Classifications

• • 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
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
  • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• • 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
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • 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
• • 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
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• • 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
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C

Definitions

• the invention relates to a mixture containing
• the invention relates to the use of the mixture as a pressure-sensitive adhesive.
• Radiation-crosslinkable polymers and their use as an adhesive for. B. as a hotmelt adhesive, z. B. from EP-A 246 848 or EP-A 377 199 known.
• the cohesion i. H. the internal strength of the adhesive layer, after coating the adhesive on a support achieved by subsequent photochemically induced crosslinking.
• Adhesion adheresion to the substrate
• cohesion are opposite application properties. Measures that improve adhesion generally result in cohesion deterioration and vice versa.
• Radiation-crosslinkable pressure-sensitive adhesives often have the disadvantage here that good adhesion and cohesion at high layer thicknesses is no longer achieved.
• EP-A 1 578 823, EP-A 628 616 and EP-A 1 469 036 disclose mixtures of radiation-curable polyacrylates and oligomers having a plurality of acrylic groups, and also the use of these mixtures as pressure-sensitive adhesives.
• DE-A 19 701 124 describes pressure-sensitive adhesives which have a content of dihydrocyclopentadienyl (meth) acrylate.
• the object of the present invention was an improvement of the cohesion with at the same time good or sufficient adhesion, as well as a good heat resistance, in particular also with high layer thicknesses of the pressure-sensitive adhesive.
• the initially defined mixture and its use was found as a pressure-sensitive adhesive.
• the mixture according to the invention contains as essential constituents polymers A) and compounds B).
• the polymer A) is preferably composed of free-radically polymerizable compounds (monomers).
• the polymer is at least 40 wt .-%, more preferably at least 60 wt .-%, most preferably at least 80 wt .-% of so-called main monomers.
• the main monomers are selected from C 1 -C 20 -alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinylaromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers having from 1 to 10 carbon atoms Alcohols, aliphatic hydrocarbons having 2 to 8 carbon atoms and 1 or 2 double bonds or mixtures of these monomers.
• (meth) acrylic acid alkyl ester having a Ci-Cio-alkyl radical such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
• mixtures of (meth) acrylic acid alkyl esters are also suitable.
• Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for. As vinyl laurate, stearate, vinyl propionate, vinyl versatate and vinyl acetate.
• Suitable vinylaromatic compounds are vinyltoluene a- and p-methylstyrene, a-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
• nitriles are acrylonitrile and methacrylonitrile.
• the vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
• vinyl ethers are, for. As vinyl methyl ether or vinyl isobutyl ether. Vinyl ether is preferably from 1 to 4 C-containing alcohols.
• hydrocarbons having 2 to 8 carbon atoms and one or two olefinic double bonds may be mentioned butadiene, isoprene and chloroprene, ethylene or propylene.
• Preferred main monomers are the C 1 to C 10 alkyl acrylates and methacrylates, in particular C 1 to C 8 alkyl acrylates and methacrylates, the acrylates in each case being particularly preferred. Very particular preference is given to methyl acrylate, ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate, and mixtures of these monomers.
• the polymer may contain other monomers, for.
• monomers with carboxylic acid sulfonic acid or phosphonic acid groups.
• hydroxyl-containing monomers in particular Ci-Cio-hydroxyalkyl (meth) acrylates, (meth) acrylamide and ureido-containing monomers such as ureido (meth) acrylates.
• Phenyloxyethylglycol mono- (meth) acrylate, glydidyl acrylate, glycidyl methacrylate, amino (meth) acrylates such as 2-aminoethyl (meth) acrylate may be mentioned as further monomers.
• Monomers which, in addition to the double bond, carry further functional groups eg. As isocyanate, amino, hydroxy, amide or glycidyl, z. B. improve adhesion to substrates.
• Particularly suitable are cyclic lactams such as N-vinylpyrrolidone or N-vinylcaprolactam.
• the polymer is preferably at least 40 wt .-%, more preferably at least 60 wt .-% and most preferably at least 80 wt .-% of d-C2o-alkyl (meth) acrylates, in particular the above-mentioned alkyl (meth ) acrylates.
• polymer A) has a content of crosslinkable groups with non-acrylic, crosslinkable double bonds (short-crosslinkable groups).
• Crosslinkable double bonds are, in particular, those which are free-radically polymerizable with other double bonds (ie crosslink by radical polymerization) or those which form radicals by splitting off a hydrogen atom (ie crosslink by reactions of these radicals).
• crosslinkable groups come into consideration, for.
• Example the allyl group or cyclic hydrocarbon group having at least one non-aromatic double bond.
• the cyclic hydrocarbon group is in particular a dihydrodicyclopentadienyl group of the formula:
• crosslinkable group can be bound to the polymer in particular by copolymerization with monomers containing the crosslinkable group (crosslinkable monomers).
• Suitable crosslinkable monomers are, for.
• monomers containing a required for the polymerization reactive ethylenically unsaturated group and the above crosslinkable group are retained since, under the conditions of polymerization, first the reactive ethylenically unsaturated group (eg an acrylic or methacrylic group) polymerizes.
• Allyl (meth) acrylate or monomers having a (meth) acrylic group and a dihydrodicyclopentadienyl group may be mentioned as monomers.
• the (meth) acrylic group may be bound directly or indirectly (i.e., via an organic group as a spacer to the dihydrodicyclopentadienyl group, preferred is dihydrodicyclopentadienyl (meth) acrylate of the formula:
• the polymer A) preferably has a crosslinkable group content of from 0.0001 to 0.5 mol / 100 g of polymer, particularly preferably 0.0002 to 0.1 and very particularly preferably from 0.001 to 0.02 and in particular from 0.003 to 0 , 01 mol / 100g polymer.
• it is a by irradiation with high-energy light, for. B. UV light or electron beam crosslinkable polymer.
• the polymer z. B. by the above crosslinkable groups or even if hydrogen protons can be separated from the polymer main chain photochemically, in particular using a photoinitiator or by electron beams, so that a radical is formed, which can undergo further chemical reactions.
• the mixture contains a photoinitiator.
• the photoinitiator may be z. These are photoinitiators in which a chemical bond is cleaved, so that 2 radicals are formed, which initiate the further crosslinking or polymerization reactions.
• H-abstractors which detach a hydrogen atom from the polymer chain
• these are photoinitiators with a carbonyl group. This carbonyl group slides into a C-H bond to form a C-C-O-H moiety.
• Both classes of photoinitiators may be used alone or in admixture.
• the photoinitiator or at least one of the photoinitiators is bound to the polymer A).
• a photoinitiator which is incorporated by radical copolymerization in the polymer chain.
• the photoinitiator preferably contains an acrylic or (meth) acrylic group for this purpose.
• Suitable copolymerizable photoinitiators are acetophenone or benzophenone derivatives which contain at least one, preferably one, ethylenically unsaturated group.
• the ethylenically unsaturated group is preferably an acrylic or methacrylic group.
• the ethylenically unsaturated group may be bonded directly to the phenyl ring of the acetophenone or benzophenone derivative. In general, there is a spacer group (spacer) between the phenyl ring and the ethylenically unsaturated group.
• the spacer group may, for. B. contain up to 100 carbon atoms.
• Suitable acetophenone or Benzophenonderivate are z.
• EP-A 346 734 EP-A 377 199 (claim 1), DE-A 4 037 079 (claim 1) and DE-A 3 844 444 (claim 1) described and are by this reference also in the present
• acetophenone and benzophenone derivatives are those of the formula:
• R 11 is an organic radical having up to 30 C atoms
• R 21 is an H atom or a methyl group
• R 3 is an optionally substituted phenyl group or a C 1 -C 4 -alkyl group.
• R 11 particularly preferably represents an alkylene group, in particular a C 2 -C 8 -alkylene group.
• R 31 particularly preferably represents a methyl group or a phenyl group.
• the mixture according to the invention preferably contains from 0.0001 to 0.5 mol, more preferably from 0.0002 to 0.1, very preferably from 0.003 to 0.01 mol of the photoinitiator, or the molecule group which is active as a photoinitiator and bonded to the polymer , per 100 g of the weight sum of A) + B).
• the polymer A) preferably has a K-value of 10 to 100, especially from 30 to 80, particularly preferably from 40 to 60, as measured in tetrahydrofuran (1% solu- tion, 21 0 C).
• the K value according to Fikentscher is a measure of the molecular weight and viscosity of the polymer.
• the molecular weight associated with the above K value range is much higher than the molecular weight of compounds B).
• the average molecular weight (both the number average molecular weight and the weight average molecular weight) of the polymer A) is generally at least twice, in particular at least 10 times as high as that of the compounds B).
• the glass transition temperature (Tg) of the polymer A) is preferably -60 to +10 0 C, more preferably -55 to 0 0 C, most preferably -55 to -10 0 C.
• the glass transition temperature of the polymer can be determined by conventional methods such as differential thermal analysis or differential scanning calorimetry (see, for example, ASTM 3418/82, so-called “midpoint temperature”).
• Polymers A) can be obtained by copolymerization of the monomeric components using the customary polymerization initiators and optionally regulators be prepared, wherein at the usual temperatures in bulk, in emulsion, z. B. in water or liquid hydrocarbons, or polymerized in solution.
• the polymers are prepared by polymerizing the monomers in a solvent (solution polymerization), in particular in solvents with a Siedebe- kingdom from 50 to 1500 0 C, preferably from 60 to 120 0 C using the customary amounts of polymerization initiators at generally 0.01 to 10, in particular from 0.1 to 4 wt .-%, based on the total weight of the monomers is prepared.
• Particularly suitable solvents are alcohols, such as methanol, ethanol, n- and iso-propanol, n- and iso-butanol, preferably isopropanol and / or isobutanol, and hydrocarbons, such as toluene and, in particular, benzines having a boiling range of from 60 to 120 ° C.
• alcohols such as methanol, ethanol, n- and iso-propanol, n- and iso-butanol, preferably isopropanol and / or isobutanol
• hydrocarbons such as toluene and, in particular, benzines having a boiling range of from 60 to 120 ° C.
• ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and esters, in the case of ethyl acetate and mixtures of solvents of the type mentioned, with mixtures comprising isopropanol and / or isobutanol in amounts of from 5 to 95, in particular from 10 to 80 , preferably from 25 to 60 wt .-%, based on the solution mixture used, are preferred.
• Suitable polymerization initiators in the solution polymerization are, for example, azo compounds, ketone peroxides and alkyl peroxides.
• the solvent can be removed, optionally under reduced pressure, operating at elevated temperatures, for example in the range of 100 to 150 0 C.
• the polymers can then be used in a solvent-free state, ie as melts.
• Suitable compounds B) are customary free-radically polymerizable monomers having a defined chemical structural formula and an actual molecular weight of less than 200 g / mol (referred to below as compounds B1).
• Compounds B1 have a polymerizable group.
• Compounds B1 which may be mentioned in particular are the abovementioned monomers from which the polymer A) can be synthesized. Particularly noteworthy are acrylic monomers with an acrylic or methacrylic group.
• compounds B which do not fall under B1 are referred to below as B2.
• compounds B2 are (meth) acrylate compounds, the acrylate compounds, ie the derivatives of acrylic acid, being preferred in each case.
• Preferred (meth) acrylate compounds B2 contain from 2 to 20, preferably from 2 to 10 and very particularly preferably from 2 to 5, copolymerizable, ethylenically unsaturated double bonds.
• the weight-average molecular weight M w of the compounds B2 is preferably below 5000, more preferably below 3000 g / mol (determined by gel permeation chromatography with polystyrene as standard and tetrahydrofuran as eluent). With very particular preference it is less than 2000 and in particular less than 1000 g / mol.
• the M w of B2 is particularly preferably greater than 250 and very particularly preferably greater than 400 g / mol.
• (meth) acrylate compounds may be mentioned (meth) acrylic acid esters and in particular acrylic acid esters of polyhydric alcohols, in particular those which contain, in addition to the hydroxyl groups, no further functional groups or at most ether groups.
• examples of such alcohols are, for. B. bifunctional alcohols such as ethylene glycol, propylene glycol, and their higher-condensed representatives, eg. B.
• diethylene glycol triethylene glycol, dipropylene glycol, tripropylene glycol, etc., butanediol, pentanediol, hexanediol, neopentyl glycol, alkoxylated phenolic compounds such as ethoxylated or propoxylated bisphenols, cyclohexanedimethanol, trifunctional and higher functional alcohols such as glycerol, Trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol and the corresponding alkoxylated, in particular ethoxy- and propoxylated alcohols.
• alkoxylated phenolic compounds such as ethoxylated or propoxylated bisphenols
• cyclohexanedimethanol trifunctional and higher functional alcohols
• trimethylolethane
• the alkoxylation products are obtainable in a known manner by reacting the above alcohols with alkylene oxides, in particular ethylene oxide or propylene oxide.
• alkylene oxides in particular ethylene oxide or propylene oxide.
• the degree of alkoxylation per hydroxyl group is 0 to 10, d. H. 1 mol of hydroxyl group may preferably be alkoxylated with up to 10 mol of alkylene oxides.
• polyester (meth) acrylates which are the (meth) acrylic esters of polyesterols.
• Polyesterole z. B. into consideration, as they can be prepared by esterification of polycarboxylic acids, preferably dicarboxylic acids, with polyols, preferably diols.
• the starting materials for such hydroxyl-containing polyesters are known to the person skilled in the art.
• Succinic acid, glutaric acid, adipic acid, sebacic acid, o-phthalic acid, their isomers and hydrogenation products and also esterifiable derivatives, such as anhydrides or dialkyl esters of the acids mentioned, may preferably be used as dicarboxylic acids.
• Suitable polyols are the abovementioned alcohols, preferably ethylene glycol, propylene glycol-1, 2 and -1, 3, butanediol-1, 4, hexanediol-1, 6, Neopentylglycol, cyclohexanedimethanol and polyglycols of the type of ethylene glycol and propylene glycol into consideration.
• Polyester (meth) acrylates can in several stages or one-stage, such as. As described in EP 279 303, be prepared from acrylic acid, polycarboxylic acid, polyol.
• Epoxy (meth) acrylates are, for. B. such as those by reaction of epoxidized olefins or poly- or mono- or diglycidyl ethers, such as bisphenol A diglycidyl ether, with (meth) acrylic acid are available.
• Urethane (meth) acrylates are, in particular, reaction products of hydroxyalkyl (meth) acrylates with polyisocyanates or diisocyanates (also see R. Holmann, U.V. and E. B. Curing Formulation for Printing Inks and Paints, London 1984).
• compounds B in particular compounds B2 and mixtures of B2 and B1 are suitable.
• compounds B) consist overall of at least 50% by weight, more preferably at least 75% by weight, of compounds B2).
• Preferred compounds B2 are the abovementioned (meth) acrylic esters.
• Compounds B regardless of whether they are B1, B2 or mixtures of B1 and B2, are preferably liquid at 21 ° C., 1 bar; if it is at 21 0 C, 1 bar solid compounds, these compounds should dissolve well in the polymer A).
• the viscosity of the compounds B or of the mixture of the compounds B is preferably 0.01 to 50 Pas, more preferably 0.04 to 10 Pas at 23 0 C, 1 bar, measured according to DIN EN ISO 3219; most preferably, the viscosity is 0.04 to 2 and in particular 0.04 to 1 Pas.
• compounds B have on average 1 to 5, preferably 1.5 to 3, particularly preferably 2 to 3, in a particular embodiment 2 to 2.5 polymerizable groups per molecule.
• the mixture of A) and B) is suitable as a binder, for. B. for pressure-sensitive adhesives, wherein the weight fraction of A) is preferably at most 99 wt .-%, more preferably at most 95 wt% and preferably at least 30 wt .-%, more preferably at least 50 or at least 60 wt .-%.
• the proportion by weight of B) is preferably not more than 70% by weight, more preferably not more than 50% by weight or not more than 40% by weight and preferably at least 1% by weight, particularly preferably at least 5% by weight.
• Suitable weight ranges of A) and B) are in particular:
• All weights for A) and B) are based on the total weight of A) and B).
• the mixture of A) and B) can be prepared by conventional methods.
• polymer A) is heated, e.g. B. to temperatures between 50 and 130 0 C, and compounds A), optionally together with other additives, stirred.
• the mixture is suitable as a binder for pressure-sensitive adhesives.
• the pressure-sensitive adhesives may consist solely of the mixture of A) and B).
• hot-melt adhesives containing water or other solvents eg. B. from the solution of A), possibly in small amounts and be applied from the melt.
• the pressure-sensitive adhesive or hot melt pressure-sensitive adhesive preferably contains less than 5 parts by weight, in particular less than 2 or 1 part by weight, of water and / or solvent per 100 parts by weight of the total weight of A) and B). Particularly preferably, the pressure-sensitive adhesive or hot melt pressure-sensitive adhesive is substantially free of water and other solvents.
• the pressure-sensitive adhesive preferably contains at least one photoinitiator (see above). Insofar as this is not a photoinitiator bound to the polymer, the photoinitiator may be added to the mixture of A) and B) or already to the components A) or B) at any time.
• additives which can be added to the pressure-sensitive adhesive, z.
• fillers dyes, flow control agents and in particular tackifiers (tackifying resins).
• Tackifiers are z.
• natural resins such as rosins and their by disproportionation or isomerization, polymerization, dimerization, hydrogenation resulting derivatives.
• These may be in their salt form (with, for example, monovalent or polyvalent counterions (cations) or preferably in their esterified form.)
• Alcohols used for the esterification may be monohydric or polyhydric, for example, methanol, ethanediol, Diethylene glycol, triethylene glycol, 1, 2,3-propanethiol, pentaerythritol.
• hydrocarbon resins e.g., coumarone-indene resins, polyester terpene resins, hydrocarbon resins based on unsaturated C-H compounds, such as butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentadiene, cyclopentadiene, cyclohexadiene, styrene, a-methylstyrene , Vinyltoluene use.
• unsaturated C-H compounds such as butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentadiene, cyclopentadiene, cyclohexadiene, styrene, a-methylstyrene , Vinyltoluene use.
• tackifiers are increasingly also polyacrylates, which have a low molecular weight used.
• these polyacrylates have a weight average molecular weight Mw below 30,000.
• the polyacrylates are preferably at least 60, in particular at least 80 wt .-% of C1-C8 alkyl (meth) acrylates.
• Preferred tackifiers are natural or chemically modified rosin resins. Rosin resins consist predominantly of abietic acid or abietic acid derivatives.
• the amount by weight of tackifiers is z. B. 5 to 100 parts by weight. particularly preferably 10 to 50 parts by weight. based on 100 parts by weight of the total weight of A) + B).
• the pressure sensitive adhesives are preferably used as hot melt pressure sensitive adhesives, i. H. they are applied from the melt to the desired carrier.
• the pressure-sensitive adhesives or hot-melt adhesives according to the invention are suitable for the production of self-adhesive articles, such as labels, adhesive tapes or adhesive films, e.g. B. protective films.
• the self-adhesive articles generally consist of a carrier and a one or both sides, preferably one-sidedly applied layer of the adhesive.
• the carrier material may be, for. As paper, plastic films of polyolefins or PVC act.
• the self-adhesive articles are produced, in particular, by applying the pressure-sensitive adhesive to the support and then crosslinking with UV light or electron beams.
• a particular advantage of the invention is that self-adhesive articles with large application quantities, i. H. can be made with thick pressure-sensitive adhesive layers.
• the amount applied may in particular be more than 100 g, preferably more than 150 g, more preferably more than 200 g and very particularly preferably more than 250 g per square meter of carrier.
• the coated support is irradiated with high energy light, preferably UV light, to achieve the desired crosslinking.
• the radiation energy can z. B. 10 mJ / cm2 to 1500 mJ / cm2 irradiated area.
• labels or mounting tapes are preferred.
• protective films are also preferred.
• the protective film should protect objects during transport or storage.
• the protective films can be removed from the object without residue by hand again.
• the self-adhesive products are suitable for a wide variety of substrates.
• the substrates may, for. B. of metals, paper, cardboard, wood, plastics, etc.
• the heat resistance is improved, ie the bonds hold even at high temperatures.
• the mixtures or pressure-sensitive adhesives according to the invention are particularly suitable for mounting tapes, which in industrial production, for. B. of motor vehicles, find uses. Examples
• a polymerization apparatus consisting of glass reactor with heating-cooling circuit, reflux condenser, stirrer, thermocouple, nitrogen inlet and Dosiergefä touch 456 g of methyl ethyl ketone (MEK) are introduced and heated to 80 0 C in a gentle stream of nitrogen. 120 g of a monomer mixture consisting of 94.7% n-butyl acrylate, 5% acrylic acid and 0.3% dihydrodicyclopentadienyl acrylate are added.
• MEK methyl ethyl ketone
• Example 2 Mixture with polymer from Example 1
• a polymerization apparatus consisting of glass reactor with heating-cooling circuit, reflux condenser, stirrer, thermocouple, nitrogen inlet and Dosiergefä on 667.1 g of methyl ethyl ketone (MEK) are introduced and heated to 80 0 C in a gentle stream of nitrogen. There are 90 g of a monomer mixture consisting of 94.7% n.Butylacrylat, 5% acrylic acid and 0.3% Dihydrodicyclopentadienylacrylat added. After again reaching 80 0 C.
• MEK methyl ethyl ketone
• Example 4 Mixture with polymer from Example 3
• a polymerization apparatus consisting of glass reactor with heating-cooling circuit, reflux condenser, stirrer, thermocouple, nitrogen inlet and dosing 228 g of methyl ethyl ketone (MEK) are introduced and heated to 80 0 C in a gentle stream of nitrogen.
• MEK methyl ethyl ketone
• a polymerization apparatus consisting of glass reactor with heating-cooling circuit, reflux condenser, stirrer, thermocouple, nitrogen inlet and dosing 228 g of methyl ethyl ketone (MEK) are introduced and heated to 80 0 C in a gentle stream of nitrogen. 60.3 g of a monomer mixture consisting of 94.4% of n-butyl acrylate, 5% of acrylic acid, 0.3% of a photoinitiator of the formula IV and 0.3% of dihydrodicyclopentadienyl acrylate are added.
• MEK methyl ethyl ketone
• the coated films were irradiated with UV light.
• the irradiation dose is given in the table (H spectrum, Hg mean pressure, 120 W / cm).
• the pressure-sensitive adhesive coated carrier was cut into 25 mm wide test strips. To determine the shear strength, the test strips with a bonded area of 25 mm 2 were glued onto the test area made of steel (Afera steel), rolled once with a 1 kg roller, stored for 10 min (in standard atmosphere, 50% relative humidity). ness 1 bar, 23 0 C) and then suspended with a 1 kg weight (under standard climate). The measure of shear strength was the time to fall off the weight; in each case the average of 5 measurements was calculated.
• peel strength (adhesion)
• a 2.5 cm wide test strip was glued to the test surface (made of steel or polyethylene, see table) and rolled once with a 1 kg roller. He was then clamped with one end in the upper jaws of a tensile-strain tester. The tape was peeled off the test surface at 300 mm / min. At a 180 ° angle d. H. the adhesive strip was bent over and pulled off parallel to the test plate and the required effort was measured. The measure of peel strength was the force in N / 2.5 cm, which resulted as an average of five measurements.
• the peel strength was determined 24 hours after the bonding. After this time, the adhesive power has fully developed.
• the samples were prepared as for the shear test, glued to steel (Afera steel) but rolled 4 times with a 2 kg roll and stored for 16 hours in standard climate. The samples were then suspended in an air-conditioned oven, loaded with 1 kg and the temperature was increased in increments of 0.5 ° C / min. As a measure of the heat resistance is the temperature at which the weight drops. Indicated is the average of three measurements.

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• 2007
  • 2007-10-22 WO PCT/EP2007/061284 patent/WO2008049805A1/de active Application Filing

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