DE2637691A1 - PROCESS FOR IMPROVING THE BONDING AND / OR PAINTABILITY OF MOLDED PLASTIC PARTS MANUFACTURED WITH THE USE OF RELEASE AGENTS - Google Patents

Description

Bayer Aktiengesellschaft

263769Ί

Central area of patents, trademarks and licenses

5090 Leverkusen, Bayerwerk Sft-by

2 AUG. 19/6

Process for improving the bondability and / or paintability of molded plastic parts produced using release agents

The invention relates to a method that enables molded parts, in particular polyurethane carpet backing coatings, to make adhesive and / or paintable in spite of adhesive residues adhering to the manufacturing process.

It is known that release waxes or oils are frequently used for subsequent gluing of a wide variety of molded articles affect or prevent paintwork.

Especially when bonding textile floor coverings with polyurethane backing coatings on screed or wood it was observed that because of the release wax adhering in a very small amount with the commercially available adhesives, E.g. dispersion adhesives based on latex or acrylate, insufficient bonding with the substrate has been achieved.

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When trying to improve the gluability and paintability, it has been found that the addition of emulsifiers, wetting agents and dispersants to the release agents unexpectedly can achieve a substantial increase in the bondability and paintability.

The present invention thus relates to a method to improve the bondability and / or paintability of manufactured using release agents Plastic molded parts, characterized in that the Release agents known per se emulsifiers, dispersants or wetting agents can be added.

One embodiment of the method according to the invention exists in that the emulsifiers, dispersants or wetting agents are not added to the release agent, but afterwards be applied to the molded part.

According to the invention, sodium lauryl sulfonate, adducts of lauryl alcohol and 3-10 mol of ethylene oxide, 3-benzyl-4-hydroxy-biphenyl polyglycol ether, Di-sec-butyl-naphthalene sulfonate, dinaphthyl methanesulfonate and / or adducts of Stearylamine and 4-10 moles of ethylene oxide are preferred.

Also suitable are, for example, polyethers made from oleyl alcohol and approx. 50 mol ethylene oxide, polyesters made from castor oil and ethylene oxide or polyether esters made from abietic acid and approx. 40 mol ethylene oxide.

In general, the following are suitable according to the invention: detergent raw materials such as Texapon® (Na lauryl sulfate, Henkel), alkyl sulfates and sulfonates, fatty acid alkali salts and soaps;

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Emulsifiers and dispersants, such as polyethers or polyether esters from ethylene oxide and oleyl alcohol, oleic acid, lauryl alcohol, abietic acid, castor oil or stearylamine.

When added to the release agent, they make the release agent hydrophilic and thereby improve its wettability with the predominantly aqueous adhesives, without significantly affecting the release effect during the demolding process. When applied subsequently, the good wetting effect ensures that it is evenly distributed on the Surface, which leads to equally good results when gluing or painting.

Depending on the effectiveness of the emulsifiers or wetting agents or their influence on the release effect, they can be used in quantities between 10 and 80% by weight, based on the release agent, can be used. Sufficient for subsequent application mostly small amounts, e.g. 10% by weight based on the release agent, which is sprayed on in the form of aqueous solutions, -be painted or -brushed.

The starting components to be used according to the invention for the production of the molded bodies are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, as described, for example, by W.Siefken in Justus Liebigs, Annalen der Chemie, 562, pages 75 to 136, for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate and

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any mixtures of these isomers, 1-isocyanato-3,3,5 ^ trimethyl-5-isocyanatomethyl-cyclohexane (DAS 1 202 785, American patent 3 401 190), 2,4- and 2,6-hexahydrotolylene diisocyanate and any mixtures of these isomers , Hexahydro-1,3- and / or -A , 4-phenylene diisocyanate, perhydro-2,4 ¹ - and / or ^^ '- diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2, 4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-disocyanate, naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ', 4 "- triisocyanate, polyphenyl-polymethylene-polyisocyanates, as obtained by aniline-formaldehyde condensation and subsequent phosgenation and described, for example, in British patents 874 430 and 848 671, m- and p-isocyanatophenylsulfonyl isocyanates according to American patent 3 454 606, perchlorinated aryl polyisocyanates, such as those in German Auslegeschrift 1 157 601 (American patent 3 277 138 ) are described, polyisocyanates containing carbodiimide groups, as described in German patent specification 1,092,007 (American patent specification 3,152,162) , diisocyanates as described in American patent specification 3,492,330, polyisocyanates containing allophanate groups, as described, for example, in British Pat Patent specification 994 890, the Belgian patent specification 761 626 and the published Dutch patent application 7 102 524 are described containing isocyanurate groups

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Polyisocyanates, such as are described, for example, in American patent specification 3,001,973, in German patents 1,022,789, 1,222,067 and 1,027,394, as well as in German laid-open specifications 1,929,034 and 2,004,048, polyisocyanates containing urethane groups, as described in sB in Belgian patent 752 261 or in American patent 3 394 164, polyisocyanates containing acylated urea groups according to German patent 1 230 778, polyisocyanates containing biuret groups, such as those described, for example, in German patent 1 101 394 (American patents 3 124 605 and 3,201,372) and in British patent specification 889 050, polyisocyanates prepared by telomerization reactions, as described, for example, in American patent specification 3,654,106, polyisocyanates containing ester groups, as described, for example, in British patents 965,474 and

Are 1,072,956, referred to in United States Patent Specification 3,567,763 and in German Patent 1,231,688, reaction products of the abovementioned isocyanates with acetals according to German Patent 1,072,385, polymeric fatty acid radicals containing polyisocyanates according to the American patent 3,455,883.

It is also possible to use the isocyanate group-containing distillation residues obtained in the technical production of isocyanates, optionally dissolved in one or more of the aforementioned polyisocyanates to be used. It is also possible to use any desired mixtures of the aforementioned polyisocyanates to use.

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The technically easily accessible polyisocyanates, for example 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers ("TDI"), polyphenyl-polymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and are particularly preferred subsequent phosgenation are produced ("crude MDI") and carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups and polyisocyanates containing biuret groups ( ^II modified polyisocyanates ").

To be used according to the invention for the production of the moldings Starting components are also compounds with at least two isocyanate-reactive hydrogen atoms of a molecular weight usually from 400-10,000. This includes amino groups, thiol groups or Compounds containing carboxyl groups, preferably polyhydroxy compounds, in particular two to eight Compounds containing hydroxyl groups, especially those with a molecular weight of 800 to 10,000, are preferred 1000 to 6000, e.g. at least two, usually 2 to 8, but preferably 2 to 4, hydroxyl groups Polyester, polyether, polythioether, polyacetals, Polycarbonates and polyester amides, such as those used for the production of homogeneous and cellular polyurethanes are known per se.

The polyester containing hydroxyl groups in question are, for example, reaction products of polyvalent, preferably divalent and possibly additionally trivalent Alcohols with polybasic, preferably dibasic, carboxylic acids. Instead of the free polycarbonate

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acids can also be the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof for the preparation the polyester can be used. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted, e.g. by halogen atoms, and / or unsaturated be.

Examples include: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrachlorophthalic anhydride, a mixture of trimachlorophthalic anhydride, a mixture of tri-chlorophthalic anhydride, a mixture of oleic, maleic anhydride, and with monomeric fatty acids, dimethyl terephthalate and bis-glycol terephthalate. Examples of polyhydric alcohols include ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), hexanediol (1,6), octanediol (1, 8), neopentyl glycol, ^ γΐΐοΈ ^ ¥ η ^ -ΐ ^ βΐίΐΑη.αΐχΐ ^ 4-BrsHrydroxymethylcyclohexan), 2-Methy 1-1, 3-propanedicrt> Glycerin, Trimethylolpropane, Hexanetriol- (J, 2,6), ButantrjLol- (1, 2,4), tri- ^ --__ methylolethane, pentaerythritol, quinitol, mannitol and sorbitol, methyl glycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, and dibutylene glycols, and dibutylene glycols. The polyesters can have neutral terminal carboxyl groups. Polyesters made from lactones, for example ε-caprolactone or hydroxycarboxylic acids, for example Ui-hydroxycaproic acid, can also be used.

The polyethers which can be used according to the invention and which contain at least two, generally two to eight, preferably two to three, hydroxyl groups are also those of the type known per se and are, for example, by poly-

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merlsation of epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, for example in the presence of BF ₃ , or by adding these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as water, alcohols, ammonia or Amines, for example ethylene glycol, propylene glycol- (1,3) or - (1,2), trimethylolpropane, 4,4'-dihydroxydiphenylpropane, aniline, ethanolamine or ethylenediamine. Sucrose polyethers, as described, for example, in German Auslegeschriften 1,176,358 and 1,064,938, are also suitable according to the invention. In many cases those polyethers are preferred which predominantly (up to 90% by weight, based on all OH groups present in the polyether) have primary OH groups. Also polyethers modified by vinyl polymers, such as those "for example by polymerizing styrene and acrylonitrile in the presence of PolyJithjirA ^ iffclPtllhl ^ n ^
3 383 351, 3 304 273 ^ -3-5τ2Τ ° Ο9Τ, 3 110 695, German ^ '

are suitable, as are polybutadienes containing OH-ppenes.

Among the polythioethias are in particular the condensate sationsproduk ^ ts- ^ of thiodiglycol - with aigja ^ & eibaf and / oder'mxCanderen glycols, dicarboxylic acids, formaldehyde, Aminocarboxylic acids or amino alcohols listed. Depending on the co-components, these are the products to polythio mixed ethers, polythioether esters or polythioether ester amides.

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As polyacetals come e.g. those from glycols, such as diethylene glycol, triethylene glycol, 4,4'-dioxäthoxydiphenyldimethy! Methane, Hexanediol and formaldehyde preparable compounds in question. Also through polymerization cyclic acetals can be produced according to the invention suitable polyacetals.

Polycarbonates containing hydroxyl groups are those of the type known per se, e.g. by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol or tetraethylene glycol with diaryl carbonates, e.g. diphenyl carbonate, or phosgene can be produced.

The polyesteramides and polyamides include, for example, the predominantly linear condensates obtained from polybasic saturated and unsaturated carboxylic acids or their anhydrides and polybasic saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures. - ^ "

Also already containing urethane or urea groups Polyhydroxy compounds and optionally modified natural polyols, such as castor oil, carbohydrates or starch, can be used. Addition products of alkylene oxides with phenol-formaldehyde resins or also of urea-formaldehyde resins can be used according to the invention.

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Representatives of these compounds to be used according to the invention are e.g. in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology ", written by Saunders-Frisch, Interscience Publishers, New York, London, Volume I, 1962, pages 32-42 and pages 44-54 and Volume II, 1964, pages 5-6 and 198-199, as well as im Plastics manual, Volume VII, Vieweg-Höchtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. on pages 45-71. '

Mixtures of the abovementioned compounds with at least two opposite isocyanates can of course be used reactive hydrogen atoms with a molecular weight of 400-10,000, e.g. mixtures of polyethers and polyesters, are used ^ - ^ __

Compounds with at least two isocyanate-reactive hydrogen atoms and having a molecular weight of 32-400 are also suitable as starting components which can optionally be used according to the invention. In this case too, maoTflerm ^ e ^ Hj ^ roxYJLgruppen and / or amino groups and / or thiol groups and / or compounds containing carboxyl groups, preferably compounds containing hydroxyl groups and / or amino groups, which serve as chain extenders or crosslinking agents. These compounds generally have 2 to 8 isocyanate-reactive hydrogen atoms, preferably 2 or 3 reactive hydrogen atoms.

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Examples of such compounds include: ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), pentanediol (1,5), hexanediol (1,6), octanediol (1,8), neopentyl glycol, 1,4-bishydroxymethyl-cyclohexar., 2-methyl-1,3-propanediol, Glycerine, trimethylolprpane, hexanetriol- (1,2,6), trimethylolethane, Pentaerythritol, quinitol, mannitol and sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, Polyethylene glycols with a molecular weight of up to 400, dipropylene glycol, polypropylene glycols with a molecular weight up to 400, dibutylene glycol, polybutylene glycols with a molecular weight of up to 400, 4,4'-dihydroxydiphenylpropane, Di-hydroxymethyl-hydroquinone, ethanolamine, diethanolamine, triethanolamine, 3-aminopropanol, Ethylendiamine, 1,3-diaminopropane, i-mercapto-3-aminopropane, 4-hydroxy- or -amino-phthalic acid, succinic acid, Adipic acid, hydrazine, N, N'-dimethylhydrazine, 4,4'-diaminodiphenylmethane, tolylenediamine, methylenebis-chloroaniline, Methylene-bis-anthranilic acid ester diaminobenzoic acid ester and the isomeric chlorophenylenediamines.

In this case too, mixtures of different compounds with at least two opposite isocyanates can be used reactive hydrogen atoms with a molecular weight of 32-400 can be used.

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According to the invention, however, polyhydroxyl compounds can also be used are used in which high molecular weight polyadducts or polycondensates in finely dispersed or dissolved form are included. Such modified polyhydroxy! Compounds are obtained if Polyaddition reactions (e.g. conversions between polyisocyanates and amino-functional compounds) or polycondensation reactions (e.g. between formaldehyde and phenols and / or amines) directly in situ in the above-mentioned compounds containing hydroxyl groups. Such procedures are for example in the German Auslegeschriften 1 168 and 1 260 142, as well as the German Offenlegungsschriften 2,324,134, 2,423,984, 2,512,385, 2,513,815, 2,550,796, 2,550,797, 2,550,833, and 2,550,862. It is but also possible according to US Pat. No. 3,869,413 or German Offenlegungsschrift 2,550,860 aqueous polymer dispersion with a polyhydroxyl compound to mix and then to remove the water from the mixture.

When modified polyhydroxy compounds of the type mentioned above are used as starting components in the polyisocyanate polyaddition process, polyurethane plastics with significantly improved mechanical properties are formed in many cases.

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According to the invention, water and / or volatile organic substances can also be used as blowing agents. Organic blowing agents include acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, Monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, also butane, hexane, heptane or diethyl ether are possible. A propellant effect can also be achieved by adding at temperatures above room temperature with the elimination of gases, for example nitrogen, decomposing compounds, e.g. azo compounds such as azoisobutyronitrile will. Further examples of propellants as well as details on the use of propellants can be found in the Kunststoff-Handbuch, Volume VII, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 108 and 109, 453 to 455 and 507 to 510.

According to the invention, catalysts are also often used. Catalysts which can also be used are those of the type known per se, for example tertiary amines, such as triethylamine, tributylamine, N-methyl-morpholine, N-ethyl-morpholine, N-cocomorpholine, N, N, N ¹ , N'-tetramethyl-ethylenediamine , 1,4-diaza-bicyclo- (2,2,2) -octane, N-methyl-N'-dimethylaminoethyl-piperazine, N, N-dimethylbenzylamine, bis- (N, N-diethylaminoethyl) adipate, N, N-diethylbenzylamine, pentamethyldiethylenetriamine, Ν, Ν-dimethylcyclohexylamine, N ₁ N, N ¹ , N ¹ -tetramethyl-1,3-butanediamine, Ν, Ν-dimethyl-β-phenylethylamine, 1,2-dimethylimidazole, ^ 2-methylimidazole . Mannich bases, known per se and composed of secondary amines, such as dimethylamine, and aldehydes, preferably formaldehyde, or ketones such as acetone, methyl ethyl ketone or cyclohexanone and phenols, such as phenol, nonylphenol or bisphenol, can also be used as catalysts.

Hydrogen atoms active towards isocyanate groups tertiary amines as catalysts are e.g. triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyl diethanolamine, N, N-

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Dimethyl ethanolamine and their reaction products with alkylene oxides, such as propylene oxide and / or ethylene oxide.

Silaamines with carbon-silicon bonds are also used as catalysts, as described, for example, in German patent specification 1 229 290 (corresponding to American patent specification 3,620,984) are in question, e.g. 2,2,4-trimethyl-2-silamorpholine ι, 3-diethylaminomethyl-tetramethyl-disiloxane.

Nitrogen-containing bases such as Tetraalkylammonium hydroxides, also alkali hydroxides such as sodium hydroxide, alkali phenolates such as sodium phenolate or Alkali alcoholates such as sodium methylate are suitable. Also hexahydrotriazines can be used as catalysts.

According to the invention, organic metal compounds, in particular organic tin compounds, can also be used as catalysts be used.

The organic tin compounds are preferably tin (II) salts of carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate and the tin (IV) compounds, for example dibutyltin oxide, dibutyltin dichloride, ibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate are suitable. It goes without saying that all of the abovementioned catalysts can be used as mixtures.

Further representatives of catalysts to be used according to the invention and details of the mode of action of the catalysts are described in the Kunststoff-Handbuch, Volume VII, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Hünchen 1966, for example on pages 96-102.

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The catalysts are generally used in an amount between about 0.001 and 10% by weight, based on the amount of compounds having at least two isocyanate-reactive hydrogen atoms and a molecular weight of 400 to 10,000.

According to the invention, surface-active additives such as

Emulsifiers and foam stabilizers can also be used. Suitable emulsifiers are, for example, the sodium salts of castor oil sulfonates or salts of fatty acids with amines such as oleic acid diethylamine or stearic acid diethanolamine. Alkali or ammonium salts of sulfonic acids such as, for example, of dodecylbenzenesulfonic acid or dinaphthylmethanedisulfonic acid or of fatty acids such as ricinoleic acid or of polymeric fatty acids can also be used as surface-active additives.

Particularly suitable foam stabilizers are polyether siloxanes, especially water-soluble representatives. These compounds are generally structured in such a way that a copolymer of ethylene oxide and propylene oxide is bonded to a polydimethylsiloxane radical. Such foam stabilizers are described, for example, in American patents 2,834,748 _t 2,917 and 3,629,308 .

According to the invention, reaction retarders such as acidic-reacting substances such as hydrochloric acid or organic acid halides, cell regulators of the type known per se such as paraffins or fatty alcohols or dimethylpolysiloxanes, and pigments or dyes and flame retardants of the type known per se, such as trischloroethyl phosphate, tricresyl phosphate or ammonium phosphate, can also be used and polyphosphate, also stabilizers against aging and weathering influences, plasticizers and fungistatic and bacteriostatic substances and fillers such as barium sulfate, kieselguhr, carbon black or whiting chalk can also be used.

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Further examples of optionally also to be used according to the invention surface-active additives and foam stabilizers as well as cell regulators, reaction retarders, Stabilizers, flame-retardant substances, plasticizers, dyes and fillers as well as fungistatic and bacteriostatic Active substances as well as details about the uses and effects of these additives are in Kunststoff-Handbuch, Volume VI, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on the Pages 103 to 113 described.

The reaction components are according to the invention after one-step process known per se, the prepolymer process or the semi-prepolymer process, websi one often makes use of machine facilities, e.g. those in the American patent specification 2,764,565. Details of processing facilities, which can also be considered according to the invention are published by in the Kunststoff-Handbuch, Volume VI Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 121 to 205.

According to the invention, the moldings are produced in Forms carried out. It will

Entered reaction mixture in a form. Metal, e.g. aluminum, or plastic is used as the molding material, e.g. epoxy resin. The foamable reaction mixture foams up in the mold and forms the molded body. The foam molding can be carried out so that the molded part has a cell structure on its surface, it but can also be carried out so that the molded part has a compact skin and a cellular core. According to the invention one can proceed in this connection in such a way that one enters so much foamable reaction mixture into the mold that the foam formed just fills the mold. Man but can also work in such a way that you get more foamable

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Reaction mixture enters the mold than is necessary to fill the mold interior with foam. In the latter The case is thus worked under "overcharging"; such a procedure is e.g. from the American Patents 3,178,490 and 3,182,104 are known.

In the production of the moldings described, "external release agents" known per se, such as silicone oils, used. In addition, so-called "internal release agents" can also be used, such as those from German Offenlegungsschrift 2 121 670 and 2 307 have become known.

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example 1

A carpet fabric was reversed with a polyurethane backing using a release agent (solution ^ of a polyethylene wax in trichloroethane; Acmos:
Bremen) provided.

chloroethane; Acmosil ^w 180 V from Acmos Tietjen & Co.,

5 cm wide strips of this carpet were untreated and after applying and drying a 10% aqueous solution of an emulsifier (polyether made from oleyl alcohol and ethylene oxide) on the polyurethane back with carpet adhesive (Thomsit ^ Universal, Henkel) glued to chipboard.

In the untreated case, 2-3 kp adhesive strength were measured on the strips after 3 days using a spring balance. the Back coating peeled off smoothly.

The samples treated with emulsifier, on the other hand, showed between 8 and 12 kp adhesive strength, with in most cases the backing was torn.

Example 2

®- "^ 180 V were mixtures

(Ri (R

between Acmosil \ Iy and a 10% solution of Texapon ¹ in 1,1,1-trichloroethane in the ratios 2: 1, 1: 1 and 1: 2 used as a release agent. The adhesive strengths

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ao

increased from 5 to 8 to 12 kp according to the increasing Texapon proportions.

Example 3

The methods according to Examples 1 and 2 were combined. Even with just 10% Texapon (^) additive to the release agent with subsequent emulsifier treatment, maximum values between 12 and 14 kp can be measured for adhesive strength.

To test the bondability, a universal polyacrylate dispersion adhesive with inorganic was used in the examples Filler and a filled latex dispersion adhesive are used.

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Claims (3)

1 .. A method of improving the bondability and / or painting s bility of prepared using release agents plastic moldings, characterized in that the separating means known per se, emulsifiers, dispersing or wetting agents may be added. 2. The method according to claim 1, characterized in that that the emulsifiers, dispersants or wetting agents are not added to the release agent, but afterwards to the Molded part are applied. 3. The method according to claim 1 and 2, characterized in that as emulsifiers sodium lauryl sulfonate, adducts of lauryl alcohol and 3-10 moles of ethylene oxide, 3-benzyl-4-hydroxy-bipheny1-polyglycol ether, Di-sec-butyl naphthalene sulfonate, dinaphthyl methanesulfonate and / or adducts of Stearylamine and 4-10 moles of ethylene oxide can be used. Le A 17 336 - 20 - 809808/0461 ftoSPECTED