024) = 1.79

Example 3 (according to the invention):

A mixture of 450 g of polyester I and 15 g of polyether I are dewatered for 1 hour at 110 ° C. and 15 mbar. At 60 ° C 30.24 g of Desmodur ^® H and 19.98 g Desmodur ^® I are added. The mixture is stirred at 80 ° C until a constant isocyanate content of 0.98% (corresponding to 5.05 g NCO or 0.120 mol NCO) is reached. The reaction mixture is dissolved in 773 g of acetone and cooled to 50 ° C. Into the homogeneous solution is added a solution of 5.85 g of sodium salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid (0.031 mol), 0.42 g of diethanolamine (0.004 mol) and 1.11 g of N- (2-hydroxyethyl ) ethylenediamine (0.011 mol) in 73 g of water with vigorous stirring. After 30 minutes, it is dispersed by adding 730 g of water. After distillative removal of the acetone, a solvent-free, aqueous polyurethane-polyurea dispersion having a solids content of 40.1% by weight and an average particle size of the disperse phase, determined by laser correlation, of 151 nm is obtained.
Average amino functionality: 1.91
NCO groups / (amino + hydroxyl groups) = 0.120 / (0.088 + 0.019) = 1.12

Example 4 (comparison):

A mixture of 450 g of polyester I, 42.5 g of polyester II and 9.00 g of polyether I are dehydrated for 1 hour at 110 ° C and 15 mbar. At 60 ° C 2.25 g of 1,4-butanediol, 37.81 g of Desmodur ^® H and then 24.98 g of Desmodur ^® I are added. The mixture is stirred at 80 ° C until a constant isocyanate content of 1.02% (corresponding to 5.78 g NCO or 0.138 mol NCO) is reached. The reaction mixture is dissolved in 782 g of acetone and cooled to 50 ° C. To the homogeneous solution is added a solution of 6.25 g of the sodium salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid (0.033 mol), 1.24 g of diethanolamine (0.012 mol) and 1.23 g of N- (2-hydroxyethyl ) ethylenediamine (0.012 mol) in 85 g of water with vigorous stirring. After 30 minutes, it is dispersed by adding 504 g of water. After distillative removal of the acetone, a solvent-free, aqueous polyurethane-polyurea dispersion having a solids content of 49.9% by weight and an average particle size of the disperse phase, determined by laser correlation, of 196 nm is obtained.
Average amino functionality: 1.79
NCO groups / (amino + hydroxyl groups) = 0.138 / (0.102 + 0.036) = 1.00 Table 1: Measurement of initial heat resistance and heat resistance Initial heat resistance [mm / min] Heat level 1 K [° C] Heat level 2 K [° C] Example 1 according to the invention 1.2 110 120 Example 2 according to the invention 0.6 110 120 Example 3 according to the invention 0.4 > 120 > 120 Example 4 Comparison 9.8 90 > 120

The from the aqueous polyurethane-polyurethaneurea dispersions according to the invention obtained films of Examples 1 to 3 are characterized in contrast to that of the comparative example by very good initial heat resistance from 0.4 to 1.2 mm / min and high heat levels ≥ 110 ° C out.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - US 4870129 A [0003]
• EP 0304718 A [0004]
• - DE 2551094 A [0005]
• - DE 10152405 A [0007]
• DE 102004023768 A [0008]
• - DE 2314512 A [0023]
• - DE 2314513 A [0023]
• - US 3905929 A [0023]
• - US 3920598 A [0023]
• EP 0206059 A [0059]
• - DE 3112117 A [0059]
• - DE 10024624 A [0059]

Claims (14)

Aqueous polyurethane-polyurethaneurea dispersion based on A) one or more di- or higher-functional polyol (s) having an average molecular weight of 400 to 5000 daltons, B) optionally one or more di- or higher-functional polyol component (s) with a molecular weight of 62 to 399 Dalton, C) one or more in the sense of the isocyanate polyaddition reaction mono-functional compound (s) having an ethylene oxide content of at least 50% by weight and a molecular weight of at least 400 daltons, D) one or more di- or polyisocyanate component (s) and E) a mixture E) of primary and / or secondary monoamino compounds E1) and of primary and / or secondary diamino compounds E2), characterized in that at least one of the components E1) and / or E2) carry sulfonate and / or carboxylate groups and the average amino functionality the mixture E) is between 1.65 and 1.98 and the equivalent ratio of NCO groups in the NCO prepolymer to the total amount of isocyanate-reactive amino and hydroxyl groups of the mixture E) is between 1.04 and 1.9. Aqueous polyurethane-polyurethaneurea dispersion according to claim 1, characterized in that component D) is a mixture of hexamethylene diisocyanate and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane is. Aqueous polyurethane-polyurethaneurea dispersion according to claim 1, characterized in that component E1) is diethylamine, ethanolamine or diethanolamine. Aqueous polyurethane-polyurethaneurea dispersion according to claim 1, characterized in that the component E2) 1,2-ethanediamine, 1,6-hexamethylenediamine, 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane (Isophoronediamine), piperazine, N- (2-hydroxyethyl) ethylenediamine, N, N-bis (2-hydroxyethyl) ethylenediamine, the sodium salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid or the sodium salt of N- (2-aminoethyl) -2-aminoethanecarboxylic acid is. Process for the preparation of the aqueous Polyurethane-polyurethaneurea dispersions according to claim 1, characterized in that in a first step, the components A), B), C) and D), optionally in the presence of one with water miscible but isocyanate-inert solvent, submitted in full or in part to a rector and to temperatures be heated in the range of 50 to 120 ° C, then optionally not added at the beginning of the reaction Ingredients A), B), C) or D) are added, in a second Step the chain extension with the mixture E) at temperatures from 15 to 60 ° C and before, during or after the chain extension the transfer takes place in the aqueous phase and optionally used Solvent is removed. A method according to claim 5, characterized characterized in that in the preparation of the prepolymer, the amounts used the individual components A) to D) are measured so that an isocyanate index from 1.05 to 2.5 results. A method according to claim 5, characterized characterized in that the isocyanate content of the prepolymers between 0.3 and 3.0%. A method according to claim 5, characterized characterized in that no external emulsifiers zugestezt. Adhesive compositions containing the aqueous Polyurethane-polyurea dispersions according to claim 1 and polyisocyanate compounds having at least two isocyanate groups per molecule. Use of the aqueous polyurethane-polyurea-urea dispersions according to claim 1 for the production of adhesive composites. Use according to claim 10, characterized in that the adhesive composites rubber and / or Plastic materials as substrates included Use according to claim 10, characterized in that the adhesive composites a Shoe sole and a shoe upper cover. Use according to claim 10, characterized in that the adhesive composites films and wood include. Adhesive composite containing with aqueous Polyurethane-polyurea dispersions according to claim 1 bonded substrates.