United States Patent (19) 11 Patent Number: 5,047,443
Rehmer (45) Date of Patent: Sep. 10, 1991
54 HOTMELT CONTACT ADHESIVES WHICH 4,052,527 10/1977 Pastor et al. ........................ 428/463 CAN BE CROSSLINKED WITH 4,133,731 1/1979 Hansen et al. .. 204/159.17 ULTRAVIOLET RADIATION IN THE 4,243,500 1/1981 Glennon ................................ 522/46 PRESENCE OF OXYGEN 4,438,177 3/1984 Potter et al. 428/355 4,452,955 6/1984 Boeder ................................ 525/518 75) Inventor: Gerd Rehmer, Bobenheim-Roxheim, 4,477,636 10/1984 Muroi et al. ............... - - -- - 522/04
Fed. Rep. of Germany FOREIGN PATENT DOCUMENTS
73 Assignee: BASF Aktiengesellschaft, 2357486 5/1975 Fed. Rep. of Germany, Ludwigshafen, Fed. Rep. of 2838691 3/1979 Fed. Rep. of Germany. Germany 3220875 12/1983 Fed. Rep. of Germany . (21) Appl. No.: 353,460 0208856 1/1987 Fed. Rep. of Germany . 22). Filed: May 18, 1989 Primary Examiner-Marion E. McCamish Assistant Examiner-Mark A. Chapman 30 Foreign Application Priority Data Attorney, Agent, or Firm-Oblon, Spivak, McClelland, May 21, 1988 DE Fed. Rep. of Germany ....... 3817452 Maier & Neustadt 51) Int. Cl. ......................... C08F 2/46; CO8F 24/00; (57) ABSTRACT C08G 3/00; C08J 3/28 Hotmelt contact adhesives which are crosslinkable with (52) U.S. C. ...................................... 522/46; 522/120; UV light in the air are based on copolymers which 522/121; 522/154; 525/327.2 contain tetrahydrofurfur-2-yl (meth)acrylate and/or 58) Field of Search ................. 522/46, 120, 121, 154; N-2-tetrahydrofurfuryl (meth)-acrylamide and/or alk 525/327.2 oxyalkyl (meth)acrylates and/or N-alkoxyalkyl (meth 56) References Cited )acrylamides as copolymerized units and added benzo phenone and/or benzophenone derivatives as photosen U.S. PATENT DOCUMENTS sitizers. 3,229,478 1/1966 Alonso .................................. 62/371 4,045,517 0/1977 Guerin et al. ....................... 525/203 5 Claims, No Drawings 5,047,443 2 1 methacrylic acid are disadvantageous during processing HOTMELT CONTACT ADHESIVES WHICH CAN and may give rise to flammable vapors which further BE CROSSLINKED WITH ULTRAVIOLET more irritate the mucus membrane and have a pro RADATION IN THE PRESENCE OF OXYGEN nounced odor. Even after the polymerization, relatively high contents of residual monomers are still detectable The present invention relates to hotmelt contact ad in the adhesive in these systems. hesives which can be crosslinked with UV light in the This also applies to the process for the production of air and have improved tack and peeling strength and self-adhesive coatings according to DE-A 2357 486, in very good adhesion even to metals. which a syrup, consisting of an acrylate copolymer, Contact adhesives should possess permanent tack, 10 monomeric acrylates, a diolefinically or polyolefinically good flow behavior on various surfaces and a balance unsaturated monomeric compound, such as trimethylol between adhesion and cohesion. As a rule, contact ad propane triacrylate, and a photosensitizer, e.g. me hesives are used to coat sheet-like substrates and thus to thylolbenzoin methyl ether, acetophenone or benzophe produce, for example, self-adhesive tapes or self-adhe none, is exposed to UV light after application to a film. sive labels. Frequently, the contact adhesive has to be 5 Although these contact adhesives exhibit good surface applied as a solution in organic solvents to the particular tack at room temperature, they have pronounced flow substrate and the solvent then evaporated off, so that in and insufficient shearing strength at fairly high tempera general a recovery plant is required for the solvents, tures. since otherwise solvent vapors would cause consider The radiation-curable hotmelt contact adhesives of able environmental pollution. 20 U.S. Pat. No. 4,052,527, based on polyacrylate, can only Although disadvantages of this type are avoided be processed at high temperatures and require high when aqueous contact adhesive dispersions are used, radiation doses for crosslinking, resulting in damage to the drying of aqueous formulations requires large the substrate. The polyacrylate hot melt contact adhe amounts of energy and permits only relatively low pro sives of U.S. Pat. No. 4,438,177 also have these disad duction rates. 25 vantages, apart from the high processing temperature. The most advantageous method of applying contact Furthermore, DE-A 3 613 082 describes hotmet adhe adhesives is to apply a melt of the adhesive, since in this sives based on radiation-crosslinkable polyesters which case no solvents have to be separated off. have acrylate and/or methacrylate groups and possess The contact adhesives used here are, for example, good tack; however, these products have poor heat block polymers of styrene and isoprene or butadiene, as 30 distortion resistance. Moreover, the preparation process described in, for example, U.S. Pat. No. 3,229,478. for these products is very expensive. However, hotmelt adhesives of this type require ten A particular disadvantage of the known coatings peratures of, in general, more than 180° C. to ensure that crosslinkable with UV light is their sensitivity to oxy they possess sufficient flow during the coating process. gen during the crosslinking reaction, since oxygen in Furthermore, these polymers have little resistance to 35 hibits polymerization, so that in some cases insufficient atmospheric oxygen, heat, light and solvents. Hotmelt crosslinking is achieved and greasy surfaces are ob adhesives of this type also have only poor heat distor tained. To avoid these disadvantages, exposure to UV tion resistance, light is generally carried out under inert gases, for ex Attempts have therefore already been made to pre ample under nitrogen, noble gases or carbon dioxide. pare contact adhesives from liquid polymer blends. The However, this requires very complicated apparatus. use of polyesters as a base material for contact adhesives There is therefore a need for hotmelt contact adhe in a reactive system is disclosed in, for example, Ger sives which can be crosslinked in the air, are free of man Patent 3,220,875, where hydroxypolyesters are solvents and unsaturated monomers, have little odor, reacted with alkoxysilyl compounds to give crosslink show little tendency to discoloration and are as far as able polymers, which, however, still undergo crosslink 45 possible colorless, have a sufficiently low melt viscosity ing too slowly at 100° C. Reactive systems of this type at temperatures of, preferably, from 20 to 150° C. and, all have many difficulties, such as the exact metering of in the crosslinked state, possess good tack, high shear the reactive components, their inadequate reaction rate ing strength and high peeling strength. and in particular the poor reproducibility of the proper We have found that hotmelt contact adhesives based ties of the contact adhesive coating. In all reactive sys 50 O tems, it is also difficult to achieve a balance between (A) copolymers which have a K value of from 8 to 60 adhesion and cohesion of the adhesive. During storage and are prepared by solution copolymerization of of the self-adhesive products, subsequent reactions are (a) from 0.1 to 20%, based on the weight of the copoly often observed, which may lead to considerable mers, of tetrahydrofurfur-2-yl (meth)acrylate and/or changes in the properties and even to a loss of tack. 55 N-2-tetrahydrofurfuryl (meth)acrylamide and/or alk DE-A 2 838 691 furthermore discloses radiation-cur oxyalkyl (meth)acrylates and/or N-alkoxyalkyl able materials which are based on polyacrylates and are (meth)acrylamides, suitable, inter alia, as adhesives for laminates. However, (b) from 44 to 99.9%, based on the weight of the co these have insufficient tack. Furthermore, DE-A-3 421 polymers, of monoolefinically unsaturated acyclic 826 proposes urethane/urea/acrylate resins which are 60 unsubstituted monocarboxylates of 3 to 12 carbon crosslinkable by UV radiation and have a long shelf life atoms, not more than 20% by weight of which may and can be used as coatings having good adhesion to be replaced by vinyl ethers of 3 to 20 carbon atoms, various substrates. Finally, U.S. Pat. No. 4,133,731 dis styrene, a-methylstyrene, vinyl chloride, vinylidene closes radiation-crosslinkable adhesives which have chloride and/or acrylonitrile, good heat distortion resistance and solvent resistance 65 (c) from 0 to 30%, based on the weight of the copoly and consist of blends of, in particular, styrene/butadiene mers, of monoolefinically unsaturated compounds of block copolymers, a tackifying resin and polyol acryl 4 to 25 carbon atoms which have one or more ester, ates. However, high contents of still unbonded esters of carboxamide or carboximide groups, one of which is 5,047,443 3 4. adjacent to the olefinic double bond, and from 1 to 3 N-carboxylic acids, such as maleimido-N-hexanoic acid, Carboxyl groups, and and/or reaction products of glycidyl (meth)acrylate (d) from 0 to 6%, based on the weight of the copoly and aminocarboxylic acids. Of particular interest are mers, of a, (3-monoolefinically unsaturated mono succinic monoesters of alkanediol monoacrylate and and/or di-carboxylic acids of 3 to 6 carbon atoms monomethacrylates, such as 1,2-ethanediol monoacry and/or their anhydrides late and methacrylate, 1,4-butanediol monoacrylate and at from 70 to 150° C. in the presence of from 0.25 to methacrylate, 1,6-hexanediol acrylate and methacrylate 10% by weight, based on the monomers, of a ketone and 1,8-octanediol monoacrylate and monomethacry peroxide as a polymerization initiator and from 15 to late, as well as 1,2-propanediol monoacrylate and 200% by weight, based on the monomers, of inert sol 10 monomethacrylate. Alkanediol mono(meth)acrylates of vents, and removal of the solvents during or after the this type preferably have 2 to 4 carbon atoms in the polymerization, and alkanediol radical. The concomitant use of monomers (B) from 0.01 to 10% by weight, based on the sum of the (c) for the copolymers (A) is of particular advantage for components (A) and (B), of benzophenone and/or increasing the peeling strength and reducing the melt benzophenone derivatives can be crosslinked with 15 viscosity. ultraviolet radiation in the air. Finally, it is sometimes advantageous, for example for Preferred monomers (a) for the copolymers (A) are increasing the adhesion to metal surfaces, if the copoly tetrahydrofurfur-2-yl acrylate and tetrahydrofurfur mers (A) contain not more than 6%, based on the 2-yl methacrylate. Other suitable monomers are N-2- weight of the copolymers, of ag-olefinically unsatu tetrahydrofurfurylacrylamide and -methacrylamide and 20 rated mono- and/or dicarboxylic acids of 3 to 6 carbon alkoxyalkyl (meth)acrylates and alkoxyalkyl (meth)a- atoms and/or their anhydrides as copolymerized units. crylamides, which generally have 1 to 8, preferably 1 to A content of from 0.5 to 3% of these monomers (b) is 4, carbon atoms in the alkyl groups, methoxy com generally of particular interest. Examples of such mono pounds being preferred. Examples of these are 3 mers are, in particular, acrylic acid, methacrylic acid, methoxybutyl (meth)acrylate, 2-methoxyethyl acrylate 25 itaconic acid, fumaric acid and maleic anhydride. In and methacrylate, 2-butoxyethyl acrylate and methac some cases, other monoolefinically unsaturated mono rylate, 2-ethoxyethyl acrylate and methacrylate, N-n- ners (b) which contain functional groups, e.g. acrylam butoxymethylacrylamide and -methacrylamide and N ide, methacrylamide, 2-hydroxyethyl acrylate and isobutoxymethylacrylamide and -methacrylamide and methacrylate, 4-hydroxybutyl acrylate and methacry N-methoxyethylacrylamide and -methacrylamide. The 30 late and glycidyl acrylate and methacrylate, are suitable copolymers (A) contain the monomers (a) as copoly as additional monomers in small amounts, which are merized units preferably in an amount of from 2 to 15% generally from 0 to 3%, based on the copolymer (A). by weight. The copolymers (A) are prepared at from 70 to 120 The copolymers of (A) contain monoolefinically un C., preferably from 80 to 110° C., in the presence of saturated acyclic unsubstituted monocarboxylates of 3 35 from 0.25 to 10% by weight, based on the monomers, of to 12 carbon atoms, in particular esters of acrylic and a ketone peroxide as a polymerization initiator and from methacrylic acid and vinyl esters, as copolymerized 15 to 200, preferably from 30 to 50%, by weight, based monomers (b). Particularly important monomers (b) are on the monomers of inert solvents, by solution polymer the acrylates and methacrylates of alkanols of 2 to 8 ization. Particularly suitable ketone peroxides are carbon atoms, in particular methyl acrylate, ethyl acry methyl ethyl ketone peroxide, acetyl acetone peroxide, late, n-butyl acrylate and methacrylate, isobutyl acry cyclohexanone peroxide and methyl isobutyl ketone late and methacrylate, isoamy acrylate and methacry peroxide. late and 2-ethylhexyl acrylate and methacrylate. Other Methyl isobutyl ketone peroxide and cyclohexanone suitable monomers are propyl acrylate and isopropyl peroxide are particularly important ketone peroxides. acrylate, methyl methacrylate (in small amounts) and 45 If other conventional polymerization initiators are decyl acrylate and methacrylate and dodecyl acrylate used in the preparation of the copolymers (A), the re and methacrylate. Particularly suitable vinyl esters are Sulting copolymers have a relatively high gel content vinyl propionate, and vinyl acetate, vinyl formate and and are therefore not very suitable for the preparation vinyl butyrate are also useful. The copolymerized esters of hotmelt contact adhesives. Furthermore, hotmelt of acrylic and/or methacrylic acid with alkanols of 2 to 50 contact adhesive which are rapidly crosslinkable by 8 carbon atoms are present in particular in an amount of exposure to UV light are not obtained if other aromatic from 56 to 92.9%. ketones usually used as photosensitizers, such as ben Up to 20% by weight of the monomers (b) can be Zoin or acetophenone, or other types of conventional replaced by vinyl ethers of 3 to 20 carbon atoms, such as photoinitiators are used under similar conditions. vinyl methyl ether, vinyl propionate, vinyl 2-ethylhex 55 Preferably used solvents are those which have a boil anoate, styrene, a-methylstyrene, vinyl chloride, vinyli ing range of from 50° to 150 C. and may furthermore dene chloride and/or acrylonitrile, styrene and acrylo contain small amounts of high boiling or low boiling nitrile and amounts of not more than 10% by weight components. Examples of suitable substances are hydro being of particular interest. carbons, such as toluene and gasolines which preferably Monomers (c), which may be present as copolymer 60 have a boiling range of from 60' to 120° C. Particularly ized units in the copolymers (A) in an amount of not interesting solvents are alcohols, such as methanol, more than 30, preferably from 5 to 25%, by weight, are, ethanol, n-propanol and isopropanol, isopropanol and for example, succinic monoesters and/or monoesters of isobutanol and mixtures of these, being particularly benzenedicarboxylic and/or benzenetricarboxylic acids preferred, especially isopropanol. Other suitable sol with polyhydroxyalkyl mono(meth)acrylates, such as 65 vents are ketones, such as acetone or methyl ethyl ke 2-hydroxyalkyl mono(meth)acrylates, and/or reaction tone, and esters, such as ethyl acetate, or mixtures of products of maleic anhydride with hydroxycarboxylic these or mixtures with isopropanol and isobutanol, acids and/or aminocarboxylic acids and/or malei ido whose content in this case is advantageously not less 5,047,443 6 5 than 5, particularly preferably 25%, by weight, based phenonetetracarboxylic acid. 3,3,4,4'-Benzo on the solvent mixture. phenonetetracarboxylicdianhydride,3,3,4,4-tetra(tert To carry out the polymerization, conventional regu butylperoxycarbonyl)-benzophenone, 2-, 3- and 4- al lators may also be added to the reaction mixture, for kylbenzophenones where alkyl is of 1 to 10 carbon example secondary alcohols, mercaptans, such as mer atoms, such as 2-, 3- and 4-methylbenzophenone, and 2-, captoethanol, mercaptosuccinic acid, mercaptoglycerol 3- and 4-nonylbenzophenone, dialkylbenzophenones, or 3-mercaptopropyltrinathoxysilane, ethers, such as such as 4,4'-diisopropyl-benzophenone, and halo(- dioxane and tetrahydrofuran, hydrocarbons, such as monoalkyl)benzophenones, such as 4-trifluoromethyl isopropylbenzene, and compounds such as bromoform benzophenone, and 3,3'-dimethyl-4-methoxybenzophe and carbon tetrachloride. Regulators of this type can be O none, 4-aminobenzophenone, 4-aminobenzophenone added to the reaction mixture in amounts of from 0.01 to hydrochloride, sulfate and bisulfate, 4,4'-tetrame 50% by weight, based on the sum of the solvents and thylaminobenzophenone and olefinically unsaturated regulators. benzophenone derivatives, as available commercially The polymerization is carried out in a conventional under the trade names (RUvecryl P 36 (UCB). In some manner in a polymerization apparatus which is gener 15 cases, it is advantageous to add benzophenone and/or ally provided with a stirrer, a plurality of feed vessels benzophenone derivatives of the stated type to the co and a reflux condenser. In general, a kettle is used, but polymer (A) directly after its preparation, provided a plurality of kettles connected in series, i.e. a kettle that, for example, solvent is still present in the polymeri cascade, can also be employed, the last kettle being zation mixture to ensure a particularly uniform distribu connected to a suitable apparatus for removing sol tion of the two components in one another. vents, for example a falling film evaporator. In a kettle In some cases, it has proven advantageous also to add cascade, the starting materials are generally added con from 1 to 25, in particular from 2 to 10%, by weight, tinuously, and the product is likewise removed continu based on the components (A) and (B), of (C) ously. The solvent can be distilled off gradually during polyolefinically unsaturated polyethers and/or polyes the polymerization itself, in general after a conversion 25 ters having a mean molecular weight (number average) of about 40-50%, or after the end of the polymerization, of from 250 to 5,000 to the novel hotmelt contact adhe if necessary with a reduction in the pressure or an in sives. Examples of suitable substances are polyetherols crease in the boiling point of the mixture. In general, the and polyesterols reacted with acrylic acid, as are com polymerization is carried out by initially taking some of mercially available under the trade names ARONIX(R) the solvent and of the monomer mixture and some of 30 M-6100, M-6200, M-6250, M-7100 and M-8030 (Toago the polymerization initiator in a kettle flushed with sei Chemical Ind.). Other suitable polyetherols are tri nitrogen. The reaction mixture is then heated to the propylene glycol diacrylate, tetraethylene glycol diac boil, the boiling point being kept at the desired level if rylate and diacrylates of polyethylene glycols and poly necessary by employing reduced or superatmospheric propylene glycols, The polyunsaturated polyethers pressure. The amount of polymerization initiator is pref. 35 added are, in particular, diacrylates and dimethacrylates erably from 0.1 to 6% by weight, based on the total of polytetrahydrofurans, where the polytetrahydrofu amount of monomers. After an initial polymerization rans may have molecular weights of, for example, 250, phase, the remaining monomer mixture and any further 650, 1,000 or 2,000. Such polyolefinically unsaturated polymerization initiator and any further solvent are polyethers and/or polyesters are generally preferred as added. The polymerization temperature is kept prefera 40 component (C) although monoolefinically unsaturated bly below 120° C., particularly preferably below 100 polyetherols, for example monoacrylates or monome C., in particular below 80 C. After the end of the poly thacrylates of oxyethylated and/or oxypropylated alka merization, the solvent is generally evaporated off in nols, such as the commercial products ARONIX (R) the polymerization kettle, solvent residues being re M-101 and M-111 (Toagosei Chemical Ind.), are also moved under reduced pressure, if necessary at elevated 45 suitable. By the addition of such components (C), in temperatures. The copolymer (A) is then generally many cases the melt viscosity of the hot melt contact discharged from the polymerization apparatus in the adhesive and the heat distortion resistance of cross form of a melt. However, it is also advantageous in linked adhesive bonds are improved and, when diacry some cases to separate off the solvent in downstream lates or dimethacrylates of polytetrahydrofurans are apparatuses, for example in a falling film evaporator. 50 used, crosslinked products which possess surprisingly The copolymers (A) obtained generally have a K high gloss are obtained. The addition of diolefinically value of from 8 to 60, measured at 25 C. in 1% strength unsaturated polytetrahydrofurans to the hot melt solution in tetrahydrofuran (according to DIN 53,726), contact adhesives is therefore preferred. and K values of from 12 to 60, in particular from 16 to In some cases, if the copolymers A contain from 10 to 40, are of particular interest. Their glass transition tem 55 25%, based on the weight of the copolymer, of mono peratures in the uncrosslinked state are preferably mers C) as copolymerized units, it is particularly advan below 0° C., in particular below -10° C. To prepare tageous also to add from 0.05 to 0.5% by weight, based the hotmelt contact adhesive crosslinkable with ultravi on the components (A), (B) and (C), of a reducing agent olet radiation, from 0.01 to 10, in particular from 0.05 to (D) to the hotmelt contact adhesives. 5, preferably from 0.1 to 2%, by weight, based on the Preferred components (D) are cobalt(II) salts, such as copolymer (A), of benzophenone and/or benzophenone Co(II) octoate, Co(II) naphthenate, Co(II) acetylac derivatives are then furthermore incorporated into the etonate, Co(II) acetate or Co(II) phthalocyanine, man copolymers (A). Particularly suitable benzophenone ganese(II) salts, such as Mn(II) acetate or Mn(II) acetyl derivatives are hydroxyphenones, such as 3-hydrox acetonate, vanadium(III) and (IV) salts, such as vanadi ybenzophenone and 4-hydroxybenzophenone, and ben 65 um(III) acetylacetonate and vanadium(IV) oxyacety zophenonecarboxylic acids, such as benzophenone-2- iacetonate, redox systems, such as Fe(III) salts, e.g. carboxylic acid, benzophenone-3-carboxylic acid, ben iron(II) oxalate, in combination with, for example, glu zophenone-4-carboxylic acid and 3,3',4,4'-benzo cose, quaternary ammonium salts, such as tetra-n- 5,047,443 8 7 butylammonium bromide or tetra-n-butylammonium plated brass sheet. The sheet with the strips is then iodide, and alkali metal and/or alkaline earth metal stored for 24 hours at 23° C. at 65% relative humidity. bromides and iodides, e.g. potassium iodide and magne To measure the peeling strength, the test strips are sium bromide, hydroquinone, hydroquinone mono peeled off backward and parallel to the adhesive layer methyl ether, di-tert-butyl p-cresol, tert-butyl catechol, at a speed of 300 mm/min. The force required for this sodium diethyl dithiocarbamate, diethyl thiocarbamate, purpose is measured. hydroxymethanesulfinic acid and, for example, the so In the measurement of the shearing strength, a test dium salt of hydroxymethanesulfinic acid, aliphatic strip having an area of 20 mm X45 mm is stuck to a and/or aromatic tertiary amines, such as dimethylani chromium-plated brass sheet, which is clamped verti line, diethylaniline and dimethyl-p-toluidine. O cally, and the projecting part of the adhesive strip is The components (D) are added to the components loaded with a weight of 1 kg. The time taken to break (A), (B) and (C) in general after they have been mixed, the adhesive bond is determined. The measurement is although they can also first be added together with one carried out at 23°C. All measurements are carried out in of the other components, for example copolymers of triplicate. 8. (A) (after its preparation and preferably before the sol 5 In the Examples which follow, parts and percentages vents have been separated off). are by weight. The K values are determined according The novel materials can be modified and/or com to DIN 53,726, in 176 solution in tetrahydrofuran as the pounded in a conventional manner. For example, con solvent at 25°C. The melt viscosities of the copolymers ventional tackifying resins, e.g. hydrocarbon resins, are determined using a rotational viscometer with a unmodified or modified rosins, terpene/phenol resins, 20 cone-and-plate system (Haake, Karlsruhe) at the stated ketone resins, aldehyde resins or homopolymers, such temperature; the shearing rate D is 100 l/s. as poly-2-ethylhexyl acrylate and poly-n-butyl acrylate, EXAMPLE 1. or plasticizers, for example those based on mono-, di- or A mixture of 200 parts of isopropanol, 4 parts of polyester compounds, polychlorinated hydrocarbons or 25 methyl ethyl ketone peroxide and 320 parts of a mono liquid paraffins, dyes, pigments or stabilizers or elasto mer mixture of 735 parts of 2-ethylhexyl acrylate, 140 meric substances, such as natural or synthetic rubber, parts of n-butyl acrylate, 25 parts of acrylic acid and 100 polyvinyl ether and polybutadiene oils, can be added in parts of tetrahydrofurfur-2-yl acrylate is subjected to small announts. initial polymerization under reflux. After 20 minutes, The novel hotmelt contact adhesives can be pro 30 the remainder of the monomer mixture and, at the same cessed in a conventional manner. In general, melt tem time, a mixture of 16 parts of methyl ethyl ketone perox peratures of 80 to 150° C. are sufficient. The viscosity ide and 50 parts of isopropanol are added in the course of the novel hotmelt contact adhesives in this tempera of 2 hours, after which the refluxing mixture is stirred ture is about 6-60 Pa.s. The melts can readily be applied for a further 4 hours. A clear gel-free solution of a co to sheet-like structures, such as films, paper and card 35 polymer (A1) having a K value of 25 is obtained. The board as well as wood and metals, with the aid of a solvent is distilled off from the solution at 130° C., in the conventional applicator, for example a sheet die. Films final stages under reduced pressure (0.1 bar). which are suitable as substrates may consist of, for ex 100 pars of the copolymer (A1) are mixed with 2 parts ample, polyethylene, polyamides, polyethylene glycol of benzophenone at 60° C. The resulting hotmelt terephthalate, polypropylene, polyvinyl chloride or 40 contact adhesive is used to coat a polyethylene tere aluminum. The coatings obtained using the hot melt phthalate film in such a way that a layer thickness of 25 contact adhesives can be crosslinked by exposure to um is obtained. The film is then exposed to ultraviolet ultraviolet light in the air to give coatings which have light in the air in the manner stated. A self-adhesive film good adhesive properties and high cohesion and good having a good adhesive strength is obtained. The shear peeling strength in combination with excellent aging 45 ing strength at 23° C. is greater than 100 hours, and the resistance. Carrying out the procedure under inert gas peeling strength after 24 hours is 5.5 N/2 cm. atmosphere is not necessary and also has no advantages. COMPARATIVE EXPERIMENT 1. Irradiation can be carried out using the conventional UV lamps, for example low pressure and high pressure For comparison, the preparation of the copolymer is Hg lamps which have powers of up to 100 W/cm or 50 repeated as described in Example 1, with the proviso IOre. that, instead of the methyl ethyl ketone peroxide, the The adhesive properties of sheet-like substrates Same amount of lauroyl peroxide is used. An uncross which have a contact adhesive layer can be determined linked, gel-containing copolymer (A1) which is unsuit by measuring the shearing strength as a measure of the able for hotmelt contact adhesives is obtained. cohesion, and the peeling strength as an overall measure 55 of cohesion and surface tack. Copolymer (A2) For the test, films of polyethylene glycol terephthal A mixture of 100 parts of isopropanol, 1 part of ate and polypropylene are coated in an amount of 25 methyl ethyl ketone peroxide and 160 parts out of a g/m2. The solutions are evaporated off for 1 minute at total of 500 parts of a monomer mixture of 367.5 parts of 70° C. and under 1 bar. The coated films are exposed to 60 2-ethylhexyl acrylate, 75 parts of the reaction product light from a high pressure mercury lamp having a of 1,4-butanediol monoacrylate with succinic anhy power of 80 watt/cm. dride, 12.5 parts of acrylic acid and 45 parts of tetrahy The films are then placed on a continuously revolv drofurfur-2-yl acrylate is heated to the boil. The remain ing belt so that they pass under the lamp at a distance of der of the monomer mixture is added in the course of 2 15 cm at a speed of 10 m/min; the irradiation process is 65 hours under reflux. Thereafter, a mixture of 7.5 parts of repeated once. Irradiation is carried out in the air. methyl ethyl ketone peroxide and 25 parts of toluene is 2 cm wide strips are cut from the films produced in run in over 1 hours and stirring is continued for a fur this manner, and these strips are applied to a chromium ther 4 hours with gentle refluxing. 5,047,443 10 The solvent and volatile components are removed at TABLE 2 120° C., initially under atmospheric pressure and then Results of the irradiation tests under reduced pressure (0.1 bar). Cohesion Peeling strength A copolymer (A2) having a K value of 18 is obtained. (hours) (after 24 hours) Evaluation The melt viscosity at 80° C. is 8 Pa.s. Example at 23 C. at 50° C. N/2 cm of the tack Copolymer (A3) 2 3 > 100 > 100 >1 >2 7.0. 8.0 Good tack Good tack A mixture of 100 parts ofisopropanol, 1 part of cyclo 4. > 00 >1 8.5 Good tack hexanone peroxide and 160 parts of a monomer mixture 10 5 > 100 >5 10.5 Good tack of 380 parts of 2-ethylhexyl acrylate, 75 parts of the reaction product of 1,2-ethanediol monoacrylate with succinic anhydride and 45 parts of tetrahydrofurfur-2-yl COMPARATIVE EXPERIMENTS 2 AND 3 acrylate is refluxed. The remainder of the monomer For comparison, a copolymer which can be cast at mixture is added in the course of 2 hours, the reaction 15 room temperature and consists of 20% of vinyl acetate mixture being kept under reflux, stirring is then contin and 80% of n-butyl acrylate and has a K value of 19 ued for 30 minutes and 57.5 parts of a mixture of 7.5 (measured in 1% strength solution in ethyl acetate) is parts of cyclohexanone peroxide, 25 parts of toluene prepared according to the Example of DE-A 2357 486, and 25 parts of isopropanol are then added and refluxing and 12 parts of 2-ethylhexyl acrylate and 10 parts of is continued for a further 5 hours. trimethylolpropane triacrylate are added. Part of the The solvent and volatile components are removed as mixture is mixed with 2.2% by weight of benzophehone stated for copolymer (A2). A copolymer (A3) which (Comparative Experiment 2) while the other part is has a K value of 21 and a viscosity, at 80 C., of 10 Pas mixed with 2.2% by weight of methylolbenzoin methyl is obtained. ether (Comparative Experiment 3), the mixtures are Copolymer (A4) applied in a thickness of 25 um to polyethylene glycol The procedure described for copolymer (A3) is fol terephthalate films and the adhesive properties are mea sured. The results are summarized in Table 3 below: lowed, except that the tetrahydrofurfur-2-yl acrylate is replaced by the same amount of 3-methoxybutyl acry TABLE 3 late. 30 Results of the Comparative Experiments The solvent is separated off in the manner described. Compara- Cohesion Peeling strength A copolymer (A4) having a K value of 28 and a melt tive (hours (after 24 hours) viscosity, at 50 C., of 35 Pa.s is obtained. Experiment at 23° C. at 50° C. N/2 cm) Tack 2 <0. <0. 6.5 Greasy layer Copolymer (A5) 35 3 <0.1 <0.1 7.0 Greasy layer 160 parts of a monomer mixture of 380 parts of 2 ethylhexyl acrylate, 12.5 parts of acrylic acid, 45 parts of tetrahydrofurfur-2-yl acrylate and 62.5 parts of EXAMPLES 6 AND 7 maleimido-N-hexanoic acid are added to a gently re Preparation of copolymer (A6) fluxing mixture of 100 parts of isopropanol and 2 parts 40 of methyl ethyl ketone peroxide in the course of 15 A mixture of 140 parts of toluene, 2.8 parts of methyl minutes. After a further liS minutes, the remainder of isobutyl ketone peroxide and 220 parts of a monomer the monomer mixture is added in the course of 2 hours mixture of 630 parts of 2-ethylhexyl acrylate, 2.5 parts and stirring is continued for 30 minutes at the reflux 45 acrylic acid and 5.25 parts of tetrahydrofurfur-2-yl of temperature. Thereafter, a mixture of 8 parts of methyl acrylate is refluxed. The remainder of the monomer ethyl ketone peroxide is added in the course of 1 hours mixture and, at the same time, a mixture of 50 parts of and stirring is continued for a further 4 hours at the toluene and 10.5 parts of methyl isobutyl ketone perox reflux temperature. The solvent and volatile compo ide are added to the refluxing mixture in the course of 2 nents are distilled off under reduced pressure (0.1 bar) at SO hours and stirring is continued for a further 4 hours. 120° C. A copolymer (A5) having a K value of 20 and The solvent is then removed at 130 C. under reduced melt viscosity, at 80 C., of 9 Pais is obtained. pressure. The copolymer (A6) has a K value of 27 and EXAMPLES 2 TO 5 a melt viscosity (80 C.) of 25 Pa.s. The solvent is removed at 100° C. under reduced - For the tests, the following hotmelt contact adhesives 55 pressure. The resulting copolymer (A7) has a K value of are prepared by mixing benzophenone compounds with 32 and a melt viscosity (80 C.) of 35 Pa.s. Preparation the melt of the copolymers (A2)-(A5). and testing of the hotmelt contact adhesives of Exam TABLE 1 ples 6 and 7. Copolymer Benzophenone compound For the preparation of the hotmelt contact adhesives, Example (% by weight (% by weight) 60 benzophenone and two polytetrahydrofuran di(meth)a- 2 98.0 (A2) 2.0 benzophenone crylates derived from polytetrahydrofuran having a 3 97.0 (A3) 3.0 benzophenone mean molecular weight (number average) of 650 and of 4. 99.0 (A4) 1.0 benzophenone 2,000, respectively, i.e. poly-THF-650 diacrylate and 5 97.0 (A5) 3.04-hydroxybenzophenone poly-THF-2000 dimethacrylate, are added, the compo 65 nents being kneaded to a homogeneous mass in a heat The values measured for these materials after expo able mixing unit at 100° C. The amounts in each case sure to UV light (in the air) are summarized in Table 2 and the melt viscosities of the hot melt contact adhesives below: are summarized in Table 3A below. 5,047,443 12 11 TABLE 3A We cairn: Poly-THF Benzo- Met viscos 1. A hot melt contact adhesive which is crosslinkable Exam- Copolymer diacrylate phenone ity at 80 C. with ultraviolet radiation in the air and is based on ple (parts) (parts) (parts) Pas) (A) copolymers which have a K value of from 8 to 60 6 A695.0 P-THF-650 S.O 0.25 2O and are prepared by solution copolymerization of 7 A 90.0 P-THF-2OOO. O.O 0.30 30 (a) from 0.1 to 20%, based on the weight of the co polymers, of tetrahydrofurfur-2-yl (meth)acrylate and/or N-2-tetrahydrofurfuryl (meth)acrylamide The hotmelt contact adhesive is used to coat films in and/or alkoxyalkyl (meth)acrylates and/or N a conventional manner, the coated films are exposed to 10 alkoxyalkyl (meth)acrylamides, UV light in the manner stated and the adhesive proper (b) from 44 to 99.9%, based on the weight of the ties are then measured. These are then summarized copolymers, of monoolefinically unsaturated acy Tables 4 and 5 below: clic unsubstituted monocarboxylates of 3 to 12 TABLE 4. carbon atoms, up to 20% by weight of which may Results of tests on adhesive properties 5 be replaced by vinyl ethers of 3 to 20 carbon atoms, Coating: 25 g/m’, film: polypropylene film, 40 m; styrene, a-methylstyrene, vinyl chloride, vinyli irradiation in the air dene chloride and/or acrylonitrile, Cohesion Peeling strength (c) from 0 to 30%, based on the weight of the copoly hours (after 24 hours) mers, of monoolefinically unsaturated compounds Example at 23° C. at 50 C. N/2 cm Comments of 4 to 25 carbon atoms having one or more ester, 6 > 300 > 15 6.5 Highly glossy, carboxanide or carboxinide groups, one of which transparent coating is adjacent to the olefinic double bond, and having 7 > 300 > 15 7.O Highly glossy, 1 to 3 carboxyl groups, and transparent (d) from 0 to 6%, based on the weight of the copoly coating mers, of ag-monoolefinically unsaturated mono and/or di-carboxylic acids of 3 to 6 carbon atoms and/or their anhydrides Preparation of copolymer (A8) at from 70 to 150° C. in the presence of from 0.25 to 200 parts of a monomer mixture of 600 parts of n 10% by weight, based on the monomers, of a ketone. butyl acrylate, 250 parts of 2-ethylhexyl acrylate, 100 g peroxide as a polymerization initiator and from 15 to of methyl acrylate and 50 parts of N-2-tetrahydrofurfu 200% by weight, based on the monomers, of inert sol ryl methacrylamide are added to a mixture of 160 parts vents, and removal of the solvents during or after the of ethyl acetate, 50 parts of tetrahydrofuran and 8 parts polymerization, and of cyclohxanone peroxide and initial polymerization is (B) from 0.01 to 10% by weight, based on the sum of carried out under reflux for 20 minutes. In the course of 35 the components (A) and (B), of benzophenone a further 2 hours, the remainder of the monomer mix and/or benzophenone derivatives. 2. A hotmelt contact adhesive as claimed in claim 1, ture and, at the same time, a solution of 8 parts of methyl wherein the copolymer (A) is prepared by solution ethyl ketone peroxide in 123 parts of ethyl acetate are copolymerization of added. After the end of the addition, stirring is contin 40 (a) from 2 to 15%, based on the weight of the copoly ued for a further 4 hours at the reflux temperature. A mer, of tetrahydrofurfury (meth)acrylate, copolymer having a K value of 35 is obtained. (b) from 56 to 92.9%, based on the weight of the The solvent mixture and volatile components are . copolymer, of esters of (meth)acrylic acid and alka distilled off at 100° C., the pressure is reduced and the temperature is increased to 130 C. A copolymer having 45 (c)nois of to 8 carbon atoms, from 5 to 25%, based on the weight of the copoly a neit viscosity of 8 Pa.s at 120° C. (D = 100 l/s) is mer, of succinic monoesters of alkanediol mono(- obtained. meth)acrylates and 0.75% by weight (based on resin) of benzophenone is (d) from 0.1 to 4%, based on the weight of the co stirred into the melt. polymer, of acrylic and/or methacrylic and/or 200 parts of the resin are removed and are mixed with SO maleic acid and/or their anhydrides 20 parts of a commercial tackifier (Foral 85 (R) from at from 80 to 110° C. in the presence of from 30 to 50% Hercules Inc.). by weight, based on the monomers, ofisopropanol and On a heatable coating table, polyethylene glycol tere /or isobutanol. phthalate films are coated with 25 g/m2 of the copoly 3. A hotmelt contact adhesive as claimed in claim 1, mer at 110° C. The coatings are then irradiated in the air 55 which contains, as component (B), from 0.5 to 5% by in the manner described, and the adhesive tests are weight, based on the components (A) and (B), of benzo carried out. phenone, a hydroxybenzophenone and/or a benzo TABLE 5 phenonecarboxylic acid. Results of the tests on the adhesive properties 4. A hot melt contact adhesive as claimed in claim 1, Cohesion Peeling strength 60 which contains from 1 to 25%, based on the weight of hours (after 24 hours) the said adhesive, of (C) olefinically unsaturated poly Example at 23 C. at 50 C. (N/2 cm) Comments ethers and/or polyesters having a mean molecular Copoly- > 100 >5 6.5 Tacky weight (number average) of from 250 to 5,000. ner A8 5. A hotmelt contact adhesive as claimed in claim 4, A8 -- tack > 100 >2 8.5 Tacky 65 which contains a diolefinically unsaturated polytetrahy ifier drofuran as the polyether. k sk k k