DE102006060378A1 - Residual monomer-free, aqueous polychloroprene dispersions containing a hydroxylamine derivative as stabiliser, e.g. N,N-diethylhydroxylamine, used in adhesive and sealant formulations for various substrates - Google Patents

Abstract

Residual monomer-free, aqueous polymer dispersions of polychloroprene particles also contain hydroxylamine derivatives. Residual monomer-free, aqueous dispersions containing (A) polychloroprene particles and (B) hydroxylamine derivatives of formula R 1>-N(OH)-R 2>(I), in which R 1>, R 2>H, 1-20C alkyl (linear or branched, saturated or unsaturated, optionally mono- or poly-substituted), 6-12C aryl, 7-14C aralkyl or 5-7C cycloalkyl, or R 1>and R 2>may be linked together by an optionally substituted 3-7C cycloalkyl residue . Independent claims are included for (1) adhesive and sealant formulations containing these dispersions (2) substrates coated with these formulations (3) polymer layers obtained from these dispersions .

Description

The The invention relates to water-containing compositions, in particular aqueous Polymer dispersions based on polychloroprene, process for their preparation and their use, in particular for the production of sealants and coatings, in particular for the production of adhesive coatings and a method for joining the one-sided or double-sided coated Substrates using the compositions.

Contact adhesives based on polychloroprene (CR) are predominantly solvent-based Adhesives applied to substrates to be bonded and dried become. By subsequent Add the Receives substrates under pressure one immediately connects with high initial strength after the joining process.

For ecological reasons, there is an increasing demand for suitable aqueous CR adhesive dispersions which can be processed to corresponding aqueous CR adhesive formulations. These are used, for example, in the "spray-mix" process, in which the aqueous adhesive formulation and a coagulant are conveyed separately in a spray gun and finally mixed in a spray jet, whereupon the CR adhesive coagulates on the substrate eg in "Handbook of Adhesives", Irving Skeist, Chapman, Hall, New York, 3rd ed. 1990, Part 15, page 301; R. Musch et al, Adhesives Age, January 2001, page 17, "Spray mixing adhesives based Dispercoll® ^® C for foam bonding," Technical Information of Bayer AG, no. KA-KR-0001d / 01 / 05.96 given ,

It However, it is often necessary that the aqueous CR dispersions or Formulations with additives such as stabilizers and / or to provide aging protection agents so that they have a need-based storage stability and safety of use or the adhesive layers are protected against aging or discoloration.

To latter purpose become watery Formulations advantageously mixed with zinc oxide, since this at Formulations based on polychloroprene dispersions of a fast Aging of the adhesive seam and discoloration the bonded substrates counteracts by splitting off HCl from the CR polymer.

Furthermore, anti-aging agents may be added, preferably (based on oligofunctional secondary aromatic amines or oligofunctional substituted phenols, such as products of the type 6-PPD N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine; Vulkanox ^®, Germany Lanxess GmbH), DTPD, DDA, BPH, BHT, etc. as described for example in the fourth manual for the rubber industry, 1992 edition, Bayer AG, Leverkusen Chapter Vulkanox.RTM ^®, p 423. It is particularly effective Vulkanox.RTM ^® DDA, a diphenylamine derivative.

The However, previously known zinc oxide dispersions tend to sedimentation. This sedimentation or phase separation is especially at one Use of such adhesive formulations in the "spray-mix" process is not acceptable as they to blockages of the nozzle leads. The cleaning of the nozzle is time consuming and costly and unsatisfactory from an economic point of view.

The Organic aging inhibitors, in turn, are either not discoloration-stable (Oligofunctional secondary aromatic amines) or less effective (oligofunctional substituted Phenols).

The Object of the present invention was to provide new watery, residual monomer-free and storage-stable polychloroprene dispersions and adhesive compositions which after application to the to be bonded substrates and the joining a high resistance against elimination of HCl from the polymer.

It has been found that the addition of hydroxylamine and its derivatives can significantly improve the stabilization of aqueous polychloroprene dispersions and preparations. In this case, hydroxylamines are added either in addition to the previously used anti-aging agents or the conventional anti-aging agents are partially or completely replaced by hydroxylamines. Hydroxylamines stabilize polychloroprene dispersions by trapping HCl which can be split off from the polychloroprene and act as anti-aging agents by stopping radical reactions in the dry films made from the aqueous formulations. Additional stabilization can be achieved by the use of nano-zinc oxide, which can solve the problem of sedimentation of zinc oxide dispersions, the current state of the art. In addition, nano-silica dispersions have a stabilizing effect on the resistance to HCl cleavage and discoloration of the aqueous films, dry films.

• A) Polychloropren-Partikel,
• B) Hydroxylamine der allgemeinen Formel (I),
  
  in der R¹ und R² unabhängig voneinander für Wasserstoff (H), lineare oder verzweigte, gesättigte oder ungesättigte, unsubstituierte, einfach oder mehrfach substituierte C₁-C₂₀-Alkylreste oder C₆-C₁₂-Arylreste oder C₇-C₁₄-Aralkylreste oder C₅-C₇-Cycloalkylreste stehen oder R¹ und R² durch einen unsubstituierten, einfach oder mehrfach substituierten C₃-C₇-Cycloalkylrest miteinander verbunden sind und
• C) Wasser.

The subject of the present invention is therefore a composition containing:

• A) polychloroprene particles,
• B) Hydroxylamines of the general formula (I),
  
  in the R ¹ and R ² independently of one another represent hydrogen (H), linear or branched, saturated or unsaturated, unsubstituted, mono- or polysubstituted C ₁ -C ₂₀ -alkyl radicals or C ₆ -C ₁₂ -aryl radicals or C ₇ -C ₁₄ -Aralkylreste or C ₅ -C ₇ -cycloalkyl or R ¹ and R ^{2 are joined together} by an unsubstituted, mono- or polysubstituted C ₃ -C ₇ -cycloalkyl radical and;
• C) water.

The Composition is especially in the form of an aqueous Dispersion before.

Polychloroprene particles For the purposes of the invention are particles of polychloroprene (poly (2-chloro-1,3-butadiene) and from chloroprene-containing copolymers.

The Polychloroprene (poly (2-chloro-1,3-butadiene)) particles are the composition according to the invention appropriate in the Form of watery Fed dispersions. The preparation of such polychloroprene dispersions is per se known and carried out by emulsion polymerization in the alkaline aqueous medium, see. "Ullmanns Encyclopaedia of technical chemistry ", Volume 13, p. 614, Verlag Chemie, Weinheim, New York; 4th edition 1977; "Encyclopedia of Polymer Science and Technology ", Vol. 3, pp. 705-730, John Wiley, New York 1965; "Methods of Organic Chemistry" (Houben-Weyl) XIV / 1, 733 f. Georg Thieme Verlag Stuttgart 1961.

Especially Polychloroprene dispersions are preferred by continuous Be prepared polymerization, such. described in WO02 / 24825, Example 2 and DE-A 3 002 734, Example 6, wherein the regulator content between 0.01 wt .-% and 0.5 wt .-% can be varied.

suitable copolymerizable monomers are preferably compounds of 3 to 12 C atoms and 1 or 2 copolymerizable C = C double bonds per molecule. Examples of preferred copolymerizable monomers are 2,3-dichlorobutadiene and 1-chlorobutadiene.

The in the process according to the invention to be used polychloroprene dispersion is by emulsion polymerization at 0 to 70 ° C, preferably at 5 to 45 ° C and pHs of 10 to 14, preferably pH 11 to pH 13. The activation is carried out by the usual activators or activator systems.

When examples for Activators or activator systems may be mentioned: formamidinesulfinic acid, potassium peroxodisulfate, Redox systems based on potassium peroxodisulfate and optionally a silver salt, the Na salt of anthraquinone-β-sulfonic acid, wherein, for example, compounds such as formamidinesulfinic acid, the sodium salt of hydroxymethanesulfinic acid, sodium sulfite and sodium dithionite serve as redox partners. Also redox systems based on peroxides and hydroperoxides are suitable. The preparation of the polychloroprenes according to the invention can be both continuous and discontinuous, wherein continuous polymerization is preferred.

to viscosity adjustment the polychloroprenes of the invention may conventional chain transfer agents such as mercaptans, as e.g. in DE-A 3 002 711, GB-A 1 048 235, FR-A 2 073 106, or as xanthogen disulphides, such as they e.g. in DE-A 1 186 215, in DE-A 2 156 453, DE-A 2 306 610 and DE-A 3,044,811, in EP-A-0 053 319, in GB-A-512458 and GB-A-952 156 and in US-A 2 321 693 and US-A 2 567 117 are used become.

The Polymerization usually becomes at 50% -95%, preferably at 60% -80% of the monomer conversion stopped, wherein as an inhibitor e.g. Phenothiazine, tert-butylpyrocatechol or diethylhydroxylamine can add.

at the described radical emulsion polymerization is the Monomers in the polymer chain in different configuration installed, namely in trans-1,4 and cis-1,4-position, in 1,2-position and in 3,4-position, see: "W.Obrecht in Houben-Weyl: Methods of Organic Chemistry Bd. 20 Part 3 Macromolecular Substances, (1987) p. 845 ", the 1,2-position monomer is labile, light contains cleavable chlorine atom, that for the HCl cleavage from the polymer is responsible.

To The polymerization is the remaining monomeric chloroprene by Steam distillation removed and a residual monomer-free dispersion generated. The steam distillation is carried out as e.g. described in W.Obrecht in Houben-Weyl: Methods of Organic Chemistry Bd. 20 Part 3 Macromolecular Stoffe, (1987) p. 852 ". Repeated steam distillation allows the proportion of monomeric chloroprene in the polymer to values around 100 ppm, preferably 50 ppm or lower. Such dispersions are considered residual monomer-free dispersions in the sense of the present invention. However, this is going on Process that still exists in the dispersion from the polymerization ago Stopper diethylhydroxylamine removed so far that its proportion in latex below the detection limit of> 1 ppm.

That Hydroxylamines as polymerization inhibitors, i. to stop the polymerization alone or in combination with other Abstoppern are used, is e.g. in "Methods of organic chemistry "(Houben-Weyl) XIV / 1, p. 435, 441, 746 f. Georg Thieme Verlag Stuttgart 1961, described.

Farther the effectiveness of certain hydroxylamines in suppressing the so-called popcorn formation during polymerization described.

The Stabilizing according to the invention The effect is in the finished, residual monomer-free polymer dispersion However, no longer exist because - as stated above - the described Hydroxylamines together with the remaining monomer, which consists of toxicological establish from the polymer obtained immediately after the start of the polymerization Latex by e.g. Steam distillation can be removed.

Of the Solids content of this low-monomer polychloroprene dispersion can if necessary in a further step through a concentration step (Creaming process) increased become. This creaming is done e.g. by adding alginates, as in "Neoprene Latices, John C. Carl, E.I. Du Pont 1964, p.13 ", or by a Aufrahmverfahren with the aid of a coalescing aid as described in DE-A 10 145 097, which is particularly preferred.

In a preferred embodiment According to the invention, the polychloroprene particles have an average Primary particle diameter of less than 220 nm.

Of the Term "primary particle or primary particles "refers analogously to DIN 53206; 1992-08 by suitable physical methods as Individuals recognizable particles. One can in connection with the Polychloroprene particles of "diameters" speak, since the Approximate particles spherical are.

Of the mean primary particle diameter The polychloroprene particles according to the invention preferably by means of ultracentrifuge determined, cf .: H.G. Miller, Progr. Colloid Polym. Sci. 107, 180-188 (1997). It becomes the mass agent specified.

One mean primary particle diameter greater than 220nm may be detrimental because of its distance of the residual monomer 2-chloro-1,3-butadiene from the polychloroprene Dispersion by steam distillation to undesirable Excretions can come.

In a further preferred embodiment According to the invention, the polychloroprene particles have an average Primary particle diameter of more than 60 nm.

One mean primary particle diameter less than 60 nm may be detrimental because of concentration the polymer dispersion to a solids content of> 55 wt .-% is no longer possible. For example, e.g. the concentration of styrene-butadiene (SBR) latex with a particle size of 78 nm by ammonium alginate is no longer possible (Ind. Eng. Chem. 43, 407, (1951))

Prefers the polychloroprene particles have an average primary particle diameter from 60 to 220 nm, preferably 70 to 160 nm.

The said mean primary particle diameter of the polychloroprene particles are both in the aqueous dispersions used for the preparation of the compositions of the invention as well as in the resulting inventive compositions.

The Preparation of the invention to be used Hydroxylamine is known and e.g. in "Methods of Organic Chemistry" (Houben-Weyl) X / 1, S.1097-1279. Georg Thieme Verlag Stuttgart 1971, described.

in welcher
R¹ und R² unabhängig voneinander für Wasserstoff (H), lineare oder verzweigte, gesättigte oder ungesättigte, unsubstituierte, einfach oder mehrfach substituierte C₁-C₂₀-Alkylreste oder C₆-C₁₂-Arylreste oder C₇-C₁₄-Aralkylreste oder C₅-C₇-Cycloalkylreste stehen oder R¹ und R² durch einen unsubstituierten, einfach oder mehrfach substituierten C₃-C₇-Cycloalkylrest miteinander verbunden sind.They correspond to the general formula (I)

in which
R ¹ and R ² independently of one another are hydrogen (H), linear or branched, saturated or unsaturated, unsubstituted, mono- or polysubstituted C ₁ -C ₂₀ -alkyl radicals or C ₆ -C ₁₂ -aryl radicals or C ₇ -C ₁₄ -aralkyl radicals or C ₅ -C ₇ -cycloalkyl radicals or R ¹ and R ^{2 are joined together} by an unsubstituted, mono- or polysubstituted, substituted C ₃ -C ₇ -cycloalkyl radical.

suitable Hydroxylamines are, for example, aliphatic and aromatic hydraxylamines including those which are N- and O-substituted. Preference is given to low molecular weight Hydroxylamines used which are N-substituted. Especially preferred According to the invention, N, N-diethylhydroxylamine, N-isopropylhydroxylamine, N, N-dibenzylhydroxylamine and N-tert. butylhydroxylamine used.

According to the invention the hydroxylamines of the finished polychloroprene dispersion alone or added in combination with other adjuvants. The used Quantity hangs of the type of polychloroprene dispersion, which are protected against aging should, and the desired intensity of the protective effect off and on is by those skilled in the art by preliminary preliminary experiments easy to determine. In general, one becomes the hydroxylamines in a concentration of 0.05-2 wt .-%, preferably 0.1-1 wt .-%, based on solid, add. The addition can be made at any time, preferably immediately after the preparation (polymerization) of the dispersion, or as a post-additive to a finished formulation.

The Compositions of the invention can continue to contain nano-zinc oxide particles (D1) whose average particle size is less than 150 nm, preferably less than 100 nm, more preferably less than 50 nm. Since the nano-zinc oxide particles are not spherical, one speaks more appropriately of the mean particle size in difference to the mean particle diameter.

The Nano-zinc oxide particles (D1) can in the compositions of the invention both as so-called primary particles as well as in the form of agglomerates. The term "mean Particle size of the ZnO particles "means the means of the invention Ultracentrifugation determines average particle size and excludes the size of primary particles and optionally present agglomerates thereof (see: H.G. Miller, Progr. Colloid Polym. Sci. 107, 180-188 (1997)). It becomes the mass agent specified).

The Compositions of the invention The nano-zinc oxide particles are useful in the form of aqueous Fed ZnO dispersions. This watery Dispersions can additionally organic high-boiling solvents such as triethanolamine or ethylene glycol. and / or surface modifying Contain connections. The ZnO particles can either be non-agglomerated ZnO primary particles or from ZnO agglomerates or mixtures of dispersed ZnO primary particles and ZnO agglomerates whose dimensions are as above can be described.

• I) Ein Zinkoxid-Sol wie z.B. beschrieben in WO 00/50503, hergestellt durch Redispergieren von Zinkoxid-Gelen mit einem mittleren Primärteilchengröße von < 15 nm. Als Lösemittel kommen Wasser oder Wasser-Ethylenglykol-Gemische in Frage, gegebenenfalls unter Zusatz oberflächenmodifizierender Verbindungen. oder
• II) Zinkoxid-Sole wie z.B. beschrieben in WO02/083797 mit mittleren Primärteilchengröße von < 30 nm und mittleren Agglomeratgröße von < 100 nm, z.B. hergestellt nach dem in WO02/083797 beschriebenen Verfahren.

The aqueous dispersions of zinc oxide preferably used in the present invention for the preparation of the compositions according to the invention can be prepared in different ways. However, those methods are particularly suitable in which the zinc oxide particles are prepared by precipitation from a zinc salt solution with alkali and then further processed to a dispersion. Examples are:

• I) A zinc oxide sol as described, for example, in WO 00/50503, prepared by redispersing zinc oxide gels having an average primary particle size of <15 nm. Suitable solvents are water or water-ethylene glycol mixtures, if appropriate with the addition of surface-modifying compounds. or
• II) zinc oxide sols as described, for example, in WO02 / 083797 with average primary particle size of <30 nm and average agglomerate size of <100 nm, for example prepared according to the process described in WO02 / 083797 drive.

As well suitable for the preparation of the compositions according to the invention ZnO dispersions those with surface-modified Zinc oxides, e.g. described in DE-A 10 163 256, for example be prepared by one of the methods described therein.

In a preferred embodiment of the invention, the compositions according to the invention contain further Additives, in particular silica particles (D2). The Lead silica particles in combination with zinc oxide to increase the viscosity of the adhesive dispersion. Particularly preferred is the joint use of nano-zinc oxide (D1) and silica (D2) dispersions.

Prefers is the mean silica particle size or the mean diameter the silica particles (the particles are approximately spherical) by ultracentrifugation (as indicated above), in the range of 1 to 400 nm, more preferably in the range of 5 to 100 nm, particularly preferred in the range of 8 to 50 nm. The average silica particle diameter includes the particle diameter of the primary particles and optionally present agglomerates.

The silica particles are preferably supplied to the compositions according to the invention in the form of aqueous silicon dioxide dispersions having an average particle diameter of the SiO ₂ particles of 1 to 400 nm, preferably 5 to 100 nm, particularly preferably 8 to 50 nm.

Especially the said aqueous solutions are preferred Silica dispersions in the form of hydrous silica sols the compositions of the invention fed. The particle sizes of used silica sols are subject to the incorporation into the Compositions of the invention essentially no change.

According to the invention suitable Silica dispersions can based on silica sol, silica gel, fumed silica or Precipitated silicas or Mixtures of those mentioned can be obtained and are described in DE-A 10 224 898 described.

It is also preferred that the SiO ₂ particles have hydroxyl groups on the particle surface. Particular preference is given to using aqueous silica sols as aqueous silicon dioxide dispersions.

In a further preferred embodiment of the invention, the compositions according to the invention contain at least one anti-aging agent which is different from the ZnO particles described above. Preference is given to anti-aging agents based on oligofunctional secondary aromatic amines (D3) and / or oligofunctional substituted phenols (D4), such as products of type 6-PPD, DTPD, DDA, BPH, BHT etc. as described, for example, in Handbuch für the rubber industry, Issue 1992, Bayer AG, Leverkusen, Chapter 4: Vulkanox ^® , p 423. Particularly effective is Vulkanox ^® DDA, a diphenylamine derivative.

For the production of adhesives with optimal resistance to HCl cleavage can preferably 0.1-10% by weight, more preferably 0.2-3% by weight of an anti-aging agent preferably based on oligofunctional secondary aromatic Amines (D3) or oligofunctional substituted phenols (D4) alone or in combination with 2% to 30% by weight of a silica sol dispersion (D2) are added.

Farther can the composition of the invention from 0 to 79.99% by weight of further customary adhesive assistants and additive (E).

among them For example, other polymers, e.g. polyacrylates, Polyvinylidene chloride, polybutadiene, polyvinyl acetate and / or styrene-butadiene rubbers, preferably in the form of aqueous Dispersions in a proportion of up to 30 wt .-%, based on the Solid content of the composition can be added. such Polymers can used to give the property picture of the adhesive compositions to modify.

Further examples of the adhesive auxiliaries and additives (E) are, for example, fillers, such as quartz powder, quartz sand, barite, calcium carbonate, chalk, dolomite or talc, optionally together with wetting agents, for example polyphosphates, such as sodium hexametaphosphate, naphthalenesulfonic acid, ammonium or sodium polyacrylic acid salts , wherein the fillers in amounts of preferably up to 75 wt .-%, more preferably 10 to 60 wt .-%, still preferably from 20 to 50 wt .-%, and the wetting agents in amounts of 0.2 to 0.6 wt .-%, all data based on the Solid amounts of the composition can be added.

The Amount of added fillers hangs down on the other, whether the compositions of the invention as an adhesive or used as a sealant. When used as an adhesive are maximum contents of the fillers from about 30 to 40% by weight, based on the solids content the composition. Here is a content of the polychloroprene particles greater than 40% by weight.

at The application as a sealant are maximum contents of the fillers from about 60 to 75% by weight is preferred, based on the solids content of the composition. There is one Content of the polychloroprene particles of less than 40 wt .-% preferred.

Further suitable adjuvants are, for example, in amounts of about 0.01 to 1 wt .-%, based on the solids content, to be used organic Thickeners, such as cellulose derivatives, alginates, starch, starch derivatives, Polyurethane thickener or polyacrylic acid, or in amounts of 0.05 to 5 wt .-%, based on the solids content, inorganic to be used Thickeners, such as bentonites.

to Conservation can the adhesive composition of the invention also fungicides are added. These come in, for example Amounts of 0.02 to 1% by weight, based on nonvolatiles, for use. Suitable fungicides are, for example, phenolic and Cresol derivatives or organotin compounds.

Possibly can also tackifying resins, e.g. unmodified or modified Natural resins such as rosin esters, hydrocarbon resins or synthetic Resins such as phthalate resins of the polymer dispersion according to the invention in dispersed Formed (see, e.g., in " Adhesive Resins &quot; R. Jordan, R. Hinterwaldner, pp. 75-115). Hinterwaldner Verlag Munich 1994). Preferred are alkylphenol resin and terpene-phenolic resin dispersions with softening points greater than 70 ° C, especially preferably greater than 110 ° C.

Farther can Plasticizers, such as those on adipate, phthalate or Phosphate base, for example, in amounts of 0.5 to 10 wt .-%, based be added to the solids content.

Of the Solids content of the composition according to the invention is based preferably at least about the total weight of the composition 50% by weight, more preferably at least about 60% by weight, more preferably more than 70 wt .-%, corresponding to a proportion of volatile Ingredients in the inventive composition of preferred less than about 50% by weight, more preferably less than about 40% by weight, more preferably less as about 30% by weight.

organic Solvent, such as toluene, xylene, butyl acetate, methyl ethyl ketone, Ethyl acetate, dioxane, triethanolamine, ethylene glycol or mixtures thereof can According to the invention in the Be contained in the composition. The organic solvents can the water-containing compositions of the invention in small amounts of at most about 50 wt .-%, based on the total amount the volatile one Components are added. They serve, for example, the Adhesion to difficult to bond substrates to improve.

To prepare the compositions according to the invention, aqueous dispersions of components A), B) and optionally D 1), D 2), D 3), D 4) and E) in portions of: Polychloroprene dispersion (A) from 50 to 99.95% by weight, Hydroxylamine (B) from 0.05 to 2% by weight Zinc oxide dispersion (D1) from 0 to 10% by weight, Silica dispersion (D2) from 0 to 40% by weight. at least one anti-aging agent other than zinc oxide (D3, D4) from 0 to 10% by weight other customary adhesive auxiliaries and additives (E), from 0 to 79.95% by weight in which the% by weight data in each case relate to the solids content of the composition which adds up to 100% (the following details by weight also refer to the solids content, unless stated otherwise). The solids content or solids content here does not denote the weight volatile components, such as in particular the polychloroprene, ZnO and SiO2. The volatile constituents include in particular the high-boiling solvents which can be distilled off at up to 250 ° / 15 Torr. The solids content adds up to 100% by weight. In addition, the anti-aging agent (D1) can be added in amounts of preferably 0 to 10 wt .-%, preferably 0 to 3 wt .-% based on the solids content of the composition.

One Another object of the invention is a process for the preparation the compositions according to the invention, characterized in that a water-containing polychloroprene dispersion (A) with a hydrous hydroxylamine dispersion (B) or a water-soluble Hydroxylamine added and optionally a zinc oxide dispersion (D1) and / or a silica dispersion (D2) and / or anti-aging agents (D3, D4) are metered in and optionally further customary adhesive auxiliary and additives (E) added.

The Compositions of the invention can be used as adhesives or as sealants. Prefers is the application as an adhesive.

object The present invention therefore also relates to the use of the hydroxylamine-containing Polymer dispersions for the preparation of adhesive formulations, the resulting adhesive formulations themselves coated with these Substrates and the polymer layers obtained from the polymer dispersions as well as the interconnected substrates by means of these layers.

One Adhesive according to DIN 16920 is a non-metallic substance, the parts to be joined through surface adhesion (Adhesion) and internal strength (cohesion) can connect.

Of the Application of adhesive formulations according to the invention can be determined in known ways, e.g. by brushing, pouring, knife coating, Spraying, rolling or dipping are performed. The drying of the Adhesive films may be at room or elevated temperature.

Prefers the order is carried out by spraying, such. B described in EP-A 0 624 634.

The adhesives according to the invention serve for example for bonding any substrates the same or of various kinds, such as wood, paper, plastics, textiles, Leather, rubber or inorganic materials, such as ceramics, stoneware, Glass fiber or cement, but also for impregnation, coatings and laminations of fabric and paper as a binder for fibers or for reinforcement of shoe caps and as insulation material.

Examples

A Substances used

Table 1: Polychloroprene dispersion

Tabelle 3: Zusatz- und Hilfsstoffe

• Borchers^® VP 9802: wässrige Zinkoxid-Dispersion; Partikelgröße von 50 000-150 000 nm.
• Dispercoll^® S 3030: Kieselsol mit einer spez. Oberfläche von 300 (m²/g) und einem mittleren Partikeldurchmesser von ca. 9 nm

The mean particle diameter of the polychloroprene particles was 95 nm. TABLE 2 N, N-Diethylhydroxylamine (DEHA)

Table 3: Additives and auxiliaries

• Borchers VP ^® 9802: aqueous zinc oxide dispersion; Particle size of 50,000-150,000 nm.
• Dispercoll ^® S 3030: silica sol with a spec. Surface of 300 (m ² / g) and a mean particle diameter of about 9 nm

B production the used nano-zinc oxide dispersion A

The Preparation of the nano-zinc oxide dispersion A takes place according to WO 00/50503 described method (Example 1: Preparation of a zinc oxide gel in methanol from zinc acetate dihydrate). The production of the zinc oxide sol from the zinc oxide gel success analogous to Example 7 of this document, wherein the zinc oxide gel is mixed only with water and triethanolamine and the methanol portion is removed in vacuo, leaving a nano-zinc oxide dispersion produced in triethanol / water. The mean primary particle size is 10.5 nm (number average), the zinc oxide content at 15%.

C measuring methods

C1: Determination of thermal stability (HCl stability)

The exam The dried adhesive samples are according to DIN 53381, method B.

Carrying out the measurement:

• gauge: 763 PVC Thermomat from Metrohm, CH-9101 Herisau, Switzerland

The Samples (thickness 0.1-1 mm) are cut to an edge length of approx. 2-3 mm, 0.2 g weighed into a test tube and the measurement at 180 ° C and air as a carrier gas carried out. Measured is the electrical resistance of water in which dissolves the HCl gas formed again. As HCl stability the time is given at which the electrical resistance the value of 50 μS / cm has reached. The higher the The more stable the measured sample is to HCl elimination.

Results:

D1: Determination of storage stability (Amendment the pH value)

• pH-Wert der Dispersion:

• *) erfindungsgemäßes Beispiel (¹⁾ Angaben in Gewichtsteilen der Dispersion)

2 g of diethylhydroxylamine are added with stirring to 100 g of polychloroprene dispersion and the dispersion is stored at 60.degree. After 7 and 14 days of storage, the pH is determined. Table 4: Stabilization of the pH

• pH of the dispersion:

• *) Example ( ¹ ) according to the invention in parts by weight of the dispersion)

D2: Thermostability of a formulation when using various zinc oxide dispersions and replacement of the aging inhibitor Rhenofit ^® DDA by DEHA

Table 5: HCl stability of the dispersions

• ( ¹⁾ in parts by weight of the dispersion)

D3: Influence of N, N-diethylhydroxylamine (DEHA) and nano-silicon dioxide on the stability of HCl Dispercoll C ^® formulations

Table 6: HCl stability of the dispersions

• *) Example ( ¹ ) according to the invention in parts by weight of the dispersion)
• **) based on zinc oxide content

The Formulations 7-10 correspond to Formulations 11-14, however the latter contain a hydroxylamine derivative according to the invention. If you compare Formulation 7 with 11, 8 with 12, 9 with 13 and 10 with 14 it is shown in all comparisons that in the case of hydroxylamine-containing Formulations the HCl evolution is significantly delayed, d. H. that the addition of the hydroxylamine derivative has a stabilizing effect.

Claims (11)

Aqueous residual monomer-free polymer dispersion comprising: A) polychloroprene particles and B) hydroxylamine derivatives of the general formula (I)

in which the radicals R ¹ and R ² independently of one another represent hydrogen (H), linear or branched, saturated or unsaturated, unsubstituted, mono- or polysubstituted C ₁ -C ₂₀ -alkyl radicals or C ₆ -C ₁₂ -aryl radicals or C ₇ - C ₁₄ -Aralkylreste or C ₅ -C ₇ -cycloalkyl or R ¹ and R ^{2 are joined together} by an unsubstituted, mono- or polysubstituted C ₃ -C ₇ -cycloalkyl radical. aqueous Polymer dispersion according to claim 1, characterized in that it is in the hydroxylamine derivatives (B) selected for compounds from the group consisting of N, N-diethylhydroxylamine, N-isopropylhydroxylamine, N, N-dibenzylhydroxylamine and N-tert. Butylhydroxylamine. aqueous Polymer dispersion according to claims 1 and 2, characterized in that as hydroxylamine derivatives (B) N, N-diethylhydroxylamine and / or N-isopropylhydroxylamine. aqueous Polymer dispersion according to claims 1 to 3, characterized in that 0.05 to 2 wt .-%, based on the Solid content of the dispersion containing hydroxylamine derivatives (B). aqueous Polymer dispersion according to claims 1 to 3, characterized in that 0.1 to 1.0 wt .-%, based on the solids content of the dispersion containing hydroxylamine derivatives (B) are. aqueous Polymer dispersion according to claims 1 to 5, characterized in that the hydroxylamine derivatives (B) according to be added to the Aufkonzentrationsprozess. Use of the polymer dispersions according to claims 1 to 6 for the production of adhesive and sealant formulations. Adhesive and sealant formulations containing aqueous polymer dispersions according to claims 1 to 6th Substrates coated with formulations according to claim 8. From aqueous Polymer dispersions according to claims 1 to 6 polymer layers obtained. By layers according to claim 10 interconnected Substrates.