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WO2021073883A1 - Composé adhésif durcissable sur lequel sont basées des bandes adhésives réactives - Google Patents

Composé adhésif durcissable sur lequel sont basées des bandes adhésives réactives Download PDF

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Publication number
WO2021073883A1
WO2021073883A1 PCT/EP2020/077489 EP2020077489W WO2021073883A1 WO 2021073883 A1 WO2021073883 A1 WO 2021073883A1 EP 2020077489 W EP2020077489 W EP 2020077489W WO 2021073883 A1 WO2021073883 A1 WO 2021073883A1
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Prior art keywords
weight
adhesive
polymer
mol
curable adhesive
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PCT/EP2020/077489
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German (de)
English (en)
Inventor
Marco Kupsky
Thilo Dollase
Matthias Koop
Alexander Fischer
Philipp Preuß
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Tesa SE
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Tesa SE
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/011—Crosslinking or vulcanising agents, e.g. accelerators
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

Definitions

  • the invention relates to a thermally curable adhesive based on a (co) polymer functionalized with at least one aliphatic epoxy, a latent reactive adhesive tape that contains the thermally curable adhesive, a method for bonding two substrates with the latent reactive adhesive tape, a curable 2-component adhesive based on a (co) polymer functionalized with at least one aliphatic epoxide and a method for bonding two substrates by means of the curable 2-component adhesive.
  • the invention further relates to a thermally cured adhesive which is obtained by thermally curing the thermally curable adhesive of the present invention or the curable 2-component adhesive of the present invention.
  • Reactive adhesives based on curable epoxides are used in a variety of ways today. These are used as fast-curing two-component or multi-component epoxy adhesives, for example in the production of composite materials, as adhesives for joining two or more substrates, even with extremely high strengths (structural bonds, etc.) or as curable components / curable comonomers in polymers Pressure-sensitive adhesives, adhesives, sealants and materials.
  • Epoxides are also used in combination with latently reactive crosslinking mechanisms in one-component epoxy adhesives or pressure-sensitive adhesives, adhesives, sealants and materials. These offer the user the advantage of not having to formulate the adhesives or pressure-sensitive adhesives or materials on site, are "ready to use” and impress with their long pot life (open time, processing time), their good “shelf life” (storability) and their excellent economy. State of the art
  • Latent reactive adhesive films which contain epoxides are known in the prior art, for example from EP 846 743 A1.
  • WO 98/21287 A1 describes radiation-curable precursors for thermally curable adhesive systems containing (a) a radiation-curable monomer / prepolymer syrup, which is to be understood primarily as a poly (meth) acrylate component, (b) an epoxy resin component, (c) a Photoinitiator component and (d) a nucleophilic thermal activator. Oligomeric and polymeric epoxides can be used as component (b). (Co) polymers functionalized with cycloaliphatic epoxides are not explicitly mentioned. Cycloaliphatic epoxides are basically described as having little advantage, see page 19, line 2 of the relevant publication. Curing using ammonium thiocyanate is not intended.
  • No. 4,552,604 A is an example of a so-called “dual your” system in which a poly (meth) acrylate is built up by photopolymerization in the presence of an epoxy resin. The photopolymerization of the liquid composition takes place on a liner. The photopolymerized film is then thermally hardened for bonding. Photopolymerization is used to form a polymeric matrix for the thermally curable epoxy component. Curing by means of ammonium thiocyanate is not disclosed.
  • WO 2013/101693 A1 discloses thermally curable adhesive films, produced from an acrylate monomer mixture, which is radically polymerized by means of photo-initiation, and an epoxy component. Curing by means of ammonium thiocyanate is not disclosed.
  • WO 1999/057216 A1 discloses formulations containing 20 to 80% by weight of ethylene vinyl acetate copolymers and 20 to 80% by weight of an epoxy component, which can also be a polymer.
  • a polymer containing glycidyl methacrylate is listed as a specific example.
  • the formulations described are cured photochemically. Curing by means of ammonium thiocyanate is not disclosed.
  • DE 102016207548 A1 discloses latently reactive formulations containing cycloaliphatic epoxides; curing by means of ammonium thiocyanate is not disclosed. These formulations are not sufficiently latent at elevated storage temperatures (e.g. 40 ° C), and Thermal Acid Generators (TAGs) are very expensive specialty chemicals that are relatively difficult to synthesize.
  • elevated storage temperatures e.g. 40 ° C
  • TAGs Thermal Acid Generators
  • US 3294865 A describes the use of ammonium thiocyanate as an accelerator for the crosslinking of polyepoxides with defined crosslinkers. In the systems of US 3294865 A, the ammonium thiocyanate only accelerates the reactivity between the
  • latently reactive curing systems based on aliphatic epoxides, in particular for use in latently reactive adhesive or pressure-sensitive adhesive films or foils.
  • These should have a high latency even at elevated storage temperatures (in particular 40 ° C.) in order to be able to dispense with temperature monitoring or a closed cold chain in the logistics chain.
  • these hardening systems should have better economic efficiency and availability compared to special solutions such as TAGs (Thermal Acid Generator (s) / super acids).
  • TAGs Thermal Acid Generator (s) / super acids.
  • thiocyanate salts as reactive hardeners in combination with (co) polymers based on aliphatic epoxides. This was particularly surprising and unforeseeable, since thiocyanate salts are already widely used as accelerators or catalysts, in small amounts, for the crosslinking (curing) of epoxides in combination with substances known as crosslinkers, and in particular ammonium thiocyanate alone is actually not advantageous because of unsuitable reactivity this was the task.
  • the present invention relates to a curable adhesive, comprising or consisting of the following components: at least one (co) polymer (A) functionalized with aliphatic epoxy groups and having a weight-average molar mass in the range from 5000 g / mol to 5,000,000 g / mol, preferably 5000 g / mol to 2,000,000 g / mol, more preferably 5,000 g / mol to 500,000 g / mol, at least one thiocyanate salt (B), optionally at least one matrix polymer as film former (C), which is derived from ( A) and (E) is different, optionally at least one additive (D), and optionally at least one glycidyl ether-containing compound (E), which is different from (A) to (D), the functionalized with aliphatic epoxide groups ( Co) polymer (A) is functionalized in particular with one or more cycloaliphatic epoxide groups.
  • at least one (co) polymer (A)
  • the present invention relates to a latent reactive adhesive tape which contains a thermally curable adhesive, preferably as a layer, according to the present invention, at least one matrix polymer (C), which is different from (A) and (E), as a film former is included.
  • the present invention relates to a method for bonding two substrates by means of a latent reactive adhesive tape according to the present invention, characterized by performing at least the following method steps: a) fixing a first substrate to be bonded, preferably on a holder; b) placing the latent reactive adhesive tape on the first substrate to be bonded; c) optionally heating to a first temperature above room temperature to 150 ° C, preferably at least 50 ° C and at most 120 ° C, very preferably at most 100 ° C and applying a first pressure, preferably 0.1 to 10 bar, to prefix the latent reactive adhesive tape on the first substrate to be bonded; d) applying a second substrate to be bonded to the intermediate product obtained after step b) or c); e) Postcrosslinking by heating to a second temperature above room temperature, preferably at least 120 ° C.
  • the present invention relates to a curable 2-component adhesive which has a first, preferably flowable, component comprising or consisting of the following constituents: at least one (co) polymer (A) functionalized with aliphatic epoxy groups and having a weight average molecular weight in the range from 5,000 g / mol to 5,000,000 g / mol, preferably 5,000 g / mol to 2,000,000 g / mol, more preferably 5,000 g / mol to 500,000 g / mol, optionally at least one matrix polymer as film former (C), which is different from (A) and (E), optionally at least one additive (D), and optionally at least one glycidyl ether-containing compound (E) which is different from (A) to (D), where the aliphatic epoxy Group-functionalized (co) polymer (A) is functionalized in particular with one or more cycloaliphatic epoxide groups; and a second, preferably flowable component, spatially
  • the present invention relates to a method for bonding two substrates by means of a curable 2-component adhesive according to the present invention, characterized by performing at least the following method steps: a) fixing a first substrate to be bonded, preferably on a holder; b) applying and mixing the two flowable components of the curable 2-component adhesive on the first substrate to be bonded; c) attaching a second substrate to be glued to the intermediate product obtained after step b); d) heating to a temperature of room temperature to 250 ° C., preferably below 220 ° C., preferably at most 150 ° C., very preferably below 100 ° C., a pressure preferably 0.1 to 10 bar in order to postcrosslink and obtain a composite and e) optionally removing the bonded assembly, in particular from the holder.
  • the present invention relates to a thermally cured adhesive, which by thermal curing, preferably at temperatures of at least 40 ° C, more preferably 50 ° C, even more preferably 70 ° C, preferably up to 250 ° C, more preferably up to 200 ° C, even more preferably up to 150 ° C, is obtained from a thermally curable adhesive composition according to the present invention or the curable 2-component adhesive composition according to the present invention.
  • At least one refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with constituents of the compound described herein, this indication does not refer to the absolute amount of molecules but to the type of constituent. “At least one compound containing epoxide groups” therefore means, for example, one or more different compounds containing epoxide groups, i.e. one or more different types of compounds containing epoxide groups.
  • Numerical values which are given herein without decimal places refer to the full stated value with one decimal place. For example, “99%” stands for “99.0%”.
  • the expression “approximately” or “approximately” in connection with a numerical value relates to a variance of ⁇ 10% based on the specified numerical value, preferably ⁇ 5%, particularly preferably ⁇ 1%.
  • the preferred embodiments described below for the individual components (A), (B), (C), (D) and (E) can be applied to all five aspects of the present invention.
  • Molecular weights are determined according to the invention by gel permeation chromatography on 100 ⁇ L clear-filtered sample (sample concentration 1.5 g / L). Tetrahydrofuran with 0.1% by volume of trifluoroacetic acid is used as the eluent, and 200 ppm (m / V) toluene as the internal standard. The measurement takes place at 25 ° C.
  • a column type PSS-SDV, 10 ⁇ m, ID 8.0 mm ⁇ 50 mm (details here and below in the order: type, particle size, internal diameter c length) is used as the guard column.
  • a column of the type PSS-SDV, 10 ⁇ m linear one, ID 8.0 mm ⁇ 300 mm is used for separation (columns and detector from Polymer Standards Service; detection by means of detector PSS-SECcurity 1260 RID).
  • the flow rate is 0.5 mL per minute.
  • the calibration is carried out with polystyrene standards in the separation area of the column and converted universally into a polymethyl methacrylate calibration using the well-known Mark Houwink coefficients a and K.
  • the determination of the glass transition temperature (TG) and / or exothermic / enthalpy takes place according to the invention by means of dynamic differential calorimetry (DSC; English Differential Scanning Calorimetry) on a DSC 204 F1 from Netzsch.
  • DSC dynamic differential calorimetry
  • the sample is weighed into reinforced aluminum crucibles (lid punched manually).
  • the temperature program runs two heating ramps, first it is cooled down from 25 ° C to -100 ° C with liquid nitrogen and then heated up to 180 ° C at 10 K / min. Glass transitions are recognized as steps in the thermogram.
  • the glass transition temperature is evaluated as follows (see Figure 2). There is a tangent to the baseline of the thermogram before 1 and after 2 of the level created.
  • a regression line 3 is laid parallel to the ordinate so that it intersects the two tangents in such a way that two surfaces 4 and 5 (between the one tangent, the regression line and the measurement curve) have the same content.
  • the intersection of the regression line positioned in this way with the measurement curve gives the glass transition temperature.
  • the exotherm / enthalpy is evaluated by integrating the reaction peak.
  • the glass transition temperature of the first heating curve determined in this way corresponds to the glass transition temperature of the uncrosslinked polymer.
  • the determined glass transition temperature resulting from the second heating curve corresponds to a polymer or formulation crosslinked by the thermal stress of the measurement or a polymer or formulation crosslinked by the activation of a thermal crosslinker / initiator, in the case of the presence of such an activator in a polymer or a polymer Formulation different glass transition temperature.
  • the glass transition temperature can also be determined in this way for non-reactive systems.
  • the level in the second heating curve is then evaluated as the result.
  • (co) polymer is used collectively for homopolymers or copolymers. Insofar as polymers are mentioned in the context of the text, (co) polymers are meant, unless otherwise stated in the respective reference.
  • (co) poly (meth) acrylate is to be understood as meaning polyacrylate and polymethacrylate homopolymers or copolymers of (meth) acrylic monomers and, if appropriate, further copolymerizable comonomers.
  • (meth) acrylates and the adjective “(meth) acrylic” are used to summarize the compounds from the group of acrylic acid derivatives - such as acrylic acid esters in particular - and methacrylic acid derivatives - such as methacrylic acid esters in particular.
  • (co) polymerizable means the ability of a type of monomer or a mixture of at least two types of monomers to form a (co) polymer by building up molar mass.
  • a (co) polymer functionalized with aliphatic epoxide groups which is functionalized in particular with one or more cycloaliphatic epoxide groups, is used.
  • This is also referred to below as (co) polymer (A). It is particularly preferred that this is a (meth) acrylic (co) polymer.
  • the (co) polymer (A) has a weight-average molar mass of 5,000 to 5,000,000 g / mol.
  • the weight-average molar mass of the polymer having at least one group of a (co) polymer (A) is preferably at least 10,000 g / mol, very preferably at least 20,000 g / mol. More preferably, the weight-average molar mass of the at least one group of a (co) polymer (A) is at most 2,000,000 g / mol, very preferably at most 200,000 g / mol, most preferably at most 100,000 g / mol.
  • the (meth) acrylic (co) monomers (a) functionalized with aliphatic epoxy groups have a (co) monomer proportion in the (co) polymer (A) of more than 50 to 100% by weight, preferably at least 75% by weight, very preferably at least 90% by weight.
  • the epoxy oxygen atom bridges a C-C bond, or a C-C-C assembly or a C-C-C-C assembly, preferably in all or some of the epoxy groups in at least some of the monomers functionalized with aliphatic epoxy groups.
  • the epoxy oxygen atom bridges a C-C bond, which is part of an - optionally heterosubstituted - aliphatic hydrocarbon ring (cycloaliphatic epoxy group), preferably in all or some of the epoxy groups in at least some of the monomers functionalized with aliphatic epoxy groups.
  • the (meth) acrylic (co) monomer (a) functionalized with an aliphatic epoxy group thus at least one with a cycloaliphatic epoxy group Group used or, if several (meth) acrylic (co) monomers (a) functionalized with an aliphatic epoxy group are present, for one, several or all of these (meth) acrylic (co) functionalized with an aliphatic epoxy group Monomeric (a) cycloaliphatic epoxides are used. It is particularly advantageous to use cycloaliphatic epoxides for more than 50% by weight of the (co) monomers (a), and it is particularly preferred to use exclusively cycloaliphatic epoxides for the purposes of the (co) monomers (a).
  • the (co) polymer (A) can be produced from one or more of monomers (b), (c), (d) and (e), regardless of the presence of the respective other types of monomer (b) , (c), (d) and (e):
  • the monomer fraction or (co) monomer fraction in the polymer denotes the fraction of the repeating units (building blocks) in the polymer in question which can be attributed to these (co) monomers.
  • the monomer proportions in the polymer mixture to be polymerized for the preparation of the corresponding copolymer are advantageously selected accordingly.
  • the proportion of the (co) polymer (A) in the adhesive is at least 4.9% by weight to at most 99.9% by weight, preferably 10% by weight to 90% by weight, further preferably 20% by weight % to 80% by weight, more preferably 30% by weight to 70% by weight, more preferably 40% by weight to 60% by weight.
  • the glass transition temperature of the (co) polymer (A) is preferably at least 0 ° C, very preferably at least 25 ° C, even more preferably at least 35 ° C. It is preferably at most 100 ° C, more preferably at most 80 ° C. In an alternative embodiment of the invention, however, the glass transition temperature of the (co) polymer (A) can also be below 0.degree. C., in this way pressure-sensitively adhesive systems are accessible, or above 100.degree.
  • the proportion of the at least one thiocyanate salt (hardener) (B) in the adhesive is preferably 0.1 to 50% by weight, more preferably 0.3 to 25% by weight, most preferably 0.5 to 10% by weight. -% or 1.25 to 10% by weight.
  • the proportion of matrix polymer (C) in the adhesive is at least 65% by weight and at most 94.5% by weight, preferably at least 80% by weight to at most 95% by weight , very preferably at least 87% by weight and at most 95% by weight, based in each case on the overall formulation of the curable adhesive.
  • At least one glycidyl ether-containing compound (E) can furthermore be used.
  • its proportion is preferably chosen so that only part of the hardener (B) is consumed by reaction with it. It has been shown that glycidyl ether groups can react spontaneously at room temperature with the hardener (B), in particular ammonium thiocyanate.
  • the component (E) chosen so that only a maximum of 50% of the hardener (B) is consumed by reaction with it.
  • the constituent (E) is preferably chosen so that only a maximum of 25% of the hardener (B) is consumed by reaction with it.
  • the proportion is very preferably chosen so that only a maximum of 10% of the hardener (B) is consumed by reaction with it.
  • the ratio of the glycidyl ether groups contained in the glycidyl ether-containing compound (E) to the amount of hardener (B) is typically from 1.5: 1.0 to 1.0: 1.5, advantageously from 1, 2: 1, 0 to 1, 0: 1, 2.
  • a larger excess of hardener is also possible, as is a larger excess of glycidyl ether groups.
  • the adhesive according to the first and advantageously also according to the fourth and sixth aspect of the present invention is preferably free from primary, secondary and tertiary amines and amides.
  • the adhesive according to the first and advantageously also according to the fourth and sixth aspect of the present invention is preferably essentially free of acid groups.
  • the curable adhesive preferably has a first glass transition temperature which is below the temperature at which the adhesive bond consisting of reactive adhesive film and substrates to be bonded is created by lamination, so that the formulation under the lamination conditions under pressure in a defined manner Period of time allows sufficient wetting on the substrate (s).
  • the temperature used for the lamination is called the “lamination temperature” in the context of this invention.
  • the temperature difference between the lamination temperature and the glass transition temperature is preferably at least 40 ° C., in particular at least 70 ° C. or even at least 100 ° C., the lamination temperature being above the glass transition temperature.
  • the lamination temperature is advantageously between 40.degree. C. and 100.degree. C., in particular between 50.degree. C. and 80.degree.
  • the difference between the lamination temperature and the activation temperature is advantageously at least 20 ° C, in particular at least 40 ° C.
  • the (co) polymer (A) also advantageously has a first glass transition temperature in the uncured state, which is below the temperature at which the adhesive bond consisting of reactive adhesive tape and substrates to be bonded is created by lamination.
  • the temperature difference between the lamination temperature and the glass transition temperature of the uncured (co) polymer (A) is in this case preferably at least 20 ° C., in particular at least 40 ° C., the lamination temperature being above the glass transition temperature.
  • the glass transition temperature for the cured adhesive is very preferably at least 40 ° C., in particular at least 100 ° C. higher than for the uncured adhesive system. Due to the high number of reactive groups in the (co) polymer (A) and possibly in other components (C) and / or (D), it may be possible that a glass transition temperature cannot be determined in the cured state due to the high degree of crosslinking or is above the decomposition temperature.
  • the glass transition temperature for the cured (co) polymer (A) itself is further advantageously at least 40 ° C., in particular at least 100 ° C. higher than for the uncured (co) polymer (A). Due to the high number of reactive groups in the (co) polymer (A), it may be possible that a glass transition temperature in the cured state cannot be determined due to the high degree of crosslinking or is above the decomposition temperature.
  • hardened system or "hardened adhesive” means in the context of this invention that the adhesive with the (co) polymer (A) is caused by the action of the hardener component and at an elevated temperature (higher than room temperature, preferably 40 to 250 ° C, more preferably 50 to 200 ° C., most preferably 70 to 150 ° C.) has been activated as a further stimulus and a reaction involving the functional groups of the (co) polymer (A) has taken place.
  • an elevated temperature higher than room temperature, preferably 40 to 250 ° C, more preferably 50 to 200 ° C., most preferably 70 to 150 ° C.
  • conversions of 0.5% or less of the functional groups can already bring about a sufficiently high glass transition temperature and be very suitable for the adhesive application. A conversion of 0.5% is mentioned here as an example.
  • the turnover required is depending on the molar mass of the (co) polymer (A) and the number of monomer units per polymer chain. Every reaction of a functional group per polymer chain can result in a doubling of the molar mass and thus a significant increase in the glass transition temperature.
  • the statement made also applies in particular to higher sales such as 1%, 5%, 10%, 25%, 50%, 75% or 100%. It is crucial that the adhesive properties are appropriate for the application after the curing has been carried out, as indicated in Tables 1 and 2 in particular below.
  • the adhesive can be pressure-sensitively tacky under standard conditions (23 ° C., 50% relative humidity). In the non-hardened state, it then has a glass transition temperature of below 0 ° C, preferably of at most -25 ° C.
  • This characteristic simplifies assembly processes such as the pre-dimensioning of adhesive tape sections for the later bonding process or also lamination steps in the manufacture of adhesive product structures and component bonding.
  • the lamination process does not necessarily have to be carried out at an elevated temperature, but can be laminated at room temperature, since sufficient contact between the adhesive and the substrates to be bonded can already be achieved via the lamination pressure.
  • pressure sensitive adhesive or “pressure sensitive adhesive” is understood to mean, as usual, those viscoelastic, polymeric compounds which - if necessary through suitable additives with other components, such as adhesive resins - at the application temperature ( unless otherwise defined, at room temperature, i.e. 23 ° C) are permanently tacky and permanently tacky and adhere to a large number of surfaces upon contact, in particular adhere immediately (which have a so-called "tack”). They are able to wet a substrate to be bonded sufficiently even at the application temperature without activation by solvents or by heat - possibly under the influence of a more or less high pressure - so that there are sufficient interactions between the mass and the substrate for adhesion can train.
  • the adhesive composition can also be non-tacky or only slightly tacky. In order to adjust this, it can then have a glass transition temperature of at least 0 ° C., preferably of at least 25 ° C., in the uncured state. It can also be significantly lower (e.g. -25 ° C. or below), especially when semicrystalline polymers are used for matrix polymers (C). This characteristic allows an advantageous placement of the adhesive products in the bonding process and prevents premature adhesion to a surface in the wrong position.
  • this characteristic is shown to be advantageous for latent reactive adhesive systems, since any reactivity in the vitreous / viscoplastic state is significantly (kinetically) reduced and an improved latency is achieved as a result. In addition to pressure, an increased temperature is then required for the lamination process.
  • the adhesive system softens, increases in its wetting behavior and can thereby form contact with the substrates to be bonded.
  • the molar mass of the (co) polymer (A) according to the invention is of central importance since, for a given adhesive, it also influences the viscoelastic properties of the melt, and here in particular the melt viscosity. The higher the molar mass, the more pronounced entanglements act as temporary cross-linking points on the viscoelastic behavior.
  • the molar mass of the (co) polymer (A) according to the invention is significantly below its entanglement molecular weight, adhesives containing these (co) polymers are correspondingly more flowable under compression conditions, ie above the glass transition temperature, and involve the risk of excessive squeezing behavior. If, on the other hand, the molar mass is too high, namely in the molar mass range in which the glass transition temperature no longer changes with the molar mass, the polymer may already be too loopy, which reduces the flow behavior so that the adhesive mass no longer flows well under compression conditions.
  • This embodiment should illustrate the inventive idea of selecting a molar mass in the molar mass range according to the invention for (co) polymers (A).
  • the (co) polymer (A) according to the invention also offers a further advantage.
  • the invention makes use of the knowledge that a reactive system in the bonding step, where squeezing can occur, through activation of the hardening reaction, a build-up in molecular weight goes through. Two processes take place here, chain growth and cross-linking. Both processes are kinetically controlled and take time. If heat is used under bonding conditions, the viscosity of the system is reduced according to its temperature dependence, which can lead to squeezing.
  • (co) polymers (A) according to the invention already have a base molar mass, so that at least a first step of chain growth has already taken place before activation and only crosslinking needs to take place to build up cohesion and further build up molar mass.
  • This further increase in molar mass leads to the preferred increase in the glass transition temperature and, together with the crosslinking, to advantageous bonding results.
  • (co) monomers (a) monomers of the formula (I) used, where -R 1 is -H or -CH 3 , -X- is -N (R 3 ) - or -O-, -R 3 is -H or -CH 3 and -R 2 is an epoxy-functionalized (hetero ) represent hydrocarbyl group. At least one monomer used for -R 2 has an epoxy-functionalized aliphatic, preferably a cycloaliphatic, group.
  • the group R 2 more preferably comprises linear, branched, cyclic or polycyclic hydrocarbons with 2 to 30 carbon atoms, which are functionalized with an aliphatic epoxide group.
  • branched and cyclic groups there are at least 3, and in the case of polycyclic groups at least 6 carbon atoms.
  • At least one monomer used for -R 2 preferably has an epoxy-functionalized cycloaliphatic group with 5 to 30 carbon atoms.
  • Particularly preferred representatives of this group are 3,4-epoxycyclohexyl-substituted monomers such as 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexyl methyl acrylate, 3,4-
  • Oxetane-containing (meth) acrylates and oxolane-containing (meth) acrylates can also be used.
  • Comonomers (a) in the (co) polymer (A) are used in an amount of at least 50% by weight, preferably at least 75% by weight, very preferably at least 90% by weight.
  • comonomers (b) have no epoxy groups.
  • comonomers (b) it is possible to use all (meth) acrylate monomers and other copolymerizable vinyl monomers known to the person skilled in the art - in particular epoxy group-free - which are mixed with (co) monomers (a) and any comonomers (c) and / or (d) and / or (e) are copolymerizable and which have a glass transition temperature as hypothetical homopolymer (in this context the glass transition temperature of the homopolymer from the corresponding monomers in the molar mass-independent glass transition temperature range, TG « , is meant) of at least 25 ° C, in particular at least 50 ° C.
  • Such monomers are also referred to as “hard monomers” in the context of this document.
  • hard monomers for. B. the Polymer Handbook (J. Brandrup, EH Immergut, EA Grulke (Ed.), 4th ed., 1999, J. Wiley, Hoboken, Vol. 1, Chapter VI / 193) can be consulted.
  • So-called macromers according to WO 2015/082143 A1 can also advantageously be used.
  • comonomers (c) have no epoxy groups.
  • all (meth) acrylate monomers and other copolymerizable vinyl monomers known to the person skilled in the art - in particular epoxy-group-free - can be used which are mixed with (co) monomers (a) and optionally present comonomers (b) and / or (d) are copolymerizable, and which have a glass transition temperature as a hypothetical homopolymer (in this context, the glass transition temperature of the homopolymer from the corresponding monomers in the molar mass-independent glass transition temperature range, TG « , is meant) of below 25 ° C, in particular at most 0 ° C.
  • Such monomers are also referred to as “soft monomers” in the context of this document.
  • soft monomers For the selection of such comonomers, the Polymer Handbook (J. Brandrup, EH Immergut, EA Grulke (ed.), 4th edition, 1999, J. Wiley, Hoboken, vol. 1, chapter VI / 193) can be consulted. So-called macromers according to WO 2015/082143 A1 can also advantageously be used.
  • comonomers (d) it is also possible to use those monomers which are copolymerizable with (co) monomers (a) and optionally present comonomers (b) and / or (c) and / or (e) and which have the adhesive properties optimize the copolymer according to the invention.
  • monomers which are copolymerizable with (co) monomers (a) and optionally present comonomers (b) and / or (c) and / or (e) and which have the adhesive properties optimize the copolymer according to the invention.
  • phosphorus-containing and silicon-containing comonomers and here acrylated or methacrylated alkoxysilane-containing comonomers are to be mentioned as advantageous. Examples are 3- (triethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl acrylate, 3-
  • Methacryloxypropyldimethyl methoxysilane Of the aforementioned compounds are 3- (triethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl acrylate, 3-
  • the comonomers (d) also preferably have no glycidyl ether or epoxy groups.
  • the proportion of comonomers (d) is preferably at most 10% by weight, based on the total weight of the copolymer.
  • a (co) polymer contains comonomer (d).
  • comonomers (d) are completely dispensed with.
  • comonomers (e) it is also possible to use those monomers which are copolymerizable with (co) monomers (a) and optionally present comonomers (b) and / or (c) and / or (d) and spontaneously with the hardener (B) can react.
  • the comonomers (e) are different from (a), (b), (c) and (d).
  • (Meth) acrylates that are functionalized with a glycidyl ether group are suitable for this.
  • Comonomers of this type are typically used in the (co) polymers (A) at a maximum of 5% by weight, preferably at most 2% by weight. In an advantageous version of this invention, however, comonomers (e) are completely dispensed with.
  • the (co) polymer (A) does not contain any Si-containing monomers.
  • the (co) polymers (A) are produced by (co) polymerization of the (co) monomers on which they are based and can be carried out in bulk, in the presence of one or more organic solvents, in the presence of water or in mixtures of organic solvents and water. The aim is to keep the amount of solvent used as low as possible.
  • Suitable organic solvents are pure alkanes (e.g. hexane, heptane, octane, isooctane, isohexane, cyclohexane), aromatic hydrocarbons (e.g. benzene, toluene, xylene), esters (e.g.
  • halogenated hydrocarbons e.g. chlorobenzene
  • alkanols e.g. methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether
  • ketones e.g. acetone, butanone
  • ethers e.g. diethyl ether, dibutyl ether
  • the aqueous polymerization reactions can be mixed with a water-miscible or hydrophilic cosolvent in order to ensure that the reaction mixture is in the form of a homogeneous phase during the monomer conversion.
  • Advantageously usable cosolvents for the present invention are selected from the following group consisting of aliphatic alcohols, glycols, ethers, glycol ethers, polyethylene glycols, polypropylene glycols, esters, alcohol derivatives, hydroxyether derivatives, ketones and the like, as well as derivatives and mixtures thereof. There are no compounds which can react with epoxy functionalities and / or which can initiate or catalyze the reaction of epoxy functionalities and / or whose reactivity with epoxy functionalities is not otherwise prevented.
  • radical sources are peroxides, hydroperoxides and azo compounds.
  • Some non-exclusive examples of typical free-radical initiators are potassium peroxodisulfate, dibenzoyl peroxide, cumene hydroperoxide, cyclohexanone peroxide, di-tert-butyl peroxide, azobisisobutyronitrile, cyclohexylsulfonylacetyl peroxide, diisopropyl percarbonate, tert-butyl peroctoate.
  • the free-radical polymerization initiator used is particularly preferably 2,2'-azobis (2-methylbutyronitrile) or 2,2-azobis- (2,4-dimethylvaleronitrile).
  • the polymerization time is - depending on the temperature and the desired conversion - between 4 and 72 hours.
  • the introduction of heat is essential for the thermally decomposing polymerization initiators.
  • the polymerization can be initiated by heating to 50 ° C. or more, depending on the type of initiator. An initiation temperature of at most 100 ° C., very preferably at most 80 ° C., is preferred.
  • nitroxides are used in a favorable procedure, such as. B. (2,2,5,5-Tetramethyl-1-pyrrolidinyl) oxyl (PROXYL), (2,2,6,6-Tetramethyl-1-piperidinyl) oxyl (TEMPO), derivatives of PROXYL or TEMPO and other nitroxides familiar to the person skilled in the art.
  • WO 96/24620 A1 describes a polymerization process in which very specific radical compounds such as.
  • B. phosphorus-containing nitroxides based on imidazolidine can be used.
  • WO 98/44008 A1 discloses special nitroxyls based on morpholines, piperazinones and piperazinediones.
  • DE 199 49 352 A1 describes heterocyclic alkoxyamines as regulators in controlled radical polymerizations.
  • ATRP Atom Transfer Radical Polymerization
  • the polymerization initiator preferably being monofunctional or difunctional secondary or tertiary halides and for the abstraction of the halide (s) Cu, Ni, Fe, Pd, Pt, Ru, Os-, Rh, Co, Ir, Ag or Au complexes can be used.
  • halide s
  • the different possibilities of the ATRP are also described in the documents of US Pat. No. 5,945,491 A, US Pat. No. 5,854,364 A and US Pat. No. 5,789,487 A.
  • a variant of the RAFT polymerization (reversible addition-fragmentation chain transfer polymerization) is carried out as a further preparation process.
  • the polymerization process is e.g. B. in the documents WO 98/01478 A1 and WO 99/31144 A1 described in detail.
  • Trithiocarbonates of the general structure R '"- S-C (S) -S-R'" (Macromolecules, 2000, 33, 243-245) are particularly advantageously suitable for the preparation.
  • the trithiocarbonates (TTC1) and (TTC2) or the thio compounds (THI1) and (THI2) are used for the polymerization, where F is a phenyl ring that is unfunctionalized or by alkyl or aryl substituents that are directly or via ester or ether bridges are linked, can be functionalized, can be a cyano group or a saturated or unsaturated aliphatic radical.
  • the phenyl ring F can optionally carry one or more polymer blocks, for example polybutadiene, polyisoprene or polystyrene, to name just a few.
  • Functionalizations can, for example Halogens, hydroxyl groups, epoxy groups, without this list claiming to be exhaustive.
  • radical polymerization initiator systems which contain radical polymerization initiators, in particular the thermally decomposing radical-forming azo or peroxo initiators listed above.
  • radical polymerization initiators in particular the thermally decomposing radical-forming azo or peroxo initiators listed above.
  • all conventional polymerization initiators known for acrylates and / or methacrylates are suitable for this.
  • radical sources which only release radicals under UV irradiation. It is important that these polymerization initiators cannot activate any reaction of the epoxy functionalities.
  • Chain transfer reagents according to the prior art can also be used for the purpose of adjusting the molar mass, provided they have no reactivity with epoxy groups or their reactivity with epoxy groups is otherwise prevented.
  • the desired molar mass is preferably set by polymerization processes, be it controlled polymerization processes or uncontrolled polymerization processes, in which no agents are used that can react with epoxy functionalities or initiate or catalyze the reaction of epoxy functionalities before the initiation of the curing reaction of the adhesive film or their reactivity with epoxy functionalities is otherwise prevented.
  • the desired molar mass can also be set, particularly preferably via the ratio of polymerization initiators and (co) monomer (s) and / or the concentration of (co) monomers.
  • At least one thiocyanate salt is used as hardener / crosslinker.
  • the thiocyanate salt (B) is particularly preferably selected from alkali metal, alkaline earth metal or ammonium thiocyanate or mixtures thereof; it is particularly preferably ammonium thiocyanate. If ammonium thiocyanate and, as further starting materials, those with glycidyl ether groups are used, there is the possibility of a two-stage crosslinking process, the first stage already taking place at low temperatures (especially below 40 ° C) and post-curing at moderate ( ⁇ 220 ° C) to high temperatures (> 220 ° C) at a later point in time. Furthermore, ammonium thiocyanate offers the advantage of excellent water solubility, which means that it can also be used advantageously in aqueous dispersions.
  • the thiocyanate salt (B) is 0.1 to 50% by weight, preferably 0.2 to 25% by weight, very preferably 0.5 to 10% by weight or 1.25 to 10% by weight .-%, based in each case on the amount of aliphatic epoxy groups used in the curable adhesive. If components with glycidyl ether groups are used, the amount of hardener (B) used is increased by the stoichiometric amount corresponding to the glycidyl ether groups.
  • Activation temperatures which are advantageous for the purposes of the present invention, i.e. temperatures at which the curing of the (co) polymers (A) can be started, are at least 60 ° C, preferably at least 75 ° C, more preferably at least 90 ° C. Curing / initiation in these temperature ranges is preferred in order not to thermally damage thermally sensitive substrates. In the case of more thermally stable substrates, higher curing temperatures, e.g. B. at 120 ° C, 150 ° C, 180 ° C, 200 ° C or even higher conceivable and even preferred for some bonding tasks. However, they lie favorably below 220 ° C.
  • the curing time can be 15 minutes or more and 2 hours or less. However, significantly shorter curing times, such as 10 s, 30 s, 60 s, 120 s, 240 s, 5 min or 10 min, or even shorter curing times are preferred.
  • Thermoplastic materials, elastomers and thermoplastic elastomers are suitable as optional film formers for adhesives according to the invention.
  • they are selected so that, in combination with the further formulation constituents, they make available those adhesives which are advantageous with regard to the production, further processing and handling of latent reactive adhesive films.
  • manufacturing processes at the adhesive tape manufacturer on the one hand and adhesive tape users on the other hand with regard to technical adhesive properties and with regard to further improvement of the dimensional stability of the adhesive films with regard to the administration of the adhesive product and the squeezing behavior in the hot lamination process to name just a few particularly important requirements.
  • thermoplastic materials are used as matrix polymers (C) which are different from the (co) polymer (A).
  • examples are semicrystalline polyolefins and ethylene-vinyl acetate copolymers (EVA).
  • Preferred polyolefins are produced from ethylene, propylene, butylene and / or hexylene, it being possible in each case for the pure monomers to be polymerized or mixtures of the monomers mentioned being copolymerized.
  • the polymerisation process and the selection of the monomers can be used to control the chemical, physical and mechanical properties of the polymer, such as the softening temperature and / or special mechanical properties.
  • Elastomers can be used very advantageously as matrix polymers (C).
  • Examples include rubber or synthetic rubber as the starting material for the adhesives.
  • the natural rubber or natural rubbers basically consist of all available qualities such as crepe, RSS, ADS, TSR or CV types, depending on the required purity and viscosity level, and the synthetic rubber or the synthetic rubbers from the group of randomly copolymerized styrene-butadiene rubbers (SBR), butadiene rubbers (BR), synthetic polyisoprenes (IR), butyl rubbers (IIR), halogenated butyl rubbers (XIIR), acrylate rubbers (ACM), EPDM, polybutylenes or polyisobutylenes can be selected.
  • Elastomers can also be (partially) hydrogenated.
  • Nitrile rubbers in particular heat-polymerized ones, and those with an acrylonitrile content between 15% and 50%, preferably between 30% and 45% and a Mooney viscosity (ML 1 + 4, 100 ° C.) between 30 and 110, are very advantageous between 60 and 90.
  • poly (meth) acrylates which are built up from (co) monomers (b), (c) and / or (d) and / or (e) and have a weight-average molar mass of typically at least 100,000 g / mol and typically at most 5,000,000 g / mol, in particular at least 250,000 g / mol and at most 2,000,000 g / mol.
  • the glass transition temperature of these poly (meth) acrylates can in particular be below 25 ° C or even below 0 ° C and in particular below -25 ° C. In this way, pressure-sensitive reactive adhesive systems are accessible.
  • Thermoplastic elastomers and, in particular, block, star and / or graft copolymers with a molecular weight Mw (weight average) of 3,000,000 g / mol or less, preferably 200,000 g / mol or less, are also advantageous. Smaller molecular weights are preferred because they are easier to process.
  • the molar mass should not be less than 50,000 g / mol.
  • SBS styrene-butadiene block copolymers
  • SIBS styrene-isoprene block copolymers
  • SIBS styrene (isoprene / butadiene) block copolymers
  • SIBS styrene-isoprene block copolymers
  • SIBS styrene-isoprene / butadiene block copolymers
  • SIBS styrene (isoprene / butadiene block copolymers
  • SIBS styrene (ethylene / butadiene block copolymers
  • SEBS styrene (ethylene / butylene) block copolymers
  • SEPS styrene (ethylene / propylene) block copolymers
  • SBBS styrene iso-butylene block copolymers
  • SiBS polymethyl methacrylate-polyacrylate block copolymers
  • thermoplastic elastomers are thermoplastic polyurethanes (TPU).
  • TPU thermoplastic polyurethanes
  • Polyurethanes are chemically and / or physically crosslinked polycondensates, which are typically built up from polyols and isocyanates and contain soft and hard segments.
  • the soft segments consist, for example, of polyesters, polyethers, polycarbonates, in each case preferably of an aliphatic nature for the purposes of this invention, and polyisocyanate hard segments.
  • materials are available which can be used advantageously for the purposes of this invention. Raw materials that are available to the formulator for this purpose are mentioned, for example, in EP 894 841 B1 and EP 1 308492 B1.
  • thermoplastic elastomers polyetherester elastomers for matrix polymers (C) can be used.
  • the adhesive of the present invention can furthermore contain at least one additive. Particularly suitable additives are described below.
  • adhesive resins (D1) are preferably up to 50% by weight, based on the low-viscosity reactive resins (D2), preferably up to 50% by weight, based on the adhesive and further additives (D3), preferably up to 50% by weight. % based on the adhesive.
  • the adhesive of the invention optionally contains one or more types of adhesive resin, advantageously those which are compatible with the (co) polymer (A) and / or the matrix polymer (C).
  • this adhesive resin has an adhesive resin softening temperature (ASTM E28) of greater than 25 ° C, in particular greater than 80 ° C.
  • ASTM E28 adhesive resin softening temperature
  • partially or fully hydrogenated or disproportionated resins based on rosin and rosin derivatives, indene-coumarone resins, terpene-phenolic resins, phenolic resins, hydrogenated polymers of dicyclopentadiene, partially, selectively or fully hydrogenated hydrocarbon resins can be used as adhesive resins (D1) in the adhesive Based on C5, C5 / C9 or C9 monomer streams, polyterpene resins based on ⁇ -pinene and / or ß-pinene and / or d-limonene, hydrogenated polymers of preferably pure C8 and C9 aromatics can be used.
  • the abovementioned tackifier resins can be used either alone or as a mixture.
  • hydrogenated resins with a degree of hydrogenation of at least 90%, preferably of at least 95%, are preferred.
  • DACP value diacetone alcohol cloud point
  • MMAP value mixed methylcylohexane aniline point
  • Low molecular weight reactive resins can optionally but advantageously be used. They preferably have a softening temperature (in particular glass transition temperature) below room temperature, preferably below 0 ° C, very preferably below -25 ° C. Their weight-average molar mass is preferably less than 5000 g / mol, preferably less than 1000 g / mol. They are preferably used in a proportion in the adhesive of at most 50% by weight, very preferably at most 25% by weight, most preferably at most 10% by weight.
  • These low-viscosity reactive resins are in particular cyclic ethers, that is to say compounds which carry at least one oxirane group, or oxetanes.
  • Usable reactive resins can be monofunctional, difunctional, trifunctional, tetrafunctional or more functional to polyfunctional, the functionality being based on the cyclic ether group.
  • Examples are 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate (EEC) and derivatives, dicyclopendadiene dioxide and derivatives, 3-ethyl-3-oxetanemethanol and derivatives,, bis - [(3,4 -epoxycyclohexyl) methyl] adipate and derivatives, vinylcyclohexyl dioxide and derivatives, 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate) and derivatives, bis [1-ethyl (3-oxetanyl) methyl) ether and derivatives, 2 - (7-Oxabicyclospiro (1,3-dioxane-5,3 '- (7-oxabicyclo [4.1.0] -heptane)), 1,4-bis ((2,3-epoxypropoxy) methyl) cyclohexan
  • reactive resins can be used, which can take part mechanistically or in some other way in the curing reaction of the, in particular, aliphatic epoxy groups.
  • Reactive resins can be used in their monomeric or also dimeric, trimeric, etc. up to their oligomeric form, provided that the weight-average molecular weight preferably does not reach or exceed 5,000 g / mol.
  • additives such as anti-aging agents, such as antiozonants, antioxidants, light stabilizers, fillers (D3), can be added as additives to the adhesive.
  • UV absorbers or sterically hindered amines
  • Processing aids such as rheologically effective additives (e.g. thickeners)
  • Blowing agents such as chemical foaming agents and / or expanded or expandable microballoons and / or hollow spheres such as hollow glass spheres.
  • the adhesive composition advantageously also contains one or more plasticizers.
  • plasticizers based on aliphatic or cycloaliphatic alkyl esters.
  • the esters are preferably esters of aliphatic or cycloaliphatic carboxylic acids, in particular dicarboxylic acid. Phosphoric acid esters (phosphates) can also be used.
  • the aliphatic carboxylic acid esters include alkyl or cycloalkyl adipates such as, in particular, di- (2-ethylhexyl) adipate, diisononyl adipate, Diisodecyl adipate, ditridecyl adipate and dioctyl adipate are mentioned as examples.
  • alkyl and cycloalkyl sebacates such as in particular di (2-ethylhexyl) sebacate and alkyl and cycloalkyl azelates such as in particular di (2-ethylhexyl) azelate.
  • Aliphatic or cycloaliphatic cyclohexyldicarboxylic acid diesters are particularly preferably used, in particular 1,2-diisobutylcyclohexanedicarboxylic acid ester, 1,2-di- (2-ethylhexyl) cyclohexanedicarboxylic acid ester or 1,2-diisonanedonyl ester (also referred to as "DINCH").
  • DINCH 1,2-diisonanedonyl ester
  • one advantage of the adhesive of the invention is that it can optionally exhibit its advantageous properties even without additional additives being added individually or in any combination. Nevertheless, it may be advantageous and desirable in individual cases to adjust certain further properties of the adhesive, in particular of the pressure-sensitive adhesives, adhesives, sealants or sealants, by adding additives.
  • the transparency of the mass and its color can be influenced.
  • Some formulations are optically clear, others are opaque, others are colored, black, white or gray.
  • silane-based comonomers (d) if such are used, or alternatively, further silanes can be used as adhesion promoters which are not functionalized into the inventive ones by polymerization (Co) polymers (A) are incorporated.
  • silanes that can be used for the purposes of this invention are, without wishing to restrict themselves, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriethoxysilane, octo-butyltriethoxysilane, octo-butyltriethoxysilane, octo-butyltriethoxysilane, octo-butyltriethoxysilane, octo-butyltriethoxysilane, octo-butyltriethoxysilane, octo-butyltriethoxysilane, octo-butyltriethoxysilane
  • silyl-functionalized oligomers or polymers which can be used according to the invention is polyethylene glycol which is linked to a trimethoxysilane group.
  • silanes which carry at least one functionalization are vinyltrimethoxysilane, vinyltriethoxysilane, vinyl-tri (2-methoxyethoxy) -silane,
  • Vinyltriisopropoxysilane vinyldimethoxymethylsilane, vinyltriacetoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) - ethyltriethoxysilane, 3-glycidyloxypropylsilanoxymane
  • crosslinkers examples include latently reactive diamines or multifunctional amines, dicarboxylic acids or multifunctional carboxylic acids, difunctional acid anhydrides or multifunctional acid anhydrides, primary dithiols or multifunctional primary thiols.
  • Particularly advantageous with regard to latency are those reactants which are solid at room temperature and not soluble in the polymer according to the invention or a mixture containing this polymer in the non-softened state but soluble in the softened state or both melts are miscible with one another.
  • Others are very preferred
  • crosslinkers are essentially absent.
  • the adhesives particularly preferably contain less than 0.5% by weight, preferably less than 0.2% by weight, very particularly preferably less than 0.01% by weight, based on the total weight of the adhesive, of another of ( B) different crosslinker.
  • Initiators / hardeners that are encapsulated or deactivated on the surface and chemically blocked and that are distributed and / or activated and / or loosen and / or unblocked in the film matrix under the influence of heat and can then lead to a reaction are also conceivable.
  • filler particles their structure can preferably be spherical, rod-shaped or platelet-shaped.
  • Separated particles often also called primary particles, are in accordance with the invention, as are aggregates formed from a plurality of primary particles. Such systems often show a fractal superstructure. If the particles are formed from crystallites, then the primary particle shape depends on the type of crystal lattice. Platelet-shaped systems can also be in the form of layer stacks. If fillers are used, then typically up to 50% by weight.
  • fillers are contained which are preferably selected from aerosils, silicas, silicas, dyes, pigments, carbon blacks, functionalized fillers, chalks, titanium dioxide, microballoons, nanoscale fillers or mixtures thereof. These are preferably contained in up to 50% by weight, more preferably 0.1 to 25% by weight, particularly preferably 0.5 to 10% by weight.
  • one type of filler is present in the adhesive essentially in the form of singular spherical particles, ie preferably in a proportion of more than 95%, more preferably more than 98%, most preferably more than 99%.
  • the particle diameters then have values of less than 500 nm, preferably less than 100 nm, very preferably less than 25 nm.
  • the at least one functionalized type of filler is present in the adhesive essentially in the form of singular platelet-shaped particles.
  • the layer thickness of such platelets then has values of preferably less than 10 nm and a largest diameter of preferably less than 1000 nm.
  • the at least one type of filler in the adhesive is essentially in the form of singular, rod-shaped particles.
  • these rods have a diameter of less than 100 nm and a length of less than 15 miti.
  • the rods can also be curved and / or flexible.
  • the at least one type of filler it is advantageously possible for the at least one type of filler to be present in the adhesive in the form of primary particle aggregates.
  • These aggregates have a radius of gyration (to be understood analogously to the term “radius of gyration” known from polymers) of less than 1000 nm, preferably less than 250 nm.
  • it is particularly preferred to use those filler particles whose spatial extent in at least one direction is less than 250 nm, preferably less than 100 nm, very preferably less than 50 nm to use the filler types mentioned.
  • Typical and further classes of compounds for fillers that are advantageous according to the invention are semimetal oxides of an inorganic nature, silicate-based minerals, in particular clay minerals and clays.
  • the amorphous or crystalline metal oxides which can be used according to the invention include, in particular, silicon dioxide.
  • the person skilled in the art is familiar with other systems which can also be used according to the invention. Carbonates, sulfates, hydroxides, phosphates and hydrogen phosphates are conceivable.
  • the clay minerals and clays which can be used according to the invention include, in particular, silicate systems such as serpentines, kaolins, talc, pyrophyllite, smectites such as, in particular, montmorillonite, vermiculite, lllite, mica, brittle mica, chlorite, sepiolite and palygorskite.
  • silicate systems such as serpentines, kaolins, talc, pyrophyllite, smectites such as, in particular, montmorillonite, vermiculite, lllite, mica, brittle mica, chlorite, sepiolite and palygorskite.
  • synthetic clay minerals such as hectorite and their related systems such as.
  • B. Laponite® from Laporte and Fluorhectorite and their related systems such.
  • B. Somasif® from Co-Op can be used according to the invention.
  • Filler particles can be functionalized on their surface, made hydrophobic or hydrophilic. Functionalization by means of compounds with aliphatic epoxide groups which can take part in the curing reaction is particularly advantageous.
  • the fillers do not have to be mandatory; the adhesive can, if appropriate, also function without these being added individually or in any combination. Also Among the optional fillers, those are selected which, before the initiation of the curing process, have essentially no or in particular no reaction with glycidyl or epoxy functionalities or which initiate or catalyze reactions of glycidyl or epoxy functionalities or the reaction with glycidyl or epoxy - functionalities are otherwise prevented.
  • At least one compound (E) containing glycidyl groups is additionally used in the adhesive.
  • (Co) polymers (E1) containing glycidyl ether groups and / or other glycidyl ethers or glycidyl ether-based compounds (E2) are particularly preferred.
  • (Co) polymers (E1) containing glycidyl ether groups can be obtained analogously to the (co) polymers (A) described above; only the monomer (a) is replaced by a monomer (e) containing glycidyl ether groups or by a Glycidyl ether group-containing monomers added. Glycidyl acrylate or glycidyl methacrylate are particularly preferred. All preferred embodiments for the (co) polymer (A) described above with regard to the monomers (b), (c) and (d) and the properties of the (co) polymer such as, for example, the weight-average molar mass, are preferred as described for (A) above .
  • This is typically at least 10,000 g / mol, preferably at least 20,000 g / mol and preferably at most 5,000,000 g / mol, preferably 2,000,000 g / mol and preferably at most 200,000 g / mol, most preferably at most 100,000 g / mol. It is advantageous if the proportion of comonomer (e) in the copolymer (E1) is not too high. A proportion of at most 5% by weight, even more preferably of at most 2% by weight, is preferred.
  • Preferred glycidyl ethers (E2) are at least difunctional or tri-, tetra or higher functional in relation to the glycidyl ether groups contained in the compound and have a molecular weight of 58 to below 5000 g / mol, preferably 58 to 1000 g / mol .
  • diglycidyl ethers of a polyoxyalkylene glycol or glycidyl ether monomers are suitable.
  • Examples are the glycidyl ethers of polyhydric phenols made by reacting a polyhydric phenol with an excess of chlorohydrin, such as Epichlorohydrin (e.g. the diglycidyl ether of 2,2-bis- (2,3-epoxypropoxyphenol) propane).
  • tetrahydrophthalic acid diglycidyl ester and derivatives hexahydrophthalic acid diglycidyl ester and derivatives, 1,2-ethane diglycidyl ether and derivatives, 1,3-propane diglycidyl ether and derivatives, 1,4-butane diol, diglycidyl ether and derivatives, higher ethyl alcohol diglycidyl ether and derivatives, higher 1, 4,5-alkydiglycidyl ether and alkydiglycidyl derivatives and derivatives, bis [1-ethyl (3-oxetanyl) methyl) ether and derivatives, pentaerythritol tetraglycidyl ether and derivatives, bisphenol A diglycidyl ether (DGEBA), hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol F Diglycidyl ethers, epoxyphenol novolaks
  • DGEBA digly
  • the invention also relates to a latent reactive adhesive tape.
  • Adhesives based on formulations according to the first aspect of the present invention which contain (co) polymers (A) according to the invention are particularly suitable for use in the form of reactive adhesive tapes which contain this adhesive system, preferably at least one layer thereof.
  • the layer thickness of the at least one layer of a curable adhesive composition of the invention in such reactive adhesive tapes is typically between at least 5 ⁇ m and at most 1000 ⁇ m, preferably between at least 10 ⁇ m and at most 500 ⁇ m, very advantageously between 20 ⁇ m and 250 ⁇ m.
  • Useful layer thicknesses are 30 pm, 50 pm, 75 pm, 100 pm, 125 pm, 150 pm and 200 pm (in each case within the usual error tolerances).
  • the reactive adhesive tapes are, in particular, double-sided adhesive products, even if single-sided adhesive products are also possible.
  • Such adhesive products comprising at least one layer of a curable adhesive composition of the invention are used in the simplest case in single-layer form (so that the curable adhesive layer and the reactive adhesive tape are identical), applied to a removable (temporary) carrier material.
  • All release films and papers known to the person skilled in the art, which are known from the prior art and are provided with a release layer on one or both sides, are suitable as temporary carrier material. Suitable siliconized papers and siliconized polyester films are preferred. Papers can also be coated on one or both sides with polyethylene or polypropylene.
  • a temporary carrier material is not part of the bonded composite. It is removed from the reactive adhesive tape before the substrates are bonded.
  • the reactive adhesive layer itself is not pressure-sensitively adhesive, then slightly pressure-sensitive adhesive films known to the person skilled in the art can also be used as the temporary carrier material.
  • Reactive adhesive tapes comprising at least one layer of a curable adhesive composition of the invention can also contain a further carrier material which is part of the composite even after bonding (permanent carrier).
  • a further carrier material which is part of the composite even after bonding (permanent carrier).
  • the surfaces of these carrier materials can each be pretreated chemically (primer, plasma) and / or physically (corona, flame, plasma) independently of one another in such a way that particularly good anchoring of the hardenable adhesive film layer on the carrier material can be achieved.
  • the adhesive can also be physically pretreated (corona, flame, plasma).
  • Nonwovens are preferred.
  • flat structures made of individual fibers are used as the carrier fleece. All nonwovens defined in accordance with the DIN EN 29092 standard can be used.
  • the fleece consists of loosely combined fibers that are not yet connected to one another. The strength results from the fiber's own adhesion.
  • a distinction is also made between consolidated and non-consolidated nonwovens. The fibers are randomly distributed. The nonwovens can be differentiated according to the fiber materials.
  • Mineral fibers such as glass, mineral wool or Basalt, animal fibers such as silk or wool, vegetable fibers such as cotton, cellulose, chemical fibers such as polyamide, polypropylene, polyphenylene sulfide, polyacrylonitrile, polyimide, polytetrafluoroethylene, aramid or polyester, or mixtures of the aforementioned substances can be used.
  • the fibers can be solidified mechanically by needling or water jets, chemically by adding binders or thermally by softening them in a suitable gas flow, between heated rollers or in a steam flow.
  • cellulose-based nonwovens are used.
  • the weight per unit area of the nonwovens is preferably between 4 and 100 g / m 2 , particularly preferably between 10 and 70 g / m 2 .
  • Such nonwovens are commercially available, for example, from Glatfelter.
  • the thickness of these nonwovens is preferably between 20 and 100 ⁇ m, extremely preferably between 30 and 60 ⁇ m.
  • Reactive adhesive tapes with permanent backing can have curable adhesive layers of different thicknesses and / or preferably curable adhesive layers of different types on the top and bottom. If different curable adhesive layers are used, then in particular both meet the statements relating to curable adhesives according to the invention.
  • Reactive adhesive tapes comprising at least one layer of a curable adhesive composition of the invention can also be used in two-layer or multi-layer form and without a permanent carrier.
  • the uppermost and very preferably also the lowermost layer are preferably a layer of curable adhesive according to the invention, it being possible for these to be different with regard to thickness and / or type. If different curable adhesive film layers are used, then preferably both meet the statements relating to curable adhesives according to the invention.
  • embodiments are in principle also possible which have the curable adhesive composition of the invention on the upper side have and on the underside a layer of another adhesive, such as, for example, a pressure-sensitive adhesive or a hot-melt adhesive.
  • Multi-layer reactive adhesive tapes containing permanent backing can have thicknesses of 10 ⁇ m to 1000 ⁇ m, preferably 50 ⁇ m to 500 ⁇ m, particularly preferably 100 ⁇ m to 250 ⁇ m.
  • the reactive adhesive tape can be made up in web form, for example as roll goods, as sheet goods or as a die cut and thus used to build up the bonded composite consisting of bonded substrate (I), reactive adhesive tape and bonded substrate (II).
  • the reactive adhesive tapes are preferably not pressure-sensitive adhesive at room temperature, since the material can thus be made up (e.g. punched) and made available for the further processing process very advantageously even without a temporary carrier.
  • a pressure-sensitively adhesive configuration is also conceivable and advantageous, since in such a case it can be (pre) laminated to the substrates and / or components to be joined without heat.
  • part of the invention also includes bonded assemblies comprising a first substrate, a second substrate and, arranged between them, a reactive adhesive tape according to the invention.
  • the reactive adhesive tape is present in the composite in the cured state.
  • a preferred method for producing such composites using reactive adhesive tapes according to the invention is listed as an example.
  • a die cut of the reactive adhesive tape without a temporary carrier is positioned manually, for example with the help of tweezers, on the first component (substrate (I)) or between the components to be joined (substrate (I) and substrate (II)).
  • the die-cut of the reactive adhesive tape is treated with a heat source after it has been positioned on the first component, which increases the adhesion of the die-cut to the first component. This happens at the lamination temperature.
  • an IR radiator, an iron or a heating plate for example, can be used as the heat source.
  • the die-cut is also equipped with a temporary carrier material in order to prevent the adhesive film from sticking to the tool or the heat source.
  • the first component is placed on the die cut of the reactive adhesive tape. The placement takes place on the open side.
  • the temporary carrier material is still on the back.
  • a heat source then introduces heat through the first component into the reactive adhesive tape. This takes place at the lamination temperature.
  • the adhesive film becomes tacky, ie (adhesive) sticky, and adheres more strongly to the first component than to the temporary carrier. It is advantageously heated by the first component.
  • a heating press is used to introduce the heat.
  • the stamp of the heating press is made of aluminum, brass or bronze, for example, and its shape is usually adapted to the contours of the component or the dimensions of the die cut.
  • molded parts are generally used which are adapted to the contours of the components to be bonded, thereby preventing slippage.
  • the exact positioning between the die cut and the first component can be ensured by means of guide pins in the molded part and corresponding guide holes in the temporary carrier material of the reactive adhesive tape. Other positioning options are conceivable.
  • the first component with the laminated adhesive film is removed from the molded part. The entire process can also be converted into an automatic process.
  • the method for producing a composite according to the invention therefore also relates to the method for bonding two substrates by means of a latent reactive adhesive tape according to the present invention, characterized by performing at least the following method steps: a) fixing a first substrate to be bonded, preferably on a holder; b) placing the latent reactive adhesive tape on the first substrate to be bonded; c) optionally heating to a first temperature above room temperature to 150 ° C, preferably at least 50 ° C and at most 120 ° C, very preferably at most 100 ° C and applying a first pressure, preferably 0.1 to 10 bar, to prefix the latent reactive adhesive tape on the first substrate to be bonded; d) applying a second substrate to be bonded to the intermediate product obtained after step b) or c); e) (Post) crosslinking by heating to a second temperature above room temperature, preferably at least 120 ° C and below 250 ° C, more preferably at least 150 ° C and at most 220 ° C, and applying a second pressure
  • step e pressure and temperature are applied.
  • This temperature is the activation temperature / crosslinking temperature.
  • This is done using a heating stamp made of a material with good thermal conductivity.
  • Advantageous materials are, for example, copper, brass, bronze or aluminum. However, other metals or alloys can also be used.
  • the hot press ram should preferably take the shape of the top of the one component. This shape can in turn be of a 2-dimensional or 3-dimensional nature.
  • the pressure is advantageously applied via a pneumatic cylinder. However, the application does not necessarily have to take place via air pressure. Hydraulic pressing devices or electromechanical actuators, for example via spindles, are also possible.
  • the hot press rams do not all have to be operated at the same temperature and / or the same pressure.
  • the contact times of the stamps can also be selected differently.
  • Part of the present invention is also a curable 2-component adhesive which has a first, preferably flowable, component comprising or consisting of the following constituents: at least one (co) polymer (A) functionalized with aliphatic epoxy groups and having a weight average molecular weight in the range from 5,000 g / mol to 5,000,000 g / mol, optionally at least one matrix polymer as film former (C), which is different from (A) and (E), optionally at least one additive (D), and optionally at least one glycidyl ether-containing compound (E), which is different from (A) to (D), the (co) polymer (A) functionalized with aliphatic epoxide groups in particular with a or more than one cycloaliphatic epoxide group is functionalized; and a second, preferably flowable component, spatially separated therefrom, comprising or consisting of the following constituents: at least one thiocyanate salt (B) and optionally at least one additive (D), comprising
  • constituents (A) and (E) in the first component enables an advantageous “dual-cure system” to be implemented, which is also part of the present invention. If a first component designed in this way is mixed with the second component, then a curing reaction takes place spontaneously with the participation of part of the hardener (B) from the second component and the compounds (E) containing glycidyl ether groups. This leads to a rapid increase in the cohesion of the curing adhesive, which reduces the squeezing tendency of the adhesive system, which is initially still flowable, and increases the internal strength.
  • the present invention further relates to a method for bonding two substrates by means of a curable 2-component adhesive according to the present invention, characterized by performing at least the following method steps: a) fixing a first substrate to be bonded, preferably on a holder; b) applying and mixing the two flowable components of the curable 2-component adhesive on the first substrate to be bonded; c) attaching a second substrate to be glued to the intermediate product obtained after step b); d) heating to a temperature from room temperature to 250 ° C., preferably below 220 ° C., preferably at most 150 ° C., very preferably below 100 ° C., a pressure preferably 0.1 to 10 bar, in order to postcrosslink and obtain a composite and e) optionally removing the bonded assembly, in particular from the holder.
  • Adhesives according to the invention preferably meet the requirements with regard to initial ejection resistance and squeezing tendency at least within the scope of the values given in the left column of values, more preferably those of the values given with preference: Table 1: Required profile of requirements
  • the push-out test enables statements to be made about the bond strength of an adhesive product in the direction of the normal to the adhesive layer.
  • a test specimen is produced from the aforementioned three components by pre-laminating the adhesive product with the free surface precisely onto the substrate (1) on the substrate (1) (at 70 ° C for 15 s). Then the temporary carrier is removed and this composite with the now exposed side of the adhesive product is pre-laminated concentrically on the substrate 2 (also at 70 ° C for 15 s), i.e. in such a way that the circular recess of the substrate 2 is exactly in the middle above the circular first substrate 1 is arranged (bonding area thus 282 mm 2 ). Care is taken to ensure that the total time of exposure to temperature (70 ° C) in the pre-lamination process does not exceed 30 s. The entire composite is then pressed under the action of pressure and temperature for 30 s at 180 ° C. and 10 bar, the test specimen being produced.
  • test specimens After pressing, the test specimens are stored for 24 hours at 23 ° C. and 50% relative humidity (RH) (standard test climate).
  • RH relative humidity
  • the testing is carried out as follows ( Figure 1): A tensile testing machine is equipped with a cylindrical punch (steel, diameter 7 mm) and the test specimen is clamped into a holder of the tensile testing machine via substrate (2), so that substrate (1) can only be glued through is held and can be detached by applying sufficient pressure by loosening the bond. The sample is fixed in such a way that any possible bending of the substrate (2) as a result of the force applied during the test is minimized.
  • the cylindrical punch is used to push through the hole in the substrate (2) vertically (i.e. parallel to the normal vector of the adhesive product surface) and centrically on the exposed surface of the adhesive product at a constant speed of 10 mm / s, the tests take place in the standard test climate ( 23 ° C at 50% RH).
  • That force is absorbed at which the bond fails and substrate (1) is detached from substrate (2) (detachment of the adhesive connection, recognizable by a sudden drop in force).
  • the force is given in N or standardized to the bond area (N / mm 2 or MPa). The arithmetic mean of three individual tests is calculated.
  • test specimens are prepared and tested in the same way as the push-out test (i), but after pressing the test specimens are stored for 24 h at 23 ° C and 50% relative humidity (RH) (standard test climate) and then upright (on one of the 40 mm long sides of the base plate) were subjected to moist and warm storage (72 h at 85 ° C and 85% RH) and reconditioned again for 24 h at 23 ° C and 50% RH before testing.
  • RH relative humidity
  • Dynamic differential calorimetry (Differential Scanning Calorimetry, DSC) is carried out in accordance with DIN 53765 and DIN 53765: 1994-03. Heating curves run at a heating rate of 10 K / min. The samples are measured in aluminum crucibles with a perforated lid and a nitrogen atmosphere. The first heating curve is from -100 ° C to +180 ° C, the second heating curve from +20 ° C to +250 ° C. Both heating curves are evaluated. The exotherm / enthalpy is evaluated by integrating the reaction peak.
  • Molecular weights are determined according to the invention by gel permeation chromatography on 100 ⁇ L clear-filtered sample (sample concentration 1.5 g / L). Tetrahydrofuran with 0.1% by volume of trifluoroacetic acid is used as the eluent, and 200 ppm (m / V) toluene as the internal standard. The measurement takes place at 25 ° C.
  • a column type PSS-SDV, 10 ⁇ m, ID 8.0 mm ⁇ 50 mm (details here and below in the order: type, particle size, internal diameter c length) is used as the guard column.
  • a column of the type PSS-SDV, 10 ⁇ m linear one, ID 8.0 mm ⁇ 300 mm is used for separation (columns and detector from Polymer Standards Service; detection by means of detector PSS-SECcurity 1260 RID).
  • the flow rate is 0.5 mL per minute.
  • the calibration is carried out with polystyrene standards in the separation area of the column and converted universally into a polymethyl methacrylate calibration using the well-known Mark Houwink coefficients a and K.
  • the reaction is initiated with 2 g of 2,2-azobis (2,4-dimethylvaleronitrile) (CAS 4419-11 -8) dissolved in 4 g of MEK. 1 h, 2 h, 3 h after the first addition of initiator 2 g in each case of 2,2-azobis (2,4-dimethylvaleronitrile) dissolved in 4 g of MEK and 100 g of 3,4-epoxycyclohexyl methacrylate were added to the reaction. 22 hours after the addition of the first initiator, the reaction is terminated and the polymer solution is cooled to room temperature.
  • the formulation is homogenized using a roller mixer and coated using a suitable laboratory coating table with a comma to a dry film thickness of 100 ⁇ m on a suitable release paper. After 20 minutes of storage in the digestive room, the reactive adhesive film is dried for 30 minutes at 50 ° C. in a suitable circulating air drying cabinet.
  • the film is measured using the push-out method (i) and then at room temperature (23 ° C, 50% RH) or 40 ° C in a suitable drying cabinet stored. To demonstrate the latency, the push-out measurement (i) is repeated after 8 and 16 weeks of storage. The results are shown in Figure 3.
  • the formulation is homogenized using a roller mixer and coated on a suitable release paper using a commercially available laboratory coating table with comma marks to a dry film thickness of 100 miti. After 20 minutes of storage in the digestive room, the reactive adhesive film is dried for 30 minutes at 50 ° C. in a suitable circulating air drying cabinet.
  • the film is measured using the push-out method (ii) and then stored at 40 ° C. in a suitable drying cabinet. To demonstrate the latency, the push-out measurement (ii) is repeated after 4 and 9 weeks of storage.
  • Ammonium thiocyanate heats up the mixture and reacts in an uncontrolled exothermic manner.
  • the formulation is homogenized using a roller mixer and applied using a suitable laboratory coating table with comma marks to a dry film thickness of 100 ⁇ m suitable release paper coated. After 20 minutes of storage in the digestive room, the reactive adhesive film is dried for 30 minutes at 50 ° C. in a suitable circulating air drying cabinet. No hardener (B) was added.
  • the film is measured using the push-out method (ii).
  • Example 1 dry matter
  • Desmomelt 530 dry matter, 25% by weight in MEK, Covestro
  • Dynasylan GLYEO from Evonik Industries AG
  • K -Pure CXC 1614 dry matter, 5% by weight dissolved in MEK; King Industries Inc .; a hardener for epoxy formulations known from the prior art
  • the formulation is homogenized using a roller mixer and coated on a suitable release paper to a dry film thickness of 100 ⁇ m using a commercially available laboratory coating table with comma marks. After 20 minutes of storage in the digestive room, the reactive adhesive film is dried for 30 minutes at 50 ° C. in a suitable circulating air drying cabinet. After 24 hours of storage at room temperature (23 ° C., 50% relative humidity), the film is measured using the push-out method (ii) and then stored at 40 ° C. in a suitable drying cabinet. To demonstrate the latency, the push-out measurement (ii) is repeated after 4 weeks of storage.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne : un composé adhésif thermodurcissable basé sur un (co)polymère fonctionnalisé avec au moins un époxyde aliphatique ; une bande adhésive réactive latente qui contient le composé adhésif thermodurcissable ; un procédé pour lier deux substrats au moyen de la bande adhésive réactive latente ; un composé adhésif à deux composants durcissable sur la base d'un (co)polymère fonctionnalisé avec au moins un époxyde aliphatique ; et un procédé de liaison de deux substrats au moyen du composé adhésif à deux composants durcissable. L'invention concerne également un composé adhésif durci thermiquement obtenu par durcissement thermique du composé adhésif thermodurcissable de la présente invention ou du composé adhésif à deux composants durcissable de la présente invention.
PCT/EP2020/077489 2019-10-16 2020-10-01 Composé adhésif durcissable sur lequel sont basées des bandes adhésives réactives Ceased WO2021073883A1 (fr)

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