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US20210238342A1 - Processes for producing viscous epoxy syrups and epoxy syrups obtainable thereby - Google Patents

Processes for producing viscous epoxy syrups and epoxy syrups obtainable thereby Download PDF

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US20210238342A1
US20210238342A1 US16/893,526 US202016893526A US2021238342A1 US 20210238342 A1 US20210238342 A1 US 20210238342A1 US 202016893526 A US202016893526 A US 202016893526A US 2021238342 A1 US2021238342 A1 US 2021238342A1
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epoxy
syrup
initiator
viscosity
multifunctional
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Christian Schuh
Klaus Keite-Telgenbüscher
Yao SHU
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Tesa SE
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Tesa SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G59/68—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 catalysts used
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/022—Polycondensates containing more than one epoxy group per molecule characterised by the preparation process or apparatus used
    • 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
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • 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
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • 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
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4028—Isocyanates; Thioisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • H01L51/0035—
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/63—Viscosity
    • H01L25/046—
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/80—Constructional details
    • H10K10/88—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K19/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic element specially adapted for rectifying, amplifying, oscillating or switching, covered by group H10K10/00
    • H10K19/901—Assemblies of multiple devices comprising at least one organic element specially adapted for rectifying, amplifying, oscillating or switching
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/88—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations

Definitions

  • the present invention relates to processes for producing a viscous epoxy syrup from at least one liquid multifunctional epoxy, comprising the steps of adding an initiator selected from the group consisting of electron-poor monoisocyanate, photoinitiator and thermal initiator to at least one liquid multifunctional epoxy and polymerizing the multifunctional epoxy, to a viscous epoxy syrup obtainable by the process, to an adhesive and to an adhesive tape comprising this epoxy syrup and also to the use of such an epoxy syrup, such an adhesive or such an adhesive tape.
  • an initiator selected from the group consisting of electron-poor monoisocyanate, photoinitiator and thermal initiator
  • Epoxy adhesives having pressure-sensitive properties may be prepared by addition of matrix polymers. Adhesive bond strength often increases with increasing amount of epoxy. Since most epoxies are used in liquid adhesives they have a relatively low viscosity and high epoxy contents thus do not afford pressure-sensitive tapes. High-viscosity/solid epoxies are required therefor.
  • the viscosity of epichlorohydrin-based epoxy resins is typically adjusted via the ratio of epichlorohydrin and a resulting molecular weight increase at the expense of epoxy concentration [“Epoxy Adhesive Formulations” 2006, E. M. Petrie, p. 30ff].
  • Epoxy Adhesive Formulations 2006, E. M. Petrie, p. 30ff.
  • a number of examples such as epoxy (cresol) novolacs are produced via a different synthetic route and carry the epoxy groups as a side group so that an increase in molecular weight does not lead to a reduction in epoxy concentration.
  • epoxycyclohexyl derivatives which are not produced via the epichlorohydrin route are accordingly often very liquid (e.g. Uvacure 1500). Since many epoxies are used for crosslinking reaction (they contain more than one epoxy group per molecule) they cannot simply be polymerized to increase viscosity since crosslinked and insoluble deposits are immediately formed.
  • epoxycyclohexyl monomers are preferably employed in cationically curable adhesives, in particular for UV-induced curing via photolabile acid generators.
  • AU 758128 B2 describes such storage-stable cationically curing multifunctional epoxy mixtures.
  • epoxycyclohexyl derivatives are particularly preferred so that it would be desirable to be able to produce high-viscosity epoxies from this monomer as well.
  • SG 160949 B proposes reacting diepoxies with diisocyanates. This mixture affords cyclic trimers (isocyanurates) and oxazolidinones having an M w ⁇ 3000 g/mol and a low polydispersity which can then be cured like epoxies. It is necessary to use at least difunctional substances since otherwise no reactive groups would be available for the subsequent curing. However, the compounds formed have low viscosities.
  • the present invention accordingly has for its object the provision of a process which makes it possible to produce specifically viscous adhesive resins from originally liquid epoxies.
  • the product shall be soluble in solvents and meltable by the temperature being raised.
  • the object is achieved by a process of the type referred to at the outset where the components are initially mixed and the polymerization of the multifunctional epoxy is subsequently effected such that the viscosity of the resulting epoxy syrup is at least twice as high, preferably at least four times as high and in particular at least ten times as high as the viscosity of the employed epoxy in the unreacted state.
  • This incipiently polymerizes the epoxies such that high molecular weight polyepoxies are prepared from, for example, bisepoxy monomers without these undergoing crosslinking.
  • the thus obtained epoxy syrups are ideally suited for producing epoxy adhesives having pressure-sensitive properties. It is important here that initiation is effected only after the initiator is thoroughly distributed in the epoxy. Otherwise the reactive centres are too close together and crosslinking occurs which is not yet desired at this stage. In order to achieve mixing the mixture may be stirred for example, but other forms of mixing are also conceivable and possible.
  • epoxy syrup describes epoxies having a viscosity of at least 1 Pa ⁇ s (corresponds to 1000 mPs).
  • the process according to the invention is carried out such that in the resulting epoxy syrup at least 65%, preferably at least 75%, in particular at least 80%, of the original epoxy groups are still present. A large part of the epoxy units in the syrup is thus still present in the monomer form. It is accordingly further advantageous when the resulting epoxy syrup comprises high molecular weight uncrosslinked polyepoxies. It is thus particularly useful when in the epoxy syrup a large amount of the multifunctional epoxy monomers employed is still present in unreacted form as monomer and high molecular weight, but still uncrosslinked, polyepoxies have been formed only sporadically.
  • Particularly suitable multifunctional epoxies are bisepoxies. Once polymerization has been effected a further epoxy group is available which can later bring about crosslinking in the epoxy adhesive resin.
  • Multifunctional epoxies that have proven particularly advantageous include bisepoxycyclohexyl derivatives, in particular 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carbon/late, and bisepoxies based on bisphenol-A, bisphenol-S or bisphenol-F. These make it possible to produce syrups having a viscosity which is well-suited for further processing the epoxies to afford pressure-sensitive epoxy resins.
  • the process according to the invention performs particularly well when the initiator is selected from the group consisting of photoinitiator and thermal initiator and is employed in an amount of not more than 0.1 wt %, preferably not more than 0.08 wt %, particularly preferably not more than 0.05 wt %. This allows the target viscosities to be achieved in a particularly simple and easy-to-handle fashion.
  • a particularly suitable initiator is an electron-poor monoisocyanate which is employed in an amount of not more than 10 wt %, preferably not more than 8 wt % and in particular not more than 7 wt %.
  • the reaction is particularly easily controllable when the monoisocyanate is employed in an amount of 7 ⁇ 0.5 wt %.
  • Suitable monoisocyanates are in particular selected from the group consisting of p-tolyl isocyanate, o-tolyl isocyanate and sulphonyl isocyanates, in particular p-toluenesulphonylmethyl isocyanate, o-toluenesulphonylmethyl isocyanate, 4-chlorobenzylsulphonyl isocyanate, o-toluenesulphonyl isocyanate, p-toluenesulphonyl isocyanate and benzylsulphonyl isocyanate, p-toluenesulphonyl isocyanate being particularly preferred.
  • a temperature range which has proven particularly advantageous for carrying out the process is the range between 20° C. and 120° C., preferably between 40° C. and 100° C., in particular between 80° C. and 90° C.
  • an initiator scavenger upon reaching a desired viscosity.
  • an initiator scavenger upon reaching a desired viscosity.
  • Particularly suitable initiator scavengers include a mixture of water and acetone, solutions of alkali metal/alkaline earth metal hydroxides or solutions of alkali metal/alkaline earth metal alkoxides. When a mixture of water and acetone is used a 1:1 ratio of the two components is particularly preferred.
  • the amount of initiator scavenger should preferably be equal/substantially equal to the amount of initiator. Thus, when 7 g of initiator are used it is advantageous to also use 7 g of initiator scavenger.
  • the process according to the invention is moreover particularly advantageous when the polymerization of the multifunctional epoxy is effected such that the resulting epoxy syrup has a polydispersity D of at least 3, preferably at least 5, in particular of at least 8.
  • polydispersity is not obtained as a result, for instance, of mixing different polymers but rather as a result of polymer molecules of very different sizes forming on account of the reaction conditions.
  • Polydispersity D is a measure of the distribution of the molar masses. Polydispersity D is defined as the weight-average molecular weight M w /the number-average molecular weight M n of the polymers present.
  • a large polydispersity value thus means a broad molar mass distribution from very short-chain up to long-chain macromolecules, i.e. molecules of many different chain lengths are present in the polymer.
  • the mono-, bi- and multimodal molecular weight distribution is such that molecules of low molecular weight constituents ( ⁇ 2000 g/mol) right through to very high molecular weight constituents (>300 000 g/mol) may be found.
  • This special feature of the molecular weight distribution contributes in particular to the advantageous properties according to the invention of a high epoxy content (many low molecular weight bisepoxies) coupled with the high-viscosity characteristics (very high molecular weight epoxies) of the product.
  • the process according to the invention results in a slow increase in viscosity during the polymerization.
  • the viscosity increase is attributable to the formation of very high molecular weight polyepoxies.
  • multifunctional, in particular difunctional, epoxies which very rapidly form insoluble highly crosslinked networks are concerned, the epoxy adhesive resins produced with this process remain soluble.
  • the explanation for this behaviour is that relatively few initiating species are formed by the initiator, for example the p-toluenesulphonylmethyl isocyanate, that the growing chains thus cannot meet and that consequently at very low epoxy conversions few very high molecular weight polymers are formed.
  • GPC measurements and FT-IR spectra support this theory. It is important here that initiation is effected only after the initiator is thoroughly distributed in the epoxy so that no crosslinking is effected at this stage.
  • the invention further relates to viscous epoxy syrups obtainable by the process according to the invention.
  • the present invention further relates to viscous epoxy syrups comprising multifunctional epoxy monomers and high molecular weight uncrosslinked multifunctional polyepoxies prepared therefrom, wherein the viscosity of the epoxy syrup is at least twice as high, preferably at least four times as high and in particular at least ten times as high as the viscosity of the employed epoxy in the unreacted state.
  • the molecular weight distribution of the polyepoxies present in the epoxy syrup encompasses at least the range from 2000 g/mol to 300 000 g/mol.
  • the epoxy syrup contains epoxy molecules having very different molecular weights, from very low to very high, all compounds from the low molecular weight ( ⁇ 2000 g/mol) right through to the high molecular weight (>300 000 g/mol) being present. Compounds having a lower or even higher molecular weight may also be present.
  • the viscosity increase experienced by the epoxy syrups according to the invention during storage at 25° C. is less than 5 Pa s per day. This represents a sufficient storage stability which makes it possible to store the epoxy syrups over a relatively long period of time before they are used.
  • viscous epoxy syrups where the epoxy monomer is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate and the viscosity is at least 1 Pa s (1000 mPs), preferably 10 Pa s (10 000 mPs), in particular 25 Pa s (25 000 mPs).
  • the present invention also relates to an adhesive having water vapour barrier properties, comprising an adhesive base composed of at least one epoxy syrup according to the invention, at least one elastomer, optionally a solvent, wherein the adhesive base has a water vapour permeation rate after activation of the reactive resin component of less than 100 g/m 2 d, preferably of less than 60 g/m 2 d, in particular less than 30 g/m 2 d.
  • the epoxy syrups according to the invention are particularly well-suited for such adhesives having water vapour barrier properties because, on account of their viscosity, they are readily processable and above all make it possible to produce adhesives having a sufficient viscosity so that the thus obtained adhesives are easy to handle and easy to apply.
  • the present invention moreover relates to an adhesive tape comprising a viscous epoxy syrup according to the invention or an adhesive having water vapour barrier properties according to the invention.
  • adhesive tapes allow for particularly simple application.
  • Particularly preferred initiators for the polymerization reaction include, as previously intimated, electron-poor monoisocyanates, for example p-tolyl isocyanate, p-toluenesulphonylmethyl isocyanate, o-tolyl isocyanate or o-toluenesulphonylmethyl isocyanate.
  • electron-poor monoisocyanates for example p-tolyl isocyanate, p-toluenesulphonylmethyl isocyanate, o-tolyl isocyanate or o-toluenesulphonylmethyl isocyanate.
  • derivatives of sulphonyl isocyanates R—SO 2 —NCO, R—SO 2 —CH 2 —NCO
  • photoinitiators with which the inventive molecular weight distributions may be achieved include but are not limited to:
  • sulphonium salts such as triphenylsulphonium hexafluoroarsenate, triphenylsulphonium hexafluoroborate, triphenylsulphonium tetrafluoroborate, triphenylsulphonium tetrakis(pentafluorobenzyl)borate, methyldiphenylsulphonium tetrafluoroborate, methyldiphenylsulphonium tetrakis(pentafluorobenzyl)borate, dimethylphenylsulphonium hexafluorophosphate, triphenylsulphonium hexafluorophosphate, triphenylsulphonium hexafluoroantimonate, diphenylnaphthylsul
  • ferrocenium salts such as ⁇ 5 -(2,4-cyclopentadien-1-yl)-[(1,2,3,4,5,6,9)-(1-methylethypenzene]iron.
  • Examples of commercialized photoinitiators include Cyracure UVI-6990, Cyracure UVI-6992, Cyracure UVI-6974 and Cyracure UVI-6976 from Union Carbide, Optomer SP-55, Optomer SP-150, Optomer SP-151, Optomer SP-170 and Optomer SP-172 from Adeka, San-Aid SI-45L, San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L, San-Aid SI-110L, San-Aid SI-150L and San-Aid SI-180L from Sanshin Chemical, SarCat CD-1010, SarCat CD-1011 and SarCat CD-1012 from Sartomer, Degacure K185 from Degussa, Rhodorsil Photoinitiator 2074 from Rhodia, CI-2481, CI-2624, CI-2639, CI-2064, CI-2734, CI-2855, CI-2823 and
  • Photoinitiators are used in uncombined form or as a combination of two or more photoinitiators.
  • Photoinitiators which exhibit absorption at less than 350 nm and advantageously at greater than 250 nm are advantageous. Initiators which absorb above 350 nm, for example in the range of violet light, are likewise employable. Particular preference is given to using sulphonium-based photoinitiators since they exhibit advantageous UV-absorption characteristics.
  • thermal initiators so-called thermal acid generators (TAG)
  • TAG thermal acid generators
  • thermal acid generators include benzylthiolanium salts with, for example, PF 6 ⁇ , AsF 6 ⁇ , or SBF 6 ⁇ anions described in U.S. Pat. No. 5,242,715 A, BF 3 -amine complexes described in “Study of Polymerization Mechanism and Kinetics of DGEBA with BF 3 -amine Complexes Using FT-IR and Dynamic DSC” (Ghaemy et al., Egyptian Polymer Journal, Vol. 6, No. 1, 1997), lanthanide triflates described in “Study of Lanthanide Triflates as New Curing Initiators for Cycloaliphatic Epoxy Resins” (C.
  • Such systems are commercially available from King Industries under the names TAG-2678, TAG-2713 or TAG-2172. At high temperatures these blocked acids liberate, for example, trifluoromethanesulphonic acid, p-toluenesulphonic acid or dodecylbenzylsulphonic acid which initiate cationic curing of epoxies.
  • FIG. 1 shows the molecular weight distribution of Uvacure syrups polymerized over time periods of different durations.
  • FIG. 2 shows that even at 80° C. virtually no further polymerization still takes place while without addition of an initiation scavenger the polymerization proceeds vigorously.
  • Dynamic viscosity is a measure for the flowability of the fluid coating material. Dynamic viscosity may be determined according to DIN 53019. A viscosity of less than 10 8 Pa ⁇ s is described as a fluid. Viscosity is measured in a cylindrical rotational viscometer with a standard geometry according to DIN 53019-1 at a measurement temperature of 23° C. and a shear rate of 1 s ⁇ 1 .
  • the molecular weight determinations for the number-average molecular weights M n and the weight-average molecular weights M w were effected by means of gel permeation chromatography (GPC).
  • the eluent employed was THF (tetrahydrofuran) comprising 0.1 vol % of trifluoroacetic acid. The measurement was effected at 25° C.
  • a PSS-SDV 10 ⁇ ID 8.0 mm ⁇ 50 mm precolumn was employed. PSS-SDV 10 ⁇ ID 8.0 mm ⁇ 300 mm columns were used for separation. The sample concentration was 1.5 g/l and the flow rate was 0.5 ml per minute. Measurements were performed against poly(methyl methacrylate) standards.
  • the photoinitiator has an absorption maximum in the range from 320 nm to 360 nm and was provided as a 50 wt % solution in propylene carbonate
  • Uvacure 1500 In a 21 polymerization reactor 1 kg of Uvacure 1500 was heated to 85° C. under a nitrogen atmosphere. The Uvacure 1500 has a viscosity of 0.25 Pa s. The initiator was added in countercurrent with nitrogen and the solution was stirred slowly.
  • samples were taken at different reaction times during the reaction and analyzed by means of GPC and viscometry.
  • FIG. 1 shows the molecular weight distribution of Uvacure syrups polymerized over time periods of different durations. What is striking is the enormously broad distribution containing many molecules smaller than 1000 g/mol but also chains of in some cases up to greater than 10 6 g/mol which bring about the high viscosity.
  • FIG. 2 shows that even at 80° C. virtually no further polymerization still takes place while without addition of an initiation scavenger the polymerization proceeds vigorously.
  • a photoinitiator triarylsulphonium hexafluoroantimonate
  • 1 kg of Epon Resin 828 under exclusion of light and under a nitrogen atmosphere at 23° C. with stirring (50 rpm).
  • Initiation of the reaction was effected by 2-minute irradiation with 4 medium pressure Hg lamps positioned radially around the polymerization reactor.
  • samples were taken at different reaction times during the reaction and analyzed by means of GPC and viscometry.
  • Example 3 shows that with thermal initiators too, viscous epoxy syrups can be prepared in solution and without protective gas.

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Abstract

A process for producing a viscous epoxy syrup from at least one liquid multifunctional epoxy, comprising the steps of:adding an initiator selected from the group consisting of electron-poor monoisocyanate, photoinitiator and thermal initiator to at least one liquid multifunctional epoxy;mixing the components;polymerizing the multifunctional epoxy such that the viscosity of the resulting epoxy syrup is at least twice as high, preferably at least four times as high and in particular at least ten times as high as the viscosity of the employed epoxy in the unreacted statemakes it possible to produce epoxy adhesives having pressure-sensitive properties.

Description

  • This application is a continuation of U.S. patent application Ser. No. 15/171,037, filed Jun. 2, 2016, which claims foreign priority benefit under 35 U.S.C. § 119 of German Patent Application No. 10 2015 210 346.3, filed Jun. 4, 2015, the entire disclosures of each of which are incorporated herein by reference.
  • The present invention relates to processes for producing a viscous epoxy syrup from at least one liquid multifunctional epoxy, comprising the steps of adding an initiator selected from the group consisting of electron-poor monoisocyanate, photoinitiator and thermal initiator to at least one liquid multifunctional epoxy and polymerizing the multifunctional epoxy, to a viscous epoxy syrup obtainable by the process, to an adhesive and to an adhesive tape comprising this epoxy syrup and also to the use of such an epoxy syrup, such an adhesive or such an adhesive tape.
  • Epoxy adhesives having pressure-sensitive properties may be prepared by addition of matrix polymers. Adhesive bond strength often increases with increasing amount of epoxy. Since most epoxies are used in liquid adhesives they have a relatively low viscosity and high epoxy contents thus do not afford pressure-sensitive tapes. High-viscosity/solid epoxies are required therefor.
  • The viscosity of epichlorohydrin-based epoxy resins is typically adjusted via the ratio of epichlorohydrin and a resulting molecular weight increase at the expense of epoxy concentration [“Epoxy Adhesive Formulations” 2006, E. M. Petrie, p. 30ff]. A number of examples such as epoxy (cresol) novolacs are produced via a different synthetic route and carry the epoxy groups as a side group so that an increase in molecular weight does not lead to a reduction in epoxy concentration.
  • However apart from the epoxy novolacs referred to hereinabove and the oligomers produced with epichlorohydrin, there are no processes for obtaining epoxies, in particular also epoxies other than those mentioned, in a high-viscosity state.
  • More specialized epoxy monomers, for example epoxycyclohexyl derivatives, which are not produced via the epichlorohydrin route are accordingly often very liquid (e.g. Uvacure 1500). Since many epoxies are used for crosslinking reaction (they contain more than one epoxy group per molecule) they cannot simply be polymerized to increase viscosity since crosslinked and insoluble deposits are immediately formed. These epoxycyclohexyl monomers are preferably employed in cationically curable adhesives, in particular for UV-induced curing via photolabile acid generators.
  • There is therefore a need for a method of increasing the viscosity of epoxies not obtained via the epichlorohydrin route.
  • AU 758128 B2 describes such storage-stable cationically curing multifunctional epoxy mixtures. To achieve storage stability of the multifunctional epoxy resins it is necessary according to this document to avoid undesired premature polymerization. This is achieved by adding 0.0005 to 10 wt % of an organic and/or inorganic alkaline earth metal or alkali metal compound during the polymerization of multifunctional epoxy monomers. Polymerization before desired crosslinking is thus to be avoided in any event. In addition to the inventive stabilization of these adhesives it follows from this document that for cationically curable liquid adhesives epoxycyclohexyl derivatives are particularly preferred so that it would be desirable to be able to produce high-viscosity epoxies from this monomer as well.
  • SG 160949 B proposes reacting diepoxies with diisocyanates. This mixture affords cyclic trimers (isocyanurates) and oxazolidinones having an Mw<3000 g/mol and a low polydispersity which can then be cured like epoxies. It is necessary to use at least difunctional substances since otherwise no reactive groups would be available for the subsequent curing. However, the compounds formed have low viscosities.
  • The present invention accordingly has for its object the provision of a process which makes it possible to produce specifically viscous adhesive resins from originally liquid epoxies. The product shall be soluble in solvents and meltable by the temperature being raised.
  • The object is achieved by a process of the type referred to at the outset where the components are initially mixed and the polymerization of the multifunctional epoxy is subsequently effected such that the viscosity of the resulting epoxy syrup is at least twice as high, preferably at least four times as high and in particular at least ten times as high as the viscosity of the employed epoxy in the unreacted state. This incipiently polymerizes the epoxies such that high molecular weight polyepoxies are prepared from, for example, bisepoxy monomers without these undergoing crosslinking. The thus obtained epoxy syrups are ideally suited for producing epoxy adhesives having pressure-sensitive properties. It is important here that initiation is effected only after the initiator is thoroughly distributed in the epoxy. Otherwise the reactive centres are too close together and crosslinking occurs which is not yet desired at this stage. In order to achieve mixing the mixture may be stirred for example, but other forms of mixing are also conceivable and possible.
  • All viscosities reported in this application relate, unless otherwise stated, to a measurement at 23° C. according to DIN 53019-1.
  • The term “epoxy syrup” describes epoxies having a viscosity of at least 1 Pa·s (corresponds to 1000 mPs).
  • It is particularly advantageous when the process according to the invention is carried out such that in the resulting epoxy syrup at least 65%, preferably at least 75%, in particular at least 80%, of the original epoxy groups are still present. A large part of the epoxy units in the syrup is thus still present in the monomer form. It is accordingly further advantageous when the resulting epoxy syrup comprises high molecular weight uncrosslinked polyepoxies. It is thus particularly useful when in the epoxy syrup a large amount of the multifunctional epoxy monomers employed is still present in unreacted form as monomer and high molecular weight, but still uncrosslinked, polyepoxies have been formed only sporadically.
  • Particularly suitable multifunctional epoxies are bisepoxies. Once polymerization has been effected a further epoxy group is available which can later bring about crosslinking in the epoxy adhesive resin.
  • Multifunctional epoxies that have proven particularly advantageous include bisepoxycyclohexyl derivatives, in particular 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carbon/late, and bisepoxies based on bisphenol-A, bisphenol-S or bisphenol-F. These make it possible to produce syrups having a viscosity which is well-suited for further processing the epoxies to afford pressure-sensitive epoxy resins.
  • The process according to the invention performs particularly well when the initiator is selected from the group consisting of photoinitiator and thermal initiator and is employed in an amount of not more than 0.1 wt %, preferably not more than 0.08 wt %, particularly preferably not more than 0.05 wt %. This allows the target viscosities to be achieved in a particularly simple and easy-to-handle fashion.
  • In addition to these classical initiators for cationic epoxy curing, specific isocyanates are surprisingly also particularly suitable as initiators for the present invention.
  • A particularly suitable initiator is an electron-poor monoisocyanate which is employed in an amount of not more than 10 wt %, preferably not more than 8 wt % and in particular not more than 7 wt %. The reaction is particularly easily controllable when the monoisocyanate is employed in an amount of 7±0.5 wt %. Suitable monoisocyanates are in particular selected from the group consisting of p-tolyl isocyanate, o-tolyl isocyanate and sulphonyl isocyanates, in particular p-toluenesulphonylmethyl isocyanate, o-toluenesulphonylmethyl isocyanate, 4-chlorobenzylsulphonyl isocyanate, o-toluenesulphonyl isocyanate, p-toluenesulphonyl isocyanate and benzylsulphonyl isocyanate, p-toluenesulphonyl isocyanate being particularly preferred.
  • A temperature range which has proven particularly advantageous for carrying out the process is the range between 20° C. and 120° C., preferably between 40° C. and 100° C., in particular between 80° C. and 90° C.
  • There is a correlation between the temperature and the amount of initiator. The more initiator is added the lower the temperature required to achieve the same reaction rate. While, for example, in the case of the electron-poor isocyanates 10 wt % of initiator will bring about only a very slow rate at room temperature, at 85° C. 7 wt % of initiator is sufficient to carry out the reaction within just a few hours.
  • It is moreover advantageous when the polymerization is stopped by addition of an initiator scavenger upon reaching a desired viscosity. This makes it possible to make the obtained epoxy syrups storage-stable. Even at higher temperatures of 80° C. for example, the obtained epoxy syrups are storage-stable over several months. Particularly suitable initiator scavengers include a mixture of water and acetone, solutions of alkali metal/alkaline earth metal hydroxides or solutions of alkali metal/alkaline earth metal alkoxides. When a mixture of water and acetone is used a 1:1 ratio of the two components is particularly preferred.
  • The amount of initiator scavenger should preferably be equal/substantially equal to the amount of initiator. Thus, when 7 g of initiator are used it is advantageous to also use 7 g of initiator scavenger.
  • The process according to the invention is moreover particularly advantageous when the polymerization of the multifunctional epoxy is effected such that the resulting epoxy syrup has a polydispersity D of at least 3, preferably at least 5, in particular of at least 8. However, the polydispersity is not obtained as a result, for instance, of mixing different polymers but rather as a result of polymer molecules of very different sizes forming on account of the reaction conditions. Polydispersity D is a measure of the distribution of the molar masses. Polydispersity D is defined as the weight-average molecular weight Mw/the number-average molecular weight Mn of the polymers present. A large polydispersity value thus means a broad molar mass distribution from very short-chain up to long-chain macromolecules, i.e. molecules of many different chain lengths are present in the polymer.
  • For the present invention this means that the mono-, bi- and multimodal molecular weight distribution is such that molecules of low molecular weight constituents (<2000 g/mol) right through to very high molecular weight constituents (>300 000 g/mol) may be found.
  • This special feature of the molecular weight distribution contributes in particular to the advantageous properties according to the invention of a high epoxy content (many low molecular weight bisepoxies) coupled with the high-viscosity characteristics (very high molecular weight epoxies) of the product.
  • It was found that, surprisingly, the process according to the invention results in a slow increase in viscosity during the polymerization. The viscosity increase is attributable to the formation of very high molecular weight polyepoxies. Although multifunctional, in particular difunctional, epoxies which very rapidly form insoluble highly crosslinked networks are concerned, the epoxy adhesive resins produced with this process remain soluble. The explanation for this behaviour is that relatively few initiating species are formed by the initiator, for example the p-toluenesulphonylmethyl isocyanate, that the growing chains thus cannot meet and that consequently at very low epoxy conversions few very high molecular weight polymers are formed. GPC measurements and FT-IR spectra support this theory. It is important here that initiation is effected only after the initiator is thoroughly distributed in the epoxy so that no crosslinking is effected at this stage.
  • The invention further relates to viscous epoxy syrups obtainable by the process according to the invention. The present invention further relates to viscous epoxy syrups comprising multifunctional epoxy monomers and high molecular weight uncrosslinked multifunctional polyepoxies prepared therefrom, wherein the viscosity of the epoxy syrup is at least twice as high, preferably at least four times as high and in particular at least ten times as high as the viscosity of the employed epoxy in the unreacted state.
  • It is preferable when the molecular weight distribution of the polyepoxies present in the epoxy syrup encompasses at least the range from 2000 g/mol to 300 000 g/mol. This means the epoxy syrup contains epoxy molecules having very different molecular weights, from very low to very high, all compounds from the low molecular weight (<2000 g/mol) right through to the high molecular weight (>300 000 g/mol) being present. Compounds having a lower or even higher molecular weight may also be present.
  • It is preferable when the viscosity increase experienced by the epoxy syrups according to the invention during storage at 25° C. is less than 5 Pa s per day. This represents a sufficient storage stability which makes it possible to store the epoxy syrups over a relatively long period of time before they are used.
  • Particular preference is given to viscous epoxy syrups where the epoxy monomer is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate and the viscosity is at least 1 Pa s (1000 mPs), preferably 10 Pa s (10 000 mPs), in particular 25 Pa s (25 000 mPs). The present invention also relates to an adhesive having water vapour barrier properties, comprising an adhesive base composed of at least one epoxy syrup according to the invention, at least one elastomer, optionally a solvent, wherein the adhesive base has a water vapour permeation rate after activation of the reactive resin component of less than 100 g/m2d, preferably of less than 60 g/m2d, in particular less than 30 g/m2d. The epoxy syrups according to the invention are particularly well-suited for such adhesives having water vapour barrier properties because, on account of their viscosity, they are readily processable and above all make it possible to produce adhesives having a sufficient viscosity so that the thus obtained adhesives are easy to handle and easy to apply.
  • The present invention moreover relates to an adhesive tape comprising a viscous epoxy syrup according to the invention or an adhesive having water vapour barrier properties according to the invention. Such adhesive tapes allow for particularly simple application.
  • One area of application for which the present epoxy syrups/the adhesive produced therefrom or the adhesive tape produced therefrom are exceptionally suitable is the encapsulation of assemblies in the field of organic electronics. However countless further applications requiring a pressure-sensitive epoxy resin adhesive are also conceivable.
  • Particularly preferred initiators for the polymerization reaction include, as previously intimated, electron-poor monoisocyanates, for example p-tolyl isocyanate, p-toluenesulphonylmethyl isocyanate, o-tolyl isocyanate or o-toluenesulphonylmethyl isocyanate. Particular preference is given to derivatives of sulphonyl isocyanates (R—SO2—NCO, R—SO2—CH2—NCO), for example 4-chlorobenzylsulphonyl isocyanate, o-toluenesulphonyl isocyanate, p-toluenesulphonyl isocyanate, benzylsulphonyl isocyanate.
  • Examples of photoinitiators with which the inventive molecular weight distributions may be achieved include but are not limited to:
  • sulphonium salts (see for example U.S. Pat. Nos. 4,231,951 A, 4,256,828 A, 4,058,401 A, 4,138,255 A and US 2010/063221 A1) such as triphenylsulphonium hexafluoroarsenate, triphenylsulphonium hexafluoroborate, triphenylsulphonium tetrafluoroborate, triphenylsulphonium tetrakis(pentafluorobenzyl)borate, methyldiphenylsulphonium tetrafluoroborate, methyldiphenylsulphonium tetrakis(pentafluorobenzyl)borate, dimethylphenylsulphonium hexafluorophosphate, triphenylsulphonium hexafluorophosphate, triphenylsulphonium hexafluoroantimonate, diphenylnaphthylsulphonium hexafluoroarsenate, tritolylsulphonium hexafluorophosphate, anisyldiphenylsulphonium hexafluoroantimonate, 4-butoxyphenyldiphenylsulphonium tetrafluoroborate, 4-butoxyphenyldiphenylsulphonium tetrakis(pentafluorobenzyl)borate, 4-chlorophenyldiphenylsulphonium hexafluoroantimonate, tris(4-phenoxyphenyl)sulphonium hexafluorophosphate, di(4-ethoxyphenyl)methylsulphonium hexafluoroarsenate, 4-acetylphenyldiphenylsulphonium tetrafluoroborate, 4-acetylphenyldiphenylsulphonium tetrakis(pentafluorobenzyl)borate, tris(4-thiomethoxyphenyl)sulphonium hexafluorophosphate, di(methoxysulphonylphenyl)methylsulphonium hexafluoroantimonate, di(methoxynaphthyl)methylsulphonium tetrafluoroborate, di(methoxynaphthyl)methylsulphonium tetrakis(pentafluorobenzyl)borate, di(carbomethoxyphenyl)methylsulphonium hexafluorophosphate, (4-octyloxyphenyl)diphenylsulphonium tetrakis(3,5-bistrifluoromethylphenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulphonium tetrakis(pentafluorophenyl)borate, tris(dodecylphenyl)sulphonium tetrakis(3,5-bistrifluoromethylphenyl)borate, 4-acetamidophenyldiphenylsulphonium tetrafluoroborate, 4-acetamidophenyldiphenylsulphonium tetrakis(pentafluorobenzyl)borate, dimethylnaphthylsulphonium hexafluorophosphate, trifluoromethyldiphenylsulphonium tetrafluoroborate, trifluoromethyldiphenylsulphonium tetrakis(pentafluorobenzyl)borate, phenylmethylbenzylsulphonium hexafluorophosphate, 5-methylthianthrenium hexafluorophosphate, 10-phenyl-9,9-dimethylthioxanthenium hexafluorophosphate, 10-phenyl-9-oxothioxanthenium tetrafluoroborate, 10-phenyl-9-oxothioxanthenium tetrakis(pentafluorobenzyl)borate, 5-methyl-10-oxothianthrenium tetrafluoroborate, 5-methyl-10-oxothianthrenium tetrakis(pentafluorobenzyl)borate and 5-methyl-10,10-dioxothianthrenium hexafluorophosphate or p-toluenesulphonyl isocyanate or iodonium salts (see for example U.S. Pat. Nos. 3,729,313 A, 3,741,769 A, 4,250,053 A, 4,394,403 A and US 2010/063221 A1) such as diphenyliodonium tetrafluoroborate, di(4-methylphenyl)iodonium tetrafluoroborate, phenyl-4-methylphenyliodonium tetrafluoroborate, di(4-chlorophenyl)iodonium hexafluorophosphate, dinaphthyliodonium tetrafluoroborate, di(4-trifluoromethylphenyl)iodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, di(4-methylphenyl)iodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, di(4-phenoxyphenyl)iodonium tetrafluoroborate, phenyl-2-thienyliodonium hexafluorophosphate, 3,5-dimethylpyrazolyl-4-phenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, 2,2′-diphenyliodonium tetrafluoroborate, di(2,4-dichlorophenyl)iodonium hexafluorophosphate, di(4-bromophenyl)iodonium hexafluorophosphate, di(4-methoxyphenyl)iodonium hexafluorophosphate, di(3-carboxyphenyl)iodonium hexafluorophosphate, di(3-methoxycarbonylphenyl)iodonium hexafluorophosphate, di(3-methoxysulphonylphenyl)iodonium hexafluorophosphate, di(4-acetamidophenyl)iodonium hexafluorophosphate, di(2-benzothienyl)iodonium hexafluorophosphate, diaryliodonium tristrifluoromethylsulphonylmethide such as diphenyliodonium hexafluoroantimonate, diaryliodonium tetrakis(pentafluorophenyl)borate such as diphenyliodonium tetrakis(pentafluorophenyl)borate, (4-n-desiloxyphenyl)phenyliodonium hexafluoroantimonate, [4-(2-hydroxy-n-tetradesiloxy)phenyl]phenyliodonium hexafluoroantimonate, [4-(2-hydroxy-n-tetradesiloxy)phenyl]phenyliodonium trifluorosulphonate, [4-(2-hydroxy-n-tetradesiloxy)phenyl]phenyliodonium hexafluorophosphate, [4-(2-hydroxy-n-tetradesiloxy)phenyl]phenyliodonium tetrakis(pentafluorophenyl)borate, bis(4-tert-butylphenyl)iodonium hexafluoroantimonate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium trifluorosulphonate, bis(4-tert-butylphenyl)iodonium tetrafluoroborate, bis(dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dodecylphenyl)iodonium trifluoromethylsulphonate, di(dodecylphenyl)iodonium hexafluoroantimonate, di(dodecylphenyl)iodonium triflate, diphenyliodonium bisulphate, 4,4′-dichlorodiphenyliodonium bisulphate, 4,4′-dibromodiphenyliodonium bisulphate, 3,3′-dinitrodiphenyliodonium bisulphate, 4,4′-dimethyldiphenyliodonium bisulphate, 4,4′-bissuccinimidodiphenyliodonium bisulphate, 3-nitrodiphenyliodonium bisulphate, 4,4′-dimethoxydiphenyliodonium bisulphate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, (4-octyloxyphenyl)phenyliodonium tetrakis(3,5-bistrifluoromethylphenyl)borate and (tolylcumyl)iodonium tetrakis(pentafluorophenyl)borate or
  • ferrocenium salts (see for example EP 542 716 B1) such as η5-(2,4-cyclopentadien-1-yl)-[(1,2,3,4,5,6,9)-(1-methylethypenzene]iron.
  • Examples of commercialized photoinitiators include Cyracure UVI-6990, Cyracure UVI-6992, Cyracure UVI-6974 and Cyracure UVI-6976 from Union Carbide, Optomer SP-55, Optomer SP-150, Optomer SP-151, Optomer SP-170 and Optomer SP-172 from Adeka, San-Aid SI-45L, San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L, San-Aid SI-110L, San-Aid SI-150L and San-Aid SI-180L from Sanshin Chemical, SarCat CD-1010, SarCat CD-1011 and SarCat CD-1012 from Sartomer, Degacure K185 from Degussa, Rhodorsil Photoinitiator 2074 from Rhodia, CI-2481, CI-2624, CI-2639, CI-2064, CI-2734, CI-2855, CI-2823 and CI-2758 from Nippon Soda, Omnicat 320, Omnicat 430, Omnicat 432, Omnicat 440, Omnicat 445, Omnicat 550, Omnicat 550 BL and Omnicat 650 from IGM Resins, Daicat II from Daicel, UVAC 1591 from Daicel-Cytec, FFC 509 from 3M, BBI-102, BBI-103, BBI-105, BBI-106, BBI-109, BBI-110, BBI-201, BBI-301, BI-105, DPI-105, DPI-106, DPI-109, DPI-201, DTS-102, DTS-103, DTS-105, NDS-103, NDS-105, NDS-155, NDS-159, NDS-165, TPS-102, TPS-103, TPS-105, TPS-106, TPS-109, TPS-1000, MDS-103, MDS-105, MDS-109, MDS-205, MPI-103, MPI-105, MPI-106, MPI-109, DS-100, DS-101, MBZ-101, MBZ-201, MBZ-301, NAI-100, NAI-101, NAI-105, NAI-106, NAI-109, NAI-1002, NAI-1003, NAI-1004, NB-101, NB-201, NDI-101, NDI-105, NDI-106, NDI-109, PAI-01, PAI-101, PAI-106, PAI-1001, PI-105, PI-106, PI-109, PYR-100, SI-101, SI-105, SI-106 and SI-109 from Midori Kagaku, Kayacure PCI-204, Kayacure PCI-205, Kayacure PCI-615, Kayacure PCI-625, Kayarad 220 and Kayarad 620, PCI-061T, PCI-062T, PCI-020T, PCI-022T from Nippon Kayaku, TS-01 and TS-91 from Sanwa Chemical, Deuteron UV 1240 from Deuteron, Tego Photocompound 1465N from Evonik, UV 9380 C-D1 from GE Bayer Silicones, FX 512 from Cytec, Silicolease UV Cata 211 from Bluestar Silicones and Irgacure 250, Irgacure 261, Irgacure 270, Irgacure PAG 103, Irgacure PAG 121, Irgacure PAG 203, Irgacure PAG 290, Irgacure CGI 725, Irgacure CGI 1380, Irgacure CGI 1907 and Irgacure GSID 26-1 from BASF.
  • Further systems likewise usable in accordance with the invention are known to those skilled in the art. Photoinitiators are used in uncombined form or as a combination of two or more photoinitiators.
  • Photoinitiators which exhibit absorption at less than 350 nm and advantageously at greater than 250 nm are advantageous. Initiators which absorb above 350 nm, for example in the range of violet light, are likewise employable. Particular preference is given to using sulphonium-based photoinitiators since they exhibit advantageous UV-absorption characteristics.
  • Thermal initiators for the cationic polymerization of epoxies
  • Examples of thermal initiators, so-called thermal acid generators (TAG), include benzylthiolanium salts with, for example, PF6 −, AsF6 −, or SBF6 − anions described in U.S. Pat. No. 5,242,715 A, BF3-amine complexes described in “Study of Polymerization Mechanism and Kinetics of DGEBA with BF3-amine Complexes Using FT-IR and Dynamic DSC” (Ghaemy et al., Iranian Polymer Journal, Vol. 6, No. 1, 1997), lanthanide triflates described in “Study of Lanthanide Triflates as New Curing Initiators for Cycloaliphatic Epoxy Resins” (C. Mas et al., Macromolecular Chemistry and Physics, 2001, 202, No. 12) or blocked superacids such as, for example, ammonium triflate; ammonium perfluorobutanesulphonate (PFBuS); ammonium Ad-TFBS [4-adamantanecarboxyl-1,1,2,2-tetrafluorobutanesulphonate]; ammonium AdOH-TFBS [3-hydroxy-4-adamantanecarboxyl-1,1,2,2-tetrafluorobutanesulphonate]; ammonium Ad-DFMS [adamantanylmethoxycarbonyldifluoromethanesulphonate]; ammonium AdOH-DFMS [3-hydroxyadamantanylmethoxycarbonyldifluoromethanesulphonate]; ammonium DHC-TFBSS [4-dehydrocholate-1,1,2,2-tetrafluorobutanesulphonate]; and ammonium ODOT-DFMS [hexahydro-4,7-epoxyisobenzofuran-1(3H)-one, 6-(2,2′-difluoro-2-sulphonatoacetic acid ester)].
  • Such systems are commercially available from King Industries under the names TAG-2678, TAG-2713 or TAG-2172. At high temperatures these blocked acids liberate, for example, trifluoromethanesulphonic acid, p-toluenesulphonic acid or dodecylbenzylsulphonic acid which initiate cationic curing of epoxies.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 shows the molecular weight distribution of Uvacure syrups polymerized over time periods of different durations.
  • FIG. 2 shows that even at 80° C. virtually no further polymerization still takes place while without addition of an initiation scavenger the polymerization proceeds vigorously.
    •  EXAMPLES
  • Methods of Measurement
  • Viscosity Measurement:
  • Dynamic viscosity is a measure for the flowability of the fluid coating material. Dynamic viscosity may be determined according to DIN 53019. A viscosity of less than 108 Pa·s is described as a fluid. Viscosity is measured in a cylindrical rotational viscometer with a standard geometry according to DIN 53019-1 at a measurement temperature of 23° C. and a shear rate of 1 s−1.
  • Molecular Weight Distribution:
  • The molecular weight determinations for the number-average molecular weights Mn and the weight-average molecular weights Mw were effected by means of gel permeation chromatography (GPC). The eluent employed was THF (tetrahydrofuran) comprising 0.1 vol % of trifluoroacetic acid. The measurement was effected at 25° C. A PSS-SDV 10μ ID 8.0 mm×50 mm precolumn was employed. PSS-SDV 10μ ID 8.0 mm×300 mm columns were used for separation. The sample concentration was 1.5 g/l and the flow rate was 0.5 ml per minute. Measurements were performed against poly(methyl methacrylate) standards.
  • The values reported in this document for the number-average molar mass Mn, the weight-average molar mass Mw and the polydispersity relate to the determination by gel permeation chromatography (GPC)/the evaluation of such measurements.
  • Materials Employed:
  •
    Uvacure 1500 cycloaliphatic bisepoxy from
    Cytec ((3,4-epoxycyclohexane)
    methyl 3,4-epoxycyclohexylcarboxylate)
    Epon Resin 828 difunctional bisphenol-A/epichlorohydrin
    liquid epoxy having a weight per
    epoxy of 185-192 g/eq from Momentive.
    p-toluenesulphonyl electron-poor monoisocyanate
    isocyanate (TSI)
    TAG-2678 ammonium blocked
    trifluoromethanesulphonic acid
    from King Industries.
    triarylsulphonium cationic photoinitiator from
    hexafluoroantimonate Sigma-Aldrich The photoinitiator
    has an absorption maximum in the
    range from 320 nm to 360 nm and
    was provided as a 50 wt %
    solution in propylene carbonate
    • Example 1: Initiation with Electron-Poor Monoisocyanates
  • In a 21 polymerization reactor 1 kg of Uvacure 1500 was heated to 85° C. under a nitrogen atmosphere. The Uvacure 1500 has a viscosity of 0.25 Pa s. The initiator was added in countercurrent with nitrogen and the solution was stirred slowly.
  • To enable determination of the molecular weight distributions and viscosities, samples were taken at different reaction times during the reaction and analyzed by means of GPC and viscometry.
  • TABLE 1
    GPC results for inventive epoxy syrups initiated with TSI
    amount of
    TSI Mw Mn reaction time temperature
    [%] [g mol−1] [g mol−1] D [h] [° C.]
    6 13 500 780 17.4 3.25 100
    6 11 100 740 15.1 4.25 100
    6 22 000 790 27.9 5.25 100
    7 22 500 830 27.3 1.0 100
    7 59 700 830 71.7 2.25 100
    7 78 400 850 92 3.75 100
    7.4   5100 630 8 0.5 100
    7.4   6000 600 9.9 1 100
    7.4 16 100 650 24.8 3.3 100
  • It is apparent that polydispersity increases with increasing reaction time. For the substances used in the example there is a reaction rate maximum at an amount of TSI of 7 wt %. The use of a greater amount of initiator does not result in higher reaction rates here.
  • TABLE 2
    viscosities of inventive epoxy syrups initiated with TSI
    amount of TSI reaction time viscosity
    [%] [min] [Pa s]
    6 30 10.9
    6 60 40
    6 90 67.2
    6 130 132
    6 180 203
    6 230 334
    7 30 39.6
    7 60 115
    7 90 230
    7 120 420
    7 190 1536
    7 210 1956
  • It is readily apparent also from table 2 that a greater amount of initiator causes the reaction to proceed markedly more rapidly and that a viscosity increase is achieved very much more rapidly.
  • FIG. 1 shows the molecular weight distribution of Uvacure syrups polymerized over time periods of different durations. What is striking is the enormously broad distribution containing many molecules smaller than 1000 g/mol but also chains of in some cases up to greater than 106 g/mol which bring about the high viscosity.
  • Stopping the Reaction
  • After the desired viscosity has been reached the reaction is stopped by adding an amount of a water-acetone mixture equal to the amount of initiator (1:1 ratio) as initiation scavenger. FIG. 2 shows that even at 80° C. virtually no further polymerization still takes place while without addition of an initiation scavenger the polymerization proceeds vigorously.
    • Example 2: Initiation with Highly-Dilute Photoinitiators
  • In a 21 glass reactor a photoinitiator (triarylsulphonium hexafluoroantimonate) was added to 1 kg of Epon Resin 828 under exclusion of light and under a nitrogen atmosphere at 23° C. with stirring (50 rpm). Initiation of the reaction was effected by 2-minute irradiation with 4 medium pressure Hg lamps positioned radially around the polymerization reactor.
  • To enable determination of the viscosities, samples were taken at different reaction times during the reaction and analyzed by means of GPC and viscometry.
  • TABLE 3
    viscosities of inventive epoxy syrups initiated
    with triarylsulphonium hexafluoroantimonate
    amount of photoinitiator viscosity after 120 h
    [%] [mPa s]
    0.004 500
    0.01 860
    0.02 1300
  • It is apparent that markedly smaller amounts of initiator are required and that for a given reaction time viscosities increase with increasing amount of initiator.
    • Example 3: Initiation with Highly-Dilute Thermal Initiators
  • 0.02% of TAG-2678 was added to a 30% solution of Uvacure 1500 in toluene and the mixture was heated under reflux. After the desired reaction time the cooling was deactivated and the solvent removed. As in the other examples a completely transparent colourless epoxy syrup was obtained. Even after 1 h of reaction time, viscosities more than double the viscosity of the reactant were measured.
  • Example 3 shows that with thermal initiators too, viscous epoxy syrups can be prepared in solution and without protective gas.

Claims (21)

1-21. (canceled)
22. Epoxy adhesive obtained by a process comprising:
providing an at least one liquid multifunctional epoxy;
adding to the at least one liquid multifunctional epoxy an initiator selected from the group consisting of an electron-poor monoisocyanate, a photoinitiator, and a thermal initiator;
mixing the at least one liquid multifunctional epoxy and the initiator;
cationically polymerizing the at least one liquid multifunctional epoxy, thereby forming an epoxy syrup comprising an at least one uncrosslinked polyepoxy; and
mixing the epoxy syrup with further components to form an epoxy adhesive,
wherein:
a viscosity of the epoxy syrup is at least twice as high as a viscosity of the at least one liquid multifunctional epoxy before the addition of the initiator; and
the cationic polymerization is stopped upon reaching a desired viscosity by the addition of an initiator scavenger.
23. Epoxy adhesive according to claim 22, wherein the at least one liquid multifunctional epoxy is a bisepoxy.
24. Epoxy adhesive according to claim 22, wherein the at least one liquid multifunctional epoxy is a bisepoxycyclohexyl derivative or a bisepoxy based on bisphenol A, bisphenol S, or bisphenol F.
25. Epoxy adhesive according to claim 22, wherein:
the initiator is selected from the group consisting of a photoinitiator and a thermal initiator; and
the initiator is present in an amount of not more than 0.1 wt %.
26. Epoxy adhesive according to claim 22, wherein:
the initiator is an electron-poor monoisocyanate; and
the initiator is present in an amount of not more than 10 wt %.
27. Epoxy adhesive according to claim 26, wherein the initiator is selected from the group consisting of a p-tolyl isocyanate, an o-tolyl isocyanate, and a sulphonyl isocyanate.
28. Epoxy adhesive according to claim 26, wherein the process is carried out at a temperature between 20° C. and 120° C.
29. Epoxy adhesive according to claim 22, wherein the initiator scavenger comprises a mixture of water and acetone, a solution comprising an alkali metal hydroxide, a solution comprising an alkaline earth metal hydroxide, a solution comprising an alkali metal hydroxide, or a solution comprising an alkaline earth metal alkoxide.
30. Epoxy adhesive according to claim 22, wherein the epoxy syrup has a polydispersity D of at least 3.
31. Epoxy adhesive according to claim 22, wherein:
the at least one liquid multifunctional epoxy is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate; and
the viscosity of the epoxy syrup is at least 1 Pa s (1000 mPs).
32. Adhesive tape comprising an epoxy adhesive according to claim 22.
33. Epoxy adhesive according to claim 22, wherein:
the at least one liquid multifunctional epoxy comprises a plurality of original epoxy groups; and
at least 65% of the plurality of original epoxy groups are present in the epoxy syrup.
34. Epoxy adhesive according to claim 22, wherein the viscosity of the epoxy syrup is at least 10 Pa s.
35. Epoxy adhesive according to claim 22, wherein the epoxy syrup has a weight-average molecular weight Mw in the range of 5,100 to 78,400 g/mol.
36. Epoxy adhesive according to claim 22, wherein the at least one uncrosslinked polyepoxy has a molecular weight of from 2,000 to 300,000 g/mol.
37. Viscous epoxy syrup comprising an at least one multifunctional epoxy monomer and an at least one uncrosslinked multifunctional polyepoxy prepared from the at least one multifunctional polyepoxy monomer by cationic polymerization, wherein:
a viscosity of the viscous epoxy syrup is at least twice as high as a viscosity of a syrup of the at least one multifunctional epoxy monomer; and
the cationic polymerization was stopped upon reaching a desired viscosity.
38. The viscous epoxy syrup according to claim 37, wherein the viscosity of the viscous epoxy syrup is at least 10 Pa s.
39. The viscous epoxy syrup according to claim 37, wherein the viscous epoxy syrup has a weight-average molecular weight Mw in the range of 5,100 to 78,400 g/mol.
40. The viscous epoxy syrup according to claim 37, wherein the at least one uncrosslinked multifunctional polyepoxy has a molecular weight of from 2,000 to 300,000 g/mol.
41. Process for producing an epoxy adhesive comprising:
providing an at least one liquid multifunctional epoxy;
adding to the at least one liquid multifunctional epoxy an initiator selected from the group consisting of an electron-poor monoisocyanate, a photoinitiator, and a thermal initiator;
mixing the at least one liquid multifunctional epoxy and the initiator;
cationically polymerizing the at least one liquid multifunctional epoxy, thereby forming an epoxy syrup comprising an at least one uncrosslinked polyepoxy; and
mixing the epoxy syrup with further components to form an epoxy adhesive,
wherein:
a viscosity of the epoxy syrup is at least twice as high as a viscosity of the at least one liquid multifunctional epoxy before the addition of the initiator; and
the cationic polymerization is stopped upon reaching a desired viscosity by the reduction of the temperature at which the epoxy syrup is formed.
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Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3729313A (en) 1971-12-06 1973-04-24 Minnesota Mining & Mfg Novel photosensitive systems comprising diaryliodonium compounds and their use
US3741769A (en) 1972-10-24 1973-06-26 Minnesota Mining & Mfg Novel photosensitive polymerizable systems and their use
AU497960B2 (en) 1974-04-11 1979-01-25 Minnesota Mining And Manufacturing Company Photopolymerizable compositions
US4058401A (en) 1974-05-02 1977-11-15 General Electric Company Photocurable compositions containing group via aromatic onium salts
US4256828A (en) 1975-09-02 1981-03-17 Minnesota Mining And Manufacturing Company Photocopolymerizable compositions based on epoxy and hydroxyl-containing organic materials
US4138255A (en) 1977-06-27 1979-02-06 General Electric Company Photo-curing method for epoxy resin using group VIa onium salt
US4231951A (en) 1978-02-08 1980-11-04 Minnesota Mining And Manufacturing Company Complex salt photoinitiator
US4250053A (en) 1979-05-21 1981-02-10 Minnesota Mining And Manufacturing Company Sensitized aromatic iodonium or aromatic sulfonium salt photoinitiator systems
US5089536A (en) 1982-11-22 1992-02-18 Minnesota Mining And Manufacturing Company Energy polmerizable compositions containing organometallic initiators
KR100189642B1 (en) 1991-02-18 1999-06-01 디어터 크리스트 Method of coating or sealing of electronic components or component groups
US5721289A (en) * 1994-11-04 1998-02-24 Minnesota Mining And Manufacturing Company Stable, low cure-temperature semi-structural pressure sensitive adhesive
JP3973266B2 (en) * 1997-07-01 2007-09-12 横浜ゴム株式会社 Moisture curable one-part epoxy resin adhesive composition
DE19753461A1 (en) 1997-12-02 1999-06-10 Espe Dental Ag Storage-stable, cationically polymerizing preparations with improved curing behavior
US6100007A (en) * 1998-04-06 2000-08-08 Ciba Specialty Chemicals Corp. Liquid radiation-curable composition especially for producing cured articles by stereolithography having high heat deflection temperatures
JP2003105109A (en) * 2001-09-28 2003-04-09 Toray Ind Inc Method for manufacturing molded article
CA2631273C (en) * 2005-11-30 2014-03-18 Ashland Licensing And Intellectual Property Llc Prepregs and cured in place solid surfaces prepared therefrom
DE102005062441B4 (en) * 2005-12-27 2012-05-24 Lohmann Gmbh & Co. Kg A polymer and a structural adhesive based on this polymer, and a process for the preparation of this structural adhesive, and the use thereof
US8809458B2 (en) 2006-12-01 2014-08-19 Kaneka Corporation Polysiloxane composition
KR20100084561A (en) * 2007-10-26 2010-07-26 다우 글로벌 테크놀로지스 인크. Epoxy resin composition containing isocyanurates for use in electrical laminates
DE102012202377A1 (en) 2011-10-21 2013-04-25 Tesa Se Adhesive, in particular for encapsulating an electronic device
DE102012206273A1 (en) * 2012-04-17 2013-10-17 Tesa Se Crosslinkable adhesive with hard and soft blocks as permeant barrier
DE102014208111A1 (en) * 2014-04-29 2015-10-29 Tesa Se Process for producing a bond on permeate sensitive surfaces
DE102015210345A1 (en) 2015-06-04 2016-12-08 Tesa Se Water-vapor-blocking adhesive with partially polymerized epoxy syrup

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