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WO2025026781A1 - Procédé permettant d'assembler, d'enrober ou de revêtir des substrats, et composé durcissable à cet effet - Google Patents

Procédé permettant d'assembler, d'enrober ou de revêtir des substrats, et composé durcissable à cet effet Download PDF

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Publication number
WO2025026781A1
WO2025026781A1 PCT/EP2024/070709 EP2024070709W WO2025026781A1 WO 2025026781 A1 WO2025026781 A1 WO 2025026781A1 EP 2024070709 W EP2024070709 W EP 2024070709W WO 2025026781 A1 WO2025026781 A1 WO 2025026781A1
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WO
WIPO (PCT)
Prior art keywords
curable
wavelength
mass
photoinitiator
irradiation
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.)
Pending
Application number
PCT/EP2024/070709
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German (de)
English (en)
Inventor
Kilian RAUCHEISEN
Martina Metzger
Markus True
Vitalij Schimpf
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Delo Industrieklebstoffe GmbH and Co Kgaa
Original Assignee
Delo Industrieklebstoffe GmbH and Co Kgaa
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Application filed by Delo Industrieklebstoffe GmbH and Co Kgaa filed Critical Delo Industrieklebstoffe GmbH and Co Kgaa
Publication of WO2025026781A1 publication Critical patent/WO2025026781A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto 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
    • C08G59/20—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
    • C08G59/18—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
    • C08G59/68—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
    • C08G59/686—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 containing nitrogen
    • 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
    • C08G59/70—Chelates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

  • the invention relates to a method for joining, casting or coating substrates using a curable mass which can be activated by irradiation with actinic radiation, a curable mass and the use of such a curable mass.
  • EP 3 894 458 B1 discloses cationically polymerizable materials with two photoinitiators that can release an acid at different wavelengths.
  • the materials can be activated by irradiation with a first wavelength and fixed by irradiation with a second wavelength.
  • the achievable light fixation strengths are low.
  • the cationically polymerizable material contains one or more acrylates, which, however, already lead to solidification of the material when irradiated with the first wavelength, so that the material can no longer be dosed without restriction.
  • US 4 849 320 A describes a photolithographic process using a mass containing two photoinitiators and a mixture of radical and cationically polymerizable components.
  • the mass is irradiated with radiation of a wavelength that is suitable for activating the radical photoinitiator in order to initially solidify the mass.
  • the solidified mass is then irradiated with actinic radiation of a wavelength that is suitable for activating the cationic photoinitiator in order to create a structure in defined areas.
  • actinic radiation of a wavelength that is suitable for activating the cationic photoinitiator in order to create a structure in defined areas.
  • the mass outside these areas which was only partially hardened radically in the first step, is removed.
  • the photoinitiators are selected so that their absorption ranges do not overlap and can be specifically activated separately using different wavelengths. Activation of the radical photoinitiator in the first exposure step immediately leads to solidification of the mass.
  • US 5,707,780 A also describes masses that comprise mixtures of radically and cationically polymerizable components that can be activated simultaneously by irradiation with an argon laser at different wavelengths.
  • the masses are characterized by a high initial strength after curing, which can be achieved by adjusting the ratio of the extinction coefficients of the radical and cationic photoinitiators to one another.
  • the described masses can be used in additive manufacturing. Sequential exposure is not disclosed. After exposure, the mass solidifies immediately.
  • US 5 472 991 A discloses a process for the two-stage hardening of a dental material based on acrylates.
  • the dental materials used contain at least two different photoinitiators that can be sequentially excited by light of different wavelengths. After the first exposure to a wavelength of 450 nm or greater, the dental material has already solidified to such an extent that it can be brought into its final shape by mechanical modeling. Complete hardening is achieved by irradiation at a second wavelength that is shorter than the first wavelength.
  • JP 2017 149 813 A describes radiation-curable acrylate compositions which contain at least one (meth)acrylate and two photoinitiators for radical polymerization. Furthermore, the use of styrene-based compounds for the targeted control of the molecular weight is described. revealed. Despite the use of two initiators, separate activation and fixation is not provided.
  • US 11 518087 B2 describes a process for additive manufacturing in which curable masses with at least two different types of monomers and at least two photoinitiators that have different excitation wavelengths are used. Selective exposure to a first wavelength already leads to at least partial curing of the mass. The mechanical behavior of the systems described can be adjusted by specifically controlling the excitation wavelengths. However, the masses do not have an open time and are not suitable for joining processes.
  • WO 2001 092 362 A1 describes photoactivatable coatings based on polyisocyanates, thiols and a photolatent base. These can be cured within minutes after irradiation or exposure to light, forming a polythiourethane network.
  • EP 3 789 416 A1 describes radiation-curable compositions which comprise at least one polythiol, one polyisocyanate, one ethylenically unsaturated compound and one photolatent base. Additives such as a photoinitiator for radical polymerization can also be included. Curing of the compositions by exposure to different wavelengths is not provided for. A process using the composition provides for immediate solidification of the composition upon exposure for the layer-by-layer construction of additively manufactured structures.
  • the invention is based on the object of avoiding the above-described disadvantages of the methods and compositions known from the prior art and of providing curable materials which can advantageously be activated in a first irradiation step and fixed in a further irradiation step.
  • the materials should enable a method with which the strength build-up can be controlled in a targeted manner by means of light fixation and at the same time reliable curing in shadow zones is ensured, in particular in the case of substrates which cannot be penetrated by radiation.
  • this object is achieved by a method according to claim 1 using a curable mass, by a curable mass according to claim 7 and the use of such a mass according to claim 10.
  • the method according to the invention for joining, casting or coating substrates using a curable mass comprises the following steps: a) providing the curable mass, wherein the curable mass comprises the following components:
  • the method according to the invention is characterized by a process for activating and curing the mass that can be precisely controlled by irradiation at different wavelengths, which on the one hand enables reliable curing even in shadow zones through the (pre-)activation of the first curable component (A) - while at the same time still allowing the activated mass to be processed during an open time.
  • the use of the second curable component (B) based on at least one radically radiation-curable compound creates the possibility of fast and reliable fixation of the curable mass by irradiation at a second wavelength, with the irradiation taking place in a separate step.
  • Activating the mass here and below means that the activated mass hardens after a specified period of time without any further energy input, even in shadow areas where the mass cannot be irradiated with actinic radiation of the second wavelength 2.
  • the specified period of time is in particular a maximum of 24 hours. Within this period of time, the mass exceeds the gel point and changes to the solid state. The final hardening of the mass does not have to be completed at this point, however.
  • Final curing refers to a state at which the maximum strength build-up of the mass is complete. This means that the mechanical properties of the mass essentially no longer change. In particular, there is no further increase in the elastic modulus of the mass.
  • Final curing is particularly to be achieved within a maximum of seven days. completed, preferably within three days, particularly preferably within one day, i.e. within 24 hours.
  • fixation refers to the build-up of a strength of the mass beyond which no more flow of the mass can take place, or the level of strength beyond which joined parts, in particular substrates, can be handled in subsequent processes without causing destruction of the adhesive bond, in particular the substrate bond.
  • the use of the radical-scavenging inhibitor (E) ensures that radicals generated in the curable mass during irradiation with actinic radiation of the first wavelength Ai, i.e. during activation of the mass in step b), do not lead to polymerization of the second curable component (B), which is undesirable at this time. In this way, further handling of the activated mass during the open time is prevented from being made difficult or impossible, and thus a particularly flexible process for joining, casting or coating is provided. This is also possible in particular without having to rely on formulations of the curable mass in separate packaging units.
  • the multi-stage process sequence is further made possible by a targeted activation of the first photoinitiator (C) and the second photoinitiator (D) at different wavelengths.
  • the second wavelength A2 is different from the first wavelength Ai.
  • the second wavelength A2 is shorter than the first wavelength Ai.
  • the difference between the wavelength i used for irradiating and activating the first photoinitiator (C) and the wavelength ⁇ 2 used for irradiating and activating the second photoinitiator (D) is in particular at least 20 nm, preferably at least 30 nm.
  • the difference between the wavelengths i and ⁇ 2 is preferably chosen so that there is no overlap between the emission spectra of the radiation sources.
  • Monochromatic laser light can be used to irradiate the mass.
  • radiation sources are preferably used which have a singular emission maximum at the respective predetermined wavelength Ai or A 2 .
  • the radiation source is preferably an LED curing lamp, as is commercially available.
  • the first wavelength Ai lies in particular in a range from 380 to 750 nm, while the second wavelength A 2 lies in particular in a range from 200 to 400 nm.
  • the mass remains liquid until the end of the open time, as described below.
  • the irradiation with the first wavelength Ai i.e. the activation of the first photoinitiator (C) ensures that a polymerization reaction is initiated in the first curable component (A), which enables reliable final curing even in shadow zones, even if the shadow zones may no longer be accessible in a subsequent irradiation.
  • step d) can be carried out in one embodiment within a processing time which preferably corresponds at most to the open time of the curable mass after activation of the curable mass by irradiation with actinic radiation of the first wavelength i.
  • the molar ratio of inhibitor (E) to first photoinitiator (C) in the curable mass is in particular in a range from 0.4:1 to less than 20:1, preferably in a range from 0.4:1 to less than 10:1 or 1:1 to 10:1, particularly preferably in a range from 1:1 to 5:1.
  • a too low molar proportion of the inhibitor (E), based on the first photoinitiator (C), can lead to masses which become at least partially solid and can no longer be joined after the first irradiation, i.e. irradiation of the mass with actinic radiation of the first wavelength Xi. in particular by a polymerization of the second curable component (B) which is undesirable at this time.
  • the inhibitor (E) is used in too high a proportion or in too large an excess of the amount of substance, this can lead to the curable mass not being able to build up sufficient fixing strength when irradiated with actinic radiation of the second wavelength A2, since the radicals generated by the second photoinitiator (D) are intercepted to too great an extent by the inhibitor (E) and are therefore not available for the polymerization of the second curable component (B).
  • the molar ratio of inhibitor (E) to second photoinitiator (D) in the curable composition can be 1:2 or less, preferably 1:5 or less, particularly preferably 1:10 or less.
  • step b) the curable mass is dosed onto the first substrate and activated by irradiation with actinic radiation of the first wavelength Ai.
  • the order of dosing and activation in step b) depends only on the dosing and exposure device used in the respective process.
  • the curable mass can first be dosed onto the first substrate and then activated by irradiation with actinic radiation of the first wavelength Ai.
  • the curable mass can be activated before dosing onto the first substrate. Suitable dosing devices for flow activation of the curable mass by irradiation are described in DE 3 702 999 A1 and DE 10 2007 017 842 A1.
  • the second substrate can optionally be fed to the activated curable mass on the first substrate as step c).
  • the two substrates are then aligned with each other.
  • the substrates to be joined can thus be aligned exactly with each other within the open time. This is particularly important for joining processes for the production of electro-optical components, for example camera modules.
  • the second irradiation step d) The activated mass is then fixed and thus converted into a dimensionally stable state.
  • substrates for bonding are displays, sensors, electronic components and housings.
  • the method according to the invention also makes it possible to achieve reliable curing or fixing of the activated mass at room temperature without additional heat input. However, this does not exclude the possibility that curing can be accelerated by heating the fixed mass.
  • the method therefore further comprises the following step: e) heating the fixed curable mass on the first substrate or in the substrate composite.
  • the method according to the invention can optionally comprise an additional tempering step, which serves in particular for faster curing or for accelerated achievement of the final strength of the mass.
  • step a) It may also be advantageous to heat the curable mass when providing it in step a) and/or to heat one or more of the substrates before dosing the curable mass in step b) and/or before joining in step c), which can also accelerate the final curing.
  • steps d) and e) are carried out simultaneously, i.e. for the activated curable mass to be fixed by irradiation with actinic radiation of the second wavelength ⁇ 2, while the curable mass is heated on the substrate or in the substrate composite.
  • the invention further relates to a curable mass which can be used in particular in the above-described method according to the invention for joining, casting or coating substrates.
  • the curable composition according to the invention for joining, casting or coating substrates comprises the following components: (A) a first curable component selected from the group consisting of cationically polymerizable compounds, addition-curable compounds, moisture-curable compounds, and combinations thereof,
  • compositions according to the invention are characterized in that they enable a high light-fixing strength and light-fixing speed, while at the same time they are suitable for a controlled curing process that can be controlled by irradiating the curable compositions in a multi-stage process.
  • the invention further relates to the use of the curable mass as described above for joining, casting or coating substrates.
  • One-component or “one-component mass” means in the sense of the invention that the said components of the mass are present together in one packaging unit.
  • liquid means that at 23 °C the loss modulus G” determined by viscosity measurement is greater than the storage modulus G’ of the mass in question.
  • the “open time” refers to the time after the first irradiation of the curable mass, i.e. after irradiation with actinic radiation of the first wavelength Ai, during which the activated mass has not yet exceeded its gel point. During this time, the mass changes its properties in terms of viscosity and adhesion only insignificantly. It is possible to join a second substrate within the open time.
  • the open time is limited by the time at which a thread is pulled and/or at the latest by the time until a skin is formed, which can be determined by haptic measurement. Within the open time, the method according to the invention can be carried out reliably.
  • the activated masses remain at least partially joinable beyond the specified open time before they solidify to such an extent that no further flow or pressing onto another substrate is possible.
  • step c) of the method according to the invention if carried out, is preferred within the open time.
  • the open time can be influenced by the irradiated energy dose as well as by the temperature.
  • At least difunctional means that each molecule contains two or more units of the respective functional group. Unless otherwise stated, all weight proportions listed below refer to the total weight of the mass.
  • the curable composition for carrying out the process according to the invention contains, in addition to components (B) to (E), at least one cationically polymerizable compound (A1) as the first curable component (A).
  • the first photoinitiator (C) of the curable composition of the first embodiment is preferably a photolatent acid (C1).
  • the curable composition for carrying out the process according to the invention contains, in addition to components (B) to (E), at least one addition-crosslinkable compound (A2) as the first curable component (A).
  • the first photoinitiator (C) of the curable composition of the second embodiment is preferably a photolatent base (02).
  • the curable composition for carrying out the process according to the invention contains, in addition to components (B) to (E), as the first curable component (A), at least one moisture-crosslinkable compound (A3).
  • the first photoinitiator (C) of the curable composition of the third embodiment is preferably a photolatent acid (01).
  • the curable composition comprises a first curable component (A) selected from the group consisting of cationically polymerizable compounds (A1), addition-crosslinkable compounds (A2), moisture-crosslinkable compounds (A3) and combinations thereof.
  • A1 cationically polymerizable compounds
  • A2 addition-crosslinkable compounds
  • A3 moisture-crosslinkable compounds
  • the components described below can therefore be used alone or in combination with each other as component (A).
  • the first curable component (A) through its respective components used in interaction with the first photoinitiator (C) matched to the first curable component (A), provides a curing mechanism which enables a time-delayed final curing of the curable mass even in shadow zones.
  • Suitable cationically polymerizable compounds (A1) preferably comprise one or more at least difunctional epoxy-containing compounds. At least “difunctional” means that the epoxy-containing compound contains at least two epoxy groups.
  • Component (A1) may comprise, for example, cycloaliphatic epoxides, aromatic and aliphatic glycidyl ethers, glycidyl esters or glycidyl amines and mixtures thereof.
  • Difunctional cycloaliphatic epoxy resins are known in the art and include compounds that carry both a cycloaliphatic group and at least two oxirane rings. Examples of representatives are 3-cyclohexenylmethyl-3-cyclohexylcarboxylate diepoxide, 3,4-epoxycyclohexylalkyl-3',4'-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3',4'-epoxy-6-methylcyclohexanecarboxylate, vinylcyclohexene dioxide,
  • Aromatic epoxy resins can also be used.
  • aromatic epoxy resins are bisphenol A epoxy resins, bisphenol F epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, biphenyl epoxy resins, 4,4'-biphenyl epoxy resins,
  • Isocyanurates and other heterocyclic compounds substituted with epoxy groups can also be used in the curable mass. Examples include triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate.
  • polyfunctional epoxy resins of all the resin groups mentioned, toughly elasticized epoxy resins and mixtures of different epoxy resins can also be used in the composition according to the invention.
  • monofunctional epoxides can also be used as reactive diluents.
  • Examples of commercially available epoxy-containing compounds are products sold under the trade names CELLOXIDETM 2021 P, CELLOXIDETM 8000 by Daicel Corporation, Japan, as EPIKOTETM RESIN 828 LVEL, EPI KOTETM RESIN 166, EPI KOTETM RESIN 169 by Momentive Specialty Chemicals B.V., the Netherlands, as EpiloxTM resins of the product series A, T and AF by Leuna Harze, Germany, or as EPICLONTM 840, 840-S, 850, 850-S, EXA850CRP, 850-LC by DIC K.K., Japan, Omnilane 1005 and Omnilane 2005 by IGM Resins B.V., Syna Epoxy 21 and Syna Epoxy 06 by Synasia Inc., TTA21, TTA26, TTA60 and TTA128 from Jiangsu Tetra New Material Technology Co. Ltd., and THI-DE, DE-102 and DE-103 from Nippon Oil.
  • oxetane-containing compounds can also be used as cationically polymerizable compounds (A1) in the curable mass.
  • Processes for producing oxetanes are known in particular from US 2017/0198093 A1.
  • oxetanes bis(1-ethyl-3-oxetanyl-methyl)ether (DOX), 3-allyloxymethyl-3-ethyloxetane (AQX), 3-ethyl-3-[(phenoxy)-methyloxetane (POX), 3-ethyl-3-hydroxymethyl-oxetane (OXA), 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene (XDO), 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxetane (EHOX).
  • DOX bis(1-ethyl-3-oxetanyl-methyl)ether
  • AQX 3-allyloxymethyl-3-ethyloxetane
  • POX 3-ethyl-3-[(phenoxy)-methyloxetane
  • OXA 3-ethyl-3-hydroxymethyl-oxetane
  • the epoxides and/or oxetanes of the composition according to the invention are preferably cationic photoinitiator (C1), which will be described in more detail later.
  • vinyl ethers can also be used as cationically polymerizable component (A1) in the composition according to the invention.
  • Suitable vinyl ethers are trimethylolpropane trivinyl ether, ethylene glycol divinyl ether and cyclic vinyl ethers and mixtures thereof.
  • vinyl ethers of polyfunctional alcohols can be used.
  • the cationically polymerizable component (A1) can comprise one or more alcohols that are used as reactive flexibilizers.
  • higher molecular weight polyols can be used to flexibilize masses with at least one cationically polymerizable compound.
  • Suitable polyols are available, for example, based on polyethers, polyesters, polycaprolactones, polycarbonates or (hydrogenated) polybutadienediols.
  • Examples of commercially available higher molecular weight polyols are products sold under the trade names ETERNACOLL UM-90 (1/1), Eternacoll UHC50-200 from UBE Industries Ltd., as CapaTM 2200, CapaTM 3091 from Perstorp, as Liquiflex H from Petroflex, as Merginol 901 from HOBIIM Oleochemicals, as Placcel 305, Placcel CD 205 PL from Daicel Corporation, as Priplast 3172, Priplast 3196 from Croda, as Kuraray Polyol F-3010, Kuraray Polyol P-6010 from Kuraray Co., Ltd., as Krasol LBH-2000, Krasol HLBH-P3000 from Cray Valley or as Hoopol S-1015-35 or Hoopol S-1063-35 from Synthesia Internacional SLU are available.
  • ETERNACOLL UM-90 (1/1) Eternacoll UHC50-200 from UBE Industries Ltd.
  • CapaTM 2200
  • the list of cationically polymerizable compounds (A1) is to be seen as exemplary and not exhaustive. A mixture of the cationically polymerizable compounds (A1) mentioned is also within the meaning of the invention.
  • composition according to the invention can also contain addition-crosslinkable compounds (A2).
  • the addition-crosslinkable compound (A2) comprises an isocyanate (A2-1), together with an isocyanate-reactive compound.
  • the group of suitable isocyanates (A2-1) includes aliphatic, cycloaliphatic, heterocyclic and aromatic isocyanates.
  • the isocyanate (A2-1) is at least difunctional.
  • polyisocyanates examples include dimeric 2,4-diisocyanatotoluene, dimeric 4,4'-diisocyanatodiphenylmethane, 3,3'-diisocyanato-4,4'-dimethyl-N,N'-diphenylurea, the isocyanurate of isophorone diisocyanate, hexamethylene diisocyanate and its isocyanurate, pentamethylene diisocyanate and its isocyanurate, 1,4-phenylene diisocyanate, naphthalene-1,5-diisocyanate and addition products of diisocyanates with short-chain diols such as 1,4-butanediol or 1,2-ethanediol.
  • the isocyanates (A2-1) can be used alone or in a mixture of two or more of the isocyanates.
  • the addition-crosslinkable compound (A2) can comprise at least one thiol (A2-2) as an isocyanate-reactive compound.
  • the thiol (A2-2) is preferably an at least difunctional thiol.
  • the at least difunctional thiol is selected from the group consisting of ester-based thiols, polyethers with reactive thiol groups, polythioethers, polythioether acetals, polythioether thioacetals, polysulfides, thiol-terminated urethanes, thiol derivatives of isocyanurates and glycoluril, and combinations thereof.
  • ester-based thiols based on 2-mercaptoacetic acid examples include trimethylolpropane trimercaptoacetate,
  • Pentaerythritol tetramercaptoacetate and glycol dimercaptoacetate available under the brand names ThiocureTM TMPMA, PETMA and GDMA respectively from Bruno Bock.
  • ester-based thiols include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutylate), glycol di(3-mercaptopropionate) and tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, which are available under the brand names ThiocureTM TMPMP, PETMP, GDMP and TEMPIC from Bruno Bock.
  • Examples of commercially available (thio)ether-based thiols include DMDO (1,8-dimercapto-3,6-dioxaoctane), available from Arkema S.A., DMDS (dimercaptodiethyl sulfide) and DMPT (2,3-di((2-mercaptoethyl)thio)-1-propane-thiol), both available from Bruno Bock.
  • ester-free thiols With regard to increased resistance of the cured mass to temperature and humidity, the use of ester-free thiols is particularly preferred. Examples of ester-free thiols can be found in JP 2012 153 794 A, which is incorporated into the description by reference.
  • TMPI tris(3-mercaptopropyl)isocyanurate
  • the at least difunctional thiol of component (A2-1) therefore comprises tris(3-mercaptopropyl)isocyanurate, alone or in admixture with other at least difunctional thiols.
  • Ester-free thiols based on a glycoluril compound are known from EP 3 075 736 A1. These can also be used in the compositions of further addition-crosslinkable resin components according to the invention, alone or in a mixture with other at least difunctional thiols.
  • Ester-free thiols based on olefins or terpenes are disclosed in US 9 340 716 B2. These can also be used in the compositions of further addition-crosslinkable resin components according to the invention, alone or in a mixture with other at least difunctional thiols. Higher functional thiols, which are obtainable, for example, by oxidative dimerization processes of at least difunctional thiols, can also be used.
  • At least difunctional thiols can be synthesized by reaction of at least difunctional thiiranes with a thiol.
  • primary thiols react more quickly with isocyanates than secondary or tertiary thiols.
  • primary thiols may be advantageous because they enable faster curing, while in processes that require a longer open time, secondary or tertiary thiols may be preferred.
  • composition according to the invention can also contain moisture-crosslinkable compounds (A3).
  • the moisture-crosslinkable compound (A3) is selected from the group of silanes.
  • Suitable silanes include monofunctional, particularly low molecular weight silanes, di- or higher functional silane-modified oligomers and/or polymers. These are not further restricted structurally.
  • silane-modified polymers are polyethers or polyacrylates with terminal alkoxysilane groups.
  • ⁇ -Alkoxysilanes with at least two alkoxysilane-containing end groups are available commercially, for example from Kaneka Belgium NV under the names Kaneka MS Polymer or Kaneka Silyl.
  • ⁇ -Alkoxysilanes based on polyether are also available from Wacker Chemie AG under the names Geniosil STP-E15 and STP-E35.
  • a-alkoxysilane compounds can also be used.
  • at least difunctional a-alkoxysilane compounds are used.
  • the preparation of a-alkoxysilane-terminated compounds is described in WO 03/014226 A1, among others. described in detail.
  • many of the preferred a-silanes based on polyethers or polyurethanes are commercially available from Wacker Chemie AG. These are sold commercially under the brand name GENIOSIL STP-E. Examples include the types Geniosil STP-E10 and STP-E30.
  • alkoxysilane compounds In addition to the polymeric compounds that can be crosslinked with moisture, monofunctional low-molecular alkoxysilane compounds can also be used. These alkoxysilanes contain a monovalent organic residue and are generally used to increase storage stability and to improve adhesion or flexibility.
  • Suitable monofunctional y-alkoxysilanes with different organic radicals are available, for example, under the trade names Dynasylan VTMO, Dynasylan GLYMO, Dynasylan MEMO, Dynasylan MTMS from Evonik Industries AG.
  • Examples of commercially available monofunctional a-alkoxysilanes are products from Wacker Chemie AG. Corresponding methacrylate or carbamate functionalized a-alkoxysilanes are available under the names GENIOSIL XL 32, XL 33, XL 63 or XL 65. Higher molecular weight monofunctional alkoxysilanes can also be used. Such compounds are usually used to increase flexibility and can be purchased from Wacker Chemie AG under the names Geniosil XM 20 and XM25, for example.
  • Partially condensed monofunctional alkoxysilanes can also be used. Such products are commercially available, for example, under the name Dynasylan 6490 or Dynasylan 1146 from Evonik Industries AG.
  • one or more of the alkoxysilanes mentioned can be used as moisture-crosslinkable compound (A3).
  • the first curable component (A) is present in the composition, based on the total weight of the composition, in particular in a proportion of 5 to 90 wt.%, preferably in a proportion of 10 to 85 wt.%.
  • compositions according to the invention comprise a second curable component (B) consisting of at least one radically radiation-curable compound.
  • the second curable component (B) serves in particular to enable rapid, precise, controllable and reliable fixing of the already activated mass by irradiation with actinic radiation of the second wavelength ⁇ 2, in particular at the latest as soon as the end of the open time of the activated mass is reached.
  • the radically radiation-curable compound (B) is not further restricted structurally as long as it contains ethylenically unsaturated double and/or triple bonds.
  • Suitable examples include (meth)acrylates, allyl compounds, vinyl compounds, methallyl compounds, isoprenes, butadienes and propargyles.
  • compositions preferably contain at least one difunctional radically radiation-curable compound.
  • radiation-curable compounds based on (meth)acrylates are used.
  • both aliphatic and aromatic (meth)acrylates can be used.
  • (meth)acrylates are referred to as both the derivatives of acrylic acid and methacrylic acid as well as combinations and mixtures thereof.
  • the following radiation-curable compounds are suitable, for example: isobornyl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, behenyl acrylate, 2-methoxyethyl acrylate and other mono- or polyalkoxylated alkyl acrylates, isobutyl acrylate, isooctyl acrylate, lauryl acrylate, tridecyl acrylate, isostearyl acrylate, 2-(o-Phenylphenoxy)ethyl acrylate, acryloylmorpholine, N,N-dimethylacrylamide, 4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,10-decanediol diacrylate, tricyclodecanedimethanol diacrylate, dipropylene glycol diacryl
  • TMPTA trimethylolpropane triacrylate
  • DPHA dipentaerythritol hexaacrylate
  • Higher-functional acrylates derived from multiply branched or dendrimeric alcohols can also be used advantageously
  • Radiation-curable compounds with allyl groups are also suitable, such as 1,3,5-triallyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, which is commercially available as TAICROS® from Evonik.
  • Compounds containing allyl groups lead to rapid fixing processes when irradiated with the second wavelength X 2 , particularly in the presence of thiols.
  • Unhydrogenated polybutadienes with free double bonds such as the Poly BD® types, can also be used as radiation-curing compounds.
  • Urethane acrylates based on polyesters, polyethers, polycarbonate diols and/or (hydrogenated) polybutadiene diols can be used as higher molecular weight radiation-curable compounds in the second curable component (B).
  • radiation-curable hybrid compounds can be used which have both radically polymerizable groups and cationically polymerizable epoxy groups.
  • Examples of commercially available products that have both radically polymerizable groups and cationically polymerizable epoxy groups include 3,4-epoxycyclohexyl methyl methacrylate (TTA15) from Jiangsu Tetra New Material Technology Co., Ltd., UVACURE 1561 from UCB, Solmer SE 1605 from Melrob Ltd. and Miramer PE210HA from Miwon Europe GmbH.
  • TTA15 3,4-epoxycyclohexyl methyl methacrylate
  • UVACURE 1561 from UCB
  • Solmer SE 1605 from Melrob Ltd.
  • Miramer PE210HA from Miwon Europe GmbH.
  • the radiation-curable hybrid compounds mentioned can be used advantageously in particular in curable compositions according to the first embodiment.
  • radiation-curable hybrid compounds can be used which have both radically polymerizable groups and addition-crosslinkable groups.
  • suitable hybrid compounds further include hydroxy(meth)acrylates, isocyanato(meth)acrylates, epoxy(meth)acrylates, vinyl ether(meth)acrylates or oxetane(meth)acrylates.
  • Examples of commercially available products that contain both radically polymerizable groups and addition-crosslinkable groups include Karenz MOI and Karenz AOI from Resonac, Laromer PR 9000 from BASF, glycidyl methacrylate, Ebecryl 4141 and Ebecryl 4596 from Allnex.
  • the radiation-curable hybrid compounds mentioned can be used advantageously in particular in masses according to the second embodiment.
  • a combination of several radiation-curable compounds is also within the scope of the invention.
  • the second curable component (B) is present in the composition according to the invention in particular in a proportion of 5 to 50% by weight, preferably in a proportion of 10 to 40% by weight, in each case based on the total weight of the curable composition.
  • the curable composition comprises a first photoinitiator (C), which is a photolatent acid (C1) or a photolatent base (C2).
  • C a first photoinitiator
  • C1 a photolatent acid
  • C2 a photolatent base
  • the first photoinitiator (C) can be activated upon irradiation with actinic radiation of a first wavelength i and initiates a polymerization reaction in the curable mass, which enables reliable final curing even in shadow zones.
  • the first photoinitiator (C) is particularly matched to the first curable component (A). This means that the polymerization reaction of the first curable component (A) is determined in particular by the activation of the first photoinitiator (C).
  • the photolatent acid (C1) preferably comprises at least one photolatent acid generator which releases an acid upon irradiation with actinic radiation of a first wavelength i, and in particular a photolatent acid generator based on a metallocenium compound for cationic polymerization.
  • metallocenium salts An overview of various metallocenium salts is disclosed in EP 0 542 716 B1.
  • Examples of different anions of the metallocenium salts are HSOr, PFe', SbFe', AsFe', CI', Br,
  • the photolatent acid (C1) based on a metallocenium compound is selected from the group of ferrocenium salts.
  • ferrocenium salts examples include cumenylcyclopentadienyliron(II) hexafluorophosphate (Irgacure 261); naphthalenylcyclopentadienyliron(II) hexafluorophosphate, benzylcyclopentadienyliron(III) hexafluorophosphate and cyclopentadienylcarbazoleiron(II) hexafluorophosphate.
  • cumenylcyclopentadienyliron(II) hexafluorophosphate Irgacure 261
  • naphthalenylcyclopentadienyliron(II) hexafluorophosphate examples include benzylcyclopentadienyliron(III) hexafluorophosphate and cyclopentadienylcarbazoleiron(II) hexafluorophosphate.
  • the photolatent acid (C1) preferably absorbs in the visible region of the electromagnetic spectrum. This means that the photolatent acid (C1) can preferably be activated at a first wavelength i > 380 nm.
  • the photolatent acid (C1) can preferably be activated by radiation with a wavelength of i > 400 nm, preferably i > 460 nm.
  • the first wavelength i i.e. the activation wavelength of the curable mass
  • the first wavelength i is in a range from 400 to 750 nm.
  • Suitable photolatent bases (C2) preferably comprise one or more compounds and derivatives derived from the group of cyclic amidine bases, cyclic guanidine bases, alpha-aminoacetophenones, Dihydropyridines, imidazolium compounds, carbamates, biguanidinium compounds and mixtures thereof.
  • the corresponding salts of the substance classes mentioned are also suitable as photolatent bases (C2).
  • Cyclic amidine bases include compounds based on 1,5-diazabicyclo[4.3.0]nonene, 1,8-diazabicyclo[5.4.0]undecene, 1,11-diazabicyclo[8.4.0]tetradecene, such as 1,8-diazabicyclo[5.4.0]undec-7-ene-anthracene-tetraphenylborate.
  • Structural analogues such as 2,3,4,6,7,8-hexahydropyrrolo[1,2-a]pyrimidin-1-ium tetraphenylborate, 1-(anthracen-9-ylmethyl)-2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepin-1-ium tetraphenylborate or 1-(anthracen-9-ylmethyl)-2,3,4,6,7,8-hexahydropyrrolo[1,2-a]pyrimidin-1-ium tetraphenylborate can also be used advantageously.
  • cyclic guanidine bases can be selected from the group of bicyclic guanidine compounds and include, for example, 1,5,7-triazabicyclo[4.4.0]dec-5-ene-H-tetraphenylborate, 1-(anthracen-9-ylmethyl)-9-ethyl-3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidin-1-ium-tetraphenylborate and 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidin-1-ium-tetraphenylborate.
  • Suitable alpha-aminoacetophenones are, for example, 2-benzyl-2-(dimethylamino)-1-(4-methoxyphenyl)butan-1-one, 2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one. Further compounds can be found in EP 0 284 561 B1.
  • photolatent bases based on dihydropyridine are N-methylnifedipine, N-butyl-2,6-dimethyl-4-(2-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid diethyl ester and N-methyl-2,6-dimethyl-4-(4,5-dimethoxy-2-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylic acid diethyl ester.
  • a suitable photolatent base based on an imidazolium compound is 3-(anthracen-9-ylmethyl)-1-methyl-1 H-imidazol-3-ium tetraphenylborate.
  • a suitable photolatent base based on a carbamate is anthracen-9-ylmethyldiethylcarbamate.
  • Examples of photolatent bases based on biguanidinium compounds are 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate, (Z)-([bis(dimethylamino)methylidene]amino)-N-cyclohexyl(cyclohexylamino)methaniminium tetrakis(3-fluorophenyl)borate and 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidium 2-(3-benzoylphenyl)propionate.
  • the compounds mentioned are commercially available under the name CGI 277 from BASF SE, Irgacure 369, Irgacure 907, Irgacure 379 each from IGM Resins and WPBG-345, WPBG-300, WPBG-266, WPBG-018 from Wako Chemicals Europe GmbH.
  • the decomposition products of the photolatent base (C2) preferably have a pKs of greater than 7 after irradiation with actinic radiation of the first wavelength Ai.
  • the pKs changes by at least one.
  • the photolatent base (C2) preferably absorbs in the visible region of the electromagnetic spectrum. This means that the photolatent base (C2) can preferably be activated at a first wavelength i > 380 nm.
  • the photolatent base (C2) can preferably be activated by radiation with a wavelength of Ai > 400 nm.
  • the first photoinitiator (C), i.e. the photolatent acid (C1) or the photolatent base (C2), is contained in particular in a proportion of 0.01 to 5 wt.%, based on the total weight of the curable mass, but preferably in proportions of 0.05 to 3 wt.%.
  • the composition in particular for use in the process according to the invention, contains a second photoinitiator (D) for the radical polymerization of component (B).
  • the second photoinitiator (D) is accordingly a radical former.
  • the second photoinitiator (D) enables the mass previously activated in step b) to be fixed by irradiation with actinic radiation of the second wavelength A2.
  • the second photoinitiator (D) forms Wavelength ⁇ 2 radicals which result in a polymerization of the second curable component (B) or trigger a polymerization of the second curable component (B).
  • the second photoinitiator (D) can be used as the second photoinitiator (D), such as, for example, a-hydroxy ketones, benzophenone, a,a'-diethoxyacetophenone, 4,4-diethylaminobenzophenone, 2,2-dimethoxy-2-phenyl-acetophenone, 4-isopropylphenyl-2-hydroxy-2-propyl ketone, 1-hydroxycyclohexylphenyl ketone, isoamyl-p-dimethylaminobenzoate, methyl-4-dimethylaminobenzoate, methyl-o-benzoylbenzoate, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-isopropylthioxanthone, dibenzosuberone, 2,4,6-trimethylbenzoyl-dip
  • the IRGACURE TM types from BASF SE can be used, for example the types IRGACURE 184, IRGACURE 500, IRGACURE 1179, IRGACURE 2959, IRGACURE 745, IRGACURE 651, IRGACURE 369, IRGACURE 907, IRGACURE 1300, IRGACURE 819, IRGACURE 819DW, IRGACURE 2022, IRGACURE 2100, IRGACURE 784, IRGACURE 250, IRGACURE TPO, IRGACURE TPO-L.
  • the DAROCUR TM types from BASF SE can be used, such as the types DAROCUR MBF, DAROCUR 1173, DAROCUR TPO and DAROCUR 4265.
  • the second photoinitiator used as component (D) in the compositions according to the invention can preferably be activated by actinic radiation having a wavelength of from 200 to 400 nm, particularly preferably from 250 to 380 nm.
  • the second photoinitiator (D) is preferably selected such that it is not activated upon irradiation of the curable mass with the first wavelength i. According to the invention, the second photoinitiator (D) is activated in the process according to the invention by irradiating the mass at the second wavelength A 2 .
  • the second photoinitiator (D) can be combined with a suitable sensitizer.
  • the difference between the wavelength i used for irradiating and activating the first photoinitiator (C) and the wavelength A 2 used for irradiating and activating the second photoinitiator (D) is in particular at least 20 nm, preferably at least 30 nm.
  • the second photoinitiator (D) is present in the compositions in particular in a proportion of 0.01 to 5 wt.%, preferably 0.5 to 3 wt.%, in each case based on the total weight of the composition.
  • the sum of the proportions of the first photoinitiator (C) and the second photoinitiator (D), based on the total weight of the mass, is in particular at most 10 wt.%, preferably at most 5 wt.%.
  • the curable composition in particular for use in the process according to the invention, contains as an essential constituent at least one inhibitor (E) for intercepting radicals generated when the curable composition is irradiated with actinic radiation of the first wavelength Ai.
  • the inhibitor (E) ensures that the curable mass has an open time upon irradiation with actinic radiation of the first wavelength i, within which the activated mass remains dosable or joinable.
  • the inhibitor is further selected in relation to its proportion in the curable mass so that when the already activated mass is irradiated with the second Wavelength ⁇ 2 in step d) a sufficient amount of radicals is formed by the second photoinitiator (D), which enable the polymerization of the second curable component (B) and thus lead to a fixation of the mass.
  • the inhibitor (E) can therefore be regarded as a radical scavenger which, on the one hand, protects the radiation-curable component (B) from premature conversion at the time of activation of the first curable component (A), and, on the other hand, is consumed by the radicals formed when the second photoinitiator (D) is activated, thus enabling the targeted conversion of the radiation-curable component (B) at the desired time.
  • the inhibitor (E) ensures that the radiation-curable component (B) does not cure for at least the period of the open time.
  • the open time can therefore be controlled via the proportion and type of inhibitor (E).
  • the irradiation dose for activating the first photoinitiator (C) and/or its proportion in the mass can be varied, and vice versa.
  • the irradiation dose, the proportion of the first photoinitiator (C) and the proportion of the inhibitor (E) are coordinated in such a way that the mass remains liquid during the open time after activation of the first photoinitiator (C).
  • the curing behavior of the mass can be further controlled via the ratio of the proportions of the inhibitor (E) and the second photoinitiator (D) and/or the irradiation dose for activating the second photoinitiator (D), since the consumption of the inhibitor (E) occurs more quickly the more radicals are generated from the second photoinitiator (D) in this step.
  • the inhibitor (E) is not further restricted structurally.
  • the inhibitor (E) comprises one or more compounds selected from the group consisting of hindered phenols, thioethers, phosphites, hindered amines (HALS), optionally substituted styrenes, nitrous acid esters, alkyl nitrites, dithiocarbamates, and combinations thereof.
  • HALS hindered amines
  • inhibitors (E) are 2,6-di-tert-butyl-4-methylphenol, 4-methoxyphenol, 1,4-dihydroxybenzene, 1,4-benzoquinone, (2, 2, 6, 6- Tetramethylpiperidinyl-1-1)oxyl, isoeugenol, a-tocopherol, 4-tert-butylcatechol, 1,2,3-trihydroxybenzene, 3,4,5-trihydroxybenzoic acid, lauryl gallate
  • 1,1-diphenylethylene, ⁇ -methylstyrene, tert-butyl nitrite, tetraethylthiuram disulfide and 2,4-diphenyl-4-methyl-1-pentene can advantageously be used in the curable composition, in particular for carrying out the process according to the invention.
  • CTA reagents which are typically used for RAFT polymerizations, can be used as inhibitors (E).
  • chain transfer agents which are typically used for RAFT polymerizations
  • dithiobenzoates such as benzyl benzodithioate, trithiocarbonates such as S,S-dibenzyl trithiocarbonate and dithiocarbamates such as tetraethylthiuram disulfide (TEDS) and tetramethylthiuram disulfide.
  • the inhibitor (E) may also include hexaarylbiimidazoles (HABI) or derivatives thereof.
  • HABI hexaarylbiimidazoles
  • Typical commercially available hexaarylbiimidazoles are 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (BCIM HABI), 2,2'-bis(2-methoxyphenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2-(2- ethoxyphenyl)-1-[2-(2-ethoxyphenyl)-4,5-diphenyl-2H-imidazol-2-yl]-4,5-diphenyl- 1 H-imidazole (LEDCIIR 110), 2,2',4-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)- 4', 5'
  • the inhibitor (E) is present in the curable mass in particular in a proportion of 0.01 to 1.5 wt.%, based on the total weight of the mass, preferably in proportions of 0.1 to 1.5 wt.%.
  • the molar ratio of inhibitor (E) to first photoinitiator (C) in the curable composition is in particular in a range from 0.4:1 to 20:1, preferably in a range from 0.4:1 to 10:1 or 1:1 to 10:1, particularly preferably in a range from 1:1 to 5:1.
  • the molar ratio of inhibitor (E) to second photoinitiator (D) in the curable composition can be 1:2 or less, preferably 1:5 or less, particularly preferably 1:10 or less.
  • compositions according to the invention may further contain optional constituents as additives (F).
  • the additives (F) are preferably selected from the group of fillers, dyes, photosensitizers, pigments, anti-aging agents, fluorescent agents, accelerators (F1), adhesion promoters, drying agents, crosslinkers, flow improvers, wetting agents, thixotropic agents, diluents, non-reactive flexibilizers, non-reactive polymeric thickeners, flame retardants, corrosion inhibitors, plasticizers, tackifiers and combinations thereof.
  • the first curable component (A) contains a cationic polymerizable compound (A1)
  • an accelerator (F1) for curing the mass by cationic polymerization can be added to the curable mass.
  • Peroxy compounds of the perester, diacyl peroxide, peroxydicarbonate and/or hydroperoxide type can be used as accelerators (F1). Hydroperoxides are preferably used. Cumene hydroperoxide in a 70 to 90% (v/v) solution in cumene is used as a particularly preferred accelerator.
  • the skin formation of the curable mass is accelerated after irradiation and activation of the first photoinitiator (C1) with the first wavelength i.
  • the proportion of peroxy compounds is selected so that a sufficient open time remains in the process according to the invention for joining and optionally aligning a second substrate.
  • the length of the open time required depends on the processing process carried out in each case.
  • the accelerator (F1), in particular the peroxy compound, is contained in particular in a proportion of 0 to 5 wt.%, based on the total weight of the mass.
  • the mass ratio between the first photoinitiator (C 1 ), for example ferrocenium hexafluoroantimonate, and the peroxy compound, for example cumene hydroperoxide, can be varied within wide limits.
  • a mass ratio of 1:0.1 to 1:6 is used, particularly preferably from 1:2 to 1:4.
  • a formulation of the compositions according to the invention in particular for use in the process according to the invention, comprises at least the components (A) to (E) described above.
  • the mass consists of the following components, each based on the total weight of the mass:
  • the inhibitor is preferably selected from the group consisting of hindered phenols, thioethers, phosphites, hindered amines (HALS), optionally substituted styrenes, nitrous acid esters, alkyl nitrites, dithiocarbamates and combinations thereof. More preferably, the inhibitor comprises 1,1-diphenylethylene, a-methylstyrene, tert-butyl nitrite, tetraethylthiuram disulfide and 2,4-diphenyl-4-methyl-1-pentene and combinations thereof.
  • HALS hindered amines
  • the mass preferably comprises or consists of the following components, each based on the total weight of the mass: (A) 10 to 85 wt.% of a cationically polymerizable compound (A1) comprising at least one difunctional epoxide as the first curable component,
  • the mass preferably comprises or consists of the following components, each based on the total weight of the mass:
  • the at least difunctional isocyanate (A2-1) can be completely or partially replaced by a hybrid compound of component (B) which carries radically radiation-curable groups together with isocyanate groups.
  • inhibitor (E) in the compositions of the second embodiment are substituted styrenes, nitrous acid esters or alkyl nitrites and dithiocarbamates.
  • the masses of the second embodiment form a polythiourethane network in the cured state. This is characterized by high media resistance.
  • the mass preferably comprises or consists of the following components, each based on the total weight of the mass:
  • compositions according to the invention of all embodiments are preferably provided as one-component compositions.
  • the curable mass described above is particularly suitable for use in joining, casting or coating substrates. This also includes gluing, molding or sealing substrates.
  • the curable masses are particularly suitable for applications in which the strength build-up is to be controlled in a targeted manner by fixing light and at the same time reliable curing in shadow zones is to be ensured, especially in the case of non-transparent substrates.
  • This property profile is particularly required in the production of electro-optical components, such as camera modules, the joining of displays or encapsulations with complex geometries, for example sensor encapsulations.
  • Housing bonding or application in fuel cells are also conceivable with the previously described masses, in particular when using cationically polymerizable compounds (A1) with 1,1-diphenylethylene, tert-butyl nitrite and/or 2,4-diphenyl-4-methyl-1-pentene as inhibitor (E).
  • the masses can be activated by irradiation with the first wavelength Ai in the flow.
  • the liquid mass is irradiated with actinic radiation, for example during dosing, before leaving the dosing apparatus and is thereby activated.
  • Dosing devices that have a penetrable zone and suitable LED irradiation devices are commercially available from DELO Industrie Klebstoffe GmbH & Co. KGaA under the trade name DELO-ACTIVIS and are described, for example, in DE 10 2021 133 731 A1.
  • the use of such a flow activation apparatus offers the advantage that the dosing and activation of the mass can take place in a single process step. This reduces the equipment effort and saves installation space in industrial plants.
  • the dosing pressure of the mass in a flow activation apparatus is preferably 15 bar or less.
  • the dosing pressure is particularly preferably below 10 bar in order to ensure process-safe and reliable activation of the mass.
  • Typical dosing rates have volume flows of 1 to 15 cm 3 /min, preferably 2 to 10 cm 3 /min. Dosing rates that are too low can lead to premature hardening within the apparatus. Dosing rates that are too high, on the other hand, can lead to incomplete activation of the mass at a given irradiation power.
  • step c After activation of the mass by actinic radiation with the first wavelength Ai, it has an open time within which the activated mass remains liquid and does not yet exceed the gel point.
  • the subsequent process steps, in particular the feeding and joining of another substrate (step c), can be carried out reliably within the open time.
  • the activated mass it is also possible for the activated mass to remain at least partially joinable beyond the specified open time before it solidifies to such an extent that no further flow or pressing onto another substrate is possible.
  • the open time of the activated masses is preferably at least 0.1 minute, and up to 30 minutes, more preferably up to 15 minutes or up to 5 minutes. Shorter open times of 0.1 to 1 minute are particularly suitable for fast industrial production processes. When using a flow activation apparatus, however, a longer open time can be advantageous for reasons of process reliability, in particular an open time of 1 minute or more, preferably an open time in the range of more than 5 to 30 minutes.
  • hardenable masses with very short open times of less than one minute can only be processed to a limited extent in a joining process after activation and are also not suitable for flow activation.
  • the mass After fixing with actinic radiation with the second wavelength ⁇ 2, the mass has at least a so-called "green strength" or handling strength. This means that after fixing, no more flowing occurs. Components in joints remain fixed relative to one another and can thus be fed into further production steps, for example manually.
  • the mass activated and fixed according to the method according to the invention typically hardens completely within 7 days at room temperature, preferably within 3 days, particularly preferably within one day, i.e. within 24 hours. For faster hardening or to accelerate the final hardening of the mass, the mass can be heated either during or after the light fixation in step d).
  • the masses were each irradiated with a DELOLUX 20 LED lamp from DELO Industrie Klebstoffe GmbH & Co. KGaA. Different lamps were used for different wavelengths. The respective exposure times, intensities and wavelengths can be found in the tables below for the test examples.
  • Room temperature is defined as 23 ⁇ 2 °C.
  • Crosslinking or “curing” is defined as a polymerization reaction beyond the gel point.
  • the gel point is the point at which the storage modulus G’ becomes equal to the loss modulus G”.
  • the determination is carried out using a haptic test using a toothpick on glue drops (10 mg) on a glass slide. A triplicate determination is carried out and the arithmetic mean of the measured values obtained gives the open time.
  • the glue drops are activated with an LED surface emitter (DELOLUX 20) under predefined conditions depending on the intended application. The activation conditions such as intensity, duration and wavelength of the irradiation can be found in the following tables for the test examples. At the end of the irradiation, a stop watch is started.
  • the expected increase in viscosity is assessed haptically in comparison to a non-activated reference sample of the same size and geometry.
  • the geometry of the activated adhesive drop is manipulated with the toothpick in a vertical movement by pulling the tip of the toothpick upwards from the center of the adhesive drop, with the toothpick held at an angle of approx. 45° to the slide. If the activated adhesive drop does not return to its original geometry within 1 s of manipulation with the tip of the toothpick, the stopwatch is stopped and the end of the adhesive's open time is reached.
  • the mass is subjected to an optical assessment after irradiation with actinic radiation of the second wavelength ⁇ 2.
  • the intensity, duration and wavelength of the irradiation can be found in the tables below for the test examples.
  • the haptic test is carried out using a plastic spatula.
  • Masses that have a skin after irradiation and no longer flow are classified as “yes” with regard to their light fixation. Masses that have no skin after irradiation or that continue to flow are classified as “no” with regard to their light fixation.
  • DSC measurements of the reactivity of radiation-induced curing are carried out in a dynamic differential scanning calorimeter (DSC) of the type DSC3+ from Mettler Toledo.
  • DSC dynamic differential scanning calorimeter
  • 6 to 10 mg of the liquid sample are poured into an open Weighed into an aluminum crucible (40 pL) and exposed at 30 °C for 5 min.
  • Intensity and wavelength can be found in the following tables for the test examples.
  • the peak time is evaluated after subtracting the energy input caused by the LED lamp.
  • the liquid and soluble components are first mixed and then the fillers and optionally other solids are incorporated using a laboratory stirrer, laboratory dissolver or a speed mixer (Hauschild) until a homogeneous mass is formed.
  • a laboratory stirrer laboratory dissolver or a speed mixer (Hauschild) until a homogeneous mass is formed.
  • Masses containing photoinitiators that are sensitive to visible light must be prepared under light outside the excitation wavelength of the respective photoinitiators or sensitizers.
  • A2-1 Isocyanates
  • A2-1-1 Desmodur Ultra N3600 Aliphatic polyisocyanate (HDI isocyanurate), available from Covestro
  • C-2) CGI-277 (2-benzyl-1-(3,5-dimethoxyphenyl)-2-(dimethylamino)butan-1- one), available from BASF
  • Component E Inhibitors
  • composition of the respective curable masses is given in the following tables 1 to 3. All weight proportions listed below refer to the total weight of the curable masses. Table 1: Examples according to the first embodiment.
  • Table 2 Examples according to the second embodiment.
  • Table 3 Examples according to the third embodiment.
  • Examples E1 to E7 in Table 1 show compositions of the first embodiment based on at least one cationically polymerizable compound (A1) for use in the process according to the invention.
  • the compositions contain a photolatent acid (C-1) as the first photoinitiator (C) for the first curable component (A).
  • the activated masses of examples E1 to E6 initially remain liquid after irradiation with light of the first wavelength Ai and have open times in the range of 1.5 to 22 minutes. They are therefore suitable for pre-activation.
  • masses with a longer open time such as example E6, can be used reliably in a flow-through activation apparatus. Shorter open times are suitable for bonding processes in which components are joined within a short time. Even if no fixing by irradiation with light of the second wavelength A2 takes place according to step d) of the described process, the masses become solid and harden after 24 hours at the latest.
  • this means that the masses of examples E1 to E7 are suitable for reliably hardening after activation with light of the first wavelength Ai even in shadow zones that are not accessible to irradiation with light of the second wavelength A2 in step d).
  • all examples E1 to E7 can be fixed by irradiation with light of the second wavelength A 2.
  • the viscosity of the masses is preferably at most 500 Pas.
  • Different open times can be set by the proportion of inhibitor (E) or the molar ratio of inhibitor (E) to the first photoinitiator (C), which can be activated when irradiated with the first wavelength Ai.
  • a smaller proportion of inhibitor (E) with a molar ratio of components (E) to (C) reduced by a factor of 7 in example E7 leads to an open time of 1 minute, in direct comparison to an otherwise analogous formulation according to example E2.
  • fixing of the mass according to example E7 after irradiation with light of the second wavelength A 2 remains possible, since there is an excess of the second photoinitiator (D) in relation to inhibitor (E), which can be activated when irradiated with light of the second wavelength A2.
  • Comparative example V3 has a high proportion of the inhibitor (E) of over 1.5 wt.% with a molar ratio of the inhibitor (E) to the first photoinitiator (C) of 23.5:1.
  • the mass cannot be activated by irradiation with light of the first wavelength Ai under the selected conditions, but remains liquid even after 24 hours. Light fixation by irradiating the mass with light of the wavelength A 2 is also not successful under the conditions of comparative example V3.
  • Example E3 shows the use of an alternative inhibitor (E-2). With the same molar ratio (E) to (D) and (E) to (C) compared to example E2, a similar open time can be achieved after activation by irradiation with the first wavelength Ai.
  • example E5 shows a formulation using an alternative resin system comprising a cycloaliphatic epoxide and a polyol.
  • the composition can also be used advantageously in the process according to the invention.
  • Comparative example V1 shows a formulation based on the prior art according to EP 3 894 458 B1.
  • the mass contains no inhibitor (E) and solidifies immediately after irradiation with light of the first wavelength Ai and is therefore unsuitable for use in the process according to the invention due to the lack of an open time.
  • the mass according to example E6 which is comparable to the mass of comparative example V1 and additionally contains an inhibitor (E-1) based on a methylstyrene dimer, can be activated by irradiation with light of the first wavelength Ai without the mass immediately solidifying. After activation, the mass has an open time of 22 minutes and can be fixed by irradiation with light of the second wavelength A 2 .
  • the process according to the invention can be carried out independently of the resin system used and can be made possible solely by the addition of the inhibitor (E).
  • the composition according to comparative example V2 which contains a cationically polymerizable compound based on a glycidyl ether (A1-1)
  • A1-1 glycidyl ether
  • the proportion of the inhibitor (E) in the curable mass is selected depending on the amount of the photoinitiator (C) and the irradiation dose so that the activated mass can be cured within 24 hours.
  • Examples E8 to E13 in Table 2 show compositions of the second embodiment based on at least one addition-crosslinkable compound (A2) for use in the process according to the invention.
  • the compositions contain a photolatent base (C-2) as the first photoinitiator (C) for the first curable component (A).
  • Examples E8 to E13 are suitable for carrying out the process according to the invention and, after activation by irradiation with light of the first wavelength Ai, cure reliably even in shadow zones.
  • the masses have open times of 1.5 to 3.5 minutes and can be fixed by irradiation with light of the second wavelength A2.
  • Comparative example V4 does not use the first photoinitiator (C).
  • the mass can be fixed by irradiation with light of the second wavelength A2, but cannot be activated. This means that the mass remains liquid even after 24 hours after irradiation with light of the first wavelength Ai and has no measurable open time. It is therefore not suitable for curing in shadow areas.
  • the second photoinitiator (D) is omitted as in comparative example V5
  • the masses do indeed harden after irradiation with light of the first wavelength Ai without any further energy input after 24 hours.
  • fixation in accordance with step d) of the process according to the invention is not possible.
  • omitting the inhibitor (E) leads to masses which have no open time and solidify immediately after irradiation with light of the first wavelength Ai.
  • the mass of comparative example V7 has a high proportion of the inhibitor (E) of over 1.5% by weight.
  • a high proportion of the inhibitor (E) based on the total weight of the mass, can lead to masses that can no longer be activated in accordance with the invention, even if the molar ratio of the inhibitor (E) to the first photoinitiator (C) is in a range that is otherwise suitable for carrying out the process according to the invention.
  • Example E14 in Table 3 shows a composition of the third embodiment based on at least one moisture-crosslinkable compound (A3) comprising a ⁇ -alkoxysilane compound.
  • the composition of Example E14 has a proportion of inhibitor (E) of 0.37% by weight with a molar ratio of inhibitor (E) to first photoinitiator (C) of 3:1.
  • the molar ratio of inhibitor (E) to second photoinitiator (D) is 1:6.
  • the composition can be activated by irradiation with light of the first wavelength Ai and fixed by irradiation with light of the second wavelength A2.
  • the open time after the first irradiation is 12 minutes.
  • the composition is suitable for use in the process according to the invention.
  • Comparative example V8 on the other hand, does not add an inhibitor (E). Without the addition of component (E), it is not possible to ensure that the process can be carried out step by step or that the build-up of strength can be controlled. Irradiation with light of the first wavelength Ai as well as with light of the second wavelength A2 leads directly to a solidification of the mass. The mass of comparative example V8 cannot therefore be used in the process according to the invention.
  • the cured masses of all described embodiments of the invention achieve a compressive shear strength of at least 1 MPa on aluminum after their final curing.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention se rapporte : à un procédé permettant d'assembler, d'enrober ou de revêtir des substrats à l'aide d'un composé durcissable ; à un composé durcissable ; et à une utilisation du composé durcissable pour assembler, enrober ou revêtir des substrats. Le composé durcissable comprend : un premier composant durcissable (A) et un second composant durcissable (B) ; un premier photo-initiateur (C) pour le premier composant durcissable (A), lequel premier photo-initiateur peut être activé lorsqu'il est irradié par un rayonnement actinique ayant une première longueur d'onde λ1 ; un second photo-initiateur (D) pour le second composant durcissable (B), lequel second photo-initiateur peut être activé lorsqu'il est irradié par un rayonnement actinique ayant une seconde longueur d'onde λ2, la seconde longueur d'onde λ2 étant différente de la première longueur d'onde λ1 ; et au moins un inhibiteur de piégeage de radicaux (E) pour piéger des radicaux générés lors de l'irradiation du composé durcissable avec un rayonnement actinique ayant la première longueur d'onde λ1. Dans le procédé, le composé durcissable est dosé sur un premier substrat et activé par irradiation avec un rayonnement actinique ayant la première longueur d'onde λ1. Le composé durcissable activé est ensuite fixé par irradiation avec un rayonnement actinique ayant la seconde longueur d'onde λ2. L'invention se rapporte également à un composé durcissable et à une utilisation d'un composé durcissable.
PCT/EP2024/070709 2023-08-03 2024-07-22 Procédé permettant d'assembler, d'enrober ou de revêtir des substrats, et composé durcissable à cet effet Pending WO2025026781A1 (fr)

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