US 2003.0143413A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2003/0143413 A1 Storbeck et al. (43) Pub. Date: Jul. 31, 2003

(54) PRODUCING PRESSURE-SENSITIVELY (30) Foreign Application Priority Data ADHESIVE PUNCHED PRODUCTS Nov. 22, 2001 (DE)...... 101 57 1534 (75) Inventors: Reinhard Storbeck, Hamburg (DE); Marc Husemann, Hamburg (DE); Publication Classification Matthias Koch, Hamburg (DE); Maren Klose, Seevetal (DE) (51) Int. Cl." ...... B32B 27/00; B32B 27/30 (52) U.S. Cl...... 428/500; 428/522 Correspondence Address: KURT BRISCOE NORRIS, MCLAUGHLIN & MARCUS, PA. (57) ABSTRACT 220NEW EAST YORK, 42ND NY STREET, 10017 (US) 30TH FLOOR A process for producing preSSure-Sensitively adhesive punched products from backing material coated with pres (73) Assignee: tesa Aktiengesellschaft Sure Sensitive adhesive, wherein Said pressure Sensitive adhesive is oriented Such that it (21) Appl. No.: 10/219,523 possesses a preferential direction and, (22) Filed: Aug. 15, 2002 the punching process is carried out continuously. Patent Application Publication Jul. 31, 2003 Sheet 1 of 5 US 2003/0143413 A1

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PRODUCING PRESSURE-SENSITIVELY 0008 Anisotropically oriented PSAS possess the ten ADHESIVE PUNCHED PRODUCTS dency to move back into the initial State following Stretching in a given direction, as a result of their “entropy-elastic' 0001. The relates to a process for producing behavior. punched products and to punched products thus obtainable. 0009 Suitable in principle for the inventive process are 0002 All presently known pressure sensitive adhesives all PSAS which exhibit an orientation, examples being those (PSAs) are characterized by a more or less pronounced flow based on natural or synthetic rubbers such as butyl rubber, behavior. When strongly pronounced, this flow behavior is , butadiene-acrylonitrile, Styrene-butadiene-Styrene also known as the cold flow or bleeding of a PSA. This copolymers and Styrene-isoprene-Styrene copolymers, and inherent behavior of a PSA leads to problems when punch also those based on linear polyesters and copolyesters, ing Self-adhesive materials. The two common punching polyurethanes, polysiloxane elastomers, based on acrylic methods, flatbed punching and rotary punching, are affected block copolymers, especially those with diblocks and/or by these problems. For example, punched products may be triblocks, in which at least one block component is based on removed as well during matrix Stripping, because the cold polyacrylates, and, additionally, PSAS based on Straight flow of a PSA does not allow clean separation of the acrylics, but with very Special advantage anisotropic PSAS adhesive. Where matrix Stripping is carried out manually based on polyacrylate and/or polymethacrylate. after the punching operation, as in Asia, for example, these problems are exacerbated, Since the adhesive then has Suf 0010) Surprisingly, in the form of a layer, anisotropically ficient time available to coalesce. oriented acrylic PSAs of this kind exhibit resilience of the PSA following punching and/or cutting operations, at 0003) A further problem arises in the kiss-cut process. In the cut and punched edge, this recession being utilized the kiss-cutting of Self-adhesive materials, the release mate inventively for the punching of shapes which do not flow rial is part-punched as well, i.e., the punching tools penetrate together again (coalesce). This property is not known for any to a more or leSS defined depth into the Substrate material of the pressure sensitive adhesives which have hitherto (=release material). As a result, the antiadhesively finished belonged to the state of the art. (FIG. 1 shows one edge of Surface of the release material (in the majority of cases, the a punched product of this kind following the punching release materials are Siliconized; this applies to all release Systems described; Satas, 3rd edition, chapters 26 and 27) is process. The recession of the pressure Sensitive adhesive, always destroyed. The adhesive is able to flow into the caused by anisotropic orientation, can be seen.) substrate material of the release material (, PET, PP, 0011. The monomers are preferably chosen such that the PE) and adhere. The punched product can no longer be resulting polymers can be used as pressure Sensitive adhe removed readily from the Siliconized release material, Since Sives at room temperature or at higher temperatures, espe the edges of the punched product are Stuck to the Substrate. cially Such that the resulting polymers possess pressure In a downstream processing Step, Such as automatic dispens Sensitively adhering properties in accordance with the ing, for example, the punched product or the matrix lattice “Handbook of Pressure Sensitive Adhesive Technology” by Surrounding the punched products and intended for removal Donatas Satas (van Nostrand, New York, 1989). may tear during Stripping. Such tears nowadays cause mas Sive disruptions to production. The effects described apply to 0012. The polymers which can be used with preference all product Structures, Such as adhesive transfer tapes, and for the inventive process are preferably obtainable by poly also to Substrates coated on one or both Sides, Such as , merizing a monomer mixture composed of acrylic esters nonwovens, , layS or foams. and/or methacrylic esters and/or their free acids with the formula CH=CH(R)(COOR), where R=H or CH and 0004. It is an object of the invention, therefore, to R is an alkyl chain having 1-20 carbon atoms or H. improve the production of punched products by avoiding, or else at least considerably reducing, the above-described 0013 The molar M of the polyacrylates used are disadvantages of the prior art. preferably 2200 000 g/mol. 0005 Surprisingly and in a manner unforeseeable for the 0014 Very preferably, use is made for the inventive skilled worker, this object is achieved through the use of process of acrylic or methacrylic monomers composed of anisotropic pressure Sensitive adhesives in the punching acrylates and methacrylates having alkyl groups of 4 to 14 process. The main claim accordingly relates to a proceSS for carbon atoms, preferably from 4 to 9 carbon atoms. Specific producing pressure Sensitively adhesive punched products examples, without wishing to be restricted by this listing, from backing material provided with a preSSure Sensitive include methyl acrylate, methyl methacrylate, ethyl acrylate, adhesive, Said pressure Sensitive adhesive being anisotropic n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, by Virtue of possessing a preferential direction, and the n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, n-octyl punching proceSS being carried out continuously. The Sub methacrylate, n-nonyl acrylate, lauryl acrylate, Stearyl acry late, behenyl acrylate, and the branched isomers thereof, claims relate to preferred developments of this process. Such as isobutyl acrylate, 2-ethylhexyl acrylate, 2-ethyl Further claims relate to the punched products thus obtain hexyl methacrylate, isooctyl acrylate, and isooctyl meth able. acrylate, for example. 0006 Pressure Sensitive Adhesives 0015. Further classes of compounds which can be used 0007 Anisotropic pressure sensitive adhesives which can include monofunctional acrylates and methacrylates of be employed for the inventive proceSS are Sometimes bridged cycloalkyl alcohols, composed of at least 6 carbon referred to below as anisotropically oriented, or Simply as atoms. The cycloalkyl alcohols may also be Substituted, by oriented, PSAS. -6 alkyl groups, halogen atoms or cyano groups, for US 2003/0143413 A1 Jul. 31, 2003 example. Specific examples include cyclohexyl methacry phenyl methacrylate, t-butylphenyl acrylate, t-butylphenyl lates, isobornyl acrylate, isobornyl methacrylate and 3,5- methacrylate, 4-biphenyl acrylate and methacrylate, 2-naph dimethyladamanty1 acrylate. thyl acrylate and methacrylate, and mixtures of those mono 0016. In one procedure monomers are used which carry mers, this list not being conclusive. polar groupS. Such as carboxyl radicals, Sulfonic and phoS 0022. For the inventive process it is also possible to use phonic acid, hydroxyl radicals, lactam and lactone, N-Sub oriented block copolymers based on acrylate and/or meth Stituted amide, N-Substituted amine, carbamate, epoxy, thiol, acrylate. Here, mention may be made in particular, by way alkoxy, and cyano radicals, ethers or the like. of example, of those pressure Sensitive adhesives based on at least one block copolymer, the weight fractions of the 0017 Examples of moderate monomers are N,N- block copolymers totaling at least 50% of the pressure dialkyl-substituted amides, such as N,N-dimethylacryla mide, N,N-dimethylmethacrylamide, N-tert-butylacryla Sensitive adhesive, and at least one block copolymer being mide, N-vinyl-pyrrolidone, N-vinylactam, composed at least in part on the basis of (meth)acrylic acid dimethylaminoethyl methacrylate, dimethylaminoethyl derivatives, and additionally at least one block copolymer acrylate, diethylaminoethyl methacrylate, diethylaminoethyl comprising at least the unit P(A)-P(B)-P(A) comprising at acrylate, N-methylolmethacrylamide, N-(butoxymethyl least one polymer block P(B) and at least two polymer )methacrylamide, N-methylolacrylamide, N-(ethoxymethy blocks P(A), where l)acrylamide, N-isopropylacrylamide, this list not being con 0023) P(A) independently of one another represent clusive. homopolymer or copolymer blocks of monomers A, the polymer blocks P(A) each having a Softening 0.018 Further preferred examples are hydroxyethyl acry temperature in the range from +20 C. to +175 C., late, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, allyl alcohol, maleic anhy 0024 P(B) represents a homopolymer or copolymer dride, itaconic anhydride, itaconic acid, glyceridyl meth block of monomers B, the polymer block P(B) acrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, having a Softening temperature in the range from 2-butoxyethyl methacrylate, 2-butoxyethyl acrylate, cyano -130° C. to +10 C., ethyl methacrylate, cyanoethyl acrylate, glyceryl methacry 0.025) the polymer blocks P(A) and P(B) are not late, 6-hydroxyhexyl methacrylate, Vinylacetic acid, tetrahy homogeneously miscible with one another, and drofurfuryl acrylate, B-acryloyloxypropionic acid, trichloroacrylic acid, fumaric acid, crotonic acid, aconitic 0026 the pressure sensitively adhesive system is acid, dimethylacrylic acid, this list not being conclusive. oriented by Virtue of possessing a preferential direc tion, the refractive index measured in the preferential 0019. In another very preferred procedure, monomers direction, nM, being greater than the refractive used include Vinyl esters, Vinyl ethers, Vinyl halides, indeX measured in a direction perpendicular to the Vinylidene halides, and Vinyl compounds with aromatic preferential direction, n. cycles and heterocycles in the C. position. Here again, mention may be made nonexclusively of Some examples: 0027. In a very advantageous procedure, the inventive Vinyl acetate, Vinylformamide, Vinylpyridine, ethyl vinyl process uses an oriented preSSure Sensitive adhesive which ether, Vinyl chloride, Vinylidene chloride and acrylonitrile. exhibits shrinkback behavior, the shrinkback being at least 3% as determined by test B (shrinkback measurement in the 0020. In another very preferred procedure, moreover, free film). In a development of the inventive process, photoinitiators containing a copolymerizable double bond preSSure Sensitive adhesives are used in which the Shrink are used. Suitable photoinitiators include Norrish I and back is at least 30%, in one preferred embodiment at least Norrish II photoinitiators. Examples are benzoin acrylate 50%. and an acrylated benzophenone from UCB (Ebecryl P36(R). In principle it is possible to copolymerize any photoinitiator 0028. A feature of pressure sensitive adhesives used with which is known to the skilled worker and which is able to preference is that the refractive index measured in the crosslink the polymer by a free-radical mechanism under preferential direction, nv., is greater than the refractive UV irradiation. An overview of possible photoinitiators index measured in a direction perpendicular to the prefer which can be used and which can be functionalized with a ential direction, ns. The refractive index n of a medium is double bond is given in Fouassier: “Photoinitiation, Photo given by the ratio of the Speed of light in a vacuum, co, to polymerization and Photocuring: Fundamentals and Appli the Speed of light in the medium in question, c. Accordingly, n=co/c, n being a function of the wavelength of the light in cations”, Hanser-Verlag, Munich 1995. For further details, question. A measure of the orientation of the preSSure use is made of Carroy et al. in “Chemistry and Technology sensitive adhesive is the difference An between the refractive of UV and EB Formulation for Coatings, Inks and Paints', index nv measured in a preferential direction (stretching Oldring (Ed.), 1994, SITA, London. direction VR) and the refractive index ns measured in a 0021. In another preferred procedure, monomers which direction (SR) perpendicular to the preferential direction. In possess a high Static glass transition temperature are added other words, An=nv-ns, and this figure is obtainable by to the comonomers described. Suitable components include the measurements described in test C. aromatic vinyl compounds, Such as Styrene, in which case the aromatic nuclei are preferably composed of C to Cs 0029 With great preference, in the pressure sensitive units and may also contain heteroatoms. Particularly pre adhesives used for the inventive process, the difference ferred examples include 4-vinylpyridine, N-vinylphthalim An=nl-nsis is at least 1.10. ide, methylstyrene, 3,4-dimethoxystyrene, 4-Vinylbenzoic 0030. In a further development, resins may be admixed to acid, benzyl acrylate, benzyl methacrylate, phenyl acrylate, the polyacrylate PSAS. AS tackifying resins for addition it is US 2003/0143413 A1 Jul. 31, 2003 possible without exception to use any tackifier resins which al. in “Chemistry and Technology of UV and EB Formula are known and are described in the literature. AS represen tion for Coatings, Inks and Paints”, Oldring (Ed.), 1994, tatives, mention may be made of pinene resins, indene SITA, London. resins, and roSins, their disproportionated, hydrogenated, 0035) Preparation Processes for Pressure Sensitive Adhe polymerized, esterified derivatives and Salts, the aliphatic Sives Used with Advantage and aromatic hydrocarbon resins, terpene resins and terpene phenolic resins, and also C5, C9, and other hydrocarbon 0036 For polymerization the monomers are chosen such resins. Any desired combinations of these and other resins that the resulting polymers can be used as pressure Sensitive may be used in order to adjust the properties of the resulting adhesives at room temperature or higher temperatures, par adhesive in accordance with what is desired. In general it is ticularly Such that the resulting polymers possess preSSure possible to use any resin which is compatible (soluble) with Sensitive adhesive properties in accordance with the “Hand the corresponding polyacrylate; in particular, reference may book of Pressure Sensitive Adhesive Technology” by Dona be made to all aliphatic, aromatic, and alkylaromatic hydro tas Satas (van Nostrand, New York, 1989). carbon resins, hydrocarbon resins based on pure monomers, 0037. In order to obtain a preferred polymer glass tran hydrogenated hydrocarbon resins, functional hydrocarbon Sition temperature Ts 25 C., in accordance with the above resins, and natural resins. Express reference is made to the remarks, the monomers are very preferably Selected in Such depiction of the state of the art in the “Handbook of Pressure a way, and the quantitative composition of the monomer Sensitive Adhesive Technology” by Donatas Satas (van mixture advantageously chosen in Such a way, that the Nostrand, 1989). polymer is obtained with the desired TG in accordance with the Fox equation (G1) (cf. T. G. Fox, Bull. Am. Phys. Soc. 0.031 Furthermore, it is also possible optionally to add 1 (1956)123). plasticizers, fillers (e.g. fibers, carbon black, Zinc oxide, dioxide, chalk, Solid or hollow glass beads, micro beads made of other materials, Silica, Silicates), nucleators, 1 W (G1) blowing agents, compounding agents and/or aging inhibi T - X. Tan tors, in the form for example of primary and Secondary antioxidants or in the form of light Stabilizers. 0032. Additionally, crosslinkers and promoters for 0038. In this equation, n represents the serial number of crosslinking may be admixed. Examples of Suitable the monomers used, W denotes the fraction of the crosslinkers for electron beam crosslinking and UV respective monomer n (in 96 by weight) and T denotes the crosslinking include difunctional or polyfunctional acry respective glass transition temperature of the homopolymer lates, difunctional or polyfunctional isocyanates (including of the respective monomer n, in K. those in blocked form), and difunctional or polyfunctional 0039. In order to prepare the poly(meth)acrylate PSAs it epoxides. is advantageous to carry out conventional radical polymer 0.033 For optional crosslinking with UV light, UV-ab izations. For the polymerizations proceeding by a radical Sorbing photoinitiators may be added to the polyacrylate mechanism it is preferred to use initiator Systems which PSAs. Useful photoinitiators which are very good to use additionally comprise further radical initiators for the poly include benzoin ethers, Such as benzoin methyl ether and merization, especially thermally decomposing, radical benzoin isopropyl ether, for example, Substituted acetophe forming azo or peroxo initiators. In principle, however, any nones, Such as 2,2-diethoxyacetophenone (available as Irga customary initiators that are familiar to the skilled worker cure 651(R) from Ciba Geigy(R), 2,2-dimethoxy-2-phenyl-1- for acrylates are Suitable. The production of C-centered phenylethanone, dimethoxyhydroxyacetophenone, radicals is described in Houben Weyl, Methoden der Orga Substituted C-ketols, Such as 2-methoxy-2-hydroxypro nischen Chemie, Vol. E 19a, pp. 60-147. These methods are piophenone, for example, aromatic Sulfonyl chlorides, Such employed preferentially in analogy. as 2-naphthylsulfonyl chloride, for example, and photoac 0040 Examples of radical sources are peroxides, hydro tive oximes, Such as 1-phenyl-1,2-propanedione 2-(O- peroxides, and azo compounds, Some nonexclusive ethoxycarbonyl)oxime. examples of typical radical initiators that may be mentioned here include potassium perOXOdisulfate, dibenzoyl peroxide, 0034. The abovementioned photoinitiators and others cumene hydroperoxide, cyclohexanone peroxide, di-t-butyl which can be used, including those of the Norrish I or peroxide, azodiisobutyronitrile, cyclohexylsulfonyl acetyl Norrish II type, may contain the following radicals: ben peroxide, diisopropyl percarbonate, t-butyl perOctoate, and Zophenone, acetophenone, benzil, benzoin, hydroxyalky lphenone, phenyl cyclohexyl ketone, anthraquinone, trim benzpinacol. In one very preferred version, 1,1'-azobis(cy ethylbenzoylphosphine oxide, methylthiophenyl clohexanecarbonitrile) (Vazo 88TM from DuPont) or azodi morpholine ketone, aminoketone, azobenzoin, thioxan isobutyronitrile (AIBN) is used as radical initiator. thone, hexaarylbisimidazole, triazine, or fluorenone, it being 0041. The average molecular weights M of the pressure possible for each of these radicals to be further substituted Sensitive adhesives formed in the course of the radical by one or more halogen atoms and/or one or more alkoxy polymerization are very preferably chosen Such as to be groupS and/or one or more amino groups or hydroxyl situated within a range from 200 000 to 4 000 000 g/mol; groups. A representative Overview is given by Fouassier: Specifically for further use as hotmelt pressure Sensitive “Photoinitiation, Photopolymerization and Photocuring: adhesives with anisotropic behavior, PSAS having average Fundamentals and Applications”, Hanser-Verlag, Munich molecular weights M of from 400 000 to 1400 000 g/mol 1995. For further details, it is possible to consult Carroy et are prepared. The average molecular weight is determined US 2003/0143413 A1 Jul. 31, 2003 by size exclusion (GPC) or matrix-assisted yllithium, cyclohexyllithium, and octyllithium, with this list desorption/ionization (MALDI making no claim to completeness. Furthermore, initiators MS). based on Samarium complexes are known for the polymer 0042. The polymerization may be carried out in bulk, in ization of acrylates (Macromolecules, 1995, 28, 7886) and the presence of one or more organic Solvents, in the presence can be used here. of water, or in mixtures of organic Solvents and water. The 0048 Moreover, it is also possible to use difunctional aim is to minimize the amount of Solvent used. Suitable initiators, Such as 1,1,4,4-tetraphenyl-1,4-dilithiobutane or organic Solvents are pure alkanes (e.g., hexane, heptane, 1,1,4,4-tetraphenyl-1,4-dilithioisobutane. Coinitiators may octane, isooctane), aromatic hydrocarbons (e.g., benzene, likewise be used. Suitable coinitiators include lithium toluene, xylene), esters (e.g., ethyl, propyl, butyl or hexyl halides, alkali metal alkoxides or alkylaluminum com acetate), halogenated hydrocarbons (e.g., chlorobenzene), pounds. In one very preferred version the ligands and alkanols (e.g., methanol, ethanol, ethylene glycol, ethylene coinitiators are chosen Such that acrylic monomers, Such as glycol monomethyl ether), and ethers (e.g., , n-butyl acrylate and 2-ethylhexyl acrylate, for example, can dibutyl ether) or mixtures thereof. A water-miscible or be polymerized directly and need not be generated in the hydrophilic coSolvent may be added to the aqueous poly polymer by a transesterification with the corresponding merization reactions in order to ensure that in the course of alcohol. monomer conversion the reaction mixture is in the form of 0049. In order to prepare polyacrylate PSAS having a a homogeneous phase. CoSolvents which can be used with advantage for the present invention are chosen from the narrow molecular weight distribution, controlled radical following group, consisting of aliphatic alcohols, glycols, polymerization methods are also Suitable. For the polymer ethers, glycol ethers, pyrrolidines, N-alkylpyrrolidinones, ization it is then preferred to use a control reagent of the N-alkylpyrrollidones, polyethylene glycols, polypropylene general formula: glycols, amides, carboxylic acids and Salts thereof, esters, organoSulfides, Sulfoxides, Sulfones, alcohol derivatives, (I) hydroxy ether derivatives, amino alcohols, ketones, and the S like, and also derivatives and mixtures thereof. RN ls - R' 0043. The polymerization time is between 2 and 72 S S hours, depending on conversion and temperature. The higher (II) the reaction temperature can be chosen, i.e., the higher the S thermal stability of the reaction mixture, the lower the R us reaction time. Ns R1 0044) For the initiators which undergo thermal decom position, the introduction of heat is essential to initiate the 0050 in which R and R', chosen independently of one polymerization. For the thermally decomposing initiators another or identical, are the polymerization can be initiated by heating at from 50 to 0051 branched and unbranched C to Cs alkyl 160 C., depending on initiator type. radicals; C to Calkenyl radicals; C to Cs alkynyl 0.045 For the preparation of acrylic hotmelt PSAs it may radicals, also be of advantage to polymerize the acrylic PSAs in bulk. It is particularly appropriate here to employ the prepolymer 0052 C to C alkoxy radicals; ization technique. The polymerization is initiated with UV 0053 C. to C alkynyl radicals; C to Cs alkenyl light but conducted only to a low conversion rate of about radicals; C to Cs alkyl radicals Substituted by at 10-30%. This polymer syrup can then be welded into films, least one OH group or a halogen atom or a silyl ether; for example (in the most simple case, ice cubes) and then polymerized in water to a high conversion rate. The resulting 0054 C. to Cls heteroalkyl radicals having at least pellets can then be employed as acrylic hotmelt adhesives, one oxygen atom and/or one NR* group in the the film materials used for the melting operation being, with carbon chain, R representing any (especially particular preference, those which are compatible with the organic) radical; polyacrylate. 0055 C to C alkynyl radicals, C. to Cs alkenyl 0046) Another advantageous preparation process for the radicals, C to Cs alkyl radicals Substituted by at poly(meth)acrylate PSAS is anionic polymerization. In this least one ester group, amine group, carbonate group, case it is preferred to use inert Solvents as the reaction cyano group, isocyanato group and/or epoxide group medium, Such as aliphatic and cycloaliphatic hydrocarbons, and/or by Sulfur, for example, or else aromatic hydrocarbons. 0056 C to C cycloalkyl radicals; 0047. In this case the living polymer is generally repre 0057 C to Caryl or benzyl radicals; sented by the structure P(A)-Me, in which Me is a metal from group I, Such as lithium, Sodium or potassium, and 0.058 hydrogen. P(A) is a growing polymer block of the monomers A. The 0059 Control reagents of type (I) are chosen preferably molar mass of the polymer to be prepared is controlled by the ratio of initiator concentration to monomer concentra from further-restricted compounds, as follows: tion. Examples of Suitable polymerization initiators include 0060 Halogen atoms therein are preferably F, Cl, Br or n-propyllithium, n-butyllithium, Sec-butyllithium, 2-naphth 1, more preferably Cl and Br. AS alkyl, alkenyl, and US 2003/0143413 A1 Jul. 31, 2003

alkynyl radicals in the various Substituents, both linear the corresponding Self-adhesive tapes would exhibit very and branched chains are outstandingly Suitable. high outgassing behavior. In order to circumvent this draw back of low conversions, in one particularly preferred pro 0061 Examples of alkyl radicals containing from 1 to 18 cedure the polymerization is initiated a number of times. carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-eth 0073. As a further controlled radical polymerization ylhexyl, t-octyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, method it is possible to carry out nitroxide-controlled poly hexadecyl and octadecyl. merizations. In an advantageous procedure, radical Stabili 0062) Examples of alkenyl radicals having from 3 to 18 zation is effected using nitroxides of type (Va) or (Vb): carbon atoms are propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2- (Va) dodecenyl, isododecenyl and oleyl. R5 R6 0.063 Examples of alkynyl having from 3 to 18 carbon atoms are propynyl, 2-butynyl, 3-butynyl, n-2-octynyl and ">ukR3 R8 n-2-octadecynyl. O 0064. Examples of hydroxy-substituted alkyl radicals are (Vb) hydroxypropyl, hydroxybutyl and hydroxyhexyl. R R10 0065 Examples of halogen-substituted alkyl radicals are dichlorobutyl, monobromobutyl and trichlorohexyl. 0.066 A suitable C-Cls heteroalkyl radical having at least one oxygen atom in the carbon chain is, for example, -CH-CH-O-CH-CH 0067 Examples of C-C cycloalkyl radicals include cyclopropyl, cyclopentyl, cyclohexyl and trimethylcyclo 0.074 where R3, R4, R5, R6, R7, R8, R9, and R10 hexyl. independently of one another denote the following com pounds or atoms: 0068 Examples of C-Cs aryl radicals include phenyl, naphthyl, benzyl, 4-tert-butylbenzyl or further substituted 0075) i) halides, Such as chlorine, bromine or iodine, phenyl, Such as ethylbenzene, toluene, Xylene, mesitylene, 0076 ii) linear, branched, cyclic, and heterocyclic isopropylbenzene, dichlorobenzene or bromotoluene. hydrocarbons having from 1 to 20 carbon atoms, 0069. The above listings serve only as examples of the which may be Saturated, unsaturated or aromatic, respective groups of compounds, and make no claim to 0.077 iii) esters -COOR', alkoxides —OR'' and/ completeness. or phosphonates-PO(OR"), 0070 Moreover, compounds of the following types may also be used as control reagents 0078 where R', R', and R' stand for radicals from group ii).

(III) 0079 Compounds of structure (Va) or (Vb) may also be O attached to polymer chains of any kind (primarily in the Sense that at least one of the abovementioned radicals

RN S ls S - R' constitutes a polymer chain of this kind) and may therefore (IV) be used to construct the polyacrylate PSAS. R2 0080 With more preference, controlled regulators which can be chosen from the following list are used for the N polymerization:

R n S ls S - R' 0081) 2,2,5,5-tetramethyl-1-pyrrolidinyloxyl (PROXYL), 3-carbamoyl-PROXYL, 2,2-dimethyl 4,5-cyclohexyl-PROXYL, 3-oxo-PROXYL, 3-hy 0071 where likewise R2 may be chosen independently of droxylimine-PROXYL, 3-aminomethyl-PROXYL, R and R1 but from the above-recited group for these 3-methoxy-PROXYL, 3-t-butyl-PROXYL, 3,4-di-t- radicals. butyl-PROXYL 0072. In the case of the conventional “RAFT process, 0082 2.2,6,6-tetramethyl-1-piperidinyloxyl polymerization is normally carried out only to low conver (TEMPO), 4-benzoyloxy-TEMPO, 4-methoxy sions (WO 98/01478 A1) in order to obtain very narrow TEMPO, 4-chloro-TEMPO, 4-hydroxy-TEMPO, molecular weight distributions. As a result of the low 4-oxo-TEMPO, 4-amino-TEMPO, 2.2,6,6-tetra conversions, however, these polymers cannot be used as ethyl-1-piperidinyloxyl, 2.2,6-trimethyl-6-ethyl-1- PSAs and in particular not as hotmelt PSAs, since the high piperidinyloxyl fraction of residual monomers adversely affects the technical adhesive properties; the residual monomers would contami 0083 N-tert-butyl 1-phenyl-2-methylpropyl nitrox nate the Solvent recyclate in the concentration proceSS and ide US 2003/0143413 A1 Jul. 31, 2003

0084) N-tert-butyl 1-(2-naphthyl)-2-methylpropyl is that of concentration using a single- or twin-Screw nitroxide extruder. The twin-Screw extruder may be operated corotat ingly or counterrotatingly. The Solvent or water is distilled 0085 N-tert-butyl 1-diethylphosphono-2,2-dimeth off preferably by way of Several vacuum Stages. Moreover, ylpropyl nitroxide counterheating is carried out depending on the 0.086 N-tert-butyl 1-dibenzylphosphono-2,2-dim temperature of the Solvent. The residual Solvent fractions are ethylpropyl nitroxide preferably <1%, more preferably <0.5% and very preferably 0.087 N-(1-phenyl-2-methylpropyl) 1-dieth <0.2%. The hotmelt is processed further from the melt. ylphosphono-1-methylethyl nitroxide 0096. In one preferred embodiment, orientation within the PSA is produced by the coating process. For coating as 0088 di-t-butyl nitroxide a hotmelt, and hence also for orientation, it is possible to 0089 diphenyl nitroxide employ a variety of coating techniques. In one embodiment the polyacrylate PSAS are coated by a roll coating process, 0090) t-butyl t-amyl nitroxide. and the orientation is produced by drawing. Various roll 0.091 A range of further polymerization methods in coating techniques are described in the “Handbook of Pres accordance with which the PSAS may alternatively be sure Sensitive Adhesive Technology” by Donatas Satas (van prepared can be chosen from the prior art: Nostrand, New York, 1989). In another version the orienta tion is achieved by coating through a melt die. A distinction 0092 U.S. Pat. No. 4,581,429 Adiscloses a controlled can be made here between the contact proceSS and the non growth radical polymerization process which uses as its contact process. Orientation of the PSA here can be pro initiator a compound of the formula R'R"N-O-Y, in duced on the one hand within the coating die, by virtue of which Y denotes a free radical species which is able to the die design, or else following emergence from the die, by polymerize unsaturated monomers. In general, how a drawing process. The orientation is freely adjustable. The ever, the reactions have low conversion rates. A par draw ratio can be controlled, for example, by the width of ticular problem is the polymerization of acrylates, the die gap. Drawing occurs whenever the layer thickness of which takes place only with very low yields and molar the PSA film on the backing material to be coated is less than masses. WO 98/13392 A1 describes open-chain the width of the die gap. alkoxyamine compounds which have a symmetrical Substitution pattern. EP 735 052 A1 discloses a process 0097. In another preferred process, the orientation is for preparing thermoplastic elastomers having narrow achieved by extrusion coating. Extrusion coating is prefer molar mass distributions. WO 96/24620A1 describes a ably performed using an extrusion die. The extrusion dies polymerization process in which very specific radical used may originate with advantage from one of the three compounds, Such as phosphorus-containing nitroxides following categories: T-dies, fishtail dies, and coathanger based on imidazolidine, are used. WO 98/44008 A1 dies. The individual types differ in the design of their flow discloses Specific nitroxyls based on morpholines, pip channel. Through the form of the extrusion die it is likewise erazinones and piperazinediones. DE 199 49 352 A1 possible to produce an orientation within the hotmelt PSA. describes heterocyclic alkoxyamines as regulators in Additionally, here, in analogy to melt die coating, it is controlled-growth radical polymerizations. Corre likewise possible to obtain an orientation following emer sponding further developments of the alkoxyamines or gence from the die, by drawing the PSA tape film. of the corresponding free nitroxides improve the effi 0098. In order to produce oriented acrylic PSAs, it is ciency for the preparation of polyacrylates (Hawker, particularly preferred to carry out coating onto a backing contribution to the National Meeting of The American using a coathanger die, Specifically in Such a way that a Chemical Society, Spring 1997; Husemann, contribu polymer layer is formed on the backing by means of a tion to the IUPAC World Polymer Meeting 1998, Gold movement of die relative to backing. Coast). 0099. The time which elapses between coating and 0093. As a further controlled polymerization method, crosslinking is preferably short. In one preferred procedure, atom transfer radical polymerization (ATRP) can be used crosslinking is carried out after less than 60 minutes, in advantageously to Synthesize the polyacrylate PSAS, in another preferred procedure, after less than 3 minutes, and in which case use is made preferably as initiator of monofunc a very preferred procedure, in an inline process, after leSS tional or difunctional Secondary or tertiary halides and, for than 5 Seconds. abstracting the halide(s), of complexes of Cu, Ni, Fe, Pd, Pt, 0100. The backing material to which the PSA is applied Ru, Os, Rh, Co, Ir, Ag or Au (EPO 824 111A1; EP826 698 may be a single-sided or double-sided adhesive tape with at A1; EP824 11.0 A1; EP 841 346 A1; EP 850 957 A1). The least one permanent backing (or carrier). various possibilities of ATRP are further described in U.S. 0101. In one preferred procedure, coating is carried out Pat. Nos. 5,945,491 A, 5,854,364A, and 5,789,487 A. directly onto a backing material. The PSA is applied pref erably to one or both sides of the backing material. Suitable 0094. Orientation, Coating Processes, Application of the backing materials include, in principle, films such as BOPP Pressure Sensitive Adhesive to the Backing Material or MOPP, PET or PVC, for example, or papers or nonwov 0.095. In order to produce oriented PSAs, the polymers ens (based on: cellulose or polymers). Also Suitable, more described above are preferably coated as hotmelt Systems over, as coating Substrates are foams (e.g., PUR, PE, (i.e., from the melt). For the production process it may PE/EVA, EPDM, PP, PE, silicone, etc.) or release papers therefore be necessary to remove the solvent from the PSA. (glassine paper, kraft paper, polyolefin-coated paper) or In principle it is possible here to use any of the techniques release films (PET, PP or PE, or combinations of these known to the skilled worker. One very preferred technique materials). US 2003/0143413 A1 Jul. 31, 2003

0102) As an alternative, it is also possible to punch medium. As a result of the contact medium it is possible in unbacked PSA tapes. In this case, the Support material to turn to carry out very rapid cooling of the PSA. Advanta which the PSA is applied comprises a temporary Support, on geously, is then carried out onto the backing which the material to be punched, Such as an adhesive tape material later. which is unbacked per se, is reversibly placed. Particularly 0112 Furthermore, as the contact medium it is also Suitable for this purpose are correspondingly coated Support possible to use a material which has the capacity to bring materials, Such as the release paperS or release films about contact between the PSA and the Surface of the roller, described above. especially a material which fills the cavities between back 0103 Temporary supports of this kind may also be used ing material and roller Surface (for example, unevennesses in additionally for materials with a backing, particularly for the roller surface, bubbles). In order to implement this Stabilization purposes during the punching operation. technology, a rotating cooling roller is coated with a contact 0104. Additionally, and particularly for the purpose of medium. In one preferred procedure the contact medium separating the individual PSA webs, the material to be chosen is a liquid, Such as water, for example. punched may advantageously be lined with release film or 0113 Examples of appropriate additives to water as the release paper. contact medium include alkyl alcohols Such as ethanol, 0105 The best orientation effects are obtained by depo propanol, butanol, and hexanol, without wishing to be Sition onto a cold Surface. Consequently, the backing mate restricted in the Selection of the alcohols as a result of these rial during coating Should be cooled directly by means of a examples. Also especially advantageous are longer-chain roller. The roller can be cooled by a liquid film/contact film alcohols, polyglycols, ketones, amines, carboxylates, Sul from the outside or inside, or by a coolant gas. The coolant fonates, and the like. Many of these compounds lower the gas may likewise be used to cool the adhesive emerging Surface tension or raise the conductivity. from the coating die. In one preferred procedure the roller is 0114. A lowering in the surface tension may also be wetted with a contact medium, which is then located achieved by adding Small amounts of nonionic and/or between the roller and the backing material. Preferred anionic and/or cationic Surfactants to the contact medium. embodiments for the implementation of Such a technique are The most simple way of achieving this is by using commer described later on below. cial washing compositions or Solutions, preferably in a 0106 For this process it is possible to use both a melt die concentration of a few g/l in water as the contact medium. and an extrusion die. In one very preferred procedure the Particularly Suitable compounds are special Surfactants roller is cooled to room temperature, in an extremely pre which can be used even at low concentrations. Examples thereof include Sulfonium Surfactants (e.g., f-di(hydroxy ferred procedure to temperatures below 10° C. The roller alkyl)sulfonium salt), and also, for example, ethoxylated ought to rotate as well. nonylphenylsulfonic acid ammonium Salts or block copoly 0107. In a further procedure as part of this preparation mers, especially diblocks. Here, reference may be made in process, moreover, the roller is used for crosslinking of the particular to the state of the art under “surfactants” in oriented PSA. Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edi 0108 UV crosslinking is effected by irradiation with tion, 2000 Electronic Release, Wiley-VCH, Weinheim 2000. Shortwave ultraViolet radiation in a wavelength range from 0115 AS contact media it is possible to use the above 200 to 400 nm, depending on the UV photoinitiator used, mentioned liquids, even without the addition of water, in especially using high or medium preSSure lamps each case alone or in combination with one another. with an output of from 80 to 240 W/cm. The irradiation intensity is adapted to the respective quantum yield of the 0116. In order to improve the properties of the contact UV photoinitiator, the degree of croSSlinking to be brought medium (for example, for increasing the shearing resistance, about, and the extent of the orientation. reducing the transfer of Surfactants or the like to the Surface of the liner, and thus improve cleaning possibilities of the 0109) A further option is to crosslink the polyacrylate end product), Salts, gels, and similar Viscosity-increasing PSA with electron beams. Typical irradiation equipment additives may also be added with advantage to the contact which may be used include linear Systems, Scanner medium and/or to the adjuvants used. Systems, and Segmented cathode Systems, where electron beam accelerators are concerned. A detailed description of 0117 Moreover, the roller can be macroscopically the State of the art, and the most important process param Smooth or may have a Surface with a low level of structuring. eters, can be found in Skelhorne, Electron Beam Processing, It has been found appropriate for the roller to possess a in Chemistry and Technology of UV and EB formulation for Surface Structure, especially a Surface roughening. This Coatings, Inks and Paints, Vol. 1, 1991, SITA, London. The allows wetting by the contact medium to be improved. typical acceleration Voltages are situated in the range 0118. The coating process proceeds to particularly good between 50 kV and 500 kV, preferably between 80 kV and effect if the roller is temperature-controllable, preferably 300 kV. The scatter doses employed range between 5 and with a range from -30° C. to 200 C., with very particular 150 kGy, in particular between 20 and 100 kGy. preference from 5° C. to 25° C. 0110. It is also possible to employ both crosslinking 0119) The contact medium is preferably applied to the methods, or other methods which permit high-energy irra roller. A Second roller, which takes up the contact medium, diation. may be used for continuous wetting of the coating roller. It 0111. In a further preferred preparation process, the ori is, however, also possible to carry out contactleSS applica ented PSAS are coated onto a roller provided with a contact tion, by Spraying, for example. US 2003/0143413 A1 Jul. 31, 2003

0120 For the variant of the preparation process in which conventionally from Solution or from water. In one preferred the roller is used Simultaneously for use, for example, with procedure, then, this drawn PSA is in turn crosslinked with electron beams, it is common to use a grounded metal roller actinic radiation. which absorbs the incident electrons and the X-radiation that has formed. 0129. Punching Processes 0.130. In the inventive process the punching process takes 0121. In order to prevent corrosion, the roller is com place continuously. For punching processes of this kind it is monly coated with a protective coat. This coat is preferably possible with outstanding effect to make use, for example, of selected so that it is wetted effectively by the contact rotary punches. The punching process may be a punch medium. In general, the Surface is conductive. It may also be through proceSS or a kiss-cut process. Accordingly, the more favorable, however, to coat it with one or more coats following variants may be implemented advantageously: of insulating or Semiconducting material. 0131 the punching process severs the adhesive on 0122) Where a liquid is used as the contact medium, one the backing material completely, outstanding procedure is to run a Second roller, advanta 0132 the punching process severs the adhesive on geously having a wettable or absorbent Surface, through a the backing material incompletely, bath containing the contact medium, Said roller then becom ing wetted by or impregnated with the contact medium and 0.133 the punching process severs the adhesive applying a film of Said contact medium by contact with the coated backing material completely, roller. 0.134 the punching process does not sever or only 0123. In one preferred procedure, the PSA is coated partly Severs the adhesive-coated backing material. directly on the contact medium roller, and crosslinked. For 0.135 Advantageously, the backing material with the PSA this purpose it is possible in turn to use the methods and applied to it can be introduced into the punching proceSS in equipment described for UV crosslinking and EB crosslink Such a way that the working direction (machine direction, ing. Then, following crosslinking, the oriented PSA is trans MD) corresponds to the preferential direction VR of the PSA ferred onto a backing material. The backing materials or, alternatively, perpendicularly thereto. Very advanta already cited can be used. geously, the PSA guided through the punching proceSS and the punching tools are aligned with respect to one another in 0.124. The characterization of the orientation within the Such a way that the punched incisions extend preferably acrylic PSAS is dependent on the coating process. The perpendicular to the preferential direction of the PSA. orientation can be controlled, for example, by the die 0.136. Application of the PSA to the backing material, and temperature and coating temperature and also by the the Subsequent punching process, can be implemented in an molecular weight of the polyacrylate PSA. inline process, i.e., in a combined unit and/or in a continuous 0.125 The degree of orientation is freely adjustable Sequence. through the die gap width. The thicker the PSA film 0.137 Alternatively, it may be very advantageous to sepa expressed from the coating die, the greater the extent to rate the coating process from the punching proceSS in terms which the adhesive can be drawn to a relatively thin PSA film on the backing material. This drawing operation may be of time and/or space. freely adjusted not only by the freely adjustable die width 0.138. These punching operations may advantageously be but also by the web speed of the decreasing backing mate built into operations, So that the inventive process advanta rial. geously comprises two or more, or all, of the following StepS. Described by way of example is the processing of a 0.126 The orientation of the adhesive can be measured double-sided PSA tape. with a polarimeter, by infrared dichroism, or using X-ray Scattering. It is known that in many cases the orientation in 0.139 Variant A, Continuous Operation: acrylic PSAs in the uncrosslinked state is retained only for 0140) 1. Unwinding of the double-sided test adhesive a few days. During rest or Storage, the System relaxes and tape and of the Siliconized auxiliary release material. loses its preferential direction. As a result of crosslinking 0141 2. Laminating a siliconized auxiliary release after coating, this effect can be strengthened significantly. material upstream of the rotary punching from The relaxation of the oriented polymer chains converges above onto the open, Sticky Side of the test adhesive toward Zero, and the oriented PSAS can be stored for a very tape. long period of time without loSS of their preferential direc tion. 0142. 3. Rotary punching: severing of the siliconized auxiliary release material and of the adhesive bond. 0127. In addition to measuring the orientation by deter Ideally, penetration of the punching tools into the mining the An (test C), the measurement of the Shrinkback Siliconized Surface of the original release material of in the free film (see test B) is likewise suitable for deter the double-sided test adhesive tape is minimal. mining the orientation and the anisotropic properties of the 0.143 4. Matrix stripping: stripping of the lattice. The PSA. punched products remain on the original release mate 0128. In addition to the processes described, the orienta rial. tion may also be produced following coating. In that case, 0144) 5. Rolling up of the finished products (i.e., then, an extensible backing material is preferably employed, punched products on original release material backing, with the PSA being drawn at the same time as stretching. In lined with auxiliary release material) and of the this case it is also possible to use acrylic PSAS coated Stripped matrix. US 2003/0143413 A1 Jul. 31, 2003

0145 Variant B, Continuous Operation: 0164. Experiments 0.165. The invention is described below by means of 0146 1. Unwinding of the double-sided test adhesive experiments, without wishing to impose any unnecessary tape and of the Siliconized auxiliary release material. restriction by the choice of Samples investigated. 0147 2. Laminating of the test adhesive tape with the 0166 The following test methods have been employed. Sticky Side downward onto a Siliconized auxiliary release material upstream of the rotary punching cyl 0167) Gel Permeation Chromatography GPC (Test A) inder. 0.168. The average molecular weight Mw and the poly dispersity PD were determined by gel permeation chroma 0.148. 3. Rotary punching: severing of the double-sided tography. The eluent used was THF containing 0.1% by Siliconized auxiliary release material and of the adhe volume trifluoroacetic acid. Measurement was made at 25 Sive bond. Ideally, penetration of the punching tools C. The precolumn used was PSS-SDV, 5u, 10 A, ID 8.0 into the Siliconized Surface of the auxiliary release mmx50 mm. Separation was carried out using the columns material is minimal. PSS-SDV, 5u, 10 and also 105 and 106 each with ID 8.0 mmx300 mm. The sample concentration was 4 g/l, the flow 0149 4. Matrix stripping:pping strippingpping of the lattice. The rate 1.0 ml per minute. Measurement was made against punched products remain on the Siliconized auxiliary PMMA standards. release material. 0169 Measurement of the Shrinkback (Test B) 0150 5. Rolling up of the finished products (i.e., 0170 Strips with a width of at least 30 mm and a length punched products on auxiliary release material back of 20 cm were cut parallel to the coating direction of the ing, lined with original release material) with the hotmelt. At application rates of 100 g/m, 4 strips were punched products, and of the Stripped matrix. laminated to one another, at 50 g/m 8 strips were laminated to one another, in order to give comparable layer thick 0151 Examples of the speed at which the adhesive nesses. The Specimen obtained in this way was then cut to coated backing material runs through the unit are from 0.1 a width of exactly 20 mm and was overStuck at each end m/min to 100 m/min. Common current real-life speeds for with paper Strips, with a spacing of 15 cm. The test Specimen punching processes are from 10 to 30 m/min. thus prepared was then Suspended vertically at RT and the 0152 FIG. 2 and FIG. 3 illustrate, by way of example, change in length was monitored over time until no further two cross sections through punching units of this kind, FIG. Shrinkage of the sample could be found. The initial length 2 including an integrated laminating Station. In these figures, reduced by the final value was then reported, relative to the the reference numerals have the following meanings: initial length, as the Shrinkback, in percent. 0171 For measuring the orientation after a longer time, 0153 1 rotary punching unit the coated and oriented pressure Sensitive adhesives were Stored in the form of Swatches for a prolonged period, and 0154 2 matrix stripper then analyzed. O155 3 unwinder for the siliconized release material 0172 Measurement of the Birefringence (Test C) 0156 4 unwinder for the material to be punched, 0173 Version 1 especially the adhesive tape 0.174. Two crossed polarization filters were placed in the O157) 5 winder for the matrix sample beam of a Uvikon 910 spectrophotometer. Oriented acrylates were fixed between two slides. The path length of 0158 6 winder for the finished product the oriented Sample was determined from preliminary experiments by means of thickness gauges. The Sample thus 0159) 7 tension station prepared was placed in the measuring beam of the Spectro photometer with its direction of orientation deviating in each 0160 8 laminating Station case by 45 from the optical axes of the two polarization 0161) Use filters. The was then monitored over time by means of a time-resolved measurement. 0162 The invention additionally provides punched prod 0.175. The transmission data were then used to determine ucts which can be or have been obtained by the inventive the birefringence in accordance with the following relation proceSS in one of its embodiments. ship: 0163 Punched products of this kind can be used as T=sin(1xR) Single-sided or double-sided adhesive products, for adhesive bonding in the home and in industry, especially in automo tive construction, in the electrical and industry, R An for all assembly purposes, Such as for assembly of Signs, - A l badges, and film keyboards, for example, in the medical T = - Sector (patches, wound coverings) and the like, to mention o but a few exemplary applications. Generally Speaking, the punched products can be used wherever punched single An = -arcsintd WT. sided adhesive labels and double-sided adhesive films are presently in use. US 2003/0143413 A1 Jul. 31, 2003

0176) In the formulae, constantly at this external temperature. After a reaction time of 1 hour a further 40g of AIBN were added. After 5 hours 0177) d=sample thickness and 10 hours, dilution was carried out in each case with 15 0178 2-wavelength kg of acetone/isopropanol (95:5). After both 6 hours and 8 hours, 100 g of dicyclohexyl peroxydicarbonate (Perkadox 0179 I=intensity of the emergent (transmitted) light 16(R), Akzo Nobel) in solution each in 800g of acetone were beam added. The reaction was terminated after a time of 24 hours, 0180) I=intensity of the incident light beam and the product was cooled to room temperature. Determi nation of the molecular weight by test A gave an Mw-801 0181 Version 2 000 g/mol with a polydispersity Mw/Mn=5.7. 0182. The birefringence was measured with an experi mental Setup Such as described analogously in the Encyclo 0188) i) Sample Preparation for Determining the Shrink pedia of Polymer Science, John Wiley & Sons, Vol. 10, p. back 505, 1987 as a circular polariscope. The light emitted by a 0189 The pressure sensitive adhesives in solution were diode-pumped Solid-State laser of wavelength 2–532 nm is concentrated on a Bersdorff concentrating extruder with a first of all linearly polarized by a polarization filter and then throughput of approximately 40 kg/h at a temperature of circularly polarized using a 2/4 plate with =532 nm. The approximately 115 C. Following concentration the residual laser beam thus polarized is then passed through the oriented solvent fraction was less than 0.5% by weight. The compo acrylate composition. Since acrylate compositions are sition was then coated onto a 12 um PET film coated highly transparent, the laser beam is able to pass through the beforehand with 1.5 g/m silicone (polydimethylsiloxane), composition virtually unhindered. Where the polymer mol application of the composition taking place through a ecules of the acrylate composition are oriented, this results coathanger extrusion die with a die gap of 300 um and a in a change in the polarizability of the acrylate composition coating width of 33 cm, at a defined coating temperature depending on observation angle (birefringence). As a result (composition temperature) and a web speed of 10 m/min. of this effect, the electrical field vector of the circularly The draw ratio was set at 3:1 for an application rate of 100 polarized laser beam undergoes a rotation about the axis of um2 (PSA film approximately 100 um thick) and at 6:1 at an progression of the laser beam. After departing the Sample, application rate of 50 g/m2 (PSA film approximately 50 um the laser beam thus manipulated is passed through a Second thick). 2/4 plate with 2–532 nm whose optical axis deviates by 90 0190. The siliconized PET film is passed over a corotat from the optical axis of the first 2/4 plate. This filter is ing Steel roller which is cooled to 5 C. At the point of followed by a second polarization filter which likewise contact between the PSA film and the PET film, therefore, deviates by 90 from the first polaroid filter. Finally, the the PSA film is immediately cooled. The application rate intensity of the laser beam is measured using a photoSensor. was 50 or 100 g/m. In the inline process, after a section of 0183 Preparation of the Samples about 5 m, the PSA tape is then crosslinked either with UV 0184 Polymer 1 radiation or electron beams. 0185. A 200 L reactor conventional for radical polymer 0191 For electron beam irradiation, crosslinking was izations was charged with 2 400 g of acrylic acid, 64 kg of carried out with an instrument from Electron Crosslinking 2-ethylhexyl acrylate, 6.4 kg of N-isopropylacrylamide and AB, Halmstad, Sweden. The coated PSA tape was passed 53.3 kg of acetone/isopropanol (95:5). After gas through under the Lenard window of the accelerator over a had been passed through for 45 minutes with Stirring, the cooling roller which is present as Standard. In the irradiation reactor was heated to 58 C. and 40 g of 2,2'-azoisobuty Zone, the atmospheric oxygen is displaced by flushing with ronitrile (AIBN) were added. The external heating bath was pure nitrogen. The Web Speed was in each case 10 m/min. then heated to 75 C. and the reaction was carried out Irradiation was carried out with an accelerating Voltage of constantly at this external temperature. After a reaction time 200 kV. of 1 hour a further 40g of AIBN were added. After 5 hours 0.192 For UV irradiation, a medium pressure mercury and 10 hours, dilution was carried out in each case with 15 vapor lamp from Eltosch with an intensity of 160 W/cm’ kg of acetone/isopropanol (95:5). After both 6 hours and 8 was used. The UV dose was approximately 1.6 J/cm. hours, 100 g of dicyclohexyl peroxydicarbonate (Perkadox Irradiation was carried out under an air atmosphere. 16(R), Akzo Nobel) in solution each in 800g of acetone were added. The reaction was terminated after a time of 24 hours, 0193 In order to determine the shrinkback and therefore and the product was cooled to room temperature. Determi the extent of orientation, test B was carried out. nation of the molecular weight by test A gave an Mw =814 0194 ii) Preparation of the Oriented PSA Tapes for the 000 g/mol with a polydispersity Mw/Mn=5.2. Punching Process 0186 Polymer 2 0195 A procedure analogous to that under i) was fol 0187. A 200 L reactor conventional for radical polymer lowed. However, the backing material used was a 12 um izations was charged with 1200 g of acrylic acid, 74 kg of thick PET film which had been freshly corona pretreated. All 2-ethylhexyl acrylate, 4.8 kg of N-isopropylacrylamide and process parameters (web speed, coating temperature, draw 53.3 kg of acetone/isopropanol (95:5). After nitrogen gas ratio, polyacrylate PSA, crosslinking dose) were kept con had been passed through for 45 minutes with Stirring, the stant. To produce the punched products, the PSA was first reactor was heated to 58 C. and 40 g of 2,2'-azoisobuty coated onto the corona-treated PET film, and crosslinked, ronitrile (AIBN) were added. The external heating bath was and then the adhesive side was lined with a release paper then heated to 75 C. and the reaction was carried out (120 um polyolefinically (PE) coated paper, Siliconized on US 2003/0143413 A1 Jul. 31, 2003 both sides, 1.4 g/m polydimethylsiloxane, from Loparex or onto a 12 um thick PET film. The coating temperature was 100 um glassine release paper, Siliconized on one Side, cf. 150 C. Crosslinking was carried out with a UV dose of 2.5 table 2). In the second step, the PSA already crosslinked J/cm°. from i) was laminated onto the other side of the PET film, the PSAbeing pressed on by a roller and then the siliconized 0214) PSA Tape E PET film being delaminated. Finally, the double-sided PSA 0215 Polymer 1 in solution is blended with 0.5% by tape was rolled up. weight of isopropylthioxanthone (Speedcure ITX, from 0196. The second work step was dropped for the produc Rahn), based on the polymer. Subsequently, the blend is tion of just Single-sided adhesive specimens. concentrated as in i) and, as in ii), is coated at 2x50 g/m 0197 FIG. 4 shows a sketch of the structure of the onto a 12 um thick PET film. The coating temperature was corresponding Specimens. 150 C. Crosslinking was carried out with a UV dose of 2.0 J/cm. 0198 In FIG.4, the reference numerals have the follow ing meanings: 0216) PSA Tape F 0199. 1 anisotropic pressure sensitive adhesive 0217 Polymer 1 in solution is blended with 2% by 0200 2 PET film backing, in this case 12 um weight of Genomer 42120B (polyurethane diacrylate from Rahn) and with 30% by weight of DT 110 (terpene-phenolic 0201 3 anisotropic pressure sensitive adhesive resin from DRT). Subsequently, the blend is concentrated as in i) and, as inii), is coated at 2x100 g/monto a 12 um thick 0202) 4 release material PET film. The coating temperature was 150° C. Crosslinking 0203 iii) Preparation of the Unoriented PSA Tapes for was carried out with an EB dose of 70 kGy. the Punching Process 0218 PSA Tape G 0204. The pressure sensitive adhesives in solution were coated onto a Siliconized release paper (120 um polyolefini 0219 Polymer 1 in solution is blended with 2% by cally (PE) coated paper, siliconized on both sides, 1.4 g/m weight of Genomer 42120B (polyurethane diacrylate from polydimethylsiloxane, from LopareX or 100 um glassine Rahn) and with 30% by weight of DT 110 (terpene-phenolic release paper, Siliconized on one side, cf. table 2) (applica resin from DRT). Subsequently, the blend is concentrated as tion method: coating bar). In a drying tunnel the Solvent was in i) and, as inii), is coated at 2x50 g/monto a 12 um thick removed through a plurality of temperature Zones, heating PET film. The coating temperature was 150° C. Crosslinking being carried out at 50° C. in the first Zone, then at 80 C., was carried out with an EB dose of 70 kGy. and at 100° C. in the last three heating Zones. The web speed was 10 m/min. Following removal of the solvents thermally, 0220 PSA Tape H the 12tum thick PET film was laminated on. In a second step, dissolved PSA was coated in turn onto the PET film of this 0221) Polymer 1 in solution is blended with 2% by assembly. The solvent was removed thermally. Finally, the weight of Genomer 42120B (polyurethane diacrylate from double-sided PSA tape was rolled up. Rahn) and with 30% by weight of DT 110 (terpene-phenolic resin from DRT). Subsequently, the blend is concentrated as 0205 The second work step was dropped for the produc in i) and, as inii), is coated at 2x100 g/monto a 12 um thick tion of just Single-sided adhesive specimens. PET film. The coating temperature was 150° C. Crosslinking 0206 PSA Tape A was carried out with an EB dose of 70 kGy. 0207 Polymer 1 is concentrated as in i) and, as in ii), is 0222 PSA Tape I coated at 2x100 g/m· onto a 12 um thick PET film. The 0223 Polymer 1 in solution is blended with 0.5% by coating temperature was 150 C. Crosslinking was carried weight of isopropylthioxanthone (Speedcure ITX, from out with an EB dose of 30 kGy. Rahn), 2.5% by weight of Genomer 4212(R) (polyurethane 0208 PSA Tape B diacrylate from Rahn) and with 30% by weight of DT 110 0209 Polymer 1 is concentrated as in i) and, as in ii), is (terpene-phenolic resin from DRT). Subsequently, the blend coated at 2x50 g/m onto a 12 um thick PET film. The is concentrated as in i) and, as in ii), is coated at 2x50 g/m coating temperature was 150 C. Crosslinking was carried onto a 12 um thick PET film. The coating temperature was 150 C. Crosslinking was carried out with a UV dose of 3.0 out with an EB dose of 30 kGy. J/cm°. 0210 PSA Tape C 0224 PSA Tape J 0211 Polymer 1 is concentrated as in i) and, as in ii), is coated at 100 g/monto a 12 um thick PET film. The coating 0225 Polymer 2 in solution is blended with 2% by temperature was 150° C. Crosslinking was carried out with weight of Genomer 42120B (polyurethane diacrylate from an EB dose of 30 kGy. Rahn), with 30% by weight of Novares TK 90(R) (C5-C9 hydrocarbon resin from VFT Rittgers) and 8% by weight of 0212 PSA Tape D Reofos 65(R) (oligophosphate from Great Lakes Chemical). 0213 Polymer 1 in solution is blended with 0.5% by Subsequently, the blend is concentrated as ini) and, as in ii), weight of isopropylthioxanthone (Speedcure ITX, from is coated at 2x100 g/monto a 12 um thick PET film. The Rahn), based on the polymer. Subsequently, the blend is coating temperature was 120° C. Crosslinking was carried concentrated as in i) and, as in ii), is coated at 2x100 g/m out with an EB dose of 60 kGy. US 2003/0143413 A1 Jul. 31, 2003

0226 PSA Tape K The drying temperature was not more than 100° C. 0227 Polymer 2 in solution is blended with 2% by Crosslinking was carried out with an EB dose of 70 kGy. weight of Genomer 42120B (polyurethane diacrylate from 0242 PSA Tape T Rahn), with 30% by weight of Novares TK 90(R) (C5-C9 0243 Polymer 2 in solution is blended with 2% by hydrocarbon resin from VFT Rittgers) and 8% by weight of weight of Genomer 42120B (polyurethane diacrylate from Reofos 65(R) (oligophosphate from Great Lakes Chemical). Rahn), 30% by weight of Novares TK 90(R) (C5-C9 hydro Subsequently, the blend is concentrated as ini) and, as in ii), carbon resin from VFT Rittgers) and 8% by weight of is coated at 2x50 g/m· onto a 12 um thick PET film. The Reofos 65(R) (oligophosphate from Great Lakes Chemical). coating temperature was 120° C. Crosslinking was carried Subsequently, the blend, as in iii), is coated at 2x100 g/m out with an EB dose of 60 kGy. onto a 12 um thick PET film. The drying temperature was 0228) PSA Tape L not more than 100° C. Crosslinking was carried out with an 0229 Polymer 2 in solution is blended with 2% by EB dose of 60 kGy. weight of Genomer 42120B (polyurethane diacrylate from 0244) PSA Tape U Rahn), with 30% by weight of Novares TK 90(R) (C5-C9 hydrocarbon resin from VFT Rittgers) and 8% by weight of 0245 Polymer 2 in solution is blended with 2% by Reofos 65(R) (oligophosphate from Great Lakes Chemical). weight of Genomer 42120B (polyurethane diacrylate from Subsequently, the blend is concentrated as ini) and, as in ii), Rahn), 30% by weight of Novares TK 90(R) (C5-C9 hydro is coated at 2x100 g/monto a 12 um thick PET film. The carbon resin from VFT Rittgers) and 8% by weight of coating temperature was 120° C. Crosslinking was carried Reofos 65(R) (oligophosphate from Great Lakes Chemical). out with an EB dose of 60 kGy. Subsequently, the blend, as in iii), is coated at 2x50 g/m onto a 12 um thick PET film. The drying temperature was 0230 PSA Tape M not more than 100° C. Crosslinking was carried out with an 0231 Polymer 1, as in iii), is coated from solution at EB dose of 60 kGy. 2x100 g/m· onto a 12 um thick PET film. The drying 0246 PSA Tape V temperature was not more than 100° C. Crosslinking was carried out with an EB dose of 30 kGy. 0247 Polymer 2 in solution is blended with 2% by weight of Genomer 42120B (polyurethane diacrylate from 0232 PSA Tape N Rahn), 30% by weight of Novares TK 90(R) (C5-C9 hydro 0233 Polymer 1, as in iii), is coated from solution at carbon resin from VFT Rittgers) and 8% by weight of 2x50 g/m onto a 12 um thick PET film. The drying Reofos 65(R) (oligophosphate from Great Lakes Chemical). temperature was not more than 100° C. Crosslinking was Subsequently, the blend, as in iii), is coated at 2x100 g/m carried out with an EB dose of 30 kGy. onto a 12 um thick PET film. The drying temperature was not more than 100° C. Crosslinking was carried out with an 0234) PSA Tape O EB dose of 60 kGy. 0235 Polymer 1, as in iii), is coated from solution at 0248. Additionally as a reference example for investigat 2x100 g/m onto a 12 um thick PET film. The drying ing the punching process, a “SCOTCHOR 9690 Laminating temperature was not more than 100° C. Crosslinking was Adhesive” adhesive tape (3M, Neuss, Germany) was used. carried out with an EB dose of 30 kGy. 0236 PSA Tape P 0249 Results 0250 In a first step, 2 polymers with an average molecu 0237 Polymer 1 in solution is blended with 2% by lar weight Mw of approximately 800 000 g/mol were weight of Genomer 42120B (polyurethane diacrylate from prepared. Using these PSAs, PSA tapes A to V were pro Rahn) and with 30% by weight of DT 110 (terpene-phenolic duced. Single-sided and double-sided PSA tapes were inves resin from DRT). Subsequently, the blend, as in iii), is coated tigated, the backing or carrier material used being a 12 um from solution at 2x100 g/m· onto a 12 um thick PET film. thick PET film. In order to assess the effect of punchability The drying temperature was not more than 100 C. in different processes, a large number of different PSAs were Crosslinking was carried out with an EB dose of 70 kGy. prepared. 0238 PSA Tape R 0251) The PSA present on PSA tapes A,B,C,D,E and 0239) Polymer 1 in solution is blended with 2% by M.N.O was a straight polyacrylate without additive. A and weight of Genomer 42120B (polyurethane diacrylate from B are different only in application rate. PSA tapes D and E Rahn) and with 30% by weight of DT 110 (terpene-phenolic are identical with A and B and differ only in the addition of resin from DRT). Subsequently, the blend, as in iii), is coated UV photoinitiator and in the UV crosslinking mechanism. from solution at 2x50 g/m· onto a 12 um thick PET film. The 0252 PSA tapes F.G.H.I and PRS comprise a polyacry drying temperature was not more than 100° C. Crosslinking late/resin blend. Additionally, a difunctional acrylate is was carried out with an EB dose of 70 kGy. admixed as crosslinker. Because of the addition of resin, the 0240 PSA Tape S bond strength of the PSA tapes is significantly greater. PSA 0241 Polymer 1 in solution is blended with 2% by tapes F and G again differ in application rate, I again in the weight of Genomer 42120B (polyurethane diacrylate from UV crosslinking mechanism. Rahn) and with 30% by weight of DT 110 (terpene-phenolic 0253) PSA tapes J.K.L and T.U.V are highly tacky PSA resin from DRT). Subsequently, the blend, as in iii), is coated tapes of high bond strength. Conventional PSA tapes, Such from solution at 2x100 g/monto a 12 um thick PET film. as TU,V, with soft and tacky adhesives of this kind are US 2003/0143413 A1 Jul. 31, 2003 generally difficult, if not impossible, to punch. Therefore, products is 14 mm from tip to tip. FIG. 5 is a diagram of PSA tapes J.K.L were likewise provided with a very soft, punched products of this kind on the Support material tacky, and oriented PSA, with the polymer being based on (md=MD=machine direction). Reference 1 here refers to the polyacrylate 2. punched products, reference 2 to the Support material. 0254. In a first investigation, the degree of orientation of 0268 Results the individual adhesives was determined. For the punching 0269. By means of anisotropically oriented PSAs, dis process, the recession behavior of the oriented PSAs is tinct proceSS advantages can be achieved in all punching essential, Since this prevents the punched products from processes. AS reference products, the corresponding Solvent running together. Accordingly, below, the Shrinkback in the based products were likewise punched. Since the hotmelt free film was determined for PSA tapes A to V by methodi) products and the Solvent-based products are identical in in combination with test B. The results of these measure terms of formulation, any effect of the formulation as a cause ments are compiled in table 1. of the considerable improvement in punchability can be 0255 Table 2 gives an overview of the properties of the unambiguously ruled out. materials used by way of example for the punching process. 0270. The solvent-based adhesive tapes T.U.V are of only 0256 The examples below given an overview of the limited punchability owing to the soft PSA. The correspond punched products produced, the punching conditions ing oriented hotmelt Specimens J.K.L exhibit outstanding Selected, and the results obtained, which were observed punchability in comparison. during or after the punching process as a function of the 0271 Table 4 gives an overview of the overall punching adhesive tape used. results. 0257 Table 3 gives an overview of the criteria for evalu ating the punching experiments. 0272. As a comparison product, additionally, an adhesive tape from 3M was punched. The double-sided adhesive tape 0258 Overview of the Punching Processes Used: “Scotch (TM) 9690 Laminating Adhesive” gave comparably poor punching results. The error rate range was comparable 0259 Rotary Punch with Continuous Matrix Stripping. with that of the solvent-based adhesive tapes in table 4. 0260 The rotary punch used was from SMO, Germany. FIG. 2 shows the construction of the rotary punch. For the Example 2 different punch shapes, punching cylinders from RotoMet rics International Ltd were used in each case. 0273 Target Product 0261) The roll width of the adhesive materials used was 0274 Square punched products without connecting 130 mm. The release materials laminated to them had a roll webs, lined with Siliconized release material 1 (auxiliary width of 145 mm. release material) on a siliconized Support release material 2 (original release material). The Side edge length of one 0262 The punching experiments with double-sided adhe punched product is 5 mm. Sive tapes were carried out by partial punching (kiss cutting) on the original release material. Upstream of the rotary 0275 FIG. 6 is a diagram of punched products of this punching cylinder, a Second, auxiliary Siliconized release kind on the Support material (md=MD=machine direction). material was laminated from the top onto the open, Sticky Reference 1 here refers to the punched products, reference Side of the test adhesive tape. The auxiliary release material 2 to the Support material. used was a glassine release paper Siliconized on one Side. 0276 Results 0263. The matrix was stripped at an angle of about 800. 0277 Table 5 gives an overview of the punching results. The punching Speed was 18 m/min. The oriented adhesive tapes have only a small number of 0264. The punching experiments with single-sided adhe defects, in the majority of experiments Zero, in comparison Sive tapes were conducted by partial punching (kiss cutting) in to the Solvent Specimens. on a Siliconized auxiliary release material. Prior to the 0278. The matrix lattice has to be removed manually in punching process, the test adhesive tape was laminated on. the machine direction. Manual lattice Stripping at right The auxiliary release material used was a glassine release angles to the machine direction led to Similarly poor error paper Siliconized on one side (thickness: 100 um, from rates as in the case of the Solvent specimens. Laufenberg, Krefeld, Germany). 0265. The matix was stripped at an angle of about 80. Example 3 The punching Speed was 18 m/min. 0279 Target Product EXAMPLES 0280 Circular punched products of double-sidedly adhering material, lined with Siliconized release material 1 Example 1 (auxiliary release material) on a Siliconized Support release material 2 (original release material). The diameter of the 0266 Target Product punched products is 18 mm. 0267 Square punched products without connecting 0281 FIG. 7 is a diagram of punched products of this webs, lined with Siliconized release material 1 (auxiliary kind on the Support material (md=MD=machine direction). release material) on a siliconized Support release material 2 Reference 1 here refers to the punched products, reference (original release material). The diameter of the punched 2 to the Support material. US 2003/0143413 A1 Jul. 31, 2003

0282) Results adhesive tape used. The experiments were each conducted 0283 The circular punched products are characterized by with 20 000 linear meters of test material. Afterward, a a particular degree of difficulty. The shrinkback effect qualitative assessment of the punching tools was made. caused by the molecular stretching acts only at the top and Table 8 gives an overview of the results. bottom margins of the circle. FIG. 8 shows in detail the effect of the anisotropy on the circular punched product. VR 0294 Results indicates the direction of stretching. Positions 1 of the 0295) Anisotropically oriented pressure sensitive adhe punched product show areas without “cold flow”, i.e., areas in which the shrinkback takes effect. Positions 2 show Sives show much less of a tendency to contaminate the regions in which the pressure Sensitive adhesive has flowed punching tools than do their unoriented counterparts. AS a back (severe “fixing”). Reference numeral 3 refers to tran result of the reduced flow in the machine direction by the Sitional regions. anisotropically oriented PSAs, the contact time between 0284. Removal of the lattice matrix operates without punching tool and adhesive is reduced. Contamination of the problems, since these Separated areas act as “grip tabs in punching tools is less, and they have a much longer Service the matrix Stripping process. Additionally, manual removal life. This favorable effect is reinforced by the resilience of of the matrix lattice after a storage period of 2 weeks the anisotropically oriented PSAS. Residues of adhesives presented no problems in the direction of orientation. adhering to the punching tools are detached from the tool 0285 Table 6 gives an overview of the punching results. during the punching operation as a result of the Shrinkback. 0296 For comparison, a 3M product was punched as Example 4 well. The double-sided “Scotch (TM) 9690 Laminating 0286 Target Products Adhesive' tape had a contamination tendency that was 0287 Square punched products with a direct connecting comparable with that of the Solvent-based specimens inves edge of double-sidedly adhering material lined with sili tigated. conized release material 1 (auxiliary release material) on a 0297 FIG. 1 shows a microscopic enlargement of one Siliconized Support release material 2 (original release mate rial). The Side edge length of one punched product is 20 mm. edge of a punched product after the punching proceSS. The FIG. 9 is a diagram of such punched products on the support recession of the adhesive as a result of the anisotropic material (md=MD=machine direction). Reference numeral 1 orientation can be seen. The shrinkback in the free film refers here to the punched products, reference numeral 2 to according to test method B was 91% in this case. the Support material. 0288 The finished punched products were subsequently TABLE 1. investigated for dispensability in an automatic dispenser device. The dispenser device used was the tesa labeling Overview of shrinkback values obtained in the free film (Test B). apparatus “System 5/2”. Shrinkback in the free film 0289 Results PSA for PSA tapes Test B 0290 Table 7 gives an overview of the results obtained. Anisotropically oriented Single-sided or double-sided adhe 66% Sive tapes exhibited marked advantages in dispensing. In the 72% dispensing tests, one Self-adhesive punched portion at a time 66% is to be transferred to a folded paper carton. For this purpose 56% the shaped punched parts together with the Support material 62% were drawn over a sharp 90 edge. None of the punched 63% parts with anisotropic oriented pressure Sensitive adhesive 68% showed any flow effects in the region of the common contact 63% edge. The punched parts were detachable without problems 50% at the dispensing edge, could be individualized, and did not 59% pull any Subsequent punched parts with them. 66% 0291. The adhesive tapes based on the solvent technology 59% show Strong flow effects at the common contact edge. The O% softer the test PSA, the greater the problems which occurred O% in the dispensing process. O% 0292 Another trialed product from 3M (“Scotch (TM) O% 9690 Laminating Adhesive”) also did not provide error-free O% dispensing. In Some cases, up to four punched products were O% transferred in one detachment operation. O% O% Example 5 O% 0293. In further punching experiments, contamination of the punching tools was investigated as a function of the US 2003/0143413 A1 Jul. 31, 2003 15

0298)

TABLE 2 Overview of the single-sided and double-sided adhesive tapes used in the punching experiments. The table shows the product structure and the production process and the type of crosslinking used to produce the tape. The backing film used was a 12 lem thick PET film from SKC, Korea. PSA Product structure

Adhesive crosslinking Tape produc Application rate Application rate tape method used process open side lined side Backing film Release material

A. ESH Ho le COa ing 100 g/m 100 g/m 12 um PET 20 um polyo efinical (PE) coated paper, S iliconized on both sid CS ESH Ho le COa ing 50 g/m? 50 g/m 20 um polyo efinical y (PE) coated paper, S iliconized on both sid CS ESH Ho le COa ing 100 g/m’ 00 um glassine release (coated on one paper, siliconized on o e side) side UV Ho le COa ing 100 g/m’ 100 g/m’ 20 um polyo efinical (PE) coated paper, S iliconized on both sid CS UV Ho le COa ing 50 g/m? 50 g/m 20 um polyo efinical (PE) coated paper, S iliconized on both sid CS ESH Ho le COa ing 100 g/m 100 g/m 12 um PET 20 um polyo efinical (PE) coated paper, S iliconized on both sid CS ESH Ho le COa ing 50 g/m? 50 g/m 20 um polyo efinical (PE) coated paper S iliconized on both sid CS ESH Ho le COa ing 100 g/m’ 00 um glassine release (coated on one aper, siliconized on o e side) side UV Ho le COa ing 50 g/m’ 50 g/m’ 20 um polyo efinica (PE) coated iliconized on ides ESH Ho le COa ing 100 g/m 100 g/m 12 um PET 20 um polyo (PE) coated iliconized on ides ESH Ho le COa ing 50 g/m? 50 g/m 20 um polyo (PE) coated iliconized on ides ESH Ho le COa ing 100 g/m’ 20 um polyo (coated on one (PE) coated side) iliconized on ides ESH So we COa ing 100 g/m’ 100 g/m’ 12 um PET 20 um polyo (PE) coated iliconized on ides ESH So we COa ing 50 g/m? 50 g/m 20 um polyo (PE) coated iliconized on CS ESH So we COa ing 100 g/m 00 um glassine release (coated on one paper, siliconized on o e side) side ESH So we COa ing 100 g/m 100 g/m 12 um PET 20 um polyo efinical (PE) coated paper, S iliconized on both sid CS ESH So we COa ing 50 g/m? 50 g/m 20 um polyo efinical y (PE) coated paper, S iliconized on both sid CS ESH So we COa ing 100 g/m 00 um glassine release (coated on one paper, siliconized on o e side) side ESH So we COa ing 100 g/m 100 g/m 12 um PET 20 um polyo efinical (PE) coated paper, S iliconized on both sid CS ESH So we COa ing 50 g/m? 50 g/m 20 um polyo efinical y (PE) coated paper, S iliconized on both sid CS ESH So we COa ing 100 g/m 00 um glassine release (coated on one paper, siliconized on one side) side US 2003/0143413 A1 Jul. 31, 2003

0299) TABLE 4-continued TABLE 3 Overview of the test adhesive tapes used and the punching results of Criteria for assessing the frequency of errors during the example 1. Table 3 gives an overview of the assessment criteria employed. punching experiments. Adhesive Punching process Error rate Evaluation tape Rotary punch with continuous matrix stripping 0% The lattice matrix was removable without problems. In 3M 9690 (R) 54% punching experiments over 250 linear meters there was not a single error, i.e., no punched product was removed as well during the matrix stripping process. 0301) 1-99% Percentage of errors (missing punched products) over 250 linear meters. The error rate is based on the total number of possible punched products TABLE 5 over 250 linear meters of the test adhesive tape. 100% The lattice matrix could not be separated from the punched Overview of the test adhesive tapes used and the punching results of products. No punched products were individualized over example 2. The assessment criteria are shown in table 3. 250 linear meters. Adhesive Punching process tape Rotary punch with continuous matrix stripping 0300 F O% G O% J O% TABLE 4 K O% P 14% Overview of the test adhesive tapes used and the punching results of R 12% example 1. Table 3 gives an overview of the assessment criteria employed. T 35% U 24% Adhesive Punching process tape Rotary punch with continuous matrix stripping A. O% 0302) B O% C O% D O% TABLE 6 E O% F O% Overview of the test adhesive tapes used and the punching results of G O% example 3. The assessment criteria are shown in table 3. H O% I O% Adhesive Punching process J O% tape Rotary punch with continuous matrix stripping K O% L O% 9. M 18% J O% N 5% K O% O 9% P 21% P 56% R 16% R 34% T 39% S 22% U 27% T 84% U 65% V 40% 0303)

TABLE 7 Overview of the test adhesive tapes used and the punching results of example 4. The assessment criteria are shown in table 3. Punching Adhesive tape process Assessment of dispensing properties Rotary punch with Punched products can be dispensed without Hotmelt process continuous matrix losses over 250 linear meters T stripping Some of the punched products cannot be (Comparative specimen individualized. 2 cohering punched products to J) are transferred to the substrate. Solvent process Punched products can be dispensed without Hotmelt process losses over 250 linear meters P Some of the punched products cannot be (Comparative specimen individualized. 2 cohering punched products to F) are transferred to the substrate. Solvent process US 2003/0143413 A1 Jul. 31, 2003 17

TABLE 7-continued Overview of the test adhesive tapes used and the punching results of example 4. The assessment criteria are shown in table 3. Punching Adhesive tape process Assessment of dispensing properties L Punched products can be dispensed without Hotmelt process losses over 250 linear meters V Some of the punched products cannot be (Comparative specimen individualized. 2 cohering punched products to L) are transferred to the substrate. Solvent process 3M 9690 Some of the punched products cannot be individualized. Up to 4 cohering punched products are transferred to the substrate.

0304

TABLE 8 Results relating to contamination of the punching tools. Assessment of punching tool Adhesive tape Production process contamination J Hotmelt process Slight contamination of the punching tools with adhesive T Solvent process Pronounced contamination of the punching (Comparative tools with adhesive specimen to J) F Hotmelt process No contamination of the punching tools with adhesive P Solvent process Severe contamination of the punching tools (Comparative with adhesive specimen to F) 3M 9690 Pronounced contamination of the punching tools with adhesive US 2003/0143413 A1 Jul. 31, 2003 18

0305) APPENDIX

TITLE: PRODUCING PRESSURE-SENSITIVELY ADHESIVE PUNCHED PRODUCTS

LIST OF INVENTORS: 1. Dr. Reinhard STORBECK Nationality: German Stintelstra?e 89L, D-224.57 Hamburg, Germany

2. Dr. Marc HUSEMANN Nationality: German Strehlowweg 48; D-22605 Hamburg, Germany

3. Matthias KOCH Nationality: German Lutterothstra?e 35, D-20255 Hamburg, Germany

4. Maren KLOSE Nationality: German Am Grasweg 17C; D-21217 Seevetal, Germany CLAIM TO PRIORITY: Priority is hereby claimed under 35 USC 119 on the basis of Gcrman Application No. 101 57 153.4, filed on November 22, 2001. ASSIGNMENT: This application shall be effected in the name of tesa Akticngesellschaft.

“Express Mail” Mailing Label No. EV 151224950 US Dale of Deposit: Au%f /3, 222 I hereby certify that this correspondence is being deposited with the United States Postal Serviccs "Express Mail Post Office to Addrcsscc” service under 37 CFR 1.10 on the date indicated above and is addressed to the: Hon. Commissioner for Patents, Washington, D.C. 20231, Box Patent Application.

NORRISMcLAUGHLIN & MARCUS

Jennifer

US 2003/0143413 A1 Jul. 31, 2003

What is claimed is: Sensitive adhesive is a single-sided or double-sided adhesive 1. A process for producing pressure-Sensitively adhesive tape with at least one permanent backing. punched products from backing material coated with pres 8. The process as claimed in at least one of claims 1 to 6, Sure Sensitive adhesive, wherein wherein Said backing material coated with pressure Sensitive Said pressure Sensitive adhesive is oriented Such that it adhesive is a temporary Support on which the material to be possesses a preferential direction and, punched is reversibly placed. the punching process is carried out continuously. 9. The process as claimed in at least one of the preceding 2. The process as claimed in claim 1, wherein the punch claims, wherein the punching proceSS completely Severs the ing process takes place using a rotary punch. preSSure Sensitive adhesive on the backing material. 3. The process as claimed in at least one of the preceding claims, wherein the oriented pressure Sensitive adhesive 10. The process as claimed in at least one of claims 1 to exhibits shrinkback, the shrinkback as determined by test B 8, wherein the punching process does not completely Sever (shrinkback measurement in the free film) is at least 3%. the pressure Sensitive adhesive on the backing material. 4. The proceSS as claimed in at least one of the preceding 11. The process as claimed in at least one of the preceding claims, wherein the refractive indeX measured in the pref claims, wherein the punching proceSS completely Severs the erential direction, nv., is greater than the refractive indeX backing material coated with pressure Sensitive adhesive. measured in a direction perpendicular to the preferential 12. The process as claimed in at least one of claims 1 to direction, nsr. 10, wherein the punching proceSS does not Sever, or only 5. The process as claimed in claim 4, wherein the differ ence An=nvR-nsis is at least 1:10. partly Severs, the backing material coated with preSSure 6. The process as claimed in at least one of the preceding Sensitive adhesive. claims, wherein Said pressure Sensitive adhesive is based on 13. A punched product obtainable by a process as claimed polyacrylate and/or polymethacrylate. in at least one of the preceding claims. 7. The proceSS as claimed in at least one of the preceding claims, wherein Said backing material coated with pressure