DE102011105209A1 - Pressure-sensitive- and structural adhesive polymerizate present in band form, produced by free radical polymerization under ultra-violet, useful e.g. for coating molded part with polymerizate and applying on anti-adhesive carrier material - Google Patents
Pressure-sensitive- and structural adhesive polymerizate present in band form, produced by free radical polymerization under ultra-violet, useful e.g. for coating molded part with polymerizate and applying on anti-adhesive carrier material Download PDFInfo
- Publication number
- DE102011105209A1 DE102011105209A1 DE102011105209A DE102011105209A DE102011105209A1 DE 102011105209 A1 DE102011105209 A1 DE 102011105209A1 DE 102011105209 A DE102011105209 A DE 102011105209A DE 102011105209 A DE102011105209 A DE 102011105209A DE 102011105209 A1 DE102011105209 A1 DE 102011105209A1
- Authority
- DE
- Germany
- Prior art keywords
- adhesive
- pressure
- sensitive
- polymer
- polymerizate
- 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- Withdrawn
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 53
- 239000000853 adhesive Substances 0.000 title claims abstract description 51
- 238000000576 coating method Methods 0.000 title claims abstract description 5
- 239000011248 coating agent Substances 0.000 title claims abstract description 4
- 238000010526 radical polymerization reaction Methods 0.000 title claims abstract 3
- 239000012876 carrier material Substances 0.000 title claims description 3
- 230000000181 anti-adherent effect Effects 0.000 title 1
- 239000003822 epoxy resin Substances 0.000 claims abstract description 14
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 14
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims abstract 2
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000002998 adhesive polymer Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- 238000005304 joining Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000002390 adhesive tape Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000002313 adhesive film Substances 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000006188 syrup Substances 0.000 description 4
- 235000020357 syrup Nutrition 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000004609 Impact Modifier Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BUHVIAUBTBOHAG-FOYDDCNASA-N (2r,3r,4s,5r)-2-[6-[[2-(3,5-dimethoxyphenyl)-2-(2-methylphenyl)ethyl]amino]purin-9-yl]-5-(hydroxymethyl)oxolane-3,4-diol Chemical compound COC1=CC(OC)=CC(C(CNC=2C=3N=CN(C=3N=CN=2)[C@H]2[C@@H]([C@H](O)[C@@H](CO)O2)O)C=2C(=CC=CC=2)C)=C1 BUHVIAUBTBOHAG-FOYDDCNASA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical group OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- KHAYCTOSKLIHEP-UHFFFAOYSA-N docosyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C=C KHAYCTOSKLIHEP-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ZWEDFBKLJILTMC-UHFFFAOYSA-N ethyl 4,4,4-trifluoro-3-hydroxybutanoate Chemical compound CCOC(=O)CC(O)C(F)(F)F ZWEDFBKLJILTMC-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000003763 resistance to breakage Effects 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3209—Epoxy compounds containing three or more epoxy groups obtained by polymerisation of unsaturated mono-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—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
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
-
- 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
- C09J2301/302—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 pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- 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
-
- 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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/16—Metal
- C09J2400/163—Metal in the substrate
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
-
- 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
- C09J2463/00—Presence of epoxy resin
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
Es handelt sich bei der vorliegenden Erfindung um ein reaktives, zunächst leicht haftklebendes und schließlich strukturell klebendes Polymerisat, das insbesondere in Bandform für bevorzugt außenhautrelevante Fügestellen vorgesehen ist, d. h. für solche Fügestellen, die sichtbar bleiben und daher auch gewissen optischen Anforderungen entsprechen müssen. Bei dem reaktiven Polymerisat in Bandform handelt es sich um ein Klebeband, das sowohl eine stabile Verbindung bewirken muss als auch als Designelement fungiert. Anwendungstechnisch ist der Einsatz eines solchen Klebebandes beispielsweise zur strukturellen Verklebung zweier gekrempter Bleche miteinander an den Krempen und damit der Herstellung eines ohne Beschädigung der beteiligten Komponenten nicht mehr zu Lösenden Verbundes denkbar.The present invention is a reactive, initially slightly pressure-sensitive adhesive and finally structurally adhesive polymer, which is provided in particular in band form for preferably outer skin-relevant joints, d. H. for such joints, which must remain visible and therefore must also meet certain optical requirements. The tape-shaped reactive polymer is an adhesive tape which must both act as a stable compound and function as a design element. In terms of application technology, the use of such an adhesive tape is conceivable, for example, for the structural bonding of two crimped sheets to one another on the brim and thus the production of a composite which is no longer to be loosened without damaging the components involved.
Das für den genannten Zweck einsetzbare Klebeband muss idealerweise folgende Anforderungen erfüllen: Es soll im Ausgangszustand leicht haftklebend sein und somit eine gewisse Vorfixierung ermöglichen. Bei der Erwärmung soll das Klebeband genau in dem Maße erweichen und damit formbar werden, welches notwendig ist, um eine konkave Klebefuge zu bewirken, der Klebstoff darf aber nicht so weit erweichen, dass er komplett flüssig wird und damit auslaufen würde. Durch die anschließende Härtung muss schließlich ein Verbund entstehen, der insbesondere den Anforderungen einer hohen Bruch- und Biege- sowie Schlagfestigkeit und damit auch einer gewissen Elastizität, einer hohen Wärmebeständigkeit und einer Überlackierbarkeit entspricht. So ist es eine Kernanforderung des erfindungsgemäßen Klebstoffsystems, durch Formung des unter Einwirkung hoher Temperaturen weichen Klebstoffs eine falten- und blasenfreie, konkave, sichtbare Fügenaht in der Außenhaut des Produktes zu erzeugen. Da diese Naht im fertigen Produkt einen Teil des Designs dieses Produktes bildet, muss sie optisch fehlerfrei geformt sein.The adhesive tape that can be used for the stated purpose must ideally meet the following requirements: it should be slightly pressure-sensitive in the initial state and thus allow a certain prefixing. When heated, the adhesive tape should soften and become malleable to the extent necessary to effect a concave bondline, but the adhesive should not soften so much that it will become completely fluid and thus leak. The subsequent hardening finally requires the formation of a composite that meets in particular the requirements of high resistance to breakage and bending as well as impact and thus also a certain elasticity, high heat resistance and recoatability. Thus, it is a key requirement of the adhesive system according to the invention to produce a wrinkle- and bubble-free, concave, visible joint seam in the outer skin of the product by forming the soft under high temperature adhesive. Since this seam in the finished product forms part of the design of this product, it must be optically faultlessly shaped.
Strukturelle, hitzeaktivierbare Klebstoffe, auch in Form einer Klebefolie bzw. eines Klebebandes, sind im Stand der Technik bekannt. Strukturelle Klebstoffe sind dabei solche, die in einer Fügeverbindung eingesetzt werden und darin einen beträchtlichen Anteil an der Sicherstellung der Stabilität und/oder Funktion des Bauteils erlangen. Daher spricht man in diesem Zusammenhang auch von konstruktiven Verklebungen, von Montage- oder Konstruktionsklebstoffen bzw. strukturellen Klebstoffen. Hitzeaktivierbare strukturelle Klebstoffe basieren meist auf Polyurethanverbindungen oder auf Epoxid-Harzen.Structural, heat-activatable adhesives, also in the form of an adhesive film or an adhesive tape, are known in the prior art. Structural adhesives are those which are used in a joint connection and obtain therein a considerable share in ensuring the stability and / or function of the component. Therefore, one speaks in this context of structural bonding, assembly or construction adhesives or structural adhesives. Heat-activated structural adhesives are mostly based on polyurethane compounds or on epoxy resins.
Weder aus der Literatur noch aus dem Markt aber ist ein Klebstoffsystem bekannt, welches die genannten Anforderungen erfüllt. Bekannte hitzeaktivierbare Systeme auf Basis Polyurethan scheiden für die hier beabsichtigten Anwendungen aufgrund der zu geringen Dicke und der fehlenden haftklebenden Eigenschaften aus.Neither the literature nor the market but an adhesive system is known which meets the requirements mentioned. Known heat-activatable systems based on polyurethane are ruled out for the applications intended here due to the too small thickness and the lack of pressure-sensitive adhesive properties.
Wärmehärtbare Klebemittel auf Epoxid-Basis sind allgemein bekannt, beschrieben z. B. in
Erste Ansätze mit einem auf Lösemittelbasis polymerisierten reaktiven Haftklebeband auf Basis Epoxidharz brachten keine befriedigenden Ergebnisse: Die Dicke des Films reichte nicht dafür aus, ein für die geplante Anwendung zufrieden stellendes Sichtbild zu erzeugen, außerdem entstanden durch Verdampfung von Restlösemitteln bei der Härtung stellenweise Blasen und Kanäle im Produkt, die neben mangelhafter Optik auch mangelnde Korrosionsfestigkeit zur Folge hatten.Initial approaches using a solvent-based polymerized reactive pressure-sensitive adhesive tape based on epoxy resin did not provide satisfactory results: the thickness of the film was not sufficient to produce a satisfactory appearance for the intended application, and in addition, evaporation of residual solvents on curing caused localized bubbles and channels in the product, which, in addition to a poor appearance, also resulted in a lack of corrosion resistance.
Daraufhin wurde dann ein haftklebendes, nicht reaktives Dickschichtbandpolymerisat für den beabsichtigten Anwendungszweck geprüft. In dieser Weise war zwar ein optisch zufrieden stellendes Sichtbild zu erzielen, doch dieses nicht-strukturelle Band war nach der Applikation noch mit einer gewissen Flexibilität ausgestattet und ermöglichte so ein Bewegen der Bauteile gegeneinander, was nicht erwünscht war.Then, a pressure-sensitive, non-reactive thick-film polymer was tested for the intended application. In this way, although a visually satisfactory visual image was achieved, but this non-structural tape was still equipped with a certain flexibility after application and thus allowed a movement of the components against each other, which was not desirable.
Zur Vermeidung der beschrieben Nachteile kam schließlich die Idee auf, ein reaktives Dickschichtpolymerisat zu erzeugen, welches die Vorteile von reaktivem Haftklebeband und Dickschichtbandpolymerisat kombiniert in sich vereinigt. Diese Anforderungen zu erfüllen, gelang durch die besonderen Eigenschaften der nachfolgend näher beschriebenen Zusammensetzung eines Acrylatklebstoffes mit Epoxid- und H-aciden Gruppen im Polymer-Rückgrat, der mittels UV-Polymerisation hergestellt werden kann. Dabei handelt es sich bei dem erfindungsgemäßen Klebstoff um eine Weiterentwicklung des in
Die erfindungsgemäßen Strukturklebstoffe basieren auf einer Kombination verschiedener Acrylat- und Methacrylatmonomere mit einem Epoxidharz unter Zugabe von Photoinitiatoren, Schlagzähmodifizierern und Härtern bzw. Beschleunigern für heiß-härtende Epoxidsysteme.The structural adhesives according to the invention are based on a combination of different acrylate and methacrylate monomers with an epoxy resin with addition of photoinitiators, impact modifiers and hardeners or accelerators for hot-curing epoxy systems.
Das Klebeband ist dabei wie folgt aufgebaut: Ein beidseitig silikonisiertes bzw. allgemein abhäsiv ausgerüstetes Trägermaterial in Form einer Folie oder eines Papiers mit dem darauf aufgebrachten Klebstoffpolymerisat wird in sich gewickelt, die Dicke von Trägermaterial und Bandpolymerisat kann dabei zwischen 0,2 mm und 4,0 mm betragen.The adhesive tape is constructed as follows: a substrate material siliconized on both sides or generally abhesive in the form of a film or a paper with the adhesive polymer applied thereto is wound in it, the thickness of support material and tape polymer can be between 0.2 mm and 4, 0 mm.
Bei dem Klebstoff selbst handelt es sich um ein modifiziertes epoxifunktionelles Acrylatpolymer. Die Acrylatkomponente basiert dabei zum einen auf einer Mischung von Monomeren des Glycidylmethacrylats mit mindestens einer weiteren damit copolymerisierbaren, vorzugsweise weich machenden und/oder unpolaren Monomerkomponente wie Acryl- und Methacrylatsäureestern mit Kohlenwasserstoffresten, die 2 bis 14 C-Atome umfassen. Beispiele für solche Monomere sind Isobutylacrylat, Isooctylmethacrylat, Isooctylmethacrylat, n-Butylacrylat, n-Butylmethacrylat, n-Octylacrylat, n-Octylmethacrylat, n-Pentylacrylat, n-Pentylmethacrylat, n-Hexylacrylat, n-Hexylmethacrylat, n-Heptylacrylat, n-Nonylacrylat und deren verzweigte Isomere, bevorzugt wird hier n-Hexylmethacrylat eingesetzt.The adhesive itself is a modified epoxy-functional acrylate polymer. The acrylate component is based, on the one hand, on a mixture of monomers of glycidyl methacrylate with at least one further copolymerizable, preferably softening and / or nonpolar monomer component, such as acrylic and methacrylic acid esters having hydrocarbon radicals comprising 2 to 14 C atoms. Examples of such monomers are isobutyl acrylate, isooctyl methacrylate, isooctyl methacrylate, n-butyl acrylate, n-butyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, n-heptyl acrylate, n-nonyl acrylate and their branched isomers, preferably n-hexyl methacrylate is used here.
Zum anderen basiert die Acrylatkomponente des Klebstoffes auf einem Prepolymerisat aus Glycidylmethacrylat mit mindestens fünf unterschiedlichen Monomerkomponenten mit Kohlenwasserstoffresten, die wiederum 2 bis 14 C-Atome umfassen, so z. B.: Ethylacrylat, Methylacrylat, Propylacrylat, Isobornylacrylat, Laurylacrylat, Stearylacrylat, Propylmethacrylat, Isodecylacrylat, Behenylacrylat, 2-Hydroxyethylacrylat – um nur einige zu nennen – die im Weiteren mit den ausgewählten und damit copolymerisierbaren Monomeren der oben beschriebenen ersten Acrylatkomponente vermischt werden.On the other hand, the acrylate component of the adhesive is based on a prepolymer of glycidyl methacrylate having at least five different monomer components with hydrocarbon radicals, which in turn comprise 2 to 14 carbon atoms, such. For example: ethyl acrylate, methyl acrylate, propyl acrylate, isobornyl acrylate, lauryl acrylate, stearyl acrylate, propyl methacrylate, isodecyl acrylate, behenyl acrylate, 2-hydroxyethyl acrylate - to name a few - which are subsequently mixed with the selected and thus copolymerizable monomers of the first acrylate component described above.
Eine andere wesentliche Komponente des Klebstoffes besteht in einem festen, nicht-modifizierten Epoxidharz auf Basis Bisphenol A mit einer engen Molekulargewichtsverteilung, wie es z. B. unter dem Handelsnamen „Araldit” der Firma „Huntsman” vertrieben wird.Another essential component of the adhesive is a solid, unmodified bisphenol A-based epoxy resin having a narrow molecular weight distribution, as described, for example, in US Pat. B. under the trade name "Araldite" the company "Huntsman" is sold.
Darüber hinaus können bei der Herstellung der erfindungsgemäßen Klebstoffe bis zu 1,5 Gew.-% eines oder mehrerer Photoinitiatoren hinzugegeben werden.In addition, up to 1.5% by weight of one or more photoinitiators may be added in the preparation of the adhesives of the invention.
Besonders bevorzugt wird hierbei eine Kombination aus einem Photoinitiator, der aus der Gruppe der α-Hydroxyketone ausgewählt ist, insbesondere 1-Hydroxy-cyclohexyl-phenylketon (Irgacure® 184), mit einem Photoinitiator aus der Gruppe der Bis-Acylphosphine, vorzugsweise Phenyl-bis-(2,4,6)-trimethylbenzoyl)-phosphinoxid (Irgacure® 819). Bei dieser bevorzugten Kombination von Photoinitiatoren ist das α-Hydroxyketon in einer Menge von 0,01 bis 0,1 Gew.-% und das Bis-Acylphosphin in einer Menge von 0,5 bis 0,99 Gew.-% im erfindungsgemäßen Klebstoff enthalten.Particular preference is given here to a combination of a photoinitiator which is selected from the group of α-hydroxy ketones, in particular 1-hydroxy-cyclohexyl-phenyl ketone (Irgacure ® 184), with a photoinitiator from the group of bis-acylphosphines, preferably phenyl-bis - (2,4,6) -trimethylbenzoyl) phosphine oxide (Irgacure ® 819). In this preferred combination of photoinitiators, the α-hydroxy ketone in an amount of 0.01 to 0.1 wt .-% and the bis-acylphosphine in an amount of 0.5 to 0.99 wt .-% in the inventive adhesive ,
Des Weiteren sind dem Gemisch Katalysatoren zur Epoxidvernetzung zugesetzt. Bei diesen auch als Härter bezeichneten Katalysatoren bzw. Katalysatorsystemen handelt es sich um Stoffe, die die Härtung von Epoxidharzen oder Epoxidgruppen enthaltenden Polymeren oder Polymergemischen katalytisch auslösen. Grundsätzlich sind dabei alle gängigen Katalysatoren zur Epoxidvernetzung geeignet, aus Stabilitätsgründen werden hier jedoch keine bei Raumtemperatur vernetzenden Systeme wie z. B. Amine eingesetzt. Bevorzugt werden hingegen Katalysatorsysteme, die die Reaktion bei Temperaturen von 80°C oder höher, besonders bevorzugt bei Temperaturen von 100°C oder darüber starten (z. B. Anhydride, Ammoniumsalze organischer/anorganischer Säuren, mikrovisiertes Dicyandiamid bzw. TDI-Uron cokatalysiert mit Harnstoffderivaten oder neutralisierten Säuren). Furthermore, catalysts for the epoxide crosslinking are added to the mixture. These catalysts or catalyst systems, which are also referred to as hardeners, are substances which catalytically trigger the curing of epoxy resins or polymers or polymer mixtures containing epoxide groups. Basically all common catalysts for epoxy crosslinking are suitable for stability reasons, however, no crosslinking at room temperature systems such. As amines used. By contrast, preference is given to catalyst systems which co-catalyze the reaction at temperatures of 80 ° C. or higher, particularly preferably at temperatures of 100 ° C. or above (for example anhydrides, ammonium salts of organic / inorganic acids, microrised dicyandiamide or TDI-urone Urea derivatives or neutralized acids).
Die Katalysatoren bzw. Katalysatorsysteme werden dem polymerisationsfähigen Polymersirup hinzugefügt, wodurch die Aktivierungstemperatur und Aktivierungsdauer der Umsetzung zum strukturellen Klebeverbund beeinflusst werden kann.The catalysts or catalyst systems are added to the polymerizable polymer syrup, whereby the activation temperature and activation time of the conversion to the structural adhesive bond can be influenced.
Schließlich wird dem Klebstoffsystem noch eine Substanz hinzugegeben, die eine schlagzäh-modifizierende Wirkung hat. Grundsätzlich geeignet hierzu sind Reaktivharze mit fein darin verteilten Substanzen auf Kautschuk-Basis, speziell sogenannte Core-Shell-Materialien bestehend aus Silikonkautschuk-Partikeln definierter Größe mit diese umgebender organischer Hüllstruktur, die über reaktive Gruppen verfügt. Neben der gewünschten Verbesserung der Schlagzähigkeit weisen diese Substanzen noch weitere Vorteile auf: Sie erhöhen die Viskosität der Mischung kaum, sie weisen hohe Temperatur-, UV- und Ozon-Beständigkeiten auf und sie bewirken letztlich glattere Oberflächen und damit Beschichtungen mit niedrigerem Reibungskoeffizienten infolge der Silikonelastomer-Teilchen an der Oberfläche.Finally, a substance is added to the adhesive system, which has an impact-modifying effect. Basically suitable for this purpose are reactive resins with rubber-based substances distributed finely therein, especially so-called core-shell materials consisting of silicone rubber particles of defined size with this surrounding organic shell structure having reactive groups. In addition to the desired improvement in impact resistance, these substances have other advantages: they hardly increase the viscosity of the mixture, they have high temperature, UV and ozone resistance and they ultimately cause smoother surfaces and thus coatings with lower coefficient of friction due to the silicone elastomer Particles on the surface.
Die erfindungsgemäßen Klebstoffe sind insbesondere für die Herstellung sogenannter Dickschichtsysteme geeignet. So lassen sich mit diesen schwach haftklebenden Strukturklebstoffen Klebebänder herstellen, deren Klebstoffschicht eine Dicke bis zu 4 mm aufweisen kann.The adhesives of the invention are particularly suitable for the production of so-called thick film systems. Thus, adhesive tapes whose adhesive layer can have a thickness of up to 4 mm can be produced with these weakly adhesive structural adhesives.
Derartig dicke Klebstoff-Filme weisen im Vergleich zu dünneren Klebstoff-Filmen bei einer Reihe von Anforderungen an eine Klebeverbindung deutliche Vorteile auf, so z. B. in Fällen, in denen eine Hohlkehle zu einer signifikanten Erhöhung der Festigkeit des Klebeverbundes beträgt. Dies ist z. B. meist bei Stoßverklebungen im 90°-Winkel der Fall.Such thick adhesive films have significant advantages over a thinner adhesive film in a number of adhesive bonding requirements such as: B. in cases where a groove is a significant increase in the strength of the adhesive bond. This is z. B. usually at Stoßverklebungen in the 90 ° angle of the case.
Bei dem erfindungsgemäßen strukturellen Klebstoff bilden sich die Hohlkehlen durch die Schmelze, die bei der Erwärmung des Klebstoff-Films ab etwa 70°C. entsteht und die durch die geänderte Oberflächenspannung bzw. Verringerung der Viskosität auf den Substraten zu „kriechen” beginnt, wodurch eine komplette Benetzung des Substrats gewährleistet wird. Dadurch wird der Klebstoff sowohl in XY-Richtung als auch in Z-Richtung ausgedehnt und es bildet sich eine entsprechende Hohlkehle im Bereich der Verklebung.In the case of the structural adhesive according to the invention, the fillets are formed by the melt, which in the heating of the adhesive film from about 70 ° C. arises and which begins to "creep" due to the changed surface tension or reduction of the viscosity on the substrates, whereby a complete wetting of the substrate is ensured. As a result, the adhesive is expanded both in the XY direction and in the Z direction, and a corresponding groove is formed in the area of the bond.
Eine weitere denkbare Anwendung ist in solchen Fällen gegeben, in denen das Klebstoffsystem eine Spaltüberbrückung gewährleisten muss. Wurden hier bisher neben anderen Fügeverfahren wie z. B. dem Schweißen Flüssigklebstoffsysteme eingesetzt mit all den damit verbundenen Problematiken wie genauer Dosierung, längerer Abbindezeit etc., so gewährleisten dickere Klebstoffschichten eine deutlich bessere Spaltüberbrückung. Daher sind mit dem erfindungsgemäßen Dickschichtsystem auch Materialien verklebbar, deren Verbund aufgrund hoher Fertigungstoleranzen einen größeren Klebespalt aufweist.Another conceivable application is given in cases where the adhesive system must ensure a gap bridging. Have been here in addition to other joining methods such. B. the welding liquid adhesive systems used with all the associated problems such as accurate metering, longer setting time, etc., so ensure thicker adhesive layers significantly better gap bridging. Therefore, with the thick film system according to the invention also materials can be bonded, the composite has a larger bond gap due to high manufacturing tolerances.
Weitere Vorteile ergeben sich z. B. aus den geänderten mechanischen Kennwerten beim Einsatz dickerer Kleberschichten im Hinblick auf die Elastizität der Verbindung oder im Hinblick auf für eine bestimmte Anwendung erforderliche Schwingungsdämpfungen.Further advantages arise z. B. from the changed mechanical characteristics when using thicker adhesive layers in terms of the elasticity of the compound or with regard to required for a particular application vibration damping.
Das erfindungsgemäße Klebstoffsystem in Bandform wird hergestellt, indem die Ausgangsmonomere unter Nutzbarmachung der Lösemittelfunktion dieser Monomere im Reaktor unter Zugabe eines geeigneten Photoinitiators oder eines Photoinitiatorgemisches zu einem polymerisierbaren Sirup vermischt werden, der letztlich besteht aus:
Diesem Gemisch wird schließlich der Photoinitiator „Irgacure® 184” zugesetzt. To this mixture, the photoinitiator "Irgacure ® 184" is finally added.
Die folgenden Mengenangaben der weiteren Komponenten des erfindungsgemäßen Klebstoffsystems sind jeweils auf das Gesamtsystem bezogen:
So werden dem beschriebenen Prepolymer in einem weiteren Arbeitsschritt Komponenten wie weitere Acrylatmonomere (jeweils 0,5–10 Gew.-% Glycidylmethacrylat und n-Hexylmethacrylat), Vernetzer bzw. Härter der oben beschriebenen Art (in einer Menge von 0,5 bis 10 Gew.-%), festes Epoxidharz auf Basis Bisphenol A (5–15 Gew.-%) und Schlagzähmodifizierer in einer Menge von 10–20 Gew.-% zugegeben, ebenso ein weiterer Photoinitiator („Irgacure® 819”) für die Bandpolymerisation. Der durch die Vorvernetzung erfolgte deutliche Anstieg der Viskosität des Sirups erlaubt es nun, den Polymersirup mit einer Dicke von bis zu 4 mm auf ein abhäsives Trägermaterial als Unterlage aufzutragen. Die Zugabe des weiteren Photoinitiators bzw. Photoinitiatorgemisches ist notwendig, damit die Masse schnell und mit geringem Restmonomergehalt umgesetzt werden kann. Diese Masse wird abschließend über ein Auftragswerk in eine Bandpolymerisationsanlage gegeben und mittels UV-Licht zu einem festen, leicht haftklebenden Band auspolymerisiert.The following amounts of the further components of the adhesive system according to the invention are in each case based on the overall system:
Thus, the described prepolymer in a further step, components such as other acrylate monomers (each 0.5-10 wt .-% glycidyl methacrylate and n-hexyl methacrylate), crosslinker or hardener of the type described above (in an amount of 0.5 to 10 wt .-%), solid epoxy resin based on bisphenol a (5-15 wt .-%), and impact modifier in an amount of 10-20 wt .-% are added, as a further photoinitiator ( "Irgacure ® 819") for the belt polymerization. The significant increase in the viscosity of the syrup due to the pre-crosslinking now makes it possible to apply the polymer syrup with a thickness of up to 4 mm to an abhesive carrier material as a substrate. The addition of the further photoinitiator or photoinitiator mixture is necessary so that the composition can be reacted quickly and with low residual monomer content. This mass is finally placed over a commissioned work in a Bandpolymerisationsanlage and polymerized by UV light to a solid, slightly pressure-sensitive adhesive tape.
Die Klebkraft solcher Bänder im ungehärteten Zustand erreicht bis zu 10 N/25 mm bei einem Abzugswinkel von 90°.The bond strength of such strips in the unhardened state reaches up to 10 N / 25 mm at a take-off angle of 90 °.
Diese haftklebende Eigenschaft des Bandes gestatten es, ein mit einem solchen Band versehenes Bauteil zunächst mit leichtem Druck, aber ohne Hitze mit einem zweiten Bauteil zusammen zu fügen. In dieser Weise wird ein Verbund erzeugt, der stark genug ist, sein eigenes Gewicht zu tragen. Die Dicke des Produktes und die Erweichung bei Hitze in den pastösen Zustand gestatten es, das Band in die gewünschte Form zu bringen. Unter Laborbedingungen wurden letzteres mit abhäsiv ausgerüsteten Metallstäben erreicht, die vor eine Fügenaht geklemmt waren und den unter Hitzeeinwirkung weichen Klebstoff in eine konkave Form fließen liessen. Der nach Abkühlung gehärtete Klebstoff erreicht schließlich sowohl eine ausreichende strukturelle Festigkeit, um die geforderte Bruch- und Biegefestigkeiten zu erfüllen, als auch die nötige Hitzebeständigkeit, um z. B. beim Einbrennen eines Decklacks nicht zu erweichen.This pressure-sensitive adhesive property of the tape makes it possible to join a component provided with such a tape first with light pressure, but without heat with a second component. In this way, a composite is created that is strong enough to support its own weight. The thickness of the product and the heat softening in the pasty state make it possible to bring the strip into the desired shape. Under laboratory conditions, the latter were achieved with abhesive metal bars, which were clamped in front of a joint seam and allowed the heat-sensitive adhesive to flow into a concave mold. The cured after cooling adhesive finally reaches both sufficient structural strength to meet the required fracture and bending strengths, as well as the necessary heat resistance to z. B. not to soften when baking a topcoat.
Die Kraft, die das System letztlich halten kann, liegt bei mehr als 30 MPa (bei 9.500 N pro %2 square inch) gemessen auf Stahl im Rahmen der dynamischen Zugscherfestigkeitsprüfung bei einem Winkel von 180°. Die vollständige Vernetzung des Klebstoffs und damit auch die vollständige Härte des Systems wird erreicht zwischen 10 min. bei 170°C und 30 min. bei 120°C, die optimale Härtungstemperatur für epoxifunktionelle Gruppen liegt üblicherweise bei etwa 150°C.The force that the system can ultimately hold is more than 30 MPa (at 9,500 N per% 2 square inch) measured on steel as part of the dynamic tensile shear test at an angle of 180 °. The complete cross-linking of the adhesive and thus the complete hardness of the system is achieved between 10 min. at 170 ° C and 30 min. at 120 ° C, the optimum curing temperature for epoxy functional groups is usually about 150 ° C.
Die vorliegende Erfindung umfasst somit neben dem erfindungsgemäßen, im ungehärteten Zustand leicht haftklebenden Klebebandsystem in einer Dicke von etwa 0,2 bis 4,0 mm auch ein Verfahren zur Herstellung einer strukturellen Fügeverbindung zwischen Formteilen, umfassend die Schritte des Beschichtens eines Formteils mit dem leicht haftklebenden, erfindungsgemäßen Strukturklebstoff, des anschließenden In-Kontakt-Bringens und Verklebens dieses Formteils mit dem Fügepartner und des abschließenden strukturellen Aushärtens des Polymers bzw. Strukturklebstoffs durch Wärmebehandlung, die problemlos unter Normalatmosphäre (Luftsauerstoff) oder in einer Stickstoffatmasphäre erfolgen kann.The present invention thus comprises, in addition to the adhesive tape system of the invention in a thickness of about 0.2 to 4.0 mm, which is slightly tacky in the uncured state, also a process for producing a structural joint between moldings, comprising the steps of coating a molding with the slightly pressure-sensitive adhesive , Structural adhesive according to the invention, the subsequent contacting and bonding of this molding with the joining partner and the final structural curing of the polymer or structural adhesive by heat treatment, which can be done easily under normal atmosphere (atmospheric oxygen) or in a Stickstoffatmasphäre.
ZITATE ENTHALTEN IN DER BESCHREIBUNG QUOTES INCLUDE IN THE DESCRIPTION
Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.
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Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011105209A DE102011105209A1 (en) | 2011-06-17 | 2011-06-17 | Pressure-sensitive- and structural adhesive polymerizate present in band form, produced by free radical polymerization under ultra-violet, useful e.g. for coating molded part with polymerizate and applying on anti-adhesive carrier material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011105209A DE102011105209A1 (en) | 2011-06-17 | 2011-06-17 | Pressure-sensitive- and structural adhesive polymerizate present in band form, produced by free radical polymerization under ultra-violet, useful e.g. for coating molded part with polymerizate and applying on anti-adhesive carrier material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE102011105209A1 true DE102011105209A1 (en) | 2012-12-20 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE102011105209A Withdrawn DE102011105209A1 (en) | 2011-06-17 | 2011-06-17 | Pressure-sensitive- and structural adhesive polymerizate present in band form, produced by free radical polymerization under ultra-violet, useful e.g. for coating molded part with polymerizate and applying on anti-adhesive carrier material |
Country Status (1)
| Country | Link |
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| DE (1) | DE102011105209A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3091059A1 (en) | 2015-05-05 | 2016-11-09 | tesa SE | Adhesive tape with adhesive mass with continuous polymer phase |
| DE102015217860A1 (en) | 2015-05-05 | 2016-11-10 | Tesa Se | Adhesive tape with adhesive with continuous polymer phase |
| WO2019101916A1 (en) | 2017-11-24 | 2019-05-31 | Tesa Se | Curable composition based on fatty-acid modified epoxy resins and curing agents |
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| GB1520873A (en) | 1975-08-12 | 1978-08-09 | Evode Holdings Ltd | Joining articles with multiple component adhesive systems |
| EP0050096A1 (en) | 1980-10-14 | 1982-04-21 | Ciba-Geigy Ag | Process for bonding objects by curable adhesives |
| EP0209859A2 (en) | 1985-07-23 | 1987-01-28 | Herberts Gesellschaft mit beschränkter Haftung | Heat-curable adhesive sheet |
| EP0690896B1 (en) | 1993-03-24 | 1998-06-10 | Minnesota Mining And Manufacturing Company | Topographical sheet material and method for using same |
| DE10163589A1 (en) | 2001-12-21 | 2003-08-07 | Tesa Ag | Self-adhesive labels, processes for producing them and their use |
| DE102005062441A1 (en) | 2005-12-27 | 2007-06-28 | Lohmann Gmbh & Co. Kg | Polymers made by radical polymerisation of a mixture containing glycidyl methacrylate and H-acid monomers, used in structural adhesives which are precrosslinked with UV light and hardened by heating |
| WO2008112992A2 (en) | 2007-03-15 | 2008-09-18 | Zephyros, Inc. | Sealant material |
| WO2009124709A1 (en) | 2008-04-09 | 2009-10-15 | Zephyros Inc | Improvements in or relating to structural adhesives |
| DE102009043854A1 (en) | 2009-08-25 | 2011-03-03 | Thyssenkrupp Drauz Nothelfer Gmbh | Sheet metal part arrangement for use during e.g. side door of motor vehicle, has metal part whose open edge is arranged towards surface of deformation of another metal part that is coated with adhesive such that edge is enclosed by adhesive |
| DE102009026548A1 (en) | 2009-05-28 | 2011-03-24 | Henkel Ag & Co. Kgaa | Adhesive film or adhesive tape based on epoxides |
| DE102009042467A1 (en) | 2009-09-23 | 2011-03-24 | Audi Ag | Joining method, joining device and fastening element |
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|---|---|---|---|---|
| GB1520873A (en) | 1975-08-12 | 1978-08-09 | Evode Holdings Ltd | Joining articles with multiple component adhesive systems |
| EP0050096A1 (en) | 1980-10-14 | 1982-04-21 | Ciba-Geigy Ag | Process for bonding objects by curable adhesives |
| EP0209859A2 (en) | 1985-07-23 | 1987-01-28 | Herberts Gesellschaft mit beschränkter Haftung | Heat-curable adhesive sheet |
| EP0690896B1 (en) | 1993-03-24 | 1998-06-10 | Minnesota Mining And Manufacturing Company | Topographical sheet material and method for using same |
| DE10163589A1 (en) | 2001-12-21 | 2003-08-07 | Tesa Ag | Self-adhesive labels, processes for producing them and their use |
| DE102005062441A1 (en) | 2005-12-27 | 2007-06-28 | Lohmann Gmbh & Co. Kg | Polymers made by radical polymerisation of a mixture containing glycidyl methacrylate and H-acid monomers, used in structural adhesives which are precrosslinked with UV light and hardened by heating |
| WO2008112992A2 (en) | 2007-03-15 | 2008-09-18 | Zephyros, Inc. | Sealant material |
| WO2009124709A1 (en) | 2008-04-09 | 2009-10-15 | Zephyros Inc | Improvements in or relating to structural adhesives |
| DE102009026548A1 (en) | 2009-05-28 | 2011-03-24 | Henkel Ag & Co. Kgaa | Adhesive film or adhesive tape based on epoxides |
| DE102009043854A1 (en) | 2009-08-25 | 2011-03-03 | Thyssenkrupp Drauz Nothelfer Gmbh | Sheet metal part arrangement for use during e.g. side door of motor vehicle, has metal part whose open edge is arranged towards surface of deformation of another metal part that is coated with adhesive such that edge is enclosed by adhesive |
| DE102009042467A1 (en) | 2009-09-23 | 2011-03-24 | Audi Ag | Joining method, joining device and fastening element |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3091059A1 (en) | 2015-05-05 | 2016-11-09 | tesa SE | Adhesive tape with adhesive mass with continuous polymer phase |
| DE102015217860A1 (en) | 2015-05-05 | 2016-11-10 | Tesa Se | Adhesive tape with adhesive with continuous polymer phase |
| US10308845B2 (en) | 2015-05-05 | 2019-06-04 | Tesa Se | Adhesive tape featuring adhesive with continuous polymer phase |
| WO2019101916A1 (en) | 2017-11-24 | 2019-05-31 | Tesa Se | Curable composition based on fatty-acid modified epoxy resins and curing agents |
| WO2019101914A1 (en) | 2017-11-24 | 2019-05-31 | Tesa Se | Adhesive tapes based on epoxy resin reactive adhesives |
| WO2019101918A1 (en) | 2017-11-24 | 2019-05-31 | Tesa Se | Adhesive tapes based on epoxy resin reactive adhesives |
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