EP1451237A1 - Reticulation de polyacrylates initialises par des photo-initiateurs - Google Patents
Reticulation de polyacrylates initialises par des photo-initiateursInfo
- Publication number
- EP1451237A1 EP1451237A1 EP02791700A EP02791700A EP1451237A1 EP 1451237 A1 EP1451237 A1 EP 1451237A1 EP 02791700 A EP02791700 A EP 02791700A EP 02791700 A EP02791700 A EP 02791700A EP 1451237 A1 EP1451237 A1 EP 1451237A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyacrylates
- functionalized
- groups
- polymerization
- photoinitiator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/6266—Polymers of amides or imides from alpha-beta ethylenically unsaturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S522/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S522/904—Monomer or polymer contains initiating group
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S522/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S522/904—Monomer or polymer contains initiating group
- Y10S522/905—Benzophenone group
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2809—Web or sheet containing structurally defined element or component and having an adhesive outermost layer including irradiated or wave energy treated component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2813—Heat or solvent activated or sealable
- Y10T428/2817—Heat sealable
- Y10T428/2826—Synthetic resin or polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
- Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
Definitions
- the invention relates to a method for increasing the molecular weight of polyacrylates and their derivatives, in particular for crosslinking.
- a central problem is the length of the mesh sheet, since acrylic hotmelt PSAs are generally of low molecular weight, have a lower percentage of entanglements and therefore have to be crosslinked more. With stronger networking, the cohesion level, but the distance between the individual networking points is becoming ever smaller. The network is therefore significantly closer-meshed and the PSA has only low viscoelastic properties.
- No. 5,888,644 describes a process for the production of release lacquers.
- the starting point is multifunctional acrylates, which are implemented with polysiloxanes.
- no defined network is formed, so that this process cannot be applied to acrylic PSAs either.
- Polymers of this type are not very thermally stable, since iodides generally react with air and are easily oxidized to iodine. Consequence of this are severe discoloration. This applies in particular to hot melt processes with high temperatures.
- the object of the invention is to provide a process for building up the molecular weight of polyacrylates, in particular for their crosslinking, which does not have the disadvantages of the prior art or only has them to a reduced extent.
- the invention accordingly relates to a process for increasing the molecular weight of polyacrylates, polyacrylates which are functionalized at least in part of their chain ends by photoinitiator groups X (hereinafter also referred to as functional groups) are exposed to actinic radiation, so that a linking reaction of the polyacrylates takes place ,
- polyacrylates should also be understood to mean their derivatives and polymethacrylates and their derivatives.
- the irradiation with actinic radiation is carried out in the presence of at least one crosslinking substance, so that a linking reaction of the polyacrylates takes place, including the crosslinking substance.
- the photoinitiator groups X are located at the chain ends of the polyacrylates and are therefore also referred to below as functional end groups.
- the polyacrylates functionalized with the photoinitiator groups X very advantageously have an average molecular weight (number average) of M n in the range from 2,000 to 1,000,000 g / mol.
- the method is hereby particularly suitable for the construction or crosslinking of polyacrylate PSAs. Increasing the molecular weight in the sense of the method according to the invention is understood to mean, in particular, crosslinking, but furthermore also the construction of higher molecular (long-chain) molecules.
- the method thus allows the construction of higher molecular weight compounds from the low molecular weight components, whereby in a variant which is particularly preferred for the method according to the invention, the components (that is to say the polyacrylates containing photoinitiator groups X and optionally the crosslinking substances) are linearly linked to one another.
- the monomers are chosen such that the resulting polymers can be used for pressure-sensitive adhesives at room temperature or higher temperatures, in particular in such a way that the resulting polymers have pressure-sensitive adhesive properties in accordance with the "Handbook of Pressure Sensitive Adhesive Technology" by Donatas Satas (van Nostrand, New York 1989).
- T G of the polymers T G 25 25 ° C.
- the monomers are very preferably selected in accordance with what has been said above and the quantitative composition of the monomer mixture is advantageously chosen such that the Fox- Equation (G1) (cf. TG Fox, Bull. Am. Phys. Soc. 1 (1956) 123) gives the desired T G value for the polymer.
- n the running number of the monomers used
- w n the mass fraction of the respective monomer n (% by weight)
- T G the respective glass transition temperature of the homopolymer from the respective monomers n in K.
- Acrylic and methacrylic acid esters with alkyl groups consisting of 4 to 14 carbon atoms, preferably 4 to 9 carbon atoms, are preferably used.
- Specific examples, without wishing to be restricted by this list, are methacrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, n-octyl methacrylate, n -Nonylacrylat, laurylacrylate, stearyl acrylate, behenyl acrylate, and their branched isomers, such as Isobutyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isooctyl acrylate, isoocty
- cycloalkyl alcohols consisting of at least 6 carbon atoms.
- the cycloalkyl alcohols can also be substituted, e.g. by C1-6 alkyl, halogen or cyano.
- Specific examples are cyclohexyl methacrylate, isobomylacrylate, isobornyl methacrylate and 3,5-dimethyladamantylacrylate.
- Monomers are advantageously used, the polar groups such as carboxyl, sulfonic and phosphonic acid, hydroxy, lactam and lactone, N-substituted amide, N-substituted amine, carbamate, epoxy, thiol, ether, alkoxy. Wear cyan or the like.
- Moderate basic monomers are e.g. N, N-dialkyl substituted amides such as e.g.
- vinyl esters, vinyl ethers, vinyl halides, vinylidene halides, vinyl compounds with aromatic cycles and heterocycles in the ⁇ -position are used as comonomers.
- Aromatic vinyl compounds such as, for example, styrene, are suitable here, the aromatic nuclei preferably consisting of C 4 to C 18 building blocks and also being able to contain heteroatoms.
- Particularly preferred examples are 4-vinylpyridine, N-vinylphthalimide, methylstyrene, 3,4-dimethoxystyrene, 4-vinylbenzoic acid, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, t-butylphenyl acrylate, t-butylphenyl methacrylate, 4-biphenyl 2-acrylate and methacrylate Naphthyl acrylate and methacrylate and mixtures of those monomers.
- the polyacrylates each have a photoinitiator group X on at least part of their chain ends. These can be the same or different photoinitiator systems within a molecular chain, furthermore the photoinitiator systems of the individual polymer molecules can be chosen to be the same or different. Compounds which form at least one radical under actinic radiation are to be understood here as photoinitiators.
- photoinitiators e.g. UV light absorbing substances are used.
- Some useful photoinitiators X which are very easy to use, are benzoin ethers, such as. As benzoin methyl ether and benzoin isopropyl ether, substituted acetophenone, such as. B. 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-1-phenylethanone, dimethoxyhydroxyacetophenone, substituted ⁇ -ketols, such as. B. 2-methoxy-2-hydroxy-propiophenone, aromatic sulfonyl chlorides, such as. B. 2-naphthyl sulfonyl chloride, and photoactive oximes such.
- the above-mentioned and other usable photoinitiators X and others of the Norrish I or Norrish II type may contain the following radicals: benzophenone, acetophe non, benzil, benzoin, hydroxyalkylphenone, phenylcyclohexyl ketone, anthraquinone, trimethylbenzoylphosphine oxide, methylthiophenylmorpholine ketone, aminoketone, azobenzoin, thioxanthone, hexarylbisimidazole, triazine, or resorenone, with each of these, in addition, with each one or more halogen atoms and / or one or more alkyloxy groups and / or one or more amino groups or hydroxy groups can be substituted.
- the photoinitiators X mentioned above can be bound differently at the respective end of the polymer chain.
- the photoinitiator X is advantageously bound by the polymerization process at the chain end.
- the photoinitiator is selectively bound to the respective chain end by a polymer-analogous reaction.
- the photoinitiator is also advantageously generated by a synthesis reaction at the respective chain end.
- Linear polyacrylates each with a photoinitiator X at the respective chain end, are preferably used for crosslinking.
- the linear polyacrylates can advantageously also have branches along the main polymer chain, the side chains being able to be formed by the polymerization process; accordingly, the polyacrylates functionalized with photoinitiator groups can have at least one chain branch.
- branched polymers and star polymers are also used in a targeted manner.
- 3-arm, 4-arm, 6-arm, 8-arm or 12-arm star polymers based on poly (meth) acrylate are advantageously used.
- Hyperbranched polyacrylates can also be used. All polyacrylates carry at least one photoinitiator X at the respective chain end.
- radical polymerizations or controlled radical polymerizations are carried out to produce the polyacrylates.
- initiator systems are preferably used, which additionally contain further radical initiators for the polymerization, in particular thermally decomposing radical-forming azo or peroxo initiators.
- thermally decomposing radical-forming azo or peroxo initiators in principle, however, all customary initiators known for acrylates are suitable for this.
- C-centered radicals is described in Houben Weyl, Methods of Organic Chemistry, Vol. E 19a, pp. 60 - 147. These methods are preferably applied in analogy.
- radical sources are peroxides, hydroperoxides and azo compounds
- typical radical initiators are potassium peroxodisulfate, dibenzoyl peroxide, cumene hydroperoxide, cyclohexanone peroxide, di-t-butyl peroxide, azodiisoic acid butyronitrile, benzotyl peroxyl peroxyl peroxyl peroxyl peroxyl peroxyl peroxyl peroxyl peroxo
- the free radical initiator 1, 1 '- azo-bis- (cyclohexanecarbonitrile) (Vazo 88 TM from DuPont) is preferably used.
- the average molecular weights (number average) M n of the PSAs produced in the controlled free-radical polymerization are chosen such that they are in a range from 2,000 to 1,000,000 g / mol; PSAs with average molecular weights M n of 100,000 to 500,000 g / mol are produced specifically for further use as hotmelt PSAs.
- the average molecular weight is determined by size exclusion chromatography (gel permeation chromatography, SEC or GPC) or matrix-assisted laser desorption / ionization mass spectrometry (MALDI-MS).
- the polymerization can be carried out in bulk, in the presence of one or more organic solvents, in the presence of water or in mixtures of organic solvents and water.
- Suitable organic solvents or mixtures of solvents are pure alkanes (hexane, heptane, octane, isooctane), aromatic hydrocarbons (benzene, toluene, xylene), esters (ethyl acetate, propyl acetate, butyl or hexyl acetate), halogenated hydrocarbons ( Chlorobenzene), alkanols (methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether) and ethers (diethyl ether, dibutyl ether) or mixtures thereof.
- a water-miscible or hydrophilic cosolvent can be added to the aqueous polymerization reactions to ensure that the reaction mixture is in the form of a homogeneous phase during monomer conversion.
- Co-solvents which can be used advantageously for the present invention are selected from the following Group consisting of aliphatic alcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkylpyrrolidinones, N-alkylpyrrolidones, polyethylene glycols, polypropylene glycols, amides, carboxylic acids and salts thereof, esters, organosulfides, sulfoxides, sulfones, alcohol derivatives, hydroxy ether Amino alcohols, ketones and the like, as well as derivatives and mixtures thereof.
- the polymerization time is between 4 and 72 hours.
- the polymerization can be initiated for the thermally decomposing initiators by heating to 50 to 160 ° C., depending on the type of initiator.
- polyacrylates it may also be advantageous to manufacture the polymers in bulk.
- the prepolymerization technique is particularly suitable here.
- the polymerization is initiated with UV light but only leads to a low conversion of approximately 10-30%.
- this polymer syrup can e.g. are sealed in foils (in the simplest case ice cubes) and then polymerized through in water to a high conversion.
- These pellets can then be used as acrylic hot-melt adhesives, with film materials which are compatible with the poly (meth) acrylate being particularly preferably used for the melting process.
- Inert solvents are preferably used as the reaction medium, e.g. aliphatic and cycloaliphatic hydrocarbons, or also aromatic hydrocarbons.
- the living polymer is generally represented by the structure P L (A) -Me, where Me is a Group I metal, such as lithium, sodium or potassium, and P (A) is a growing polymer block from the monomers A.
- Me is a Group I metal, such as lithium, sodium or potassium
- P (A) is a growing polymer block from the monomers A.
- the Molecular weight of the end group-modified poly (meth) acrylate to be produced is predetermined by the ratio of initiator concentration to monomer concentration. To build up the polymer, preference is given to using acrylate and methacrylate monomers which do not have a negative effect on the anionic polymerization process or which can even be broken off completely.
- n-propyllithium, n-butyllithium, sec-butyllithium, 2-naphthyllithium, cyclohexyllithium or octyllithium this list does not claim to be complete.
- Initiators based on samarium complexes for the polymerization of acrylates are also known (Macromolecules, 1995, 28, 7886) and can be used here. With these initiators, however, it should be noted that only mono-end group-functional polyacrylates are accessible in this way by interrupting the corresponding anionic polymerization.
- carboxy groups this can be done, for example, by CO 2 with subsequent hydrolysis, for the production of hydroxyl groups, for example, by reaction with ethylene oxide and subsequent hydrolysis.
- the functionalization by X is then carried out by a polymer-analogous reaction with the hydroxy group.
- Nitroxide-controlled polymerization processes can be used to synthesize the polyacrylates.
- Difunctional initiators are preferably used for the preferred difunctional polyacrylates.
- An example of this are difunctional alkoxyamines (I).
- R 1 *, R 2 *, R 3 *, R 4 * can be different, identical or chemically linked and the pairs R 1 * and R 2 * as well as R 3 * and R 4 * each contain at least one group X or have a functional group that can be converted into X by a chemical reaction.
- R 1 * to R 4 * are preferably selected independently of one another as: i) halides, such as chlorine, bromine or iodine ii) linear, branched, cyclic and heterocyclic hydrocarbons with 1 to 20
- Carbon atoms which can be saturated, unsaturated or aromatic, iii) esters -COOR 5 * , alkoxides -OR 6 * and / or phosphonates -PO (OR 7 *) 2 , where R 5 *, R 6 * and R 7 * for Remains from group ii) are. iv) residues from ii) wherein at least one hydroxyl function or silyl ether function is additionally present.
- alkoxyamines can also be used to prepare the end-functionalized polyacrylates by nitroxide-controlled polymerization.
- the middle block which forms two radicals after initiation by heat, heat radiation or actinic radiation, can be further modified or varied.
- Various chemical structures are known to the person skilled in the art. The prerequisite is that at least two radicals are formed which are stabilized by nitroxides which carry at least one functional group X or which contain a group which is converted into X by a chemical reaction.
- nitroxides of type (II) or (III) are used in a favorable procedure:
- R 1 , R 2 # , R 3 # , R 4 # , R 5 # , R 6 # , R 7 , R 8 # independently of one another denote the following compounds or atoms and preferably at least one of the radicals R to R 6 # or R 7 # and / or R 8 # carry at least one group X or contain a group that belongs to the desired group X can be converted by a chemical reaction.
- R 1 to R 8 # are preferably selected independently of one another as: i) halides, such as chlorine, bromine or iodine ii) linear, branched, cyclic and heterocyclic hydrocarbons with 1 to 20
- Carbon atoms which can be saturated, unsaturated or aromatic, iii) esters -COOR 9 # , alkoxides -OR 10 # and / or phosphonates -PO (OR 11 # ) 2 , where R 9 , R 10 # and R 11 # for residues from group ii), iv) radicals from group ii), with at least one hydroxyl function or
- Silyl ether function is included.
- No. 4,581,429 A discloses a controlled radical polymerization process which uses an initiator of a compound of the formula R'R "NOY, in which Y is a free radical species which can polymerize unsaturated monomers.
- WO 98/13392 A1 describes open-chain alk- oxyamine compounds which have a symmetrical substitution pattern
- EP 735 052 A1 discloses a process for the production of thermoplastic elastomers with narrow molar mass distributions
- WO 96/24620 A1 describes a polymerization process in which very special radical compounds such as phosphorus-containing nitroxides based on imidazolidine are used
- WO 98/44008 A1 discloses special nitroxyls based on morpholines, piperazinones and piperazine dions DE 199 49 352 A1 describes heterocyclic alkoxyamines as regulators in controlled free-radical polymerizations.
- Trithiocarbonates of the general structure R '"- SC (S) -S-R'" (Macromolecules 2000, 33, 243-245), by means of which one or more monomers (acrylates / methacrylates) are suitable, are particularly advantageous for the preparation of end-functionalized polyacrylates ) are polymerized and parts of the regulator remain as end groups in the polymer.
- the trithiocarbonate can consist of a compound, where R '"contains a functional group X or a functional group which can be converted into a functional group X by a chemical reaction.
- a two-stage polymerization In a first step, monomers are polymerized with a trithiocarbonate, which contain at least one functional group X and then in a second step to polymerize the (meth) acrylates.
- the polymerization can take place continuously or with termination after the 1st stage and subsequent reinitiation.
- the latter method is particularly suitable for the production of end-functionalized polyacrylates with several functional groups X at each end.
- the trithiocarbonates (IV) and (V) are advantageously used for the polymerization, where ⁇ can be a phenyl ring which is unfunctionalized or functionalized by alkyl or aryl substituents which are linked directly or via ester or ether bridges, or a cyano group can be.
- ⁇ can be a phenyl ring which is unfunctionalized or functionalized by alkyl or aryl substituents which are linked directly or via ester or ether bridges, or a cyano group can be.
- ⁇ can be a phenyl ring which is unfunctionalized or functionalized by alkyl or aryl substituents which are linked directly or via ester or ether bridges, or a cyano group can be.
- ⁇ can be a phenyl ring which is unfunctionalized or functionalized by alkyl or aryl substituent
- end-functionalized polyacrylates with few or only one group X it may be advantageous to use end-functionalized trithiocarbonates.
- end-functionalized trithiocarbonates For example, particular preference is given to Trithiocarbonate types VIII and IX used.
- Group X should not affect the controlled radical polymerization.
- the group K is very variable in order to improve the control of the polymerization or to change the polymerization rate, K can be C r to C 18 alkyl, C 2 to C 8 alkenyl, C 2 to C 18 alkynyl, in each case linear or branched; Aryl, phenyl, benzyl, aliphatic and aromatic heterocycles.
- K as one or more groups -NH 2 , NH-R VI , -NR JV V I'RDV V I "I, -NH-C (O) -R 3 V v I l , -NR V v I l -C (O) -R 3 V v I "I, -NH-C (S) -R 3 V V I I , -NR VI -C (S) -R V ", C (O) R VI C (S) R VI C (O) R VI • N, - N, - N
- R v ⁇ and R v in turn compounds of the type C to C 18 alkyl, C 2 - to C 18 alkenyl, C 2 - to d ⁇ -alkynyl, each linear or branched; aryl, phenyl, benzyl, can be aliphatic and aromatic heterocycles and are independent of one another or the same.
- regulators can also be used which carry functionalized dithioester groups at the end and incorporate them at the polymer end.
- controllers of this type can have the structure XII.
- the functional group should not influence the polymerization process, but should remain on the sulfur atoms so that this group is incorporated at the end of the polymer chain.
- the dibenzylic group can be further modified and adapted in order to further improve the polymerization behavior.
- the patents WO 98/01478 A1 and WO 99/31 144 A1 are only mentioned here by way of example.
- ATRP atom transfer radical polymerization
- block copolymers preferably mono- or difunctional secondary or tertiary halides as initiators and for the abstraction of the (r) halide (s) Cu, Ni -, Fe, Pd, Pt, Ru, Os, Rh, Co, Ir, Ag or Au complexes
- s atom transfer radical polymerization
- the different possibilities of the ATRP are also described in the documents US 5,945,491 A, US 5,854,364 A and US 5,789,487 A.
- the corresponding secondary or tertiary halide should already have the desired functional group X.
- the polymerisation process also leaves halo groups as end groups.
- genides in the polymer which can also be converted into the corresponding functional groups X by substitution reactions.
- the manufacture of multiblock or star-shaped structures can be carried out according to the concept described in Macromolecules 1999, 32, 231-234. There, multifunctional halides are used for the polymerization, which then have to be converted into the desired functional group (s) X in a polymer-analogous substitution reaction.
- the polymerization processes described above can also be used to produce multi-arm, star-shaped or dendritic end-functionalized polyacrylates. By modifying the initiating connection or the controller, such connections are easily accessible.
- the following structures show examples of suitable compounds, wherein the compound XIII is a suitable substance for the preparation of a 12-arm polyacrylate via ATRP technology, the compound XIV is for the production of a 6-arm polyacrylate via RAFT technology and the compound XV for the production of a 3- poor polyacrylates via a nitroxide-controlled reaction.
- Polyacrylates made from compound XIII can e.g. by conversion (substitution reaction) of the terminal bromides into suitable end group-functionalized polyacrylates.
- Polyacrylates made from compound XIV already have a functional group X as the end group per polymer arm. However, the regulator XIV can also carry this functional group at a different position on the terminal phenyl rings or else several functional groups on the terminal phenyl rings.
- Polyacrylates made from compound XV already have 3-hydroxy groups as the terminal functional group per polymer arm, which can be used to generate X.
- the number of arms generated can be controlled by the number of groups essential for controlled radical polymerization.
- functional groups can also be exchanged, modified or specifically substituted. This measure can be used, for example, to increase or decrease the control or the rate of polymerization.
- all of the above-mentioned polymerization methods are only example compounds for the preparation of polyacrylates which are functionalized with photoinitiator groups X.
- it is also possible for all gene methods for controlled polymerization are used as long as functional groups X can be introduced at the polymer end with this polymerization method.
- other radical polymerization methods are also suitable for introducing functional groups.
- thiol-regulated compounds the thiols or dithio compounds also being able to carry functional groups X and thus end-functionalizing polyacrylates.
- functional groups can be introduced into the polymer as end groups by the initiator.
- commercial azo initiators which carry free carboxylic acid groups or hydroxyl groups which are then also incorporated into the polymer via the polymerization and can be used for the coupling reaction.
- Another possibility would be to intercept the free radical polymerization and to incorporate a functional group X in this way.
- Resins can be added to the polyacrylates for further development. All of the previously known adhesive resins described in the literature can be used as the tackifying resins to be added. Representative are the pinene, indene and rosin resins, their disproportionated, hydrogenated, polymerized, esterified derivatives and salts, the aliphatic and aromatic hydrocarbon resins, terpene resins and terpene phenolic resins as well as C5, C9 and other hydrocarbon resins. Any combination of these and other resins can be used to adjust the properties of the resulting adhesive as desired.
- all (soluble) resins compatible with the corresponding poly (meth) acrylate can be used, in particular reference is made to all aliphatic, aromatic, alkyl aromatic hydrocarbon resins, hydrocarbon resins based on pure monomers, hydrogenated hydrocarbon resins, functional hydrocarbon resins and natural resins. Attention is drawn to the presentation of the state of knowledge in the "Handbook of Pressure Sensitive Adhesive Technology" by Donatas Satas (van Nostrand, 1989).
- plasticizers plasticizers
- fillers e.g. fibers, carbon black, zinc oxide, titanium dioxide, chalk, solid or hollow glass spheres, microspheres made of other materials, silica, silicates
- nucleating agents e.g., nucleating agents, blowing agents, compounding agents and / or anti-aging agents, for example
- the polymers described above are preferably coated as hot-melt systems for the production of poly (meth) acrylate hotmelt PSAs. It may therefore be necessary for the manufacturing process to remove the solvent from the PSA.
- a very preferred method is concentration using a single or twin screw extruder.
- the twin screw extruder can be operated in the same or opposite directions.
- the solvent or water is preferably distilled off over several vacuum stages. In addition, depending on the distillation temperature of the solvent, heating is carried out.
- the residual solvent proportions are preferably ⁇ 1%, more preferably ⁇ 0.5% and very preferably ⁇ 0.2%.
- the hot melt is processed from the melt.
- the component to be added is preferably an organic compound with at least two unsaturated groups.
- di- or multifunctional methacrylates are preferred di- or multifunctional terminal vinyl compounds.
- Difunctional or multifunctional acrylics are very preferably used for the coupling reaction.
- higher molecular weight compounds (oligomers) or polymers can also be used as crosslinking substances with at least 2 vinyl compounds.
- the group of polymers can e.g. Polyacrylates, polymethacrylates, polyisobutene, polyethylene, polypropylene, polyvinyl acetate, polyurethane, polyvinyl chloride, polystyrene, polycaprolactam, polycaprolactone, polyesters, polybenzoates, polysiloxanes, polyethylene / propylene copolymers, polybutadiene, polyisoprene, polybutene, polythiophenes, polyacenyl amides, polyacenes , Polycarbonates, polyvinyl alcohol, polypropylene oxide, polyethylene oxide, polyphenylene, polychloroprene and fluorinated polymers.
- UV-absorbing photoinitiators can also be added.
- Useful photoinitiators that are very easy to use are benzoin ethers, such as. As benzoin methyl ether and benzoin isopropyl ether, substituted acetophenones, such as. B. 2,2-diethoxyacetophenone (available as Irgacure 651 ® from Ciba Geigy ® ), 2,2-dimethoxy-2-phenyl-1-phenylethanone, dimethoxyhydroxyacetophenone, substituted ⁇ -ketols, such as, for. B. 2-methoxy-2-hydroxypropiophenone, aromatic sulfonyl chlorides, such as. B. 2-naphthyl sulfonyl chloride, and photoactive oximes such.
- the above-mentioned and other usable photoinitiators can contain the following radicals: benzophenone, acetophenone, benzil, benzoin, hydroxyalkylphenone, phenylcyclohexyl ketone, anthraquinone, trimethylbenzoylphosphine oxide, methylthi-phenylphenyl , Aminoketone, azobenzoin, thioxanthone, hexarylbisimidazole, triazine, or fluorenone, each of which Residues can additionally be substituted with one or more halogen atoms and / or one or more alkyloxy groups and / or one or more amino groups or hydroxy groups.
- polyacrylates terminally functionalized with photoinitiator groups X they are coated onto a support material either from solution or from the melt.
- the carrier materials for use as pressure-sensitive adhesive are the materials which are familiar and customary to the person skilled in the art, such as foils (polyester, PET, PE, PP, BOPP, PVC), nonwovens, foams, fabrics and tissue foils and release paper (glassine, HDPE) , LDPE) is used. This list is not exhaustive.
- UV crosslinking irradiation is carried out by means of brief ultraviolet radiation in a wavelength range from 200 to 400 nm, depending on the UV photoinitiator X used, in particular using high-pressure or medium-pressure mercury lamps with a power of 80 to 240 W / cm.
- the radiation intensity is adapted to the respective quantum yield of the UV photoinitiator and the degree of crosslinking to be set.
- Typical radiation devices that can be used are linear cathode systems, scanner systems or segment cathode systems, provided they are electron beam accelerators.
- the typical acceleration voltages are in the range between 50 kV and 500 kV, preferably 80 kV and 300 kV.
- the applied Spreading cans range between 5 and 150 kGy, in particular between 20 and 100 kGy.
- part of this invention is the use of such systems for PSA tapes, in particular for single- or double-sided PSA tapes.
- the polymers constructed or crosslinked as described above and their crosslinking processes can also be used for films or release lacquers. Highly halogenated polymers could also be used as flame retardants, for example.
- heat-activatable PSAs can also be produced by the inventive method.
- the polyacrylate functionalized with photoinitiator groups X should have a glass transition temperature of greater than 25 ° C. Applications in the coating sector are also possible for the polymers according to the invention with a narrow polymer network. Polymers with a high glass transition temperature produced by the inventive method can also be used as thermoplastics.
- the test was carried out in accordance with PSTC-7.
- a 50 ⁇ m thick pressure sensitive adhesive layer is applied to a 25 ⁇ m thick PET film.
- a 1, 3 cm wide strip of this pattern is glued to a polished steel plate with a length of 2 cm with a 2 kg roll by rolling over twice.
- the platelets are equilibrated for 30 min under test conditions (temperature and humidity), but without load.
- the test weight is then attached to create a shear stress parallel to the bond area and the time taken for the bond to fail. If a holding time of 10,000 min is reached, the experiment is stopped before the perfect binding fails.
- the peel strength (adhesive strength) was tested in accordance with PSTC-1. To a thickness of 25 ⁇ m
- PET film is applied with a 50 ⁇ m thick adhesive layer.
- a 2 cm wide strip of this pattern is made on a steel plate by rolling over twice glued to a 2 kg roll. The steel plate is clamped and the self-adhesive strip is pulled off over its free end on a tensile testing machine at a peeling angle of 180 °.
- the determination of the average molecular weight M and the polydispersity PD was carried out by the company Polymer Standards Service in Mainz. THF with 0.1% by volume of trifluoroacetic acid was used as the eluent. The measurement was carried out at 25 ° C. PSS-SDV, 5 ⁇ , 10 3 A, ID 8.0 mm x 50 mm was used as guard column. The columns PSS-SDV, 5 ⁇ , 10 3 and 10 5 and 10 6 , each with ID 8.0 mm x 300 mm, were used for the separation. The sample concentration was 4 g / l, the flow rate 1.0 ml per minute. It was measured against PMMA standards.
- the bis-2,2'-phenylethyltrithiocarbonate regulator was produced starting from 2-phenylethyl bromide with carbon disulfide and sodium hydroxide according to a specification by Synth. Comm, 1988, 18 (13), 1531. Yield 72%.
- Vazo 64 TM DuPont (2,2'-azobis (isobutyronitrile)
- 0.2 g of Vazo 64 TM (DuPont) (2,2'-azobis (isobutyronitrile)) dissolved in 5 g of acetone is added.
- the polymerization was carried out at a constant outside temperature of 70 ° C. After a reaction time of 6 h, the mixture was diluted with 100 g of acetone. After a reaction time of 24 h, therefore an addition of 0.2 g of Vazo 64 TM (DuPont) (2,2'-azobis (isobutyronitrile)) dissolved in 5 g of acetone. After 30 h, the mixture was diluted with 50 g of acetone. The polymerization was stopped by cooling to room temperature after 48 h reaction time. Analysis via GPC (Test C, PMMA standards) showed a molecular weight MN of 146,000 g / mol and M w of 356,000 g / mol
- the solvent was then removed in a drying cabinet at 60 ° C. and 10 Torr vacuum. Subsequently, 1% by weight of pentaerythritol triacrylate was mixed into the melt and applied from the melt at 150 ° C. to a primed 23 ⁇ m thick PET film. The mass application was 50 g / m z .
- the PSA pattern was irradiated with a medium speed mercury lamp (120 W / cm) from Eltosch at a web speed of 20 m / min with several passes. Test methods A and B were carried out to check the adhesive properties.
- the polymerization was carried out at a constant outside temperature of 70 ° C. After a reaction time of 6 h, the mixture was diluted with 80 g of acetone. After a reaction time of 24 h, 0.2 g of Vazo 64 TM (DuPont) (2,2'-azobis (isobutyronitrile)) dissolved in 5 g of acetone was again added. After 30 h, the mixture was diluted with 50 g of acetone. The polymerization was stopped by cooling to room temperature after 48 h reaction time. Analysis via GPC (Test C, PMMA standards) showed a molecular weight MM of 166,000 g / mol and M of 421,000 g / mol.
- the polymer obtained was then purchased again in the presence of 0.5% by weight of 3- [4- (dimethylamino) phenyl] -1- [4- (2-hydroxyethoxy) phenyl] -2-propen-1-one concentrated on the polymer.
- the solvent was removed in a drying cabinet at 60 ° C and a vacuum of 10 torr.
- 1% by weight of pentaerythritol triacrylate was added in a hotmelt process (see above) and coated from the melt at 140 ° C. onto a primed 23 ⁇ m thick PET film.
- the mass application was 50 g / m 2 .
- the PSA pattern was irradiated with a medium speed mercury lamp (120 W / cm) from Eltosch at a web speed of 20 m / min with several passes. Test methods A and B were carried out to check the adhesive properties.
- Example 1 a polyacrylate with several was used with a trithiocarbonate as regulator
- Example 2 Benzoin units made at the respective polymer chain end.
- the polymer was then freed from the solvent, mixed with a multifunctional acrylate and coated from the melt. After coating, UV was irradiated with a medium-pressure mercury lamp and crosslinked directly on the support.
- a polymer provided with UV photoinitiators was coated from the melt and then UV-crosslinked.
- the polymer was reacted with an amine-functionalized UV photoinitiator in a polymer-analogous reaction. The reaction also leads to a polyacrylate with several photoinitiator molecules attached to the end of the polymer chain. This polymer was mixed with a multifunctional acrylate and UV-crosslinked after coating from the melt on the carrier.
- UV dose Measured with the Power-Puck TM from Eltosch
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
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DE10157695 | 2001-11-24 | ||
DE10157695A DE10157695A1 (de) | 2001-11-24 | 2001-11-24 | 2-Komponentenvernetzung von Endgruppenfunktionalisierten Poly(meth)acrylaten |
DE10200363 | 2002-01-08 | ||
DE10200363 | 2002-01-08 | ||
PCT/EP2002/013173 WO2003046030A1 (fr) | 2001-11-24 | 2002-11-22 | Reticulation de polyacrylates initialises par des photo-initiateurs |
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EP1451237A1 true EP1451237A1 (fr) | 2004-09-01 |
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EP02791700A Withdrawn EP1451237A1 (fr) | 2001-11-24 | 2002-11-22 | Reticulation de polyacrylates initialises par des photo-initiateurs |
EP02791702A Withdrawn EP1451238A1 (fr) | 2001-11-24 | 2002-11-22 | Reticulation au moyen de deux constituants de polyacrylates fonctionnalises au niveau de leurs extremites |
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EP02791702A Withdrawn EP1451238A1 (fr) | 2001-11-24 | 2002-11-22 | Reticulation au moyen de deux constituants de polyacrylates fonctionnalises au niveau de leurs extremites |
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US (2) | US7271203B2 (fr) |
EP (2) | EP1451237A1 (fr) |
JP (2) | JP2005510596A (fr) |
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WO (2) | WO2003046031A1 (fr) |
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DE10149077A1 (de) * | 2001-10-05 | 2003-04-24 | Tesa Ag | Verfahren zur Herstellung UV-vernetzbarer Acrylathaftklebemassen |
-
2002
- 2002-11-22 WO PCT/EP2002/013176 patent/WO2003046031A1/fr active Application Filing
- 2002-11-22 EP EP02791700A patent/EP1451237A1/fr not_active Withdrawn
- 2002-11-22 JP JP2003547477A patent/JP2005510596A/ja active Pending
- 2002-11-22 EP EP02791702A patent/EP1451238A1/fr not_active Withdrawn
- 2002-11-22 US US10/496,325 patent/US7271203B2/en not_active Expired - Lifetime
- 2002-11-22 DE DE10295498T patent/DE10295498D2/de not_active Withdrawn - After Issue
- 2002-11-22 JP JP2003547478A patent/JP2005510597A/ja active Pending
- 2002-11-22 DE DE10295497T patent/DE10295497D2/de not_active Withdrawn - After Issue
- 2002-11-22 US US10/496,324 patent/US7402632B2/en not_active Expired - Fee Related
- 2002-11-22 WO PCT/EP2002/013173 patent/WO2003046030A1/fr active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0395990A2 (fr) * | 1989-04-29 | 1990-11-07 | BASF Aktiengesellschaft | Copolymères durcissables par des radiations ultraviolettes sous une atmosphère d'oxygène de l'air |
WO1998040415A1 (fr) * | 1997-03-11 | 1998-09-17 | Carnegie Mellon University | Perfectionnements applicable a la polymerisation par transfert d'atomes ou de groupes |
Non-Patent Citations (1)
Title |
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See also references of WO03046030A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE10295497D2 (de) | 2005-01-27 |
JP2005510597A (ja) | 2005-04-21 |
DE10295498D2 (de) | 2004-11-11 |
EP1451238A1 (fr) | 2004-09-01 |
US7402632B2 (en) | 2008-07-22 |
WO2003046030A1 (fr) | 2003-06-05 |
WO2003046031A1 (fr) | 2003-06-05 |
US7271203B2 (en) | 2007-09-18 |
US20050020714A1 (en) | 2005-01-27 |
JP2005510596A (ja) | 2005-04-21 |
US20050009995A1 (en) | 2005-01-13 |
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