DE1594210A1 - Adhesives and composites and processes for their manufacture - Google Patents

Description

Ec I »PU POKT DE MEMOURS AND COMPANY ■ 10th and Market Streets', Wilmington 98, Delaware, V.StaA

Adhesives and composites and processes for their manufacture

The present invention relates to improved laminating adhesives, composites made therewith and a Process for making such adhesives. In particular, the invention relates to adhesives made from vinyl polymer modified with amine ester for laminating polyvinyl fluoride films to different carrier materials b * w. Documents and a process for their preparation.

Polyvinyl fluoride films are an excellent combination of properties such as weather resistance, abrasion resistance, solvent strength and

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Dirt resistance. In addition, polyvinyl fluoride films can easily be embossed or otherwise post-formed. These and other properties make polyvinyl fluoride films particularly suitable for use in composites and particularly as a weather-resistant, abrasion-resistant, easily cleanable, post-formed top layer with composites, but polyvinyl fluoride films are very difficult to adhere to these materials.

Most usually technically based on the formation of composites Adhesives used have relatively poor adhesive bond strength when used for laminating polyvinyl fluoride films to other substrates or substrates be used. The first requirement for an adhesive for the composites according to the invention is a*? high adhesion to polyvinyl fluoride films. at The adhesive intermediate layer, preferably not just a strong adhesive bond with the neighboring layers but also have a high cohesive strength. For composites, the thin one, for example about 0.025 - 0.13 ram (1 - 5 mil) contain thick, flexible layers of polyvinyl fluoride film, the polyvinylfluoride should preferably fail » before the adhesive interface fails either in terms of cohesion or in terms of adhesion. If the

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Glue scissors don't go all the way to the edge of the Composite is sufficient or, for example, the composite,

is partially split "or then wiöd" are in elneki such a case, one or both unvarklefefcen Schlohten if "■ - to separate" ^r edge fes adhesive tear take a look töllstindig, ύ eh spread the Schiohtspaltung <.

The 6-ply materials that were developed to improve the bond in composites of polyvinyl fluoride foils generally have one or more of the following disadvantages. If a clear or lightly pigmented film made of polyvinyl fluoride is laminated to a colored, irrigation system, the desired color effect of the sticker is often disrupted * for example by yellowing, other adhesive

wise epoxy glue, offer manufacturing aohwlerglkelten. Some such adhesives have for example in Doppe! packaging \ be supplied which must be genlscht shortly before the production I, while others, such adhesives long waste! bindtents, sometimes at elevated temperatures, require the development of a noticeable bond strength. With other polyvinyl fluoride film composites, splitting, reshaping, and other manufacturing operations cause defects and splitting of the adhesive layer.

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It is therefore an object of the present invention to provide improved To provide laminating adhesives, composites made therewith and a method for making such adhesives. ·.

Another object of the present invention is to Creation of adhesives from modified with amino esters * Vlny! Polymer for laminating polyvinyl fluoride films to various door materials or documents and «Ines Procedure for your manufacture.

Another object of the present invention is Be = Provision of stable adhesives that age longer at elevated temperatures or a hardener for, Ent-. do not require the development of their adhesive strength.

Yet another aspect of the present invention is a convenient and economical method of manufacture ßolo adhesives made from readily available materials below. " Use of ordinary equipment for low pressure processes.

Yet another object of the present invention is that Creation of composites from different materials and polyvinyl fluoride films in which the adhesive layers have both high and high adhesive strength Have KohKslonsicherung that are weatherproof and

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easy to various shapes without losing the Fornen between two-way bondage or -kohHsion! «Ssen · This and other objects of the present invention will be apparent from can be seen in the following statements. . , /

These and other objects of the present invention have been achieved by an adhesive composition comprising a vinyl addition polymer containing monovalent radicals on the carbon-carbon chain of the formula

0 RH
"» I "

-C-O-Z-N ^ R "

" ¹

where Z is an aliphatic hydrocarbon radical with 2 - 3 carbon atoms, R and R ^{1 are} hydrogen atoms or alkyl radicals of 1 - 8 carbon atoms and R * is hydrogen or a non-tertiary alicyl radical with 1 -8 carbon atoms, these being iniNirtlgen Residues are present in such an amount that the aedno-nitrogen content is in the range from about 0.01 to 6.5%, precautionary values 0.1-2 $, based on the weight of the vinyl polyacrylate, in an organic solvent.

In the process of making the adhesives of the present invention, at least two Ilthylenisoj »unsaturated · _}

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polymerizable monomers, of which at least one Contains free carboxyl groups, converted into an "organic solvent UB to produce a solution of a vinyl addition polymer containing free carboxyl groups bonded to the carbon-carbon chain" and about 75-3QQJf the free carboxyl bound to the carbon-carbon chain of the vinyl polymer for complete esterification groups theoretically required amount of an alkylenimine with 2-3 carbon atoms in the cyclic ring are su the Solution of the vinyl polymer added to the carboxyl groups of the vinyl polymer into amino-substituted ester groups via feed, the copolymerizable monomers in such Quantities are combined »that the acid equivalent of the polymer obtained about 0.01-6.0 milliMqulvalent per oram and preferably about 0.1-1.5.

The composite materials according to the invention contain a carrier or, a base, a preformed sole of polyvinylfluoride film, at least one of the surfaces of which is chemical was activated, and between the carrier and the activated surface an intermediate layer of the invention Adhesive polymer.

The adhesives according to the invention from with amine ester. modified Vinylpolyraerlsat belong to the most diverse types.

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The for use in the manufacture of the strongly bound » weatherproof composites of polyvinylfluoride films Polymers generally preferred with various carriers are those in volatile, organic solvents soluble aoryl ester resins, which are mainly composed of acrylic acid and / or methacrylic acid lower alkyl (C 1 -C 6) ester units are composed, some of which amlnoeubetltuiert Alkyl radicals of one of the following formulas

(*} -CH ₂ -CH ₂ -NH ₂ (b) -OH ₂ -CH-NH ₂ (c) "CH-CH ₂ -NH ₂

which are present in sufficient concentration "to" result in polymer with a content of 0.1-2.0 % amino carbon, based on the weight of the polymer. The preferred polymers can be predominantly either from the lower alkyl ester of acrylic acid or methacrylic acid or from various mixtures of acrylic and methacrylic acid esters! » be composed, but those polymers which contain high proportions (50-99%) of C ₁ -Co alkyl esters of methacrylic acid are particularly preferred.

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To be used as adhesives for laminating polyvinyl fluoride films to be suitable for a carrier material should be a mit Amino ester-modified vinyl polymer have a molecular weight of at least 120,000 and preferably a molecular weight in the range of 150,000-200,000.

The polymer should be at least about 5 % soluble in a volatile organic solvent with a boiling point of less than about 175 ° C. at room temperature. Preferably the polymer is about 20 - 60% at room temperature in one or a mixture of several readily accessible "inexpensive alcohols, esters, ketones, hydrocarbons or halogenlerten hydrocarbons having a boiling point of less than about 150 * C löslloh. Polymers with very high molecular weights, ie above about 1,000,000, are generally too insoluble for practical use in adhesives used as solvents, while polymers with molecular weights below about 120,000 have unsatisfactory adhesive and carbonic strength. The polymers of higher molecular weight can be used with advantage in lamination processes in which a melt is used or the adhesive is sprayed on by plaque, or in the preparation of dispersions of "stoving" enamel * and the like. The low-molar polymers

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kulargewioht can be used in combination with hydrophobic crosslinking agents, which increase your molecular weight and your carbon dioxide and adhesion strength. which have a Qlae transition temperature in the range of kO -125 * C. Those polymers which have low Olaa transition temperatures in the range from -60 to 40 ° C are, however, as high-strength, water-resistant, pressure-sensitive adhesives or for combination with crosslinking adhesives, for example an epoxy resin or an organic diisocyanate, for the formation of curable adhesive compositions for use in the Making weather resistant polyvinyl fluoride composites quite useful. Such polymers with a low transition temperature can be modified to form an adhesive with good adhesion - and carbon fiber strength by comparing them with polymers with high transition temperatures.

An essential structural feature of the inventive aminoside vinyl polymers is that they contain amino groups contain that carry at least one hydrogen atom from a bulky tertiary alkyl group, such as a tert-butyl group bonded to the amino nitrogen atom,

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unhindered 1st. Another structural feature which seems to contribute to the high adhesion capacity of these polymers is that the hydrogen-bearing amino groups are located at a considerable distance from the carbon-carbon chain of the polymer molecule. It is believed that the hydrogen atom of the amino groups promotes adhesion through hydrogen bonding to active sites on the surface of the materials with which they are in contact. The polymers according to the invention are outstanding adhesives, since the water atoms of the amino groups are not easily susceptible to hydrogen bonding, since they are bound unhindered and flexibly by the ester residue to the polymer at a noticeable distance from the more rigidly fixed polymer chain. Their unusually high degree of hydrolytic stability, ie of water resistance, which these polymer adhesives possess, is due to the insulating effect caused by the polymer chain, which does not contain any moisture-attracting bonding atoms, such as oxygen, nitrogen or sulfur, but rather is hydrocarbon-like and therefore rather hydrocarbon-like is.

Ee is not only required that the amino groups of the with amino ester modified vinyl polymers of the present invention have unhindered hydrogen atoms, but it is also preferred that the polymer at least

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contains at least about 0.1% amino nitrogen in order to provide the high adhesive strength required for polyvinyl fluoride film composites. It should be pointed out, however, that vinyl polymers modified with amino esters with a content of 0.01-0.1% amino substance have considerably better adhesion properties than the corresponding unmodified vinyl polymers. In general, polymers with a content of more than about 2.0 % amino substance have good adhesive properties in the absence of moisture, but lose much of their adhesive strength in the presence of moisture, especially at high temperatures. Apparently a large number of excess amino groups in the polymer molecule greatly increases its affinity for water, even though the polymer is insoluble in water. However, it should be noted that such polymers can be produced by mixing η with crosslinking agents, such as, for example, epoxy resins ov. r organic diisooyanates, made water-resistant.

In general, it is preferred that the amino ester modified vinyl polymers have no free carboxyl groups attached to the polymer chain, or any other release groups, such as hydroxyl or thiol groups attached to the ester residues or to the alkyl residues attached to the amino nitrogen, own. However, it has been found that polymers that either

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Contain hydroxyl groups or carboxyl groups in an amount which is equal to or less than the number of amino groups are quite satisfactory. Vinyl polymers modified with amino esters, about the same number of amino groups and free carboxyl groups have outstanding hydrolytic stability because they as a result crosslink a salt formation between the polymer molecules, when applied to a surface as an adhesive composition from a solution in an organic solvent will. Solutions of such polymers, however, are very viscous and tend to form oes and are therefore more difficult to handle, store and apply in thinner soles than the preferred adhesive polymers of the present invention. Such self-crosslinking polymers prove to be useful in the preparation of strongly adhering, tough coatings for metals and the like.

The preferred general process for producing the adhesives according to the invention from vinyl polymer modified with amino ester consists in first producing a vinyl polymer which contains sufficient free carboxyl groups, bound to the polymer chain, to ensure that the polymer has an acid milli equivalent of 0.1 - 1.5 have, and then part or the oesamthelt of the free carboxyl groups by reacting the polymer with 0.5-1.0 molar equivalents of any alkylene imine

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with 2 - ^ k carbon atoms in the oyo Ii see ring to form a polymer with an amino substance content of 0.1 * 8 * 0 % .

The acidic Zwisohenpolymerisate are preferably prepared by "ine α, β-unsaturated acid Kthyleniaoh with one or more vinyl monomers in a oopolymerislerbaren" verhtUtniemässig low boiling (75-130 ⁰ C) organic solvent is brought together, IGT about a 80 to 6O- £ To obtain a solution of the monomer mixture and then the monomers are polymerized by adding a polymerization catalyst and heating the Oemlsohs at the reflux temperature of the solution at atmospheric pressure with the exclusion of oxygen from the system by continuously flushing the reaction vessel with nitrogen or other inert oases. After the polymerization reaction has practically ended, the resulting solution of the acidic polymer is cooled to room temperature and samples are removed to determine the viscosity, molecular weight, SCure value, etc. of the polymer.

The esterification of the free carboxyl groups of the polymer is then carried out by adding an appropriate amount of an alkylenimine to the cold solution, the cold one

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The solution is kept in motion for about 15-60 minutes and then the esterification is carried out by 3 to 6 hours Heating the solution at 60 * C is completed. The resulting solution of the polymer modified with amino ester is then cooled to room temperature, samples are taken to determine the bound amino nitrogen, and the solution is used without further modification or Stored cleaning until needed for use as an adhesive mass in the manufacture of composites. Such solutions are stable and stable for long periods of time show little tendency to form oil, although they show traces of unreacted monomers and nitrogen-containing by-products in addition to small amounts of decomposition products from the polymerization catalyst. The alino ester groups attached to the vinyl polymer molecule also show no tendency to use hydroxy-substituted aaid groups to form, as is the case, for example, with aeinoesters of aonomic acids (cf. J. A. C. S., Volume 73-3. 5773; J. A. C. S., Volume 78, p. 907 and J. Org. Chem., Volume 9, P. 502). This prevents sterile hindrance of the polymer chain that a rearrangement of the amide takes place, since these adhesives hold their own good adhesion properties Maintained after long storage.

It should be noted that it is in view of the great inclination

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"totally unexpected 1st erleieren (see. Interohemioal Corporation's New Product Bulletin" Propylene imines ", p.2) _f because ·" of alkyleneimines, In Qegenwart saying a sohwaohen acid, such as carbonic acid to homopoly alkyleneimines polymers with carboxyl groups of vinyl react with the formation of the invention compounds modified with amino ester polymers, Auaserdea it is completely unexpected "that the inventive terminated polymer product forms solutions with satisfactory viscosities and not highly viscous solutions or gelatinous masses, since it would be assumed" that crosslinking between the polymer chains would occur during the imination reaction .

From the above, it can be seen that the Adhesive polymer according to the invention very quickly, easily and economy both on a large scale and on a large scale small seeds: m can be produced, since no highly specialized working methods or systems are required. This is the most legendary «to known processes for the production of vinyl polymers modified with amino esters, for example, by ammoniation of olyloidylethaorylate polymers, which cause a longer-lasting Hoohdruokreaktlon for the introduction of the amlno group and a subsequent Vacuum scraper to remove excess ammonia Requires (see above Patent 2,949,445).

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The generally preferred acidic monomers are the introduction of carboxyl groups into vinyl polymer leashes at the end of the process Conversion into amino ester groups are α, ß-monotthylenieoh unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and 5-butenoic acid, of which Acrylic acid and methacrylic acid are particularly preferred. It should be noted, however, that polymerizable, unsaturated dicarboxylic acids, such as itaoonic acid, Citraconic acid and maleic acid, or the anhydrides of such acids, can also be used in the vinyl polymer can be introduced and later hydrolyzed to form the required free carboxyl groups.

The preferred class of alkylene imines or conversion of the free carboxyl groups of a vinyl polymer to amino ester groups bind the 1,2-alkylene imines (aziridines), which have a free hydrogen atom on the hydrogen atom. Among these linen bindings, ethylene imine and 1,2-propylene imine are particularly avoided because of their accessibility and relatively low costs. N-alkyl-substituted 1,2-alkyleneimines can also be used. OewUneohtenfalls, N-alkylsubstltuierte or unsubstltuierte 1,2-Alkylenlmlne (Azetidines) door delivery of Amlnoestergruppen also be used as din solohelsdne 1,2-Imlhen in their ohenleohen reactivity and your · "properties ähnlioh Bind. For examples of

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these compounds include 2-methylaziridine, 2-ethylaziridine, 2-n-propylaziridine, 2-Ieopropylaziridine, 2-n-butylazirldine, 2-Ieoinitylaziridine, 2-seo.-Butylaziridine, 2 ~ (1 ~ methylbutyl) ~ aziridine, 2- (a-methylbutyl) -aziridine, 2 - (> methylbutyl) -azlrldln, 2-n-pentylazlrldine, 2- (1-methylpentyl) aziridine, 2- (2-methylpentyl) aziridine, 2- (3-ethylpentyl) aziridine, 2- (4-methylpentyl) aziridine, 2- (3-methylpentyl) aziridine, 2- (2-Isopropylpentyl) aziridine, 2-n-hexylaziridine, 2-n-heptylazirJLdin, 2 = n ° 0otylaziridine, 2,3-dimethyiaziridine, 2,> - Di »(2-raethylbutyl) aziridine, 2 ° ethyl» 5-n-hexylaziridih, 2 "n ~ OGtyl" 5-propylaziridine and the corresponding azetidines, such as, for example, 2-methylazetidine, 2-ethylazetidine, 2-n-propylazetidine, 2,4-dimethylazetidine, 2,4-di-n-octylazetidine, 2,3-di "(2-methylbutyl) acetylin.

The preferred amino ester modified vinyl polymers of the present invention are those which predominantly from lower alkyl esters of acrylic acid and / or Methacrylic acid are composed, but it should be noted that the exact composition of the vinyl polymer composition is not critical. The polymer must, however which have already enumerated properties and characteristics. Examples of vinyl monomers used as the main constituent of the vinyl polymers according to the invention include derivatives of α, β-unsaturated acids

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Einsehliesslioh methyl aorylate, Äfchylaorylat, propyl acrylate, tert-butyl acrylate, methyl methaorylate, ethyl methaorylate, Butyl methaorylate, ethyl-o-chloroacrylate, xthyl-a-phenylaorylate, dimethyltaoonate, xthyl ° ec ~ methoxy aorylate, propyl-α-oyanoaorylate, hexyl-a-methylthioacrylate, cyolohexyl-a-phenylsulfenyl-a-phenylsulfenyethyl-butylate, , Butyl-ß-methoxy aorylate, Cyolohexyl-ß-ohloraorylate, aorylataid, α-phenylaorylamide, Methacrylamide, Ν, Ν-DiraethylGcrylamid, N-Cyelohexylmethacryl * amide, It ac on amid, acrylonitrile, crotonitrile, a-chlorooryl «'" nitrile, methacrylonitrile, a-panconlacrylonitrile, N-phenylmaleimide, M-butyl itaconimide and mixtures thereof; Vinyl derivatives, such as for example vinyl acetate, vinyl benzoate, vinyl plmelate, Vinyl stearate, vinyl methyl ether, vinyl butyl ether, vinyl phenyl sulfide, vinyl dodeoyl sulfide, vinyl butyl sulfone, vinyl cyclohexyl sulfone, vinyl chloride, vinyl fluoride, N-vinyl benzene sulfonainld, N-vinylaoetamide, N-vinyloaprolaotam, styrene and vinyl toluene Allyl derivatives, such as, for example, allylphenyl ether, allylcyolohexyl acetate, Ν, Ν-diraethylallylamine, rthylallyloxy acetate, allylbenzene, allyloyanide and allyl ethyl sulfide; Methylene type derivatives such as diethylmethylene malonate, diketone, ethylene glycol ketene aoetal, methylenoyolopentane, vinylidene chloride and vinylidene dieulfones; spank · » those compounds, such as vinylene carbonate, Aoroleinaoetals, Methylvinylketon «, Vinylphoephonate, Allyl-

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phosphonates, vinyltrialkoxysilanes; and unsaturated hydrocarbons, such as ethylene, propylene, butadiene and the like.

Although it is preferred to produce the amino ester substituted vinyl polymers according to the invention from preformed vinyl polymers which do not contain amino groups but contain reactive groups which can be converted into amino ester groups, it should be pointed out that the vinyl polymers according to the invention are also produced directly from monomer genes which contain a monomer which possesses the desired amino ester groups. The Polymftrisationsoharge contains one of the many known vinyl polymerization catalysts, such as an azo compound or an organic peroxy ^{compound, e.g. 2.2 e} -A7, odiisobutyronitrile or cumene hydroperoxide, but the polymerization can be carried out without a catalyst if the time span required to complete the reaction is not large Role play. Unusually, the preformed acidic polymer can be prepared by emulsion polymerization of the vinyl monomer in water or another non-solvent, then recovered and dissolved in an organic solvent before it is esterified by reaction with an alkyleneimine.

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Because of its low cost, its high volatility and its good dissolving power is the preferred solvent for the adhesive polymer according to the invention a mixture of isopropyl alcohol and toluene in a weight ratio of about JO: 70. The type of solvent, however, it is not critical. Other suitable solvents, either used individually or in mixtures include the usual alcohols, esters, ketones, aromatic hydrocarbons and halogenated hydrocarbons. Examples include methyl, ethyl, n-propyl », η-butyl and higher alkyl alcohols; Methyl, ethyl, propyl, Butyl and higher alkyl acetates and propionates; Acetone, methyl ethyl ketone and diethyl ketone; Benzene and xylenes; and Ethylene chloride, chloroform and carbon tetrachloride.

The ones used in the composites of the invention Pblyvinylflubridaohioht is preferably in the form of a Slide gate. Such sheets of polyvinyl fluoride can be prepared by known methods such as those disclosed in U.S. Patent Drill 2,953,818 and U.S. Patent. ...

(OS patent application Serial No. 801 441 from 24.J.1959) »Ear-rubbed process. One method a mixture of latent LSztatgsaittel and polyvinyl fluoride fed into a heated extruder, which old a slotted tube

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A tough, coalesced (grown together) extrudate of polyvinyl fluoride is continuously pressed out in the form of a film containing latent solvent. The film can simply be dried or heated, heated and stretched in one or more directions while the solvent is removed from it are cast evaporated. films of polyvinyl fluoride may also consist of dilute _f hot solutions of the polymer in a latent solvent as described in US patents 2 Ή9 008 and 2,419,010 describe öewünschtenfalls different farbliohe and opaque effects by incorporating pigments and fillers Examples of pigments and fillers are metal oxides, hydroxides, chromates, silicates, sulfides, "sulfates and carbonates, organic dyes" and soot.

Any surface of the polyvinyl fluoride film that has a other layers of the composite materials according to the invention bonded is to be chemically activated, i.e. capable of surface absorption made by adding functional groups from one or more of the following classes in the surface layer Hydroxyl, carboxyl, carbonyl, amino and amido radicals and ethylenically unsaturated radicals are formed. middle for activating the surface of polyvinyl fluoride films

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are, for example, the action of a gaseous Lewis acid, such as boron trifluoride or aluminum triochloride or titanium tetrachloride, or a liquid composition containing a coordination complex thereof on the foil, the effects of concentrated sulfuric acid, smoking sulfur gura, carbon dioxide or hot Sodium hydroxide on the foil j, treatment of a surface the foil with an open flame while the opposite surface is cooled, and the action of a High frequency spark discharge on the foil,

In particular, for example, films made of polyvinyl fluoride can be replaced by a cover lined with stainless steel to be led by handlers, di <? ain at one temperature from about 20 to 75 * C held, gaseous mixture with a salary of e * · r:! Contains ~ 90 VoUi Boi? Trifluoride. the Lingers' ,, i the Kantmer is usually in the Grössün order of j5 = 30 seconds. I3aeh treatment with dera The resulting film is boron trifluoride either in ammonium hydroxide and washed in water and then air dried or just washed with water and dried or alternatively heated for a short period of time at a temperature of around 100 - 150 ° C.

Another method is to have at least one surface

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the polyvinyl fluoride layer with concentrated sulfuric acid, fuming sulfuric acid or sulfur trioxide, for example about 2 seconds to 1 minute, in contact bring. The product obtained is washed in water and air dried. Preferably the acid solution at a slightly elevated temperature, for example at about 25-95 ° C, kept the required contact time The higher the temperature used, the shorter it is.

Yet another method consists in briefly immersing the polyvinyl fluoride film in a Bortrlfluorld-XthylKtherat-Koraplex, the product obtained with water, Wash with acetone or ethyl ether and then wash the final product air dry. Oa boron / fluoride coordination compounds or complexes of the most varied organic Compounds, especially old amines and compounds containing oxygen, such as Xthers, alcohols, Esters, acids and amides, but other complexes than the one with diethyl ether can also be used, to activate foils made of polyvinyl fluoride ohemiech su · IHe Complexes of boron fluoride with dimethyl ether, methyl ethyl * Ether and phenol are particularly useful because they like the Diethyl ether complex at room temperature fluids are. To increase the dleeociatiociage rate d Complex is preferably slightly elevated temperatures

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is used to reduce the immersion times required to achieve a satisfactory level of chemical activation.

Another example of a method of activating tier The surface of the polyvinyl fluoride layer consists of a sheet of polyvinyl fluoride at one speed from about 50-75 m / minute (100-850 feet per minute) above • To guide a cooled metal roller and in contact with it, while the calibrated not in contact with the roller * surface through a tarpaulin, for example a Plata * a · * with a · »Fropan-Luft-Gemiaoh (1 t 25) stored «Tin gas burner, is performed.

Yet another method of activating the surface The Polyvinylfluorideohioht is the Sohioht one High-frequency spark discharge, preferably in an atmosphere of, for example, nitrogen, ammonia, boron fluoride, Oxygen or air. This can be done, for example, by guiding a polyvinyl fluoride film over a grounded metal roller and in contact with the same with a Speed from about 3 to 90 m / minute (10-300 feet per minute), while the surface distant from the orphan is below and at a close distance [for example, about 0.2 $ - 0.6 mm (0.010 - 0.025 inch)] to the rod designated as Electrode is used and is connected to a Hoohfrequenzweohseletromquelle, is performed. 909834/133 ^

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Examples of supports or supports that can be used in the composites according to the invention are metal supports, such as supports made of iron, steel, gal ~ vanized iron and steel, aluminum, aluminized Steel, chrome, bronze, brass, lead, tin and nickel and various other alloys; Load carriers and other glass-like carriers such as earthenware, stoneware and porcelain carriers; impregnated carriers such as cellulose-containing carriers impregnated with asphalt; Hard cardboard and hardboard, such as "Masonite"; Binders «asbestos cardboard and» panels and asbestos-cement panels; Wooden beams, such as beams made of birch, Oak, spruce, pine, fir, cedar, red, poplar and esohen wood; and polymeric carriers such as Carrier made from homopolymeric vinyl chloride and copolymers of this with, for example, vinylidene chloride, Vinyl acetate and fumaric acid, maleic acid and acrylic acid esters, from regenerated cellulose, from acrylic esters, from Urea, melamine »or phenol» formaldehyde resins and from Vinyl acetate »Composite supports, such as supports made of plywood or fabrics that are coated, impregnated, or both, are particularly useful. As In the following examples, shown, metal supports Before lamination, a customary passivation or anti-corrosion treatment, such as the technical for

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Preparation of documents used for painting «and are usually treated as such. Carrier, the metals, materials bound with binders, wood and other cellulosic materials, films fabrics made of vinyl chloride polymer and coated or coated and impregnated fabrics, in particular with vinyl chloride polymer, are particularly preferred. Of course it can a second layer of polyvinyl fluoride is used as the support ■ become.

The composites according to the invention are made by applying a solution of the adhesive polymer in an organic solvent to one or both surfaces of each pair of surfaces to be bonded, drying the adhesive to remove the solvent and heating the product obtained above its transition temperature, ie via the temperature at which the adhesive flows under pressure, and preferably to a temperature which is about 50-200 ^° C. above its glass transition temperature. The surfaces to be bonded by the adhesive mass are brought together and the product obtained is pressed while the adhesive is kept at about the above temperatures. With the preferred aoryl polymers, in a process for producing a laminate according to the invention, for example, the adhesive is applied to the carrier, the adhesive is dried at room temperature for about 10 seconds to 60 minutes, and the coated carrier

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at a temperature of about 125-300 ⁰ C for about 300 -10 seconds, preferably at about 150-250 ⁰ C for about 120 - 10 sec, heated, then a preformed Polyvlnylfluorldschicht immediately applied on the hot adhesive and the laminate obtained by the nip rolls guided. Alternatively, instead of or in addition to the use of nip rollers, the laminate with the helssen adhesive can be placed in a press and kept at a temperature of about 150-75 ° C. for about 1-15 minutes under sufficient pressure to intimately bond the soles to be glued together To bring contact »and preferably held under a pressure of about 1.75-35 at (25-500 pel).

The composites according to the invention can be made of a poly vinyl fluoride layer and a base bonded with a layer of the aforementioned adhesive Layer of an adhesive, the mixtures of the adhesives according to the invention or an adhesive according to the invention, mixed with antioxidants, corrosion inhibitors, pigments, matting agents, ultraviolet absorbing agents Agents, other adhesives, crosslinking agents !! and the like, contains, be glued. The composites according to the invention Of course, two or more polyvinyl adhesives glued together with the adhesive according to the invention can also be used.

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fluorldsohlohten included. Different, alternating layers of carrier and polyvinyl fluoride with Adhesive layers be connected. Bs can also be carriers, that contain two or more layers, such as plywood or coated fabric, are also used

Oils according to the invention have outstanding weather resistance and abrasion resistance and can be cleaned thoroughly. They also have excellent resistance to soaking and good resistance to soiling due to failure of the adhesive even after prolonged exposure to boiling water. Products according to the invention which contain a mouldable carrier, for example a coated fabric or a metal foil, can easily be reshaped into complicated shapes without cracking, even before the adhesive has completely set Means (such as TlO ₂ , soot or baiistthts Einkohroaat) are introduced into the Kisbetoffeohloht in order to improve the weather resistance of the composites or their appearance or to give them other desirable substances. The introduction of an antloxy-OÖ # r an ultravldltttltoht absorbent compound

ORIGINAL BATHROOM

In the Kl # bBtoffschieh is particularly useful when \ clear polyvinyl fluoride foils are laminated on plywood.

The erfindungegeinässen products are due to their. distinguished combination of weather resistance, abrasion resistance, solvent resistance and moldability excellent interlayer adhesion in many fields well usable. In the field of construction technology, both pigmented and clear polyvinyl fluoride films can be used on sub · » lay «such as cold-rolled steel, galvanized and / or aluminized steel, aluminum, plywood, hard cardboard or Hardboard, such as "Masonite", binders 1-asbestos cardboard or panels and asbestos-cement panels and cellulosic panels impregnated with asphalt, for use as walls and / or asphalt for houses and change domestic purposes, as well as technical, industrial and institutional buildings are laminated on. Laminations to metal and wood supports can be used during manufacture of signs and other signs intended for outdoor use, wall panels, wall and ceiling coverings, blinds, interior partitions, awnings and tarpaulins, in line construction, for counter tops and table tops, shop façades, Downpipes and waste pipes are used. Composites of in particular pigmented polyvinyl fluoride films Metal can be reshaped and used to replace enamelled and burned-in walls, ceilings, floors and side parts of

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Devices such as refrigerators, ice machines, Freezers, air conditioners, dryers, hot water heaters, washing machines and dryers, knobs and shelves. In vehicle construction, lamination of clear, metallized and pigmented polyvinyl fluoride films on metal supports can be used in various ways Car door and side panels, hardtops, molded parts, Interior and exterior decorations, instrument falsifications, Wheel covers and hubcaps, wounds and roofs are used for caravans and trucks and luggage carriers. Laminations of polyvinyl fluoride foils to soled or Uncovered fabrics or polyester fibers can be used as deodorant linings, seat covers, floor mats and trunk linings. Other uses include upholstery, flooring, lampshades, and book covers.

The following examples illustrate the invention without it to restrict.

example 1

The following components are in a reactionSgefMsa, that with a stirrer, reflux condenser, TheraoMeter and Nitrogen inlet tube is equipped, introduced

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Parts Methyl methacrylate 97 Methacrylic acid toluene 105 Isopropanol 45

The mixture is stirred at atmospheric pressure: under Nitrogen atmosphere for 3 hours at reflux temperature of the solvent mixture (63 ° C) heated. Then will 0.1 part of a, a ~ azo-bis-isobutyronitrile, dissolved in 10 parts a mixture of toluene and isopropanol (70/30) to the Reaction mixture is added and the polymerization is started continued for another 3 hours. The obtained polymer solution is then cooled to room temperature and by adding 125 parts of a toluene / isopropanol Oemisohes (70/10) diluted. The polymer obtained has an internal Viscosity (inherent viscosity) of 0.17, measured on a 0.5 pound solution in toluene, a acid equivalent of 0.3 * 9 and a molecular weight of about 160,000.

3 parts of 1,2-propyleneimine are added to the cold polymer solution added, and the resulting mixture is stirred for 1 hour at room temperature. The temperature is then increased to 88 ° C, and the resulting solution of the amino ester modified vinyl polymer is increased to room temperature

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cooled down. The solution has been found to contain 29.26 pounds of polymer solids and has an inherent viscosity of 0.57 in a 0.5 pound solution in toluene. A sample of the polymer isolated from the solution has been found to contain 0.48 % bound amino nitrogen.

This solution of the polymer modified with amino ester is used without further modification as an adhesive mass in the Laying of a 0.05 to (2 mil) thick, biaxially oriented, titanium dioxide pigmented polyvinyl fluoride film on 0.655 en (25 mil) aluminum foils in the following manner used

The surface of the polyvinyl fluoride film is made superficial by taking it for 10-20 seconds in a Atmosphere is maintained, which is a heated at 25 - 35 * C Oasgemisoh of air and 1-10 percent by volume boron trifluoride contains. At the end of the day, the film is treated with 5-tiger aqueous Ammonluataydroxyd and then washed with water and dried. One surface of the aluminum foils is treated with a solution of "Äoaderlte" 721 (Parker Rust Proof Corporation), A coating of amorphous chromium aluminum oxide to inhibit corrosion and improve adhesion su form. MftQh drying the treated with "Bonderite" Surface 4 ·· aluminum is the adhesive solution in one Thickness of about 0.01 am (0.4 mil) (trooken base) applied,

Θ09834 / 1331

SAD ORIGINAL

55

the adhesive solvent is allowed to evaporate in air at room temperature for 5 minutes «and the Aluminum foil is then placed in a ventilated oven at 250 ° C for about 1 1/2 minutes to allow removal, of glue! solvent to complete. Direct after the aluminum foil has been removed from the oven, the surface of the foil treated with BF is tinted with that of the melted adhesive-covered surface of the aluminum is brought into contact, and the laminate is placed between two Feed rollers that press at about 7 kg / cm (100 lbs / in.) Pressure are set, led to the two layers in intimate Contact to 'press and exclude air. After cooling, the composite material obtained is subjected to various tests to evaluate the bonding properties of the adhesive and the water resistance of the composite. the Results are as follows

Testing of the adhesive bond strength KNA Immersion test in boiling water 148+ hours

Testing in a test device of the Type Weather = O = -meter (Weather-0-

meter test) ι. ■ '' .- 1000+ hours

Cloud chamber exam: 6+ weeks Postformability test passed.

Adhesive bond strength is a measure of the ease with which a polyvinyl fluoride film can be removed from one

909834/1331

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Carrier after the adhesive has set. The test is carried out by cutting the film layer of the composite with a razor blade in a series of lines spaced 3 * 175 mm (1/8 inch) apart, peeling the ends of the resulting portions of film from the carrier and then trying is to peel off the individual sections of the film from the carrier with the help of pliers. If the 3.175 mm (1/8 inch) sections of the film can be peeled off the backing, the adhesive for use in the continuous manufacture of weatherable composites is unrecognizable, denoted by KE (none), while if the Film sections do not know that they are peeled off the backing, but tear, the bond is considered satisfactory and is denoted by KNA (cannot be peeled off), g / 2.5 ¹ * cm (g / inch ^ applied at an angle of 90 °, expressed, which is required to separate the polyvinyl fluoride film from the carrier] ·

The immersion test in boiling water is an evaluation of the Adhesive bond strength of a composite after continuous boiling of the composite Water for a period of time. To carry out this

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Testing involves exposing a series of samples to boiling water, and from time to time a sample is taken and checked as described above and checked for bubbles. The results are printed out as the tent span that the Sample maintains the bond strength of KNA and does not form bubbles * A composite nut at least 168 pieces in length Withstand exposure to boiling water "to be satisfactory (the previously known composites usually fail after about 1 to 5 hours of exposure to boiling water Water).

The test in a test device of the type Weather-0-aeter (Weather-OHoeter test) is an accelerated weather test in which a type HVDL-X Atlas Weather-One is used. To carry out this test, the composite sample alternately for 1 hour of a water spray 1 «dark« for 2 hours Lioht of a double coal · llohtbogens, a water spray for 2 hours in the dark and then 6 more hours. then the cycle is repeated. The results are all The range of times that the samples can withstand this test without blistering or losing the XMA bond is printed out.

The NebelkawnerprUprüfung is a wet for the assets united

909834/1331

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Composites to withstand exposure to high temperature and humidity. To carry out the P? ν. ν - γ <ι · < Samples <the composite material "In a closed container, exposed to eight and 38 ° C (100 * P) and 100% relative humidity. From time to time, a sample is itnoeroen and examined for blisters, and the bandage igle · It is determined in the tied state. The results are expressed as a period of time. dl · the sample stops without the formation of & ·· »and / or Ver, a« t the Blndefeetigloelt KNA.

The ^ aohforiÄrkelfceprUfuni consists of a "depression""formation in the composite material downwards and naoh whether" n under the direction of spheres with a diameter of 23.4 µm (1 *. Uöd 9.525 «β (5/8 * ) The curvature is then done with a Hasler knob, and an attempt is made to remove the film from the PUtAllunterlage.

The following component "Mird" is incorporated into a reaction, "as old" in "FtUhrir, ROoJcflu" cooler, thermometer nn <i • ti <'kflt9fftinl * ittin * srolir · T, and ^ a * Qefjieoh win! 7 1/2 hours at the RU Jkflusetemperat r of the T # et * UPMBlttels under nitrogen atmosphere.

36.

SAD ORIGINAL

part 15th
10 at the start
After 3 hours Styrene 15th Butyl aorylate 78 Methacrylic acid • 7 toluene 100 α, α-azobisobutyronitrile 0,
0,

When the polymerization reaction is complete, the resulting The solution is cooled to room temperature, then 7 parts of ethyleneimine in 10 parts of toluene are added to the cold polymer solution added, and the mixture is stirred for 1 hour at room temperature and then for 5 hours at 70 ° C. Owns after cooling the resulting solution is found to have an intrinsic viscosity of 0.30 in a 0.5 solution in toluene, an acid equivalent of 0.815 and a polymer solids content of £ 46.5 · The bound nitrogen content of the polymer is 1.10 Ji.

A polyvinyl fluoride pressure sensitive tape is made by applying about 0.3 mm (12 mil) dots of the adhesive solution to one surface of a transparent polyvinyl fluoride film that has been previously surface-received by the application of an electrical hoop voltage discharge, and then at 80 to remove the adhesive solvent ⁰ C is dried. Samples of the resulting tape then become firm against various species

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of materials, including paper, polyethylene, non-streamed plywood, galvanized steel, aluminum, lacquered wood and polyvinyl fluoride film, pressed, and in each case it is found that the tape is attached to the Material is tightly bound. For example, is a Force of 4,220 g / 6.45 om (g / inoh.) Applied to one 90 ° angle required to peel the tape from the polyvinyl fluoride film at 0 ° C. For comparison purposes, a StUok ordinary pressure-sensitive tape (office grade) applied in the same way to a polyvinyl fluoride film, and it is a force of only 1650 g / 6.45 om (g / in.) required to separate the tape and film. The polyvinyl fluoride pressure sensitive tape also retains how is found to be its superior adhesion properties at when there is prolonged tent conditions of high humidity is exposed.

Examples 3-16

Other adhesive compositions are made using Procedures similar to that described in Example 1 prepared by combining various vinyl monomers in an organic solvent, taking the monomer mixture in the presence of a suitable catalyst Formation of a vinyl polymer, containing free carboxyl groups contains, is polymerized and a part or the. entirety

- 58 -909834/1331 bad orig.nal

of the free carboxyl groups is esterified by reacting the polymer with 0.50-1.00 molar equivalent of an alkyleneimine monomer. Each of the resulting solutions of modified with amino ester polymer is then reacted with a volatile, organ * See solvent at 20 - JO% diluted and the production of dressings of Poly * ίν fluoridfollen with sheets or films of the following Mate ¹ Mn used ι QAi van ! Alloy steel, aluminum * Gperrhol « mn polyvinyl fluoride. Before lamination, the surface of the foil is activated by a brief action of a propane flame, while the surface of the galvanized steel is treated in the usual way with a zinc phosphate solution and the surface of the aluminum is passed as described in the example ^{: 1} · the lamination is then effected by applying a thin Sohioht a Klebstofflöeung glelohfunulg the TrHgeroberflXohe in an amount sufficient uir stwa C, 015 - * ⁰⁸ O at {0.6 to 3 nil) nit Aainoester "odKi zierte3 Vinylpolynerlcat absusoheiden applied, the Xiösimgsffllttel then C and then "It flame treated Polyvinylfluorufolit is Srhltsen of Trlgertteteriale in an oven at a temperature of 16O -090 * removed immediately pressed firmly against the coated with glue" rMger the composite sample obtained we-;. then i to Bevertunf 's fitness of the adhesive at the Herst' development of wet '.- *. estluidigen composite tof fen tested the Elnze.

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cure with regard to the production of the adhesive polymers and the test results of the composites are given in the following table «

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909834/1331 ^BAD ofugwal

Vinyl polymer modified with amino ester

example Pre-educated Polymer Alkylene (Amino) Inner j « Monomer " ¹ * and Acid equivalent imin viscosity - * relationship (Milliequiva: (Parts by weight) lent / g) 0.94 5 2ÄHA / MMA / MAS
20/74/6 0.70 1.2 "= -3prcpylenimine 0.65 0.52 «Ο 4th BMA / MfSA / MAS. 0.46 1,2-propylenimiri 0.57 O 50/48/4 0.24 co
00 5 MMA / fiAS 0.549 1,2-propylene imin 0 _f 25 co 97/5 1.09 6 ⁺⁺ BA / NAS 0.815 1,2-propylenirain - ^ _" 8th 95/7 u _t kB cn co * = ■ γ ++ B / S / MAS 0.549 1, 2-Propyleniinin - CO 67/50/5 1.55 8th BMA / MMA / MAS
45'45 / 10 1.17 Ethyleneίmin 0.48 0.24 9 MMA / MAS 0.549 N-methyl! Ethylene = 0.58 97/5 iinin 0.48 10 MMA / MAS 0.549 1,5-propylenimine 0.56 97/5 6.44 to
> 11 ⁺⁺⁺ MMA / MAS 5.71 Ethylene imine 0.57 KD 51/49 O ψ % • μ—

^ t Aminoester modified vinyl polymer

Belsplel Vorgebi .;,: ■ th polymer Alkylene (Amino) Inner j Monomer "*" and Acid equivalent irain viscosity I. relationship (Milliequiva (Parts by weight) lent / g) 0.16 12th MMA / MAS
99/1 0.117 Propyleneimine 0.16 0.25 co 13th MMA / MAS 0.117 Ethylene imine 0.20 O 99/1 0.78 CD
00 14th S / AN / MAS
6 ^ / 30/5 0.58 Propyleneimine 1.09 0.68 ^ j 15th BMA / S / AN / MAS 0.815 Propyleneimine 0.75 - »4s> 38/40/15/7 1.54 u> ro 16 ** Ä / MAS ' "17 Propyleneimine .i. 90/10 0.46 CTl 17th MMA / MAS 0.3 ⁽ '- ^ N- (n-octyl) -1,2- 0.36 CO 97/3. propylenimine 0.46 N) 18th MMA / MAS 0.3 ^ 9 2- (n-ootyl) - . 0.38 O OQ 97/3 ethylene / min 0.56 D. 19th MMA / AS 0.416 1,2-propyleneimine 0.33 O
Tl 97/3 O > r-

Modified with Afflinoestei Vinyl polymer

Example Preformed polymer AIkylen-: # interior ί

Monomer * and acid equivalent ^lRlin ■ Λν \\: .: Lcko; i ^ 5 ratio (milliequiva- (parts by weight) -lent / g)

Control MMA / DMAXMA none none none

A 97/3

Control MHA / t-BAXMA none none none ο, ιί B 97/7

S Control WA / MAS 0.351 none none

S C 97/3

** + The monomers are abbreviated as follows:

J ^ ι 2XHA · 2-ethylhexyl acrylate S «styrene

** * ■ ¹ ^ WA " methyl methacrylate AS" acrylic acid

, MAS * methacrylic acid AN « acrylonitrile

BMA - n-butyl methacrylate X « ethylene

BA «n-Butylaerylat DMAXMA - Dimethylamlnoäthylmethacrylat

B - butadiene t-HAXMA » tert . -Butylaminoethyl methacrylate

⁺⁺ These adhesives are pressure sensitive

The adhesive composition of this example is modified before use by incorporating 20% (based on the weight of the aminoester-modified vinyl polymer) of an epoxy resin ("Epon" 8j54, commercial product of Shell Chemical Co.) as a crosslinking agent *

i-iWT.'W

309S34 / 1311 bad oriq, _nal

Composite "test results

By-carrier
game material aluminum Adhesion
binding
speed Immersion
in boiling
water
(Hours) Postform
barges 3 aluminum KNA 168+ passed 4th plywood KNA 168+ passed 5 PVP polie KNA 168+ passed 6th aluminum 540 g / 2.54 cm
(gin.) - passed 7th galvanized
stole 900 g / 2.54 cm
(g / m.) - passed 8th galvanized
stole KNA 216+ passed 9 aluminum KNA 168+ passed 10 aluminum KNA 168+ passed 11 aluminum KNA 168+ passed 12th galvanized
stole KNA 168+ passed 13th aluminum KNA 168+ passed 14th aluminum ICNA 168+ passed 15th PVP film KNA 168+ passed 16 galvanized
stole 1900 ^ / 2.54 cm
^ r / in. ) - passed 17th aluminum KNA 168+ passed 18th plywood KNA 168+ passed 19th aluminum KNA 168+ passed control
A. aluminum The polyvinyl fluoride film and the supports
were not lost during lamination
sticks control
B. aluminum The polyvinyl fluoride film and
were during lamination "
sticks ntroll
G The polyvinyl fluoride film and
were during the lamination « the porters
i do not dle carrier
i do not

sticks.

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Claims (1)

Claims 1. adhesive mass, characterized by a content of a solution of a vinyl addition polymer which has monovalent radicals of the formula on the carbon-carbon chain O RH
η se "COZNR"
R- Contains bonded, in which Z an aliphatic hydrocarbon ^{radical with 2-3 carbon atoms, R and R 9} hydrogen atoms or alkyl radicals with 1-8 carbon atoms and R "means a Wasi * is ^ Iiafcom or a non-tertiary alkyl radical with 1 ■■ 8 carbon atoms wherein the monovalent radicals are present in an amount such ä & zz the amino nitrogen in the range of about 0.01 to 6.5% "based on the weight of the vinyl polymer, is located, in an organic solvent. 2. Adhesive composition, characterized by a solution of a vinyl addition polymer which has monovalent radicals of the formula on the carbon-carbon chain 909834 / Ί3 ⁶ 3Ί sad O RR HIl -COCC-NH ₂ RR contains bonded, In which R is a hydrogen atom or a Denotes an alkyl radical with 1-8 carbon atoms, the monovalent radicals being present in such an amount that the amino nitrogen content ranges from about 0.1 to $ 2.0, based on the weight of the vinyl polymer, in an organic solvent. 3. Adhesive mass, characterized by one in one Organic solvent-dissolved vinyl monomer-Methylaorylstture-Additlonspolymerisat, which on the carbon-carbon chain monovalent radicals from the group of -CO-CH ₂ -CHg-NH «Ο and * O -CO-CH-CH ₂ -MH ₂ Contains 3 bundles, whereby the · monovalent remainder * are present in an eolahitft mangß »that * der Aalnos ticke toff content la Β · - from about 0.1 - 2 * 0 Jf, based on da »0 * wl <4it das ^; MditionepolymerieatB, lies. BAD ORlG ¹ NAL Af 4. adhesive composition according to claim 3, characterized in that that the vinyl monomer is methyl methacrylate. 5. Adhesive composition according to claim 3, characterized in that the vinyl monomer is a mixture of styrene and butyl acrylate is. 6. A process for producing a polymer, characterized in that at least two ethylenically unsaturated, copolymerizable monomers, at least one of which contains free carboxyl groups, are reacted in a liquid medium to form a vinyl addition polymer which contains free carboxyl groups on the carbon-carbon chain that the acid equivalent of the polymer is in the range of about 0.01 to 6.0 Mi111equivalent per gram, and that the vinyl additlon polymer with about 50-100 % of the complete esterification of the free carboxyl groups theoretically required amount of an alkyleneimine with 2-3 carbon atoms reacting in the cyclic ring, the carboxyl groups of the vinyl polymer in aminosubstituier- te Estergruppen About supplying * 7. The method according to claim 6, characterized in that there is used as alkylene imine Kthyienlmin. '. ■ -'i ^ u ■■ ",, -. . - ■,. : ■■ .- ■■■■. ■ '■. "■ « ■ ■ -_ ■ "- · - ■ .. * ■ -. - .. "■. 8. T * rf Ehrfesi according to claim 6, characterized gekennseiohnet that IMUl ale alkyl «nimin 1 _r 2-propylenirain used. BATH 9. A process for the preparation of a polymer, characterized in that an α, β-ethylenically unsaturated acid and sum at least one vinyl monomer is copolymerized at the reflux temperature of the solvent in an inert atmosphere and in an organic solvent, and so a 20- to 60- $ ige solution of a vinyl addition polymer is obtained which contains free carboxyl groups bonded to the carbon-carbon "chain in such a way that the acid equivalent of the polymer is in the range of about 0.1 = 1.5 milliequivalents per gram, - and that the polymer is with about 50 - 100 $ of the amount of a 1,2-alkyleneimine theoretically required for complete esterification of the free carboxyl groups TO. Procedure according to. Claim J ₁ , characterized in that used as 1,2-alkylene imine lithylenesine. TI .'-. Method according to approached J _e characterized in that "one uses as!, S-alkylsnimine 1 _ff 2-propylenimine, 12. The method according to claim 7 * characterized in that Ban as a _s B = Mth-3rl © niseh unsaturated acid methacrylic acid used. * 1-3 *. Process aur producing a polymer, thereby marked that one is in a Stiekstoffatmöphere and ... ■ - ■■ - 49 «, ■ 909834/1331 - ' · BATH in a mixture of toluene and isopropanol in a weight ratio of 70:30 methyl methacrylate and methacrylic acid copolymerized and thus a 20 = »to 60 = # solution of a methacrylate polymer, which contains free carboxyl groups attached to the carbon-carbon chain, that the acid equivalent of the polymer in Bereiah of about O ₁₁ I - 1.5 Miliiäquivalent depending Grasmn is ₃ and that the polymer with about 50 "100% of the full esterification% e :? free carboxyl groups theoretically required amount of a 1,2-alkyleneamine to obtain a methacrylate polymer diffused with amino esters and having an amine nitrogen content in the range 0.1-2.0 $. 14. Composite material, characterized by a carrier a base ^ a vox'gefoi'Hite layer of polyvinyl fluoride film, Voss ö ©? © a Obe ^ flee at least one chemically ak ^: V-vie ^ t imtr, wia between a & m carrier or the document'ur-: dtes? The fourth surface has a layer of adhesive that contains a vinyl polymer with monovalent radicals of the formula on the carbon-carbon chain 0 RH 18 ÜB -C-O-Z-H-R " ■ at contains, in the % an aliphatic hydrocarbon radical = 50- 909834/1331 _ΆΔη ^ _n SAD. ORIGINAL with 2 - 3 carbon atoms, R and R ¹ hydrogen atoms or alkyl radicals with t - 8 carbon atoms and R "denotes a hydrogen atom or a non-tertiary alkyl radical with 1-8 carbon atoms, the monovalent radicals being present in such an amount" that the amino nitrogen content in the range from about 0.01 to 6.5% based on the weight of the vinyl polymer. 15. Composite according to claim 14, characterized in that that the carrier is a metal carrier. 16. Composite according to claim 14, characterized in that that the carrier igt a cellulosic carrier. 17. The composite according to claim 14, characterized in that that the carrier let a carrier bound with a binder. 18. Composite, characterized by a carrier or a Backing, a pre-formed layer of polyvinyl fluoride film, Let at least one of their surfaces be chemically activated, mid between the carrier and the activated surface Layer of an adhesive compound containing a vinyl ponomer methacrylic acid addition polymer contains monovalent radicals from the Orupp * of 909834/1331 "BAD ORIG'NAL a) · -C = b) -CO-CH ₂ -CH-NH ₂ a) -CO-CH-CH ₂ -NH ₂
CH, contains bound, the monovalent radicals being present in such an amount that the Arainostickfcoff content in the range of about G, t - 2 _r Öt & based on the weight of the Addifcionspolynierlsats, is » 19. Composite material, characterized by back two carriers and between these carriers ** a layer of an Klebsfeoff'-mass _r the eire Wixi $ lpaaymeT ± SB & contains ^ d «§; mn monovalent remnants of the Ö R E ff 9 t contains bonded, in which Z is an aliphatic hydrocarbon residue with 2-5 carbon atoms, M and E ^f hydrogen atoms or alkyl residues with 1-8 carbon atoms and denotes a hydrogen atom or a non-tertiary alkyl radical with 1-8 carbon atoms, the monovalent radicals being present in such an amount that the amino component content is in the range of about O ₄ OI - 6.5 %, based on the weight of the vinyl polymer . BATH