MULTICOMPONENT SYSTEM, AND METHOD FOR PRODUCING A MULTICOMPONENT SYSTEM

Abstract

A multicomponent system contains at least one first substance and at least one second substance. The multicomponent system can be activated, and the first substance and the second substance are provided in multiple portions, where the first portions are formed with at least one first functional group and are provided with a first linker, and the second portions are formed with at least one second functional group and are provided with a second linker. The first functional group reacts with the second functional group via a specified interaction which connects the two groups together, and the distance between the functional groups and the respective portions is tuned by the respective linker.

Claims

1: A multi-component system comprising at least one first substance and at least one second substance, wherein the multi-component system can be activated, wherein the at least one first substance and the at least one second substance are present in a plurality of portions of substance, wherein first portions of substance are formed with at least one first functional group and are provided with a first linker, and wherein second portions of substance are formed with at least one second functional group and are provided with a second linker, wherein the at least one first functional group reacts with and binds to the at least one second functional group via a predefined interaction, and wherein a distance of the at least one first functional group and the at least one second functional group to the respective portion of substance is tuned by the respective linker (L).

2. The multi-component system according to claim 1, wherein the first linker is longer than the second linker or vice versa.

3. The multi-component system according to claim 1, wherein the first portions of substance are connected or connectable to a larger number of portions of substance than the second portions of substance, or vice versa.

4: The multi-component system according to claim 1, wherein the at least one first functional group and the at least one second functional group are homogeneously or heterogeneously formed.

5: The multi-component system according to claim 1, wherein the first portions of substance have a substantially identical size and/or that the second portions of substance have a substantially identical size.

6: The multi-component system according to claim 1, wherein the first portions of substance and the second portions of substance have a different size.

7: The multi-component system according to claim 1, wherein the multi-component system has a network structure with interstices, wherein the network structure is formed by portions of the first substance, and at least one portion of the second substance is arranged in each of the interspaces, at least in sections of the network structure.

8. The multi-component system according to claim 1, wherein a portion of substance of the first substance and/or of the second substance is arranged in a capsule.

9: The multi-component system according to claim 8, wherein a capsule of the first substance has a different size than a capsule of the second substance.

10: The multi-component system according to claim 8, wherein capsules of the first substance have an identical size.

11: The multi-component system according to claim 1, wherein activation of the multi-component system is effected by at least one change of pressure, pH, UV radiation, osmosis, temperature, light intensity, and/or humidity.

12: The multi-component system according to claim 1, wherein the first substance and the second substance are components of a multi-component adhesive.

13: A method of preparing a multi-component system comprising at least one first substance and at least one second substance, the at least one first substance and the at least one second substance being present in a plurality of portions of substance, wherein the multi-component system can be activated, the method comprising: forming first portions of substance, with at least one first functional group and provided with a first linker, forming second portions of substance, with at least one second functional group and provided with a second linker, reacting the at least one first functional group via a predefined interaction with the at least one second functional group so that they are bound together, and wherein a distance of the at least one first functional group and the at least one second functional group to the respective portion of substance is tuned by the respective linker.

14: The method according to claim 13, wherein the first portions of substance are formed with at least one third functional group and are provided with a third link, wherein the at least one third functional group comprises at least one protective group in each case, so that only correspondingly functionalized portions of substance of the first substance can bind to portions of substance of the first substance, and wherein the method further comprises at least removing the protective groups that are initially present, only when the first portions of substance are to be linked to each other by the at least one third functional group.

15. (canceled)

16: The multi-component system according to claim 8, wherein the portion of substance of the first substance and/or of the second substance is arranged in a nanocapsule and/or a microcapsule.

17: The multi-component system according to claim 9, wherein the capsule of the first substance is larger than the capsule of the second substance.

18: The multi-component system according to claim 12, wherein the first substance and the second substance are components of a two-component adhesive.

Description

[0104] This principle can also be applied to paints, varnishes and many other materials. Further details and advantages of the invention will now be explained with reference to an embodiment shown in more detail in the drawings.

[0105] The following is shown:

[0106] FIG. 1 an embodiment of a multi-component system according to the invention with a first substance and a second substance;

[0107] FIG. 2 a further embodiment of a multi-component system according to the invention with a first substance and a second substance;

[0108] FIG. 3 a further embodiment of a multi-component system according to the invention as shown in FIG. 1 or FIG. 2;

[0109] FIG. 4 a further embodiment of a multi-component system according to the invention as shown in FIG. 1, FIG. 2 or FIG. 3;

[0110] FIG. 5 an embodiment of an inter-crosslinking of two different portions of substance/capsule population according to the invention;

[0111] FIG. 6 an example of an intra-crosslinking of two identical portions of substance/capsule population according to the invention;

[0112] FIG. 7 an embodiment of a two-component system according to the invention;

[0113] FIG. 8 an embodiment of an intra-crosslinked capsule system according to the invention:

[0114] FIG. 9 an embodiment of an inter- and intra-crosslinked two-component system according to the invention as shown in FIG. 7;

[0115] FIG. 10 a flowchart of the workflow of manufacturing a two-component adhesive tape according to the present invention;

[0116] FIG. 11A an embodiment of intra-crosslinked capsules of a one-component system according to the present invention;

[0117] FIG. 11B an embodiment of intra-crosslinked capsules of a one-component system and non-crosslinked gas-filled capsules according to the present invention;

[0118] FIG. 12A an embodiment of inter- and intra-crosslinked capsules of a two-component system according to the present invention;

[0119] FIG. 12B a schematic representation of inter- and intra-crosslinked capsules of a multi-component system and non-crosslinked gas-filled capsules according to the present invention;

[0120] FIG. 13 an illustration of microcapsule binding ratios in a two-component system according to the present invention; and

[0121] FIG. 14 an illustration of the binding of microcapsules according to the invention with the same size but with a different functionalization.

[0122] FIG. 1 shows an embodiment of a multi-component system according to the invention with a first substance and a second substance.

[0123] According to this embodiment, the multi-component system can be activated.

[0124] It is possible that the first substance and the second substance are present in multiple portions of substance.

[0125] According to this embodiment, the first substance is present in a capsule population K1.

[0126] In other words, According to this embodiment, the first portions of substance are first capsules K1.

[0127] According to this embodiment, the second substance is present in a capsule population K2.

[0128] In other words, According to this embodiment, the second portions of substance are second capsules K2.

[0129] Generally, it is possible that a portion of substance of the first substance and/or the second substance is arranged in a capsule K, in particular a nanocapsule and/or microcapsule.

[0130] Thereby, the portion of substance forms a core C (also called core) in K1 and K2, respectively, which is surrounded by a capsule shell S (also called shell). This is therefore a “core-shell” construct. In principle, however, core-shell-shell constructs are also conceivable.

[0131] According to this embodiment, the first portions of substance are formed with at least one first functional group R2 and are provided with a first linker L1.

[0132] According to this embodiment, the second portions of substance are formed with at least one second functional group R21 and provided with a second linker L2.

[0133] According to this embodiment, the first functional group R2 reacts with the second functional group R21 via a predefined interaction and binds them together.

[0134] According to this embodiment, the distance of the functional groups to the respective portion of the substance is tuned by the respective linker L.

[0135] The capsules shown in FIGS. 2-6 are identical in construction to the capsules K1 and K2 shown in FIG. 1.

[0136] According to this embodiment, the first portions of substance are formed with at least one first functional group R2 and are provided with a first linker L1.

[0137] According to this embodiment, the second portions of substance are formed with at least one second functional group R21 and provided with a second linker L2.

[0138] According to this embodiment, the first functional group R2 reacts with and the second functional group R21 via a predefined interaction and binds them together.

[0139] According to this embodiment, the distance of the functional groups to the respective portion of the substance is tuned by the respective linker L.

[0140] It is possible that the first linker L1 is longer than the second linker L2, cf. FIG. 2.

[0141] Alternatively, it is possible that the second linker L2 is longer than the first linker L1.

[0142] Alternatively, it is possible that both linkers L1 and L2 are of equal length.

[0143] FIG. 3 shows an embodiment of a multi-component system according to the invention as shown in FIG. 1 or FIG. 2.

[0144] According to this embodiment, the first portions of substance and the second portions of substance are different.

[0145] In other words, According to this embodiment, the capsules K1 of the first capsule population are different from the capsules K2 of the second capsule population.

[0146] According to this embodiment, the first portions of substance are connected or connectable to a larger number of portions of substance than the second portions of substance.

[0147] In other words, According to this embodiment, the capsules K1 are connected or connectable to a greater number of capsules K than the capsules K2.

[0148] Alternatively, it is possible that the second portions of substance are connected or connectable to a greater number of portions of substance than the first portions of substance.

[0149] In other words, it is possible that the capsules K2 are connected or connectable to a greater number of capsules K than the capsules K1.

[0150] FIG. 4 shows a further embodiment of a multi-component system according to the invention as shown in FIG. 1, FIG. 2, or FIG. 3.

[0151] According to this embodiment, the first portions of substance and the second portions of substance have substantially different sizes.

[0152] According to this embodiment, the first capsules K1 have a substantially larger size than the second capsules K2.

[0153] Generally, a capsule K1 of a first substance may have a different size than a capsule K2 of a second substance, in particular wherein the capsule K1 of the first substance is larger than the capsule K2 of the second substance.

[0154] Alternatively, it is possible for the second portions of substance to have a substantially larger size than the first portions of substance.

[0155] Alternatively, it is possible for the first portions of substance and the second portions of substance to have a substantially identical size.

[0156] It is not shown that the first portions of substance may have a substantially identical size and/or that the second portions of substance may have a substantially identical size.

[0157] FIG. 5 shows an embodiment of an inter-crosslinking of two different portions of substance according to the invention.

[0158] According to this embodiment, a capsule K1 and a capsule K2 are inter-crosslinked.

[0159] According to this embodiment, a capsule K1 and a capsule K2 are inter-crosslinked via functional groups R2 and R21.

[0160] FIG. 6 shows an embodiment of an intra-crosslinking of two equal portions of substance according to the invention.

[0161] According to this embodiment, two capsules K1 are intra-crosslinked.

[0162] According to this embodiment, the two capsules K1 are intra-crosslinked via the functional groups R2-R2.

[0163] FIG. 7 shows an embodiment of a two-component system according to the invention.

[0164] According to this embodiment, the two-component system is a two-component microcapsule system.

[0165] According to this embodiment, the two-component system is a two-component microcapsule system that has not yet reacted with each other via a predefined interaction.

[0166] In particular, two different capsule populations K1 and K2 are shown, wherein a first substance is contained in the first capsule K1 and a second substance is contained in the second capsule K2.

[0167] The capsules K1 and K2 shown are exemplary of a plurality of capsules K1 and K2, e.g. to be referred to as capsule populations.

[0168] According to this embodiment, the first substance contained in the one capsule K1 is a first adhesive component.

[0169] According to this embodiment, the second substance contained in the second capsule K2 is a second adhesive component.

[0170] In other words, the first substance and the second substance are components of a multi-component adhesive, in particular a two-component adhesive.

[0171] It is generally possible that the two different capsule populations K1 and K2 were produced in separate batch reactors.

[0172] The K1 and K2 capsules of the two capsule populations are functionalized.

[0173] The first capsules K1 were formed with two different linkers L1 and L3 of different length and with different functional groups R1 and R2 on the surface (surface functionalization).

[0174] In other words, the functional groups R are heterogeneously formed.

[0175] In an alternative embodiment, it is possible that the functional groups R are homogeneously formed.

[0176] The second capsules K2 were formed with the linker L2 and with the functional group R21.

[0177] The functional group R21 of the second capsule K2 reacts covalently with the functional group R2 of the first capsule K1.

[0178] According to this embodiment, it is possible that the first capsules K1 are connected or connectable to a greater number of capsules K than the second capsules K2.

[0179] In an alternative embodiment, it is possible that the second capsules K2 are connected or connectable to a greater number of capsules K than the first capsules K1.

[0180] The linker L3 and the functional group R1 should crosslink the first capsules K1 with each other (intra-crosslinking).

[0181] Via the linker L1 and the functional group R2 and the linker L2 and the functional group R21, the capsules K2 are covalently bound to the first capsule K1 (inter-crosslinking).

[0182] By activating both capsules K1 and K2, the contents of the capsules K1 and K2 can be released, resulting in a mixing of both components.

[0183] Generally, it is possible to tuned the number of second capsules K2 which bind to the first capsules K1 by adjusting the density of the surface functionalization or the number of functional groups R2 of the first capsule K1.

[0184] In general, two reactive substances can be separately encapsulated in the capsules K1 and K2 and bound in a specific ratio via, inter alia, covalently (e.g. click chemistry), by weak interaction, biochemically (e.g. biotin-streptavidin) or by other means.

[0185] It is generally possible for more than two different capsules Kn to encapsulate more than two different substances, e.g. reactive substances.

[0186] It is generally possible that the different capsules Kn are formed with more than two linkers Ln and with different functional groups Rn.

[0187] It is generally possible for a linker L to be any form of link between a capsule and a functional group.

[0188] It is generally possible that, in the case of heterogeneous functionalization, a functional group R can be used for binding to surfaces, fibers or textiles.

[0189] As with existing capsule systems, any conceivable substance can be introduced into the capsules K1 and/or K2 and/or Kn.

[0190] Activation of the two-component system may be accomplished by at least one of a change in pressure, pH, UV radiation, osmosis, temperature, light intensity, humidity, or the like.

[0191] In general, a two-component capsule system could be implemented in any medium.

[0192] FIG. 8 shows an embodiment of an intra-crosslinked capsule system according to the invention.

[0193] According to this embodiment, the intra-crosslinked capsule system according to the invention is an intra-crosslinked microcapsule system.

[0194] A single component system is shown.

[0195] A capsule population K1 is shown.

[0196] The capsules K1 are filled with a substance.

[0197] According to this embodiment, the capsules K1 are filled with an adhesive.

[0198] According to this embodiment, the capsules K1 are filled with a one-component adhesive.

[0199] Alternatively, the capsules K1 may be filled with any conceivable gaseous, solid, viscous and/or liquid substance.

[0200] Alternatively, the capsules K1 may be filled with living organisms and/or viruses.

[0201] The capsules K1 were functionalized.

[0202] The capsules K1 were provided with linkers L3.

[0203] It is not shown that capsules K1 are formed with functional groups R1 (on linker L3).

[0204] The linkers L3 crosslink the capsules K1 with each other (intra-crosslinking).

[0205] The distance between the capsules K1 can be tuned by the length of the linker L3.

[0206] The degree of intra-crosslinking of the capsules K1 can be tuned depending on the density of the surface functionalization R1.

[0207] The length of the linker L3 has to be chosen in such a way that the radius of the content of the released liquid of the capsules K1 slightly overlaps with the content of the adjacent capsules K1 in order to ensure cross-linking.

[0208] For a higher viscosity environmental medium (such as an adhesive tape), the length of the linker L3 would be smaller than for a lower viscosity medium such as a paste or liquid.

[0209] FIG. 9 shows an embodiment of an inter- and intra-crosslinked two-component system according to the invention as shown in FIG. 7.

[0210] The first capsules K1 and the second capsules K2 are filled with different substances.

[0211] According to this embodiment, the capsules K1 have a substantially identical size.

[0212] According to this embodiment, the capsules K2 have a substantially identical size.

[0213] According to this embodiment, the capsules K1 and the capsules K2 have a different size.

[0214] In an alternative embodiment, it is possible that the capsules K1 and the capsules K2 have a substantially identical size.

[0215] The basic system corresponds to the illustration in FIG. 8.

[0216] Moreover, the first capsules K1 are heterogeneously formed with a linker L1.

[0217] A second capsule population K2 binds to the linker L1, cf. FIG. 1.

[0218] In other words, the two-component system has a network structure with interstices, wherein the network structure is formed by the first capsules K1, and wherein at least one capsule K2 is arranged in each of the interstices, at least in sections.

[0219] It is generally possible that the two-component capsules K1 and K2 with different contents, are introduced into the gas phase. For example, they could be used in inhalers or other drug delivery systems. The inactivated capsules reach the site of action where they are activated and the contents are released. Surfaces could also be coated with this dispersion.

[0220] It is generally possible for the two-component capsules K1 and K2 with different contents to be introduced into a paste-like medium. For example, a two-component adhesive could be used for this purpose. The paste is inert and can be processed well until the capsules are activated and react with each other. As described above, the ideal mixing ratio of the adhesives is tuned by the ratio of the first and second capsules K1 and K2.

[0221] The advantage of the ideal composition of the two-component capsule systems can also be used in liquid systems. Since both capsules K1 and K2 of the two-component capsule system are in close proximity, it is very likely that the capsules K1 and K2 react faster and more defined with each other than individually in dispersion.

[0222] FIG. 10 shows a flow diagram of the workflow of manufacturing a two-component adhesive tape according to the invention.

[0223] FIG. 10 is substantially based on a two-component capsule system as shown in FIG. 7.

[0224] Overall, the production of a two-component adhesive tape according to the invention is divided into four steps S1-S4.

[0225] In a first step S1, the first capsules K1 and the second capsules K2 are functionalized, cf. FIG. 7.

[0226] In the present two-component system, the first capsules K1 are heterogeneously formed with two linkers L1 and L3 having functional groups R1 and R2.

[0227] In a separate batch reaction, the second population of capsules K2 is functionalized with linker L2 containing the functional group R21.

[0228] The functional group R21 is to be chosen such that it reacts (covalently) with the functional group R2 of the first capsule K1 in the later reaction step.

[0229] In a second step S2, the functionalized second capsules K2 are added to the functionalized first capsules K1.

[0230] The functional groups R2 and R21 bind (covalently) to each other (inter-crosslinking).

[0231] It is generally possible that a third or any number of further capsule populations K3-Kn are also added to a first capsule population K1 and/or a second capsule population K2.

[0232] Each additional capsule population K3-Kn may in turn be functionalized with at least one functional group.

[0233] In a third step S3, the heterogeneous capsule dispersion from the preceding step S2 is introduced into the adhesive, in this case an adhesive tape B, which is still low in viscosity.

[0234] A predetermined (intra)-crosslinking reaction occurs, which is formed throughout the entire area of the adhesive tape B.

[0235] In a fourth step S4, the cross-linked two-component capsule populations are applied and the adhesive tape B is dried.

[0236] In this case, the viscosity of the adhesive tape B increases significantly, but the network remains homogeneously distributed on the adhesive tape.

[0237] It is shown that in step S1, in order to prevent the first capsules K1 from cross-linking with each other prematurely during functionalization, a protective group SG may still be formed on the functional group R1 of the linker L3.

[0238] It is further shown that in step S3, the protective groups SG are removed.

[0239] It is not shown that removal of the protecting group allows intra-crosslinking of the capsules K1.

[0240] Possible applications are in different ambient media:

[0241] Based on the workflow described herein for producing a two-component adhesive tape according to the invention, the two-component encapsulation system can alternatively be applied in other media and with any encapsulated substances.

[0242] Conceivable environmental media include gas, liquid, pasty, low and high viscosity media as well as solid surface coatings.

[0243] It is generally possible for the capsules K to be nanocapsule or microcapsules.

[0244] Generally, the method enables the preparation of further multi-component systems having at least one first substance and having at least one second substance, wherein the first substance and the second substance are present in multiple portions of substance, wherein the multi-component system can be activated, comprising the following steps: [0245] the first portions of substance are formed with at least one first functional group R2 and provided with a first linker L1, [0246] the second portions of substance are formed with at least one second functional group R21 and provided with a second linker L2, [0247] the first functional group R2 reacts via a predefined interaction with the second functional group R21 so that they are linked to each other, and [0248] the distance of the functional groups R to the respective portion of substance is tuned by the respective linker L.

[0249] It is generally possible that the first portions of substance are formed with at least one third functional group R1 and provided with a third linker L3.

[0250] It is generally possible that the third functional group R1 comprises at least one protective group SG in each case, so that only correspondingly functionalized portions of the first substance can bind to the portions of the first substance.

[0251] It is generally possible that the method further comprises at least the step of initially having the protective groups SG and removing them only when the first portions of substance are to be bonded together by means of the third functional groups R1.

[0252] It is generally possible that the functional groups R1 each have at least one protecting group, so that only correspondingly functionalized portions of the second substance can bind to the portions of the first substance.

[0253] Further, it is generally possible for the method of making a multi-component system to further comprise at least the step of initially having the protecting groups and removing them only when the first and second portions of substance are to be combined by means of the first and second functional groups R2, R21.

[0254] FIG. 11A shows a schematic diagram of intra-crosslinked capsules of a single component system in a high viscosity system according to the present invention.

[0255] According to this embodiment, the crosslinked single component system is incorporated into a high viscosity system as described in FIG. 8.

[0256] The high viscosity system is an adhesive tape B.

[0257] Alternatively, other high-viscosity, liquid, gaseous, paste-like or low-viscosity systems are conceivable.

[0258] According to this embodiment, the adhesive tape B is a single-sided adhesive tape B.

[0259] Alternatively, double-sided versions of an adhesive tape B are also possible.

[0260] Usually, there is a diffusion problem with highly viscous systems, so that the contents of the capsules K1 in the adhesive tape B do not achieve cross-linking between the two materials to be bonded.

[0261] Due to the (intra)-crosslinking of the one-component system, the spacing and the degree of crosslinking of the capsules K1 can be tuned such that the contents of the capsules K1 form a crosslinking system through the highly viscous adhesive.

[0262] This basic principle can also be extended to a two-component system as shown in FIG. 12A. Therein, the (inter- and intra-) cross-linking mechanism is used.

[0263] It is not shown that the two-component system can also be introduced into the adhesive tape only with prior inter-crosslinking of the capsules K1 and the capsules K2.

[0264] FIG. 11B shows a schematic representation of intra-crosslinked capsules of a one-component system and non-crosslinked gas-filled capsules according to the present invention.

[0265] Alternatively, the non-crosslinked capsules may be filled with solid or liquid materials.

[0266] In addition to the intra-crosslinked capsules K1 of the one-component system according to FIG. 11A, a further population of non-crosslinked gas-filled capsules KG can be introduced into the highly viscous adhesive, such as an adhesive tape B, which release the gas when bursting and thus either create free space for the liquid component of the capsules K1 or enable the adhesive tape to be removed again.

[0267] It would also be conceivable to include a dissolvable placeholder (e.g., fibers or the like) in the adhesive tape B.

[0268] This would create channels in which the liquid adhesive of the capsules K1 can spread and cross-link over a large area within the adhesive tape B.

[0269] Another possibility would be to fill the liquid-filled capsules K1 into tubes and place them in the adhesive tape B.

[0270] Thus, cross-linking could occur to the extent of the tube length.

[0271] This basic principle can also be extended to a two-component system as shown in FIG. 12B.

[0272] Here, the mechanism of inter- and intra-crosslinking is used.

[0273] In addition to the first capsules K1 of the single component system, a second capsule population K2 is introduced.

[0274] This mechanism allows a two-component adhesive system to be introduced in a tape B.

[0275] The systems described are not limited to one-component capsule systems or two-component capsule systems.

[0276] Depending on the size and functionalization of the respective system, any number of capsule populations Kn can be bound and inter-crosslinked.

[0277] By combining the individual components, a very wide range of new functionalities and thus new possibilities of application can be developed.

[0278] In the following, the production of polymethyl methacrylate microcapsules is described as an example:

[0279] First, 2.5 g polymethyl methacrylate (PMMA) is dissolved in 11.5 mL toluene. Then, oil is added under stirring. For microencapsulation, the homogeneous solution is added to 45 mL of a 1 wt.-% polyvenyl alcohol (PVA) solution. The emulsion is stirred at 800 rpm for 30 min. The toluene is then evaporated. The resulting microcapsules K with a PMMA coating material are washed with distilled water and centrifuged at 5,000 rpm and dried overnight at 50° C. in a vacuum oven.

[0280] Then the surface of the microcapsules is silanized. The microcapsules are placed in a fluidized bed reactor. A 5% aqueous (3-aminopropyl)triethoxysilane (APTES) solution is used as the coating material. After the coating process, the microcapsules are dried for 1 h at 80° C. in a vacuum oven to obtain optimal binding of the aminosilane to the surface. In addition, the surface of the microcapsules K can be activated with oxygen plasma before the reaction.

[0281] For the inter-crosslinking of two capsule populations K1 and K2 (capsules K with different contents), the complementary capsule population K can be functionalized with carboxyl groups. Here, the procedure is analogous to the silanization described above. However, instead of (3-aminopropyl)triethoxysilane (APTES), a silane-PEG-COOH is used.

[0282] Subsequently, the capsules K can still be sieved with a sieve having different pore sizes in order to increase the monodispersity. This has the advantage that in the subsequent binding process, the volume ratios of the two capsule contents can be precisely tuned via the size of the capsules K.

[0283] Then the microcapsule binding takes place. The first microcapsule K1 is functionalized with primary amines, while the second microcapsule K2 is functionalized with carboxyl groups. In the next step, 80 μL of a 10% carboxyl functionalized microcapsule suspension is added to an aqueous solution and 7 μL of a 2M (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide) solution (EDC solution) and 7 μL of a 0.3 M N-hydroxysuccinimide) solution (NHS solution) are added and stirred for one hour at room temperature. The carboxyl function is converted to the active ester. Amine microcapsules K1 are then added to the solution in the same ratio as the carboxyl microcapsules K2 and allowed to bind together for two hours at room temperature with gentle stirring. The capsules are then filtered through a sieve, washed with distilled water and dried in a vacuum oven at 50° C. for one hour.

[0284] In FIG. 13, it can be seen that most of the microcapsules K bind together in a 1:1 ratio.

[0285] In addition, there are a few microcapsules K that bind in a 1:2 ratio or have not been bound at all.

[0286] In order to ensure the quality of the two-component microcapsules K, the microcapsules K are then purified via a sieve with different pore sizes according to size or according to their binding ratio. The binding ratio of the microcapsules K can also be influenced by the number of functional groups on the microcapsules K.

[0287] It is possible that microcapsules K with the same size (e.g. 8 μm) but with a different functionalization were bound together. In the case of functionalization with linear polymers, the 1:1 binding predominates, cf. FIG. 14. In the case of functionalization with polymers that exhibit multivalence, the triple binding predominates.

[0288] It is also possible that the functionalization of microcapsules occurs via adsorption.

[0289] In particular, microcapsules having plastic surfaces may be functionalized via adsorption. Preferred examples of plastic surfaces are acrylic resin, polylactic acid, nylon 6 and 12, epoxy resins, and polystyrene.

[0290] For adsorption to the surface of the microcapsules, alkyl chains or primary amines are preferably used.

[0291] The second functional group can be chosen freely and is thus available for the binding of the microcapsules in the next step.

[0292] The plastic surface of the microcapsules can be formed directly in the microencapsulation process or in a second step for a multilayer microcapsule obtained in this way.

[0293] In an alternative embodiment, the second microcapsule population may be made and/or coated with metal particles or a metal shell.

[0294] The two microcapsule populations with 4-aminobenzenethiol as binder of both microcapsule populations are added.

[0295] The primary amine binds to the microcapsules via adsorption with the plastic surface, the thiol group binds to the metal surface.

[0296] Furthermore, functionalization is possible during the micro capsulation process as described in WO2017192407.

[0297] Accordingly, for example, a mixture comprising water (20 mL), ethyl acetate (5 mL), sodium bicarbonate (0.580 g), about 1.0 mg of Sudan Black and a drop of Tween 20 is vigorously mixed (5 minutes at 500 rpm) at room temperature using a mechanical stirrer (about 500 mL). 77 mg of 1,3-bischlorosulfonylbenzene are added to the mixture, after which stirring is continued for about 3 minutes. The mixture is then treated with 3,5-diaminobenzoic acid and stirred vigorously for a further 72 hours. In order to observe the reaction taking place in the mixture, aliquots are taken thirty minutes after vigorous stirring has commenced, and every 12 hour thereafter. On microscopic observation, the aliquots show a formation of capsules of 1 to 2 micrometers in diameter, with the dye Sudan black contained therein. The reaction is completed after a few hours. It is postulated that the capsules have multiple —COOH groups on the surface.

[0298] Furthermore, functionalization during the micro capsulation process is possible according to the further methods described in WO2017192407.

[0299] Accordingly, a second portion of material can be prepared in a separate batch approach using the same method, only with primary amines on the surface.

[0300] Subsequently, the microcapsule population can be activated with COOH on the surface as in the example before with EDC/NHS, the amine capsule population is added and the capsules bind covalently to each other. In the next step, the capsules can be washed, (filtered if necessary) and dried. The capsules thus contained can then be incorporated into another environmental medium.

[0301] For example, another conceivable method of manufacture is described in Yip, J and Luk, MYA, Antimicrobial Textiles, Woodhead Publishing Series in Textiles, 2016, Pages 19-46, 3-Microencapsultion technologies for antimicrobial textiles.

[0302] It is conceivable that the microcapsules with metal particles can also be applied via charge.

[0303] Intra-crosslinking is possible.

[0304] It is conceivable that after the production of the microcapsules with metal particles on the surface, a mixture of alcohol and mercaptans (SAM polymer) is added to the capsules.

[0305] In the case of functionalized thiols, the second functional group can be chosen arbitrarily. The thiol bonds bind to the metal surface. The remainder, i.e. the second functional group of the thiol molecule, is available as a functional group for the microcapsule crosslinking.

[0306] By selecting one or more SAM polymers to be added to the microcapsules, the functional groups of the surface can be made homogeneous or heterogeneous.

[0307] In addition, the length of the linker can be tuned with a suitable mercaptan.

[0308] In one embodiment, it is possible to select ethanethiol for a short linker. For a longer linker, an 11-mercaptoundecannoic may be selected.

[0309] Furthermore, it is possible to bind the thus functionalized surface of the microcapsules with a second polymer, e.g. with a PEG, in order to further increase the length of the linker.

[0310] Disulfites, phosphoric acids, silanes, thiols, and polyelectrolytes may be used as SAM surfaces. In particular, acetylcysteine, dimercaptosuccinic acid, dimercaptopropanesulfonic acid, ethanethiol (ethyl mercaptan), dithiothreitol (DTT), dithioerythritol (DTE), captopril, coenzyme, A, cysteine, penicillamine, 1-propanethiol, 2-propanethiol, glutathione, homocysteine, mesna, methanethiol (methyl mercaptan) and/or thiophenol may be used.

[0311] Inter-crosslinking is possible.

[0312] The microcapsules containing the metal nanoparticles can be prepared as described above.

[0313] Then, a mixture of alcohol and dithioether can be added.

[0314] The one functional group R is protected.

[0315] This is how the microcapsules are functionalized.

[0316] The number of metal nanoparticles on the surface of the microcapsules can then be used to tune the number or density of the functionalization and thus the number of functional groups. This makes it possible to determine the number of microcapsules K2 that react with each other via intra- or inter-crosslinking.

[0317] In the next step, the microcapsules can be inserted into the desired environmental medium, such as a pressure-sensitive adhesive (or the like).

[0318] For inter-crosslinking, the use of 4-isocyanate butane-1-thiol is conceivable, whereby the NCO groups are protected.

[0319] The removal of the protective groups and thus the activation of the functional groups R takes place in the still low viscosity pressure sensitive adhesive. The NCO groups released in this way can crosslink with each other in an aqueous environment (e.g. the solvent of the pressure-sensitive adhesive) to form urea.

REFERENCE SIGN

[0320] B Adhesive tape [0321] C Core [0322] K Capsule/capsule population [0323] K1 Capsule 1/Capsule population 1 [0324] K2 capsule 2/capsule population 2 [0325] K3 Capsule 3/Capsule population 2 [0326] Kn Capsule n/Capsule population n [0327] KG Gas capsule [0328] L Linker [0329] L1 Linker 1 [0330] L2 Linker 2 [0331] R functional group [0332] R1 functional group 1 [0333] R2 functional group 2 [0334] R21 functional group 21 [0335] S Capsule, Shell [0336] S1 Step 1 [0337] S2 Step 2 [0338] S3 Step 3 [0339] S4 Step 4 [0340] SG protection group