Aqueous crosslinking agent composition

Abstract

The present invention relates to a polyaziridine crosslinker composition, characterized in that the polyaziridine crosslinker composition is an aqueous dispersion with a pH range of 8 to 14 and contains a dispersed polyaziridine compound, wherein the polyaziridine compound has: a. 2 to 6 structural units A, wherein R1 is H, R2 and R4 are independently selected from H or an aliphatic hydrocarbon group containing 1 to 4 carbon atoms, R3 is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms, and m is 1; b. one or more linking chains, wherein each of these linking chains links two structural units A in the structural units A; and a molecular weight in the range of 500 Daltons to 10,000 Daltons, wherein the molecular weight is determined using MALDI-TOF mass spectrometry according to the instructions. #imgabs0#

Description

[0001] The present invention relates to a polyaziridine crosslinker composition that can be used for crosslinking carboxylic acid functional polymers dissolved and / or dispersed in an aqueous medium.

[0002] Coatings provide protection, aesthetic qualities and new functionality for various base materials with huge industrial and household relevance. In this case, the demand for coatings with improved resistance (such as stain resistance and solvent resistance), improved mechanical properties and improved adhesion strength is constantly growing. One or more characteristics in these characteristics can be strengthened by means of crosslinking. Many crosslinking mechanisms of polymeric binders have been studied for many years, and for aqueous latex polymer dispersions, the most useful polymeric binders include isocyanate crosslinked, carbodiimide crosslinked, melamine crosslinked, epoxy crosslinked and aziridine crosslinked of carboxylic acid functional polymers of hydroxyl functional polymers.

[0003] Waterborne adhesives are typically colloidally stabilized by carboxylic acid groups, and coating properties can be improved by using carbodiimide or aziridine crosslinkers, as the crosslinkers react with the carboxylic acid moieties of the polymer to produce a crosslinked network. Of the state-of-the-art crosslinkers described above, aziridine crosslinkers are the most versatile for room temperature curing of carboxylic acid functional polymers.

[0004] Traditional cross-linking method generally relates to the reactive organic molecule of use low molecular weight, is dissolved in volatile organic solvent occasionally to reduce viscosity, thereby promotes that cross-linking agent is accurately dosed / mixed in the polymer composition to be cross-linked.The good miscibility of cross-linking agent and polymer composition is important for final characteristics (poor miscibility tends to cause inefficient cross-linking) and for the efficiency and user convenience of material. However, it is undesirable to use volatile organic solvent to reduce viscosity, because this will increase VOC (volatile organic compound) level. In addition, the presence of solvent in the cross-linking agent composition will reduce the formulation freedom of the coating composition formulator, and is therefore undesirable. Therefore, it will be beneficial to deliver polyaziridine cross-linking agent in water. Meanwhile, it is necessary to keep cross-linking agent performance in terms of cross-linking efficiency and storage stability, to remain on the commercial feasibility in various polymer resins.

[0005] However, currently state-of-the-art polyaziridine crosslinkers lack stability in aqueous environments. For example, CX-100 (trimethylolpropane tris(2-methyl-1-aziridine propionate); CAS No. 64265-57-2) and XAMA-7 (pentaerythritol tris[3-(1-aziridinyl)propionate; CAS No. 57116-45-7) offer very efficient reactions with carboxylic acids, but these crosslinkers are unstable in water and therefore have a limited shelf life in water. This is described, for example, in US-A-5133997. Furthermore, these polyaziridines have unfavorable genotoxicity profiles.

[0006] It is an object of the present invention to provide polyaziridine crosslinkers that can be delivered and stored in water with a longer shelf life while maintaining sufficient reactivity towards carboxylic acid functional polymers.

[0007] This object has surprisingly been achieved by providing a polyaziridine crosslinker composition, characterized in that the polyaziridine crosslinker composition is an aqueous dispersion having a pH in the range of 8 to 14 and comprising a polyaziridine compound in dispersed form, wherein

[0008] The polyaziridine compound has:

[0009] a. 2 to 6 of the following structural units A:

[0010]

[0011] in

[0012] R1 is H,

[0013] R2 and R4 are independently selected from H or an aliphatic hydrocarbon group containing 1 to 4 carbon atoms,

[0014] R3 is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms,

[0015] m is 1,

[0016] R' and R" according to (1) or (2):

[0017] (1) R' = H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms; and

[0018] R"=H, an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, an alicyclic hydrocarbon group containing 5 to 12 carbon atoms, an aromatic hydrocarbon group containing 6 to 12 carbon atoms, CH2-O-(C=O)-R"', CH2-OR"" or CH2-(OCR""'HCR""'H) n-OR""", wherein R"' is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms and R"" is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms or an aromatic hydrocarbon group containing 6 to 12 carbon atoms, n is 1 to 35, R""' is independently H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, and R""" is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms,

[0019] (2) R′ and R″ together form a saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms;

[0020] b. one or more link chains, wherein each of these link chains links two structural units A in the structural unit A; and

[0021] c. Molecular weight in the range of 500 Daltons to 10,000 Daltons.

[0022] Surprisingly, it has been found that the aqueous crosslinker compositions of the present invention have extended storage stability while still having good crosslinking efficiency for carboxylic acid-functional polymers (particularly in aqueous dispersions of carboxylic acid-functional polymers). The compositions according to the present invention show efficient reactions with carboxylic acid groups at room temperature. The compositions of the present invention are also easy to use, and their aqueous nature results in good compatibility with aqueous adhesives and therefore good mixing and low fouling during formulation. Further, these compositions generally have low viscosity, resulting in easy handling and accurate dosing. The combination of extended storage stability in water and a more favorable hazard profile enables coating manufacturers and applicators to easily and safely store and use the crosslinker compositions in two-component 2K coating systems, in which the adhesive and crosslinker are mixed shortly before application.

[0023] US-A-3523750 describes a method for modifying protein substrates such as wool with polyaziridine compounds. US-A-5258481 describes polyfunctional water-dispersible crosslinkers, which are oligomeric materials containing carbodiimide functional groups and reactive functional groups different from the carbodiimide functional groups. US-A-5241001 discloses polyaziridine compounds obtained by reacting 1-(2-hydroxyethyl)-ethyleneimine with polyisocyanates.

[0024] For all upper and / or lower boundaries of any range given herein, unless otherwise specifically stated, the boundary values are included in the given range. Thus, when it is said from x to y, it is meant to include x and y and also all intermediate values.

[0025] In this specification, the term "coating composition" encompasses paints, coatings, varnishes, adhesives, and ink compositions, but is not limited to this list. The term "aliphatic hydrocarbon group" refers to optionally (herein, "optionally") branched alkyl, alkenyl, and alkynyl groups. The term "alicyclic hydrocarbon group" refers to cycloalkyl and cycloalkenyl groups optionally substituted with at least one aliphatic hydrocarbon group. The term "aromatic hydrocarbon group" refers to a benzene ring optionally substituted with at least one aliphatic hydrocarbon group. These optional aliphatic hydrocarbon substituents are preferably alkyl groups.

[0026] Examples of alicyclic hydrocarbon groups having 7 carbon atoms are cycloheptyl and methyl-substituted cyclohexyl. Examples of aromatic hydrocarbon groups having 7 carbon atoms are methyl-substituted phenyl. Examples of aromatic hydrocarbon groups having 8 carbon atoms are xylyl and ethyl-substituted phenyl.

[0027] The aziridine group has the following structural formula:

[0028]

[0029] Polyaziridine compounds

[0030] R1 is H. R2 and R4 are independently selected from H or an aliphatic hydrocarbon group containing 1 to 4 carbon atoms. Preferably, R2 and R4 are independently selected from H or an aliphatic hydrocarbon group containing 1 to 2 carbon atoms.

[0031] R3 is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms, preferably an aliphatic hydrocarbon group containing 1 to 2 carbon atoms.

[0032] In a preferred embodiment of the present invention, R2 is H, R3 is C2H5 and R4 is H. In another more preferred embodiment of the present invention, R2 is H, R3 is CH3 and R4 is H or CH3. In another even more preferred embodiment of the present invention, R2 is H, R3 is CH3 and R4 is H.

[0033] Although the structural units A present in the polyaziridine compound may independently have different R2, R3, R4, R' and / or R", the structural units A present in the polyaziridine compound are preferably identical to each other.

[0034] Preferably, R' and R" are according to (1) or (2):

[0035] (1) R'=H or an alkyl group containing 1 to 2 carbon atoms;

[0036] R"=H, an aliphatic hydrocarbon group containing 1 to 4 carbon atoms, an alicyclic hydrocarbon group containing 5 to 12 carbon atoms, an aromatic hydrocarbon group containing 6 to 12 carbon atoms, CH2-O-(C=O)-R"', CH2-OR"" or CH2-(OCR""'HCR""'H)n-OR""", wherein R"' is an alkyl group containing 1 to 14 carbon atoms and R"" is an alkyl group containing 1 to 14 carbon atoms, n is 1 to 35, R""' is independently H or methyl, and R""" is an alkyl group containing 1 to 4 carbon atoms;

[0037] (2) R' and R" together form a saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms.

[0038] In a preferred embodiment of the present invention, R2 is H, R3 is an aliphatic hydrocarbon group containing 1 to 2 carbon atoms, R4 is H, R' is H, and R" is H, an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, an alicyclic hydrocarbon group containing 5 to 12 carbon atoms, an aromatic hydrocarbon group containing 6 to 12 carbon atoms, CH2-O-(C=O)-R"' or CH2-OR"", wherein R"' is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, preferably R"' is an aliphatic hydrocarbon group containing 3 to 12 carbon atoms, and R"" is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms. More preferably, R' is H and R" is an alkyl group containing 1 to 4 carbon atoms, CH2-O-(C=O)-R"', CH2-OR"", wherein R"' is an alkyl group containing 3 to 12 carbon atoms, such as neopentyl or neodecyl. Most preferably, R"' is a branched C9 alkyl group. R"" is preferably an alkyl group containing 1 to 14 carbon atoms, more preferably 1 to 12 carbon atoms. Non-limiting examples of R"" are ethyl, butyl, and 2-ethylhexyl.

[0039] The polyaziridine compound contains 2 to 6 structural units A, preferably 2 to 4 structural units A, more preferably 2 or 3 structural units A.

[0040] Polyaziridine compounds include one or more link chains, wherein each link chain in these link chains links two structural units A in structural unit A. The link chain present in the polyaziridine compounds is preferably composed of 4 to 300 atoms, more preferably 5 to 250 atoms, more preferably 6 to 100 atoms, most preferably 6 to 20 atoms. The atoms of the link chain are preferably C and optional N, O, S and / or P, preferably C and optional N and / or O. The link chain is preferably a set of covalently linked atoms, and the set of atoms is composed of i) carbon atoms, ii) carbon and nitrogen atoms or iii) carbon, oxygen and nitrogen atoms.

[0041] A linking chain is defined as the shortest chain of consecutive atoms linking two structural units A. The figure below shows an example of a polyaziridine compound and a linking chain between two structural units A.

[0042]

[0043] Any two structural units A present in the polyaziridine compound are linked by a linking chain as defined herein. Thus, each structural unit A present in the polyaziridine compound is connected to each other structural unit A by a linking chain as defined herein. In the case where the polyaziridine compound has two structural units A, the polyaziridine compound has one such linking chain linking these two structural units.

[0044] In the case where the polyaziridine compound has three structural units A, the polyaziridine compound has three link chains, wherein each of the three link chains links the structural unit A with another structural unit A, that is, the first structural unit A is linked to the second structural unit A through the link chain, and the first and second structural units A are both independently linked to the third structural unit A through their corresponding link chains.

[0045] The following figures show examples of polyaziridine compounds having three structural units A and three link chains, wherein each of the three link chains links two structural units A.

[0046]

[0047] Polyaziridine compounds having more than two structural units A have the number of linked chains according to the following equation:

[0048] LC = {(AN-1) x AN)} / 2, where LC = the number of linking chains in the polyaziridine compound, and AN = the number of structural units A in the polyaziridine compound. Thus, for example, if there are 5 structural units A in the polyaziridine compound, AN = 5; this means that there are {(5-1) x 5} / 2 = 10 linking chains.

[0049] The molecular weight of the polyaziridine compound according to the present invention is preferably 600 dalton to 5000 dalton. The molecular weight of the polyaziridine compound according to the present invention is preferably 3800 dalton at the most, more preferably 3600 dalton at the most, more preferably 3000 dalton at the most, more preferably 1600 dalton at the most, even more preferably 1400 dalton at the most. The molecular weight of the polyaziridine compound according to the present invention is preferably at least 700 dalton, more preferably at least 800 dalton, even more preferably at least 840 dalton, and most preferably at least 1000 dalton. As used herein, the molecular weight of the polyaziridine compound is a calculated molecular weight. The calculated molecular weight is obtained by adding the atomic masses of all atoms present in the structural formula of the polyaziridine compound. If the polyaziridine compound is present in a composition comprising more than one polyaziridine compound according to the present invention, for example, when one or more starting materials in the starting material for preparing the polyaziridine compound are a mixture, then the molecular weight calculation can be performed for each compound present alone in the composition. As described in the experimental section below, the molecular weight of the polyaziridine compounds according to the invention can be measured using MALDI-TOF mass spectrometry.

[0050] The polyaziridine compound preferably comprises one or more linking groups, wherein each of these linking groups links two structural units A in the structural unit A, and wherein each of these linking groups consists of at least one functional group selected from the group consisting of an aliphatic hydrocarbon functional group (preferably containing 1 to 8 carbon atoms), an alicyclic hydrocarbon functional group (preferably containing 4 to 10 carbon atoms), an aromatic hydrocarbon functional group (preferably containing 6 to 12 carbon atoms), an isocyanurate functional group, an iminooxadiazindione functional group, an ether functional group, an ester functional group, an amide functional group, a carbonate functional group, a carbamate functional group, a urea functional group, a biuret functional group, an allophanate functional group, a uretdione functional group, and any combination thereof. More preferably, the linking group is an array of continuous functional groups, wherein each functional group is selected from the group consisting of: an aliphatic hydrocarbon functional group (preferably containing 1 to 8 carbon atoms), an alicyclic hydrocarbon functional group (preferably containing 4 to 10 carbon atoms), an aromatic hydrocarbon functional group (preferably containing 6 to 12 carbon atoms), an isocyanurate functional group, an iminooxadiazinedione functional group, an ether functional group, an ester functional group, an amide functional group, a carbonate functional group, a carbamate functional group, a urea functional group, a biuret functional group, an allophanate functional group, and a uretdione functional group.

[0051] The term "aliphatic hydrocarbon functional group" refers to optionally branched alkyl, alkenyl and alkynyl groups. Although optional branches of C atoms are part of the linking group, they are not part of the linking chain.

[0052] The term "alicyclic hydrocarbon functional group" refers to cycloalkyl and cycloalkenyl groups that are optionally substituted with at least one aliphatic hydrocarbon group. Although the optional aliphatic hydrocarbon substituents are part of the linking group, they are not part of the linking chain. The optional aliphatic hydrocarbon substituents are preferably alkyl groups.

[0053] The term "aromatic hydrocarbon functional group" refers to a benzene ring optionally substituted with at least one aliphatic hydrocarbon group. Although the optional aliphatic hydrocarbon substituents are part of the linking group, they are not part of the linking chain. The optional aliphatic hydrocarbon substituents are preferably alkyl groups.

[0054] The isocyanurate functional group is defined as

[0055] The iminooxadiazinedione functional group is defined as

[0056] The biuret functional group is defined as

[0057] The allophanate functional group is defined as

[0058] The uretdione functional group is defined as

[0059] The figure below shows in bold the linking group of an example of a polyaziridine compound as defined herein. In this example, the linking group connecting two building blocks A in a building block A consists of the following array of consecutive functional groups: aliphatic hydrocarbon functional group 1 (straight chain CH 12 ), isocyanurate 2 (cyclic C3N3O3) functional group and aliphatic hydrocarbon functional group 3 (straight chain C6H 12 ).

[0060]

[0061] The figure below shows in bold the following example linking groups of the polyaziridine compound as defined herein. In this example, the linking group connecting the two structural units A consists of the following array of consecutive functional groups: aliphatic hydrocarbon functional group 1 (straight chain CH 12 ), isocyanurate 2 (cyclic C3N3O3) and aliphatic hydrocarbon functional group 3 (straight chain C6H 12 ).

[0062]

[0063] As defined herein, any two structural unit A in the structural unit A present in the polyaziridine compound is preferably connected by a linking group, and the linking group is as defined herein. Therefore, each structural unit A present in the polyaziridine compound is preferably connected with each other structural unit A using a linking group, and the linking group is as defined in the present invention. In the case where polyaziridine compound has two structural unit A, polyaziridine compound has this type of linking group connecting these two structural units. In the case where polyaziridine compound has three structural unit A, the polyaziridine compound has three this type of linking groups, and wherein each linking group in the three linking groups links structural unit A to another structural unit A.

[0064] The figure below shows an example of a polyaziridine compound having three structural units A and three linking groups, wherein each of the three linking groups connects two structural units A. One linking group consists of the following array of consecutive functional groups: an aliphatic hydrocarbon functional group 1 (straight chain C6H 12 ), isocyanurate 2 (cyclic C3N3O3) and aliphatic hydrocarbon functional group 3 (straight chain C6H 12 For the connection between the structural units A labeled A1 and A3, the linking group consists of the following array of consecutive functional groups: aliphatic hydrocarbon functional group 1 (straight chain C6H 12 ), isocyanurate 2 (cyclic C3N3O3) and aliphatic hydrocarbon functional group 4 (straight chain C6H 12 ), and for the connection between the structural units A labeled A2 and A3, the linking group consists of the following array of consecutive functional groups: aliphatic hydrocarbon functional group 3 (straight chain C6H 12 ), isocyanurate 2 (cyclic C3N3O3) and aliphatic hydrocarbon functional group 4 (straight chain C6H 12 ).

[0065]

[0066]

[0067] Preferably, linking group is made up of at least one functional group selected from the group consisting of: aliphatic hydrocarbon functional group (preferably containing 1 to 8 carbon atoms), alicyclic hydrocarbon functional group (preferably containing 4 to 10 carbon atoms), aromatic hydrocarbon functional group (preferably containing 6 to 12 carbon atoms), isocyanurate functional group, iminooxadiazinedione functional group, carbamate functional group, urea functional group, biuret functional group and their any combination.Linking group preferably contains isocyanurate functional group, iminooxadiazinedione functional group, biuret functional group, allophanate functional group or uretdione functional group. More preferably, linking group contains isocyanurate functional group or iminooxadiazinedione functional group. For the sake of clarity, the polyaziridine compound can be obtained from the reaction product of one or more suitable compounds B as defined below with a hybrid isocyanurate (e.g. HDI / IPDI isocyanurate), thereby producing a polyaziridine compound having a linking group consisting of an array of the following consecutive functional groups: linear C6H 12 (i.e., an aliphatic hydrocarbon functional group having 6 carbon atoms), an isocyanurate functional group (cyclic C3N3O3), and

[0068]

[0069] (i.e. an alicyclic hydrocarbon functional group having 9 carbon atoms and an aliphatic hydrocarbon functional group having 1 carbon atom). Even more preferably, the linking group consists of the following functional groups: at least one aliphatic hydrocarbon functional group and / or at least one alicyclic hydrocarbon functional group, and also an isocyanurate functional group or an iminooxadiazinedione functional group.

[0070] On the linking group, one or more substituents may be present as pendant groups on the linking group, as shown in bold in, for example, the following polyaziridine compounds. These pendant groups are not part of the linking group.

[0071]

[0072] The side groups preferably contain Among them, X, R7, R8, n' and R 10 As described below. In one embodiment of the present invention, the polyaziridine compound comprises one or more linking groups, wherein each of these linking groups links two structural units A in the structural unit A, wherein the linking group consists of the following: (i) at least two aliphatic hydrocarbon functional groups or at least two alicyclic hydrocarbon functional groups, and (ii) an isocyanurate functional group or an iminooxadiazinedione functional group, and wherein there is a pendant group on the linking group, wherein the pendant group has the following structural formula:

[0073]

[0074] n′ is the number of repeating units and is an integer of 1 to 50, preferably 2 to 30, more preferably 5 to 20.

[0075] X is O or NH, preferably X is O,

[0076] In each repeating unit, R7 and R8 are independently H or CH3,

[0077] R9 is an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group containing 1 to 8 carbon atoms, or preferably an alicyclic hydrocarbon group containing 4 to 10 carbon atoms, and

[0078] R 10 contains up to 20 carbon atoms and is an aliphatic, alicyclic or aromatic hydrocarbon group, or a combination thereof. In a preferred embodiment, R7 and R8 are H. In another more preferred embodiment, one of R7 and R8 is H, and the other of R7 and R8 is CH3. 10 Preferably contain the aliphatic hydrocarbon group (preferably CH3) of 1 to 20 carbon atoms, contain the alicyclic hydrocarbon group of 5 to 20 carbon atoms, or contain the aromatic hydrocarbon group of 6 to 20 carbon atoms.The existence of side group causes the viscosity of polyaziridine compound to reduce and therefore more easily disperses in aqueous medium.In this embodiment, polyaziridine compound preferably contains 2 structural units A. In this embodiment, the linking group is preferably composed of an array of the following consecutive functional groups: a first alicyclic hydrocarbon functional group, an isocyanurate functional group or an iminooxadiazinedione functional group, and a second alicyclic hydrocarbon functional group, and R9 is an alicyclic hydrocarbon group, wherein the first alicyclic hydrocarbon functional group and the second alicyclic hydrocarbon functional group are the same as R9, more preferably, the linking group is composed of an array of the following consecutive functional groups: a first aliphatic hydrocarbon functional group, an isocyanurate functional group or an iminooxadiazinedione functional group and a second aliphatic hydrocarbon functional group, and R9 is an aliphatic hydrocarbon functional group, wherein the first aliphatic hydrocarbon functional group and the second aliphatic hydrocarbon functional group are the same as R9.

[0079] In a preferred embodiment of the invention, the linking group present in the polyaziridine compound as defined herein is composed of the following functional groups: (i) at least one aliphatic hydrocarbon functional group and / or at least one alicyclic hydrocarbon functional group; and (ii) optionally at least one aromatic hydrocarbon functional group; and (iii) optionally an isocyanurate functional group or an iminooxadiazinedione functional group or an allophanate functional group or a uretdione functional group. Preferably, the linking group present in the polyaziridine compound of the present invention is composed of the following functional groups: (i) at least one aliphatic hydrocarbon functional group and / or at least one alicyclic hydrocarbon functional group; and (ii) optionally at least one aromatic hydrocarbon functional group; and (iii) optionally an isocyanurate functional group or an iminooxadiazinedione functional group. A very suitable way to obtain such polyaziridine compounds is to react compound B having the following structural formula with a polyisocyanate having aliphatic reactivity:

[0080]

[0081] wherein R1, R2, R3, R4, R' and R" and their priorities are as defined above, and wherein the polyisocyanate has aliphatic reactivity. The term "polyisocyanate with aliphatic reactivity" refers to compounds in which all isocyanate groups are directly bonded to aliphatic or alicyclic hydrocarbon groups, regardless of whether aromatic hydrocarbon groups are also present. The polyisocyanate with aliphatic reactivity may be a mixture of polyisocyanates with aliphatic reactivity. When compared to similar compounds but based on polyisocyanates with aromatic reactivity, polyisocyanates based on polyisocyanates with aliphatic reactivity are more The compounds have a reduced tendency to yellow over time. The term "polyisocyanates with aromatic reactivity" is intended to mean compounds in which all isocyanate groups are directly bonded to benzene or naphthalene groups, regardless of whether aliphatic or cycloaliphatic groups are also present. Preferred polyisocyanates with aliphatic reactivity are 1,5-pentamethylene diisocyanate PDI, 1,6-hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, 4,4'-dicyclohexylmethane diisocyanate H12MDI, 2,2,4-trimethylhexamethylene diisocyanate , 2,4,4-trimethylhexamethylene diisocyanate, tetramethylxylene diisocyanate TMXDI (all isomers) and higher molecular weight variants such as, for example, their isocyanurates, allophanates or iminooxadiazinediones. In this embodiment, preferably, the linking group consists of an array of the following continuous functional groups: an aliphatic hydrocarbon functional group, an aromatic hydrocarbon functional group and an aliphatic hydrocarbon functional group (for example, when TMXDI is used to prepare a polyaziridine compound), or the linking group consists of an array of the following continuous functional groups: an alicyclic hydrocarbon functional group, an aliphatic hydrocarbon functional group and an alicyclic hydrocarbon functional group ( For example, when H12MDI is used to prepare the polyaziridine compound), or more preferably, the linking group consists of an array of the following consecutive functional groups: an aliphatic hydrocarbon functional group, an isocyanurate functional group or an iminooxadiazinedione functional group and an aliphatic hydrocarbon functional group. Most preferably, in this embodiment, the linking group consists of an array of the following consecutive functional groups: an aliphatic hydrocarbon functional group, an isocyanurate functional group and an aliphatic hydrocarbon functional group (for example, when the isocyanurate of 1,6-hexamethylene diisocyanate and / or the isocyanurate of 1,5-pentamethylene diisocyanate is used to prepare the polyaziridine compound).

[0082] Preferably, the number of consecutive C atoms and optionally O atoms between the N atom of the carbamate group in the structural unit A and the next N atom present in the linking chain or being the N atom of the carbamate group of another structural unit A is at most 9, as shown, for example, in the following polyaziridine compounds having 2 or 3 structural units A.

[0083]

[0084] The polyaziridine compound preferably contains at least 5 wt%, more preferably at least 5.5 wt%, more preferably at least 6 wt%, more preferably at least 9 wt%, more preferably at least 12 wt% and preferably less than 25 wt%, preferably less than 20 wt% of urethane bonds. The aziridine equivalent weight of the polyaziridine compound (the molecular weight of the polyaziridine compound divided by the number of aziridines present in the polyaziridine compound) is preferably at least 200 daltons, more preferably at least 230 daltons and even more preferably at least 260 daltons, and preferably at most 2500 daltons, more preferably at most 1000 daltons and even more preferably at most 500 daltons.

[0085] The polyaziridine compound is preferably obtained by reacting at least a polyisocyanate with a compound B as defined above having the following formula:

[0086]

[0087] wherein the molar ratio of compound B to polyisocyanate is 2 to 6, more preferably 2 to 4, and most preferably 2 to 3, and wherein m, R', R", R1, R2, R3 and R4 are as defined above. The reaction of the polyisocyanate with compound B may be carried out by reacting equal amounts of the polyisocyanate with the isocyanate in the presence of, for example, a tin catalyst (e.g., dibutyltin dilaurate) or a bismuth catalyst (e.g., bismuth neodecanoate) at a temperature in the range of 0°C to 110°C, more preferably from 20°C to 110°C, more preferably from 40°C to 95°C, even more preferably from 60°C to 85°C. Compound B is contacted. A solvent such as dimethylformamide (DMF), acetone and / or methyl ethyl ketone may be used. The polyisocyanate contains at least 2 isocyanate groups, preferably at least 2.5 isocyanate groups on average, more preferably at least 2.8 isocyanate groups on average. A mixture of polyisocyanates may also be used as a starting material. Preferred polyisocyanates are polyisocyanates with aliphatic reactivity. The term "polyisocyanate with aliphatic reactivity" refers to compounds in which all isocyanate groups are directly bonded to aliphatic or alicyclic hydrocarbon groups, regardless of whether The presence of aromatic hydrocarbon groups is irrelevant. The polyisocyanate with aliphatic reactivity may be a mixture of polyisocyanates with aliphatic reactivity. Preferred polyisocyanates with aliphatic reactivity are 1,5-pentamethylene diisocyanate PDI, 1,6-hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, 4,4'-dicyclohexylmethane diisocyanate H12MDI, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, p-tetramethylxylene diisocyanate (p-TMXDI), ) and their meta isomers, as well as higher molecular weight variants, such as their isocyanurates or iminooxadiazinediones or allophanates or uretdiones. More preferred polyisocyanates with aliphatic reactivity are 4,4'-dicyclohexylmethane diisocyanate H12MDI, m-TMXDI, isocyanurates or iminooxadiazinediones or allophanates or uretdiones of 1,6-hexamethylene diisocyanate, and isocyanurates of 1,5-pentamethylene diisocyanate. Suitable iminooxadiazinedione trimers containing HDI are available from Covestro N3900. Suitable allophanates containing HDI are available from Covestro XP2860. Suitable uretdione containing HDI is available from Covestro N3400. Suitable HDI-based isocyanurate trimers are available from Covestro Vencorex (Tolonate TM HDT LV), Asahi Kasei (Duranate TMTPA-100), Evonik and Tosoh Obtain. Methods for preparing compound (B) and derivatives are known in the art. For example, the synthesis of 1-(2-methylaziridine-1-yl) propan-2-ol is described by S.Lesniak, M.Rachwalski, S.Jarzynski, E.Obijalska Tetrahedron Asymm.2013, 241336-1340. The synthesis of 1-(aziridine-1-yl) propan-2-ol is described by A.Baklien, MVLeeding, J.Kolm Aust.J.Chem.1968, 21, 1557-1570. The preferred aziridine compound for preparing compound B is propylene imine and ethyl aziridine. The synthesis of ethyl aziridine is, for example, described in EP0227461B1. The most preferred aziridine compound for preparing compound B is propylene imine.

[0088] Many aziridine compounds can also be obtained by making at least compound B and polyisocyanates as defined above and polyol and / or polyamine reaction. Many aziridine compounds can also be obtained by making polyisocyanates as defined above and polyol and / or polyamine reaction and making the compound so obtained react with compound B reaction. Many aziridine compounds can also be obtained by making compound B and polyisocyanates reaction and making the compound so obtained react with polyol and / or polyamine reaction. Many aziridine compounds can also be obtained by making at least compound B and isocyanate-terminated polyurethane and / or polyurethane urea reaction. (Isocyanate-terminated) polyurethane (urea) is obtained by making at least one polyol and / or polyamine react with at least one polyisocyanate. Preferred polyisocyanates are as described above. Polyol is preferably selected from the group consisting of the following: polyether polyol, polyester polyol, polythioether polyol, polycarbonate polyol, polyacetal polyol, polyvinyl polyol, polysiloxane polyol and any mixture thereof. More preferably, the polyol is selected from the group consisting of polyether polyols and any mixtures thereof. Preferred polyether polyols are polytetrahydrofuran, polyethylene oxide, polypropylene oxide or any mixtures thereof. More preferably, the polyether polyol is poly(propylene glycol). The polyoxyethylene (-O-CH2-CH2) in the polyaziridine compound x , polyoxypropylene (-O-CHCH3-CH2-) x or (-O-CH2-CH2-CH2-)x groups and / or polytetrahydrofuran (-O-CH2-CH2-CH2-CH2) xThe amount of the group is preferably at least 6 wt %, more preferably at least 10 wt %, and preferably less than 45 wt %, more preferably less than 40 wt %, and most preferably less than 35 wt % relative to the polyaziridine compound. x represents the average number of added moles of oxyethylene, oxypropylene, or tetrahydrofuran, and x is preferably an integer from 5 to 20. Examples of such polyaziridine compounds are shown below:

[0089]

[0090] The polyamine is preferably selected from the group consisting of polyether polyamines, polyester polyamines, polythioether polyamines, polycarbonate polyamines, polyacetal polyamines, polyethylene polyamines, polysiloxane polyamines and any mixtures thereof. More preferably, the polyamine is selected from the group consisting of polyether polyamines and any mixtures thereof. Preferred polyether polyamines are D-230, D-400 and D-2000. Using polyols is better than using polyamines.

[0091] Compound B is preferably obtained by reacting an at least non-OH-functional monoepoxide compound with an aziridine compound of the following formula (E):

[0092]

[0093] wherein R1, R2, R3 and R4 are as defined above. The non-OH functional monoepoxide may be a mixture of different non-OH functional monoepoxides. Non-limiting examples of non-OH functional monoepoxides are ethylene oxide, propylene oxide, 2-ethylethylene oxide, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, 4-tert-butylphenyl 2,3-epoxypropyl ether (=tert-butylphenyl glycidyl ether), cresol glycidyl ether (ortho or para) and glycidyl neodecanoate. The non-OH-functional monoepoxide is preferably selected from the group consisting of ethylene oxide (CAS No. 75-21-8), propylene oxide (CAS No. 75-56-9), 2-ethylethylene oxide (CAS No. 106-88-7), n-butyl glycidyl ether (CAS No. 2426-08-6), 2-ethylhexyl glycidyl ether (CAS No. 2461-15-6), glycidyl neodecanoate (CAS No. 26761-45-5) and any mixtures thereof. More preferably, the non-OH functional monoepoxide is selected from the group consisting of propylene oxide (CAS No. 75-56-9), 2-ethylethylene oxide (CAS No. 106-88-7), n-butyl glycidyl ether (CAS No. 2426-08-6), 2-ethylhexyl glycidyl ether (CAS No. 2461-15-6), glycidyl neodecanoate (CAS No. 26761-45-5) and any mixtures thereof.

[0094] The polyaziridine compound is preferably obtained by a process comprising at least the following steps (i) and (ii):

[0095] (i) reacting an aziridine of formula (E) with an at least non-OH-functional monoepoxide compound to obtain compound B, and

[0096] (ii) reacting compound B with a polyisocyanate.

[0097] Step (i) can be carried out, for example, by contacting one equivalent of the epoxide compound with one equivalent of aziridine at a temperature in the range of from 20° C. to 110° C., more suitably from 40° C. to 95° C., even more suitably from 60° C. to 85° C. under atmospheric pressure. The reaction of the adduct obtained in step (i) (compound (B)) with the polyisocyanate (step (ii)) can be carried out, for example, by contacting an equal amount of the polyisocyanate with the adduct in the presence of, for example, a tin catalyst (e.g., dibutyltin dilaurate) at a temperature in the range of from 20° C. to 110° C., more suitably from 40° C. to 95° C. under atmospheric pressure.

[0098] Examples of preferred polyaziridine compounds present in the polyaziridine crosslinker composition of the present invention are

[0099]

[0100] as well as

[0101]

[0102] In a preferred embodiment of the present invention, the polyaziridine compound present in dispersed form in the aqueous dispersion of the present invention has

[0103] a. 2 to 6 structural units according to formula A

[0104]

[0105] wherein R1, R2, R3, R4, R5, R' and R" and their priorities are as defined above,

[0106] b. one or more linking chains, wherein each of these linking chains links two structural units A in said structural unit A, wherein said one or more linking chains are preferably as defined above, and

[0107] c. a molecular weight of 600 to 5000 Daltons, preferably at least 700 Daltons, more preferably at least 800 Daltons, even more preferably at least 840 Daltons, most preferably a molecular weight of at least 1000 Daltons, and preferably at most 3800 Daltons, more preferably at most 3600 Daltons, more preferably at most 3000 Daltons, more preferably at most 1600 Daltons, even more preferably at most 1400 Daltons.

[0108] It has been surprisingly found that this type of polyaziridine compound has the genotoxicity of reduction compared with very commonly used trimethylolpropane tris (2-methyl -1-aziridine propionate).Polyaziridine compounds show the genotoxicity of only weak positive induction, or even they do not show genotoxicity, that is, they show the genotoxicity level suitable for naturally occurring background.Therefore, the polyaziridine compound with the genotoxicity of reduction compared with trimethylolpropane tris (2-methyl -1-aziridine propionate) has the more favorable hazard characteristics than trimethylolpropane tris (2-methyl -1-aziridine propionate), thereby greatly reducing the safety, health and environmental risks associated with its use, resulting in reducing or even removing the operation and management burden of disposing of the polyaziridine compound with reduced genotoxicity.Polyaziridine compounds preferably include one or more linking groups, wherein each linking group in the linking group connects two structural units A in the structural unit A, and the linking group and its priority are as defined above,

[0109] In this embodiment, the amount of aziridinyl-functional molecules (also referred to as aziridine-functional molecules) having a molecular weight of less than 250 daltons, more preferably less than 350 daltons, even more preferably less than 450 daltons, even more preferably less than 550 daltons and even more preferably less than 580 daltons present in the polyaziridine crosslinker composition according to the invention is preferably less than 5 wt%, more preferably less than 4 wt%, more preferably less than 3 wt%, more preferably less than 2 wt%, more preferably less than 1 wt%, more preferably less than 0.5 wt%, more preferably less than 0.1 wt%, and most preferably 0 wt%, relative to the total weight of the polyaziridine crosslinker composition, wherein the molecular weight is determined using LC-MS as described in the experimental section below. Such aziridinyl-functional molecules can be obtained as by-products during the preparation of the polyaziridine compounds as defined herein.

[0110] The average number of aziridinyl groups per aziridinyl-containing molecule in the composition is preferably at least 1.8, more preferably at least 2, more preferably at least 2.2 and preferably less than 10, more preferably less than 6 and most preferably less than 4. Most preferably, the average number of aziridinyl groups per aziridinyl-containing molecule in the composition is from 2.2 to 3.

[0111] pH of aqueous dispersion

[0112] The pH of the aqueous dispersion is at least 8. In order to further extend the shelf life of the aqueous dispersion of the present invention, it is beneficial if the pH is at least 8.5, preferably at least 9, more preferably at least 9.5. The pH of the aqueous dispersion is at most 14, preferably at most 13, more preferably at most 12 and even more preferably at most 11.5, as this allows the amount of base present in the aqueous dispersion of the present invention to be reduced while the shelf life of the aqueous dispersion remains sufficiently long. Most preferably, the pH of the aqueous dispersion is in the range of 9.5 to 11.5.

[0113] The aqueous dispersion preferably contains ammonia, a secondary amine, a tertiary amine, LiOH, NaOH, and / or KOH to adjust the pH to the desired value. Preferred amines are ammonia, a secondary amine, and / or a tertiary amine. Examples of such secondary amines include, but are not limited to, diisopropylamine, di-sec-butylamine, and di-tert-butylamine. More preferred amines are tertiary amines. Examples of such tertiary amines include, but are not limited to, n-ethylmorpholine, n-methylpiperidine, n,n-dimethylbutylamine, dimethylisopropylamine, dimethyl-n-propylamine, dimethylethylamine, triethylamine, dimethylbenzylamine, n,n-dimethylethanolamine, 2-(diethylamino)ethanol, n,n-dimethylisopropanolamine, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 2-(dimethylamino)ethanol, and 2-[2-(dimethylamino)ethoxy]ethanol. Preferred tertiary amines are n-ethylmorpholine, n-methylpiperidine, n,n-dimethylbutylamine, dimethylisopropylamine, dimethyl-n-propylamine, dimethylethylamine, triethylamine and / or dimethylbenzylamine. Most preferred is triethylamine.

[0114] The amount of water in the aqueous dispersion is preferably at least 15 wt %, more preferably at least 20 wt %, more preferably at least 30 wt %, even more preferably at least 40 wt %, based on the total weight of the aqueous dispersion. The amount of water in the aqueous dispersion is preferably at most 95 wt %, more preferably at most 90 wt %, more preferably at most 85 wt %, more preferably at most 80 wt %, even more preferably at most 70 wt %, even more preferably at most 60 wt %, based on the total weight of the aqueous dispersion.

[0115] The polyaziridine compound as defined herein is present in the aqueous dispersion in an amount of preferably at least 5 wt %, more preferably at least 10 wt %, more preferably at least 15 wt %, more preferably at least 20 wt %, even more preferably at least 25 wt %, even more preferably at least 30 wt %, even more preferably at least 35 wt %, based on the total weight of the aqueous dispersion. The polyaziridine compound as defined herein is present in the aqueous dispersion in an amount of preferably at most 70 wt %, preferably at most 65 wt %, more preferably at most 60 wt %, even more preferably at most 55 wt %, based on the total weight of the aqueous dispersion.

[0116] Preferably, at least 50% by weight, more preferably at least 80% by weight, more preferably at least 95% by weight, and even more preferably at least 99% by weight of the polyaziridine compound as defined herein is present in a dispersed form in the polyaziridine crosslinker composition. Thus, the polyaziridine crosslinker composition of the present invention comprises particles comprising the polyaziridine compound as defined herein. The particles preferably have a scattering intensity-based average hydrodynamic diameter of 30 nm to 650 nm, more preferably 50 nm to 500 nm, even more preferably 70 nm to 350 nm, and even more preferably 120 nm to 275 nm. The scattering intensity-based average hydrodynamic diameter of the particles can be controlled in a variety of ways. For example, the scattering intensity-based average hydrodynamic diameter of the particles can be controlled during the preparation of the aqueous dispersion of the present invention by using different types of dispersants and / or different amounts of dispersants and / or by applying different shear stresses and / or by applying different temperatures. For example, the scattering intensity-based average hydrodynamic diameter of the particles is inversely proportional to the amount of dispersant used in the preparation of the aqueous dispersion of the present invention; for example, the scattering intensity-based average hydrodynamic diameter of the particles decreases by increasing the amount of dispersant. For example, the average hydrodynamic diameter of the particles based on the scattered intensity is inversely proportional to the shear stress applied during the preparation of the aqueous dispersion of the present invention; for example, the average hydrodynamic diameter of the particles based on the scattered intensity decreases by increasing the shear stress. Exemplary dispersants include, but are not limited to, ATLAS supplied by Croda TM G-5000、ATLAS TM G-5002L-LQ、Maxemul TM 7101.

[0117] The solids content of the aqueous dispersion is preferably at least 5% by weight, more preferably at least 10% by weight, even more preferably at least 20% by weight, even more preferably at least 30% by weight, even more preferably at least 35% by weight. The solids content of the aqueous dispersion is preferably at most 70% by weight, preferably at most 65% by weight, more preferably at most 55% by weight. The solids content of the aqueous dispersion is most preferably in the range of 35% to 55% by weight.

[0118] The polyaziridine compound as defined above is typically obtained in the form of a composition in which, in addition to the polyaziridine compound, there may be residual starting materials, by-products and / or solvents used in the preparation of the polyaziridine compound. The composition may contain only one polyaziridine compound as defined above, but may also contain more than one polyaziridine compound as defined above. For example, when a mixture of polyisocyanates is used as a starting material, a mixture of polyaziridine compounds is obtained. The aqueous dispersion of the present invention can be obtained by dispersing the polyaziridine compound in water and adjusting the pH of the aqueous dispersion to the desired value; or dispersing the polyaziridine compound in a mixture of water and at least one base, the mixture having a pH such as to obtain an aqueous dispersion having the desired pH value; or by adding a mixture of water and a base to the polyaziridine compound. The polyaziridines can be dispersed in water or in a mixture of water and at least one base using techniques well known in the art. The dispersion of the polyaziridine compound can be assisted by solvents and / or high shear.

[0119] The aqueous dispersion can also comprise the gross weight based on the aqueous dispersion, and amount is 35 wt % at the most, preferably 30 wt % at the most, for example 25 wt % at the most, for example 20 wt % at the most, for example 12 wt % at the most, for example 10 wt % at the most, for example 8 wt % at the most, for example 5 wt % at the most, for example 4 wt % at the most, for example 3 wt % at the most, for example 2 wt % at the most, for example 1 wt % at the most, for example 0.5 wt % at the most, for example 0.2 wt % at the most, for example 0.1 wt % organic solvent at the most. The organic solvent can optionally be added before, during and / or after the polyaziridine synthesis. The organic solvent can be used to help polyaziridine compounds to be dispersed in water. If necessary, the organic solvent can be removed from the polyaziridine crosslinker composition by decompression and / or increasing the temperature subsequently. Typical organic solvents are glycols, ethers, alcohols, cyclic carbonates, pyrrolidone, dimethylformamide, dimethyl sulfoxide, n-formylmorpholine, dimethylacetamide and ketone. Preferred solvents are glycols, ethers, alcohols, cyclic carbonates and ketones.

[0120] Preferably, the dispersion of the polyaziridine compound is carried out in the presence of a dispersant. Therefore, the aqueous dispersion of the present invention preferably contains a dispersant. In the context of the present invention, a dispersant is a substance that promotes the formation of the dispersion and colloid stabilization. In the present invention, the dispersant is preferably a substance that non-covalently attaches to the polyaziridine compound and / or the dispersant is a separate molecular component with surface activity. Examples of substances that non-covalently attach to the polyaziridine compound are amphiphilic compounds containing urea and / or carbamates, such as HEUR thickeners.

[0121] More preferably, the dispersant is at least one separate surface-active molecular component. Preferred separate surface-active molecular components are:

[0122] (i) a polyaziridine compound as defined above, said polyaziridine compound containing functional groups such as sulfonate, sulfate, phosphate and / or phosphonate functional groups, preferably sulfonate and / or phosphonate groups, more preferably sulfonate groups, and / or

[0123] (ii) a polymer, said polymer preferably having a number average molecular weight of at least 2000 Daltons, more preferably at least 2500 Daltons, more preferably at least 3000 Daltons, more preferably at least 3500 Daltons, more preferably at least 4000 Daltons, and preferably at most 1,000,000 Daltons, more preferably at most 100,000, at most 10,000 Daltons, as measured by MALDI-ToF-MS as described below.

[0124] More preferred separate surface active molecule components are polymers having a number average molecular weight of at least 2000 daltons, more preferably at least 2500 daltons, more preferably at least 3000 daltons, more preferably at least 3500 daltons, more preferably at least 4000 daltons, and preferably at most 1,000,000 daltons, more preferably at most 100,000, even more preferably at most 10,000 daltons as measured with MALDI-ToF-MS as described below. Preferred polymers are polyethers, more preferably polyether copolymers, even more preferably polyether block copolymers, even more preferably poly(alkylene oxide) block copolymers, even more preferably poly(ethylene oxide)-co(propylene oxide) block copolymers. Non-limiting examples of preferred separate surface active molecule dispersants are Atlas Dispersants available from Croda. TM G-5000, Maxemul obtained from Croda TM 7101 and / or obtained from BASF P84. The amount of the surface-active molecule component alone is generally in the range of 0.1 wt% to 20 wt%, preferably at least 0.5 wt%, more preferably at least 1 wt%, even more preferably at least 2 wt%, even more preferably at least 3 wt%, based on the total weight of the aqueous dispersion.

[0125] The polyaziridine compound containing a functional group (e.g., a sulfonate, sulfate, phosphate and / or phosphonate functional group), preferably a sulfonate functional group, as defined under (i) is preferably obtained by reacting part of the isocyanate groups of the polyisocyanate used to prepare the polyaziridine compound with a hydroxyl or amine functional ion constituent unit (preferably neutralized with an inorganic base). Examples of hydroxyl or amine functional ion constituent units include 2-(cyclohexylamino)ethanesulfonic acid, 3-cyclohexyl-amino)propanesulfonic acid, methyltaurine, taurine, DS-3404. Preferably, sulfonate is used as the hydroxyl or amine functional ion constituent unit.

[0126] The crosslinking efficiency of a crosslinking agent can be assessed by evaluating the chemical resistance as defined and determined as described below.

[0127] The storage stability of the aqueous dispersion according to the invention can be assessed by storing the aqueous dispersion, in particular at elevated temperature (e.g. 50° C.), and assessing the change in viscosity of the stored aqueous dispersion, as defined and measured as described below, and / or assessing the change in chemical resistance, in particular ethanol resistance, as defined and measured as described below, of the stored aqueous dispersion.

[0128] The storage stability of the aqueous dispersion of the present invention at 50° C. is preferably at least 2 weeks, more preferably at least 3 weeks, even more preferably at least 4 weeks. Storage stable at 50° C. for at least x weeks means that after the dispersion has been stored at 50° C. for x weeks, (i) the final viscosity of the dispersion is at most 50 times higher than the starting viscosity, preferably at most 45 times higher than the starting viscosity, more preferably at most 40 times higher than the starting viscosity, more preferably at most 35 times higher than the starting viscosity, more preferably at most 30 times higher than the starting viscosity, more preferably at most 25 times higher than the starting viscosity, more preferably at most 20 times higher than the starting viscosity, more preferably at most 15 times higher than the starting viscosity, more preferably at most 10 times higher than the starting viscosity, most preferably at most 5 times higher than the starting viscosity, and / or (ii) the chemical resistance of the aqueous dispersion, as defined and measured below, decreases by at most 3 points, preferably at most 2 points, even more preferably at most 1 point. Preferably, storage stable at 50°C for at least x weeks means that after the dispersion has been stored at 50°C for x weeks, (i) the final viscosity of the dispersion is at most 50 times higher than the initial viscosity, preferably at most 45 times higher than the initial viscosity, more preferably at most 40 times higher than the initial viscosity, more preferably at most 35 times higher than the initial viscosity, more preferably at most 30 times higher than the initial viscosity, more preferably at most 25 times higher than the initial viscosity, more preferably at most 20 times higher than the initial viscosity, more preferably at most 15 times higher than the initial viscosity, more preferably at most 10 times higher than the initial viscosity, most preferably at most 5 times higher than the initial viscosity, and (ii) the chemical resistance, as defined and measured as described below, of the aqueous dispersion decreases by at most 3 points, preferably at most 2 points, even more preferably at most 1 point. 'Initial viscosity' of the aqueous dispersion means the viscosity (as defined and measured as described below) of the aqueous dispersion determined at the time of its preparation and just before storage of said aqueous dispersion at 50°C. By 'end viscosity' of an aqueous dispersion is meant the viscosity (defined and measured as described below) of an aqueous dispersion determined after storage of said aqueous dispersion at 50°C for x weeks.

[0129] The present invention also relates to a process for preparing a polyaziridine crosslinker composition according to the invention, wherein the process comprises dispersing the polyaziridine compound as defined herein in water to obtain an aqueous dispersion; and adjusting the pH of the aqueous dispersion to the desired value, or preferably wherein the process comprises dispersing the polyaziridine compound as defined herein in a mixture of water and at least one base, the mixture having a pH such as to obtain an aqueous dispersion having the desired pH value.

[0130] In a preferred embodiment of the present invention, the dispersant is a single surface-active polymer (ii) having a number average molecular weight of at least 2000 Daltons. In this preferred embodiment, the process for preparing the polyaziridine crosslinker composition according to the present invention preferably comprises

[0131] A) optionally but preferably mixing a polyaziridine compound as defined above in an organic solvent,

[0132] B) mixing the polyaziridine compound as defined above or the solution obtained in step A) with a dispersant as described above to obtain a composition comprising the polyaziridine compound and the dispersant,

[0133] C) mixing water and a base or mixing a basic aqueous medium into the composition comprising the polyaziridine compound and the dispersant to obtain a dispersion

[0134] D) Optionally, but preferably, evaporating the organic solvent from the dispersion to obtain a further dispersion, and optionally mixing additional water or alkaline aqueous medium into the further dispersion to obtain the aqueous dispersion of the present invention.

[0135] Step C) is preferably carried out using a high shear dispersing device.

[0136] The present invention also relates to the use of a polyaziridine crosslinker composition according to the present invention for crosslinking a carboxylic acid functional polymer dissolved and / or dispersed, preferably dispersed in water, wherein the amount of aziridine groups and the amount of carboxylic acid groups are selected so that the stoichiometric amount (SA) of aziridine groups based on carboxylic acid groups is 0.1 to 2.0, more preferably 0.2 to 1.5, even more preferably 0.25 to 0.95, and most preferably 0.3 to 0.8. The carboxylic acid functional polymer contains carboxylic acid groups and / or carboxylate groups, which preferably do not contain covalent bonds that prevent these groups from chemically reacting with the aziridine moiety present in the polyaziridine compound. As used herein, the amount of carboxylic acid groups present in the carboxylic acid functional polymer is the total amount of deprotonated and protonated carboxylic acid groups present in the polymer to be crosslinked (i.e., in the carboxylic acid functional polymer). Therefore, the amount of carboxylic acid groups present in the carboxylic acid functional polymer is the total amount of carboxylate groups and carboxylic acid groups present in the carboxylic acid functional polymer. The polymer to be crosslinked preferably comprises carboxylate groups that are at least partially neutralized by a base. Preferably, at least a portion of the base is a volatile base. Preferably, at least a portion of the carboxylic acid groups present in the carboxylic acid-functional polymer to be cross-linked undergoes deprotonation to obtain carboxylate groups. Deprotonation is achieved by neutralizing the carboxylic acid-functional polymer with a base. Examples of suitable bases are ammonia, secondary amines, tertiary amines, LiOH, NaOH, and / or KOH. Examples of secondary and tertiary amines are as described above. Preferred bases are tertiary amines. Preferred tertiary amines are as described above. Most preferred is triethylamine.

[0137] To avoid undesirable premature crosslinking reactions between the crosslinker and the polymer to be crosslinked during storage of the polyaziridine crosslinker composition, it is known to those skilled in the art that the polyaziridine crosslinker composition is preferably not mixed with the polymer to be crosslinked during storage of the polyaziridine crosslinker composition; the reason being that the crosslinking reaction between the crosslinker and the polymer to be crosslinked may begin immediately after the crosslinker and the polymer to be crosslinked are mixed. Therefore, it is preferred that the polyaziridine crosslinker composition of the present invention does not contain the polymer to be crosslinked. Therefore, the present invention also relates to a two-component coating system comprising a first component and a second component, each of the first component and the second component being separate and different from each other, and wherein the first component comprises a carboxylic acid-functional polymer dissolved and / or dispersed (preferably dispersed) in an aqueous medium, and the second component comprises the polyaziridine crosslinker composition of the present invention, wherein the first component and the second component are stored separately because the crosslinking reaction between the crosslinker and the polymer to be crosslinked may begin immediately after mixing the crosslinker with the aqueous composition of the polymer to be crosslinked. As used herein, a coating composition refers to a composition comprising a polymer to be crosslinked, the polymer being dissolved and / or dispersed (preferably dispersed) in water; and further comprising the polyaziridine crosslinker composition of the present invention.

[0138] The present invention also relates to a coating composition obtained by mixing the first component and the second component of a two-component system immediately before applying the coating composition, wherein the coating composition comprises aziridinyl groups Q and carboxylic acid groups in such amounts that the stoichiometric amount (SA) of aziridinyl groups Q on the carboxylic acid groups is preferably from 0.1 to 2.0, more preferably from 0.2 to 1.5, even more preferably from 0.25 to 0.95, most preferably from 0.3 to 0.8.

[0139] The present invention also relates to a coated substrate obtained by: (i) applying a coating composition as described above to a substrate, and (ii) drying the coating composition by evaporating the volatiles. The coating composition is preferably dried at a temperature below 160°C, preferably below 90°C, more preferably below 50°C, and most preferably at ambient temperature. The coating composition according to the present invention can be applied to any type of substrate, such as wood, leather, concrete, textiles, plastics, vinyl flooring, glass, metal, ceramics, paper, wood-plastic composites, and fiberglass-reinforced materials. The thickness of the dried coating on the substrate is preferably 1 to 200 microns, more preferably 5 to 150 microns, and most preferably 15 to 90 microns. If the coating composition is an ink composition, the thickness of the dried ink is preferably 0.005 to 35 microns, more preferably 0.05 to 25 microns, and most preferably 4 to 15 microns.

[0140] Non-limiting examples of cross-linkable carboxylic acid functional polymers are vinyl polymers (e.g., styrene-acrylic acid), (meth)acrylic acid copolymers, vinyl acetate (co)polymers (e.g., vinyl acetate vinyl chloride ethylene polymers), polyurethanes, condensation polymers (e.g., polyesters, polyamides, polycarbonates), and hybrids of any of these polymers where at least one of the two polymers has carboxylic acid functional groups.

[0141] The carboxylic acid functional polymer is preferably selected from the group consisting of polyesters, polycarbonates, polyamides, vinyl polymers, polyacrylates, polymethacrylates, poly(acrylate-co-methacrylates), polyurethanes, poly(urethane-co-acrylates), poly(urethane-co-methacrylates), poly(urethane-co-acrylates-co-methacrylates), polyureas, and mixtures thereof. In one embodiment of the present invention, the preferred crosslinkable carboxylic acid functional polymer is selected from the group consisting of vinyl polymers, polyacrylates, polymethacrylates, poly(acrylate-co-methacrylates), and mixtures thereof. Preferably, vinyl polymers are meant to be polymers comprising reacted residues of styrene with acrylates and / or methacrylates. In another embodiment, the carboxylic acid functional polymer is selected from the group consisting of polyurethanes, poly(urethane-co-acrylates), poly(urethane-co-methacrylates), poly(urethane-co-acrylates-co-methacrylates), polyureas, and mixtures thereof.

[0142] The acid value of the carboxylic acid functional polymer is preferably 2 mg KOH / gram carboxylic acid functional polymer to 135 mg KOH / gram carboxylic acid functional polymer, more preferably 3 mg KOH / gram carboxylic acid functional polymer to 70 mg KOH / gram carboxylic acid functional polymer, even more preferably 10 mg KOH / gram carboxylic acid functional polymer to 50 mg KOH / gram carboxylic acid functional polymer, even more preferably 15 mg KOH / gram carboxylic acid functional polymer to 50 mg KOH / gram carboxylic acid functional polymer. Where a high crosslink density is desired, the acid value of the carboxylic acid functional polymer is preferably 50 mg KOH / gram carboxylic acid functional polymer to 200 mg KOH / gram carboxylic acid functional polymer. As used herein, the acid value of the carboxylic acid functional polymer is calculated according to the formula AV = ((total moles of carboxylic acid components contained in the carboxylic acid functional polymer / total grams of components contained in the carboxylic acid functional polymer)) * 56.1 * 1000) and is expressed as mg KOH / gram carboxylic acid functional polymer. Thus, the acid value of the carboxylic acid functional polymer can be controlled by the molar amount of the carboxylic acid component used to prepare the carboxylic acid functional polymer.If the acid value cannot be properly calculated, the acid value is determined by ASTM D1639-90 (1996) e1.

[0143] The number average molecular weight M of the carboxylic acid functional polymer n The ratio of the number average molecular weight M of the carboxylic acid functional polymer to the acid value of the carboxylic acid functional polymer is preferably at least 150, more preferably at least 300, even more preferably at least 600, even more preferably at least 1000, even more preferably at least 5000, and most preferably at least 15000. As used herein, the number average molecular weight M of the carboxylic acid functional polymer is n Determined by size exclusion chromatography using NMP-MEK.

[0144] The present invention is further defined by a set of exemplary embodiments as set out below. Unless otherwise indicated herein or if it is obvious to a skilled person that it is not technically feasible, any one of the embodiments, aspects and preferred features or ranges as disclosed in this application may be combined in any combination.

[0145] [1] A polyaziridine crosslinker composition, wherein the polyaziridine crosslinker composition is an aqueous dispersion having a pH in the range of 8 to 14 and comprising a polyaziridine compound in dispersed form, wherein

[0146] The polyaziridine compound has:

[0147] a. 2 to 6 of the following structural units A:

[0148]

[0149] in

[0150] R1 is H,

[0151] R2 and R4 are independently selected from H or an aliphatic hydrocarbon group containing 1 to 4 carbon atoms,

[0152] R3 is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms,

[0153] m is 1,

[0154] R' and R" according to (1) or (2):

[0155] (1) R' = H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms; and

[0156] R"=H, an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, an alicyclic hydrocarbon group containing 5 to 12 carbon atoms, an aromatic hydrocarbon group containing 6 to 12 carbon atoms, CH2-O-(C=O)-R"', CH2-OR"" or CH2-(OCR""'HCR""'H) n -OR""", wherein R"' is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms and R"" is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms or an aromatic hydrocarbon group containing 6 to 12 carbon atoms, n is 1 to 35, R""' is independently H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, and R""" is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms,

[0157] (2) R' and R" together form a saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms,

[0158] t is 0,

[0159] R5 is H or CH3,

[0160] X is O and Y is NH;

[0161] b. one or more link chains, wherein each of these link chains links two structural units A in the structural unit A; and

[0162] c. Molecular weight in the range of 500 Daltons to 10,000 Daltons.

[0163] [2] The polyaziridine crosslinker composition according to embodiment 1, wherein R2 is H, R3 is C2H5 and R4 is H.

[0164] [3] The polyaziridine crosslinker composition according to embodiment 1, wherein R2 is H, R3 is CH3 and R4 is H.

[0165] [4] The polyaziridine crosslinker composition according to embodiment 1, wherein R2 is H, R3 is CH3 and R4 is CH3.

[0166] [5] A polyaziridine crosslinker composition according to any one of embodiments [1] to [4], wherein the linking chain consists of 4 to 300 atoms, more preferably 5 to 250 atoms, and most preferably 6 to 100 atoms, and the linking chain is a collection of covalently linked atoms, and the collection of atoms consists of i) carbon atoms, ii) carbon and nitrogen atoms, or iii) carbon, oxygen, and nitrogen atoms.

[0167] [6] The polyaziridine crosslinker composition according to any one of embodiments [1] to [5], wherein the polyaziridine compound contains 2 or 3 structural units A.

[0168] [7] The polyaziridine crosslinker composition according to any one of embodiments [1] to [6], wherein

[0169] R' and R" according to (1) or (2):

[0170] (1) R'=H or an alkyl group containing 1 to 2 carbon atoms;

[0171] R"=H, an aliphatic hydrocarbon group containing 1 to 4 carbon atoms, CH2-O-(C=O)-R"', CH2-OR"" or CH2-(OCR""'HCR""'H)n-OR""", wherein R"' is an alkyl group containing 1 to 14 carbon atoms and R"" is an alkyl group containing 1 to 14 carbon atoms, n is 1 to 35, R""' is independently H or methyl, and R""" is an alkyl group containing 1 to 4 carbon atoms;

[0172] (2) R' and R" together form a saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms.

[0173] [8] A polyaziridine crosslinker composition according to any one of embodiments [1] to [7], wherein R' is H and R" = an alkyl group containing 1 to 4 carbon atoms, CH2-O-(C=O)-R"', CH2-OR"", wherein R"' is an alkyl group containing 3 to 12 carbon atoms and R"" is an alkyl group containing 1 to 14 carbon atoms.

[0174] [9] A polyaziridine crosslinker composition according to any one of embodiments [1] to [8], wherein the polyaziridine compound comprises one or more linking groups, wherein each of these linking groups links two structural units A in the structural unit A, wherein the linking group is composed of at least one functional group selected from the group consisting of: an aliphatic hydrocarbon functional group (preferably containing 1 to 8 carbon atoms), an alicyclic hydrocarbon functional group (preferably containing 4 to 10 carbon atoms), an aromatic hydrocarbon functional group (preferably containing 6 to 12 carbon atoms), an isocyanurate functional group, an iminooxadiazinedione functional group, an ether functional group, an ester functional group, an amide functional group, a carbonate functional group, a carbamate functional group, a urea functional group, a biuret functional group, an allophanate functional group, a uretdione functional group, and any combination thereof.

[0175]

[10] A polyaziridine crosslinker composition according to embodiment [9], wherein the linking group consists of at least one aliphatic hydrocarbon functional group and / or at least one alicyclic hydrocarbon functional group and optionally at least one aromatic hydrocarbon functional group and optionally an isocyanurate functional group or an iminooxadiazinedione functional group.

[0176]

[11] The polyaziridine crosslinker composition according to embodiment [9], wherein the linking group consists of at least one aliphatic hydrocarbon functional group and / or at least one alicyclic hydrocarbon functional group and an isocyanurate functional group or an iminooxadiazinedione functional group.

[0177]

[12] The polyaziridine crosslinker composition according to any one of embodiments [1] to [8], wherein the polyaziridine compound comprises one or more linking groups, wherein each of the linking groups links two of the structural units A, wherein the linking group consists of (i) at least two aliphatic hydrocarbon functional groups and (ii) an isocyanurate functional group or an iminooxadiazinedione functional group, and wherein a pendant group is present on the linking group, wherein the pendant group has the following structural formula:

[0178]

[0179] n′ is the number of repeating units and is an integer of 1 to 50, preferably 2 to 30, more preferably 5 to 20.

[0180] X is O or NH, preferably X is O,

[0181] In each repeating unit, R7 and R8 are independently H or CH3,

[0182] R9 is an aliphatic hydrocarbon group, preferably containing 1 to 8 carbon atoms, and

[0183] R 10Preferred are aliphatic hydrocarbon groups (preferably CH 3 ) containing 1 to 20 carbon atoms, alicyclic hydrocarbon groups containing 5 to 20 carbon atoms, or aromatic hydrocarbon groups containing 6 to 20 carbon atoms.

[0184]

[13] A polyaziridine crosslinker composition, wherein the composition is an aqueous dispersion having a pH in the range of 8 to 14 and comprising a polyaziridine compound in dispersed form, wherein the polyaziridine compound has 2 to 6 structural units A as defined in embodiment [1], wherein R1, R2, R3, R4, R', R", m, t, R5, X and Y are as defined in any one of embodiments [1] to

[12] , wherein the polyaziridine compound has a molecular weight of 500 Daltons to 10,000 Daltons, and wherein the polyaziridine compound further comprises one or more linking groups, wherein Each of these linking groups connects two structural units A in the structural unit A, wherein the linking group is composed of at least one functional group selected from the group consisting of: an aliphatic hydrocarbon functional group (preferably containing 1 to 8 carbon atoms), an alicyclic hydrocarbon functional group (preferably containing 4 to 10 carbon atoms), an aromatic hydrocarbon functional group (preferably containing 6 to 12 carbon atoms), an isocyanurate functional group, an iminooxadiazinedione functional group, an ether functional group, an ester functional group, an amide functional group, a carbonate functional group, a carbamate functional group, a urea functional group, a biuret functional group, an allophanate functional group, a uretdione functional group and any combination thereof.

[0185]

[14] The polyaziridine crosslinker composition according to any one of embodiments [1] to

[13] , wherein the structural unit A is according to the following structural formula D:

[0186]

[0187]

[15] The polyaziridine crosslinker composition according to any one of embodiments [1] to

[14] , wherein the polyaziridine compound is obtained by reacting at least a polyisocyanate with a compound B having the following structural formula:

[0188]

[0189] wherein the molar ratio of compound B to polyisocyanate is 2 to 6, more preferably 2 to 4, most preferably 2 to 3, and wherein m, R', R", R1, R2, R3 and R4 are as defined in the preceding embodiments.

[0190]

[16] The polyaziridine crosslinker composition according to embodiment

[15] , wherein the polyisocyanate is a polyisocyanate having aliphatic reactivity.

[0191]

[17] The polyaziridine crosslinker composition according to embodiment

[15] or

[16] , wherein compound B is obtained by reacting at least a non-OH functional monoepoxide compound with an aziridine having the following structural formula:

[0192]

[0193] wherein R1, R2, R3 and R4 are as defined in the above embodiments.

[0194]

[18] A polyaziridine crosslinker composition according to embodiment

[17] , wherein the non-OH functional monoepoxide compound is selected from the group consisting of ethylene oxide, propylene oxide, 2-ethylethylene oxide, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, neodecanoic acid glycidyl ester and any mixture thereof.

[0195]

[19] A polyaziridine crosslinker composition according to any one of embodiments

[15] to

[18] , wherein the polyaziridine compound is a reaction product of at least compound (B), a polyisocyanate, and an alkoxy poly(propylene glycol) and / or poly(propylene glycol).

[0196]

[20] A polyaziridine crosslinker composition according to any one of embodiments [1] to

[19] , wherein the molecular weight of the polyaziridine compound is 600 Daltons to 5000 Daltons, more preferably the molecular weight of the polyaziridine compound is at least 800 Daltons, even more preferably at least 840 Daltons, even more preferably at least 1000 Daltons, and preferably at most 3800 Daltons, more preferably at most 3600 Daltons, more preferably at most 3000 Daltons, more preferably at most 1600 Daltons, even more preferably at most 1400 Daltons.

[0197]

[21] A polyaziridine crosslinker composition according to any one of embodiments [1] to

[20] , wherein the aqueous dispersion contains aziridine-functional molecules having a molecular weight of less than 580 Daltons in an amount of less than 5 wt %, based on the total weight of the aqueous dispersion, wherein the molecular weight is determined using LC-MS as described in the specification.

[0198]

[22] The polyaziridine crosslinker composition according to any one of embodiments [1] to

[21] , wherein the pH of the aqueous dispersion is at least 8.5, more preferably at least 9, and more preferably at least 9.5.

[0199]

[23] The polyaziridine crosslinker composition according to any one of embodiments [1] to

[22] , wherein the pH of the aqueous dispersion is at most 14, more preferably at most 13, even more preferably at most 12, even more preferably at most 11.5.

[0200]

[24] The polyaziridine crosslinker composition according to any one of embodiments [1] to

[23] , wherein the pH of the aqueous dispersion is in the range of 9.5 to 11.5.

[0201]

[25] A polyaziridine crosslinker composition according to any one of embodiments [1] to

[24] , wherein the aqueous dispersion contains ammonia, a secondary amine, a tertiary amine, LiOH, NaOH and / or KOH to adjust the pH to the desired value, preferably the aqueous dispersion contains a tertiary amine selected from the following: n-ethylmorpholine, n-methylpiperidine, n,n-dimethylbutylamine, dimethylisopropylamine, dimethyl-n-propylamine, dimethylethylamine, triethylamine and / or dimethylbenzylamine, most preferably contains triethylamine to adjust the pH to the desired value.

[0202]

[26] A polyaziridine crosslinker composition according to any one of embodiments [1] to

[25] , wherein the amount of water in the aqueous dispersion is at least 15 wt %, preferably at least 20 wt %, more preferably at least 30 wt %, and even more preferably at least 40 wt %, based on the total weight of the aqueous dispersion.

[0203]

[27] A polyaziridine crosslinker composition according to any one of embodiments [1] to

[26] , wherein the amount of water in the aqueous dispersion is at most 95 wt %, preferably at most 90 wt %, more preferably at most 85 wt %, more preferably at most 80 wt %, even more preferably at most 70 wt %, even more preferably at most 60 wt %, based on the total weight of the aqueous dispersion.

[0204]

[28] A polyaziridine crosslinker composition according to any one of embodiments [1] to

[27] , wherein the amount of the polyaziridine compound in the aqueous dispersion is at least 5 wt %, preferably at least 10 wt %, more preferably at least 15 wt %, more preferably at least 20 wt %, even more preferably at least 25 wt %, even more preferably at least 30 wt %, even more preferably at least 35 wt %, based on the total weight of the aqueous dispersion.

[0205]

[29] A polyaziridine crosslinker composition according to any one of embodiments [1] to

[28] , wherein the amount of the polyaziridine compound in the aqueous dispersion is at most 70 wt %, preferably at most 65 wt %, more preferably at most 60 wt %, and even more preferably at most 55 wt %, based on the total weight of the aqueous dispersion.

[0206]

[30] A polyaziridine crosslinker composition according to any one of embodiments [1] to

[29] , wherein the aqueous dispersion further comprises an organic solvent in an amount of up to 35 wt %, preferably up to 30 wt %, for example up to 25 wt %, for example up to 20 wt %, for example up to 12 wt %, for example up to 10 wt %, for example up to 8 wt %, for example up to 5 wt %, for example up to 4 wt %, for example up to 3 wt %, for example up to 2 wt %, for example up to 1 wt %, for example up to 0.5 wt %, for example up to 0.2 wt %, for example up to 0.1 wt %, based on the total weight of the aqueous dispersion.

[0207]

[31] A polyaziridine crosslinker composition according to any one of embodiments [1] to

[30] , wherein the solids content of the aqueous dispersion is at least 5 wt %, preferably at least 10 wt %, even more preferably at least 20 wt %, even more preferably at least 30 wt %, even more preferably at least 35 wt %, and at most 70 wt %, more preferably at most 65 wt % and even more preferably at most 55 wt %.

[0208]

[32] A polyaziridine crosslinker composition according to any one of embodiments [1] to

[31] , wherein the particles have an average hydrodynamic diameter based on scattering intensity of 30 nm to 650 nm, preferably 50 nm to 500 nm, more preferably 70 nm to 350 nm, and even more preferably 120 nm to 275 nm.

[0209]

[33] The polyaziridine crosslinker composition according to any one of embodiments [1] to

[32] , wherein the aqueous dispersion contains a dispersant.

[0210]

[34] A polyaziridine crosslinker composition according to any one of embodiments [1] to

[32] , wherein the aqueous dispersion contains a separate surface-active molecular component as a dispersant, and the amount of the separate surface-active molecular component is in the range of 0.1 wt % to 20 wt %, based on the total weight of the aqueous dispersion, preferably at least 0.5 wt %, more preferably at least 1 wt %, even more preferably at least 2 wt %, even more preferably at least 3 wt %.

[0211]

[35] A polyaziridine crosslinker composition according to embodiment

[34] , wherein the dispersant is a polymer having a number average molecular weight of at least 2000 Daltons, more preferably at least 2500 Daltons, more preferably at least 3000 Daltons, more preferably at least 3500 Daltons, more preferably at least 4000 Daltons, and preferably at most 1000000 Daltons, more preferably at most 100000 Daltons, at most 10000 Daltons.

[0212]

[36] A polyaziridine crosslinker composition according to any one of embodiments

[33] to

[35] , wherein the dispersant is a polyether, more preferably a polyether copolymer, even more preferably a polyether block copolymer, even more preferably a poly(alkylene oxide) block copolymer, even more preferably a poly(ethylene oxide)-co-poly(propylene oxide) block copolymer.

[0213]

[37] The polyaziridine crosslinker composition according to any one of embodiments [1] to

[36] , wherein the aqueous dispersion has a storage stability at 50°C for at least 2 weeks, more preferably at least 3 weeks, and even more preferably at least 4 weeks.

[0214]

[38] A polyaziridine crosslinker composition according to any one of embodiments [1] to

[37] , wherein the number of consecutive C atoms and optional O atoms between the N atom of the carbamate group in structural unit D and the next N atom present in the linking chain or being the N atom of the carbamate group of another structural unit D is at most 9.

[0215]

[39] A polyaziridine crosslinker composition according to any one of embodiments [1] to

[38] , wherein the polyaziridine crosslinker composition is used to crosslink a carboxylic acid functional polymer dissolved and / or dispersed, preferably dispersed, in an aqueous medium, wherein the carboxylic acid functional polymer contains carboxylic acid groups and / or carboxylate groups.

[0216]

[40] The polyaziridine crosslinker composition according to any one of embodiments [1] to

[36] , wherein the polyaziridine crosslinker composition does not contain a polymer to be crosslinked with the polyaziridine crosslinker composition.

[0217]

[41] A method for preparing a polyaziridine crosslinker composition according to any one of embodiments [1] to

[40] , wherein the method comprises dispersing the polyaziridine compound as defined in any one of the preceding embodiments in water to obtain an aqueous dispersion and adjusting the pH of the aqueous dispersion to a desired value, or wherein the method comprises dispersing the polyaziridine compound as defined in any one of the preceding embodiments in a mixture of water and at least one base, the mixture having a pH such that an aqueous dispersion having a desired pH value is obtained.

[0218]

[42] A method according to embodiment

[41] , wherein the method comprises mixing a basic aqueous medium into the polyaziridine compound as defined in any of the preceding embodiments, wherein the pH of the basic aqueous medium is selected to obtain an aqueous dispersion having a desired pH value.

[0219]

[43] The method according to embodiment

[41] or

[42] , wherein the method comprises

[0220] A) optionally but preferably mixing a polyaziridine compound as defined in any one of the preceding embodiments in an organic solvent,

[0221] B) mixing the polyaziridine compound as defined in any of the preceding embodiments or the solution obtained in step A) with a dispersant to obtain a composition comprising the polyaziridine compound and a dispersant,

[0222] C) mixing water and a base or mixing a basic aqueous medium into the composition comprising the polyaziridine compound and the dispersant to obtain a dispersion

[0223] D) optionally, but preferably, evaporating the organic solvent from the dispersion to obtain a further dispersion, and optionally mixing additional water or alkaline aqueous medium into the further dispersion to obtain an aqueous dispersion according to any one of embodiments [1] to

[39] .

[0224]

[44] Use of a polyaziridine crosslinker composition according to any one of embodiments [1] to

[40] or obtained by the method according to any one of embodiments

[41] to

[43] for crosslinking a carboxylic acid functional polymer dissolved and / or dispersed, preferably dispersed, in an aqueous medium, wherein the amount of aziridine groups and the amount of carboxylic acid groups are selected such that the stoichiometric amount (SA) of aziridine groups calculated as carboxylic acid groups is from 0.1 to 2.0, more preferably from 0.2 to 1.5, even more preferably from 0.25 to 0.95, most preferably from 0.3 to 0.8.

[0225]

[45] A two-component coating system comprising a first component and a second component, each of the first component and the second component being independent and different from each other, and wherein the first component comprises a carboxylic acid functional polymer dissolved and / or dispersed, preferably dispersed, in an aqueous medium, and the second component comprises a polyaziridine crosslinker composition according to any one of embodiments [1] to

[40] or obtained using the method according to any one of embodiments

[41] to

[43] .

[0226]

[47] A substrate having a coating obtained by: (i) applying a coating composition obtained by mixing the first component and the second component of the two-component coating system according to embodiment

[45] to the substrate; and (ii) drying the coating composition by evaporating volatiles.

[0227] The invention will now be illustrated by reference to the following examples. Unless otherwise indicated, all parts, percentages and ratios are by weight.

[0228] Particle size measurement

[0229] The average hydrodynamic diameter of the particles based on the scattered intensity was determined using a method derived from the ISO 22412:2017 standard using a Malvern Zetasizer Nano S90 DLS instrument, which was operated under the following settings: as a material, polystyrene latex was defined as having an RI of 1.590 and an absorbance of 0.10 for a demineralized water continuum with a viscosity of 0.8812 cP and an RI of 1.332 at 25 ° C. Measurements were performed in a DTS0012 disposable cuvette obtained from Malvern Instruments (Malvern, Worcestershire, United Kingdom). The measurements were performed at a 173 ° backscattering angle, averaging 3 measurements after 120 seconds of equilibrium, consisting of 10-15 sub-runs - optimized by the machine itself. The focus of the laser was located at a fixed position of 4.65 cm, and the data were analyzed using a universal data fitting process. Samples were prepared by diluting 0.05 g (1 drop) of sample dispersion in approximately 5 mL of demineralized water. If the sample still looks turbid, dilute further with distilled water until the sample becomes almost clear. This method is suitable for determining particle sizes between 2 nm and 3 μm.

[0230] pH measurement

[0231] The pH of the samples was determined according to ISO 976:2013. The samples were measured using a Metrohm 691 pH meter equipped with a combined glass electrode and a PT-1000 temperature sensor at 23° C. The pH meter was calibrated before use using buffer solutions of pH 7.00 and 9.21.

[0232] NCO determination

[0233] The NCO content of the sample was determined according to ASTM D2572-19. In this procedure, the sample is reacted with an excess of n-dibutylamine. The excess n-dibutylamine is then back-titrated with standard 1N hydrochloric acid (HCl). The difference in titration volume between the sample and the blank is a measure of the isocyanate content based on solids, according to the following formula: % NCO 固体 =[(Vb-Vm)*N*4.2] / (A*s / 100), where %NCO 固体 is the isocyanate content in solids, Vb is the volume of HCl used in the blank, Vm is the volume of HCl used in the sample, N is the normality of the HCl solution, A is the sample weight in grams, and s is the solids content of the sample in %. The measurements were performed in duplicate on a Metrohm 702SM Titrino titrator using the potentiometric endpoint (if the difference between the two replicates was <0.1%NCO , then accept the measurement result).

[0234] AV determination

[0235] The acid value (AV) of a sample's solid matter is determined based on ASTM D1639-90 (1996) e1. In this procedure, a sample dissolved in a good solvent is titrated with an alcoholic potassium hydroxide solution of known concentration (KOH). The difference in titration volume between the sample and the blank is a measure of the solid matter's acid value, according to the following formula: AV = [(Vblank - Vsample)*N KOH *56.1] / (W*S / 100), where AV is the solid acid value in mg KOH / g solid matter, Vblank is the volume of KOH solution used in the blank, Vsample is the volume of KOH solution used in the sample, and N KOH is the normality of the KOH solution, W is the sample weight in grams, and S is the solids content of the sample in %. The measurements were performed in duplicate using a potentiometric endpoint on a Metrohm 702SM Titrino titrator (the results were accepted if the difference between the two replicates was <0.1 mg KOH / g solid matter).

[0236] Chemical resistance

[0237] Chemical resistance test based on DIN 68861-1:2011-01.

[0238] Unless otherwise stated, chemical resistance testing is as follows:

[0239] The coating composition consisted of 0.9 stoichiometric amounts (SA) of total carboxylic acid reactive functional groups (e.g., aziridine) compared to the carboxylic acid functional groups. The coating composition was processed as described in the examples and then cast using a wire rod coater at a wet layer thickness of 100 μm. After casting, the film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was soaked in 1:1 ethanol: demineralized water (by weight) and placed on the film for 60 minutes (unless otherwise stated). After removing the cotton wool and allowing it to recover overnight, the spots were scored according to the following scale:

[0240] 1 Complete coating degradation

[0241] 2 Structural damage to the coating

[0242] 3 Severe markings on the coating, visible from multiple directions

[0243] 4 Slight marks on the coating, visible from certain angles

[0244] 5 No marking or gloss change observed

[0245] Viscosity measurement:

[0246] Apparent viscosity was determined according to ISO 2555:2018. Measurements were performed at 23°C on a Brookfield DVE-LV viscometer (single cylinder geometry) at 60 rpm. Spindle selection was from S62, S63, or S64, using the lowest numbered spindle (i.e., the largest spindle) that produced a torque reading between 10% and 100%.

[0247] Size exclusion chromatography using NMP-MEK

[0248] The molecular weight distribution was measured using an Alliance separation module (Waters e2695), which includes a pump, autosampler, degasser, and column oven. The eluent was 80% n-methylpyrrolidone (NMP) / 20% methyl ethyl ketone (MEK) with 0.01 M lithium bromide added. The injection volume was 150 μl. The flow rate was set to 1.0 ml / min. Three PL Mixed B (Polymer Laboratories) with guard columns (5 μm PL) were applied at a temperature of 70°C. Detection was performed at 50°C using a differential refractive index detector (Waters 2414). The sample was dissolved in the eluent at a concentration of 5 mg polymer / mL solvent. Solubility was determined using a laser pointer after stabilization at room temperature for 24 hours; if any scattering was visible, the sample was first filtered. Calculations were performed using eight polystyrene standards (Polymer Standards Service) ranging from 160 Daltons to 1,737,000 Daltons. Calculations were performed using Empower software (Waters) with a third-order calibration curve. The molar masses obtained are polystyrene equivalent molar masses (Daltons).

[0249] T by DSC g Measurement

[0250] The glass transition temperature (T) of the polymers was measured by differential scanning calorimetry (DSC) at a heating rate of 10°C / min in a N2 atmosphere at a flow rate of 50 mL / min on a TA Instruments Discovery DSC 250 device according to the following method: g): Weigh 5±0.5 mg of sample and place it in a DSC chamber at a temperature between 20°C and 25°C. Cool the sample to -120°C and equilibrate at this temperature; after equilibration, heat the sample from -120°C to 160°C at a heating rate of 5°C / min; hold the sample at this temperature for 2 minutes and then cool it to -120°C at a cooling rate of 20°C / min; once the sample reaches -120°C, maintain the temperature for 5 minutes; then heat the sample from -120°C to 220°C at a heating rate of 5°C / min (thermogram A). T is measured from this final thermogram (thermogram A). g , for T g The half-width of the steps in the observed DSC signal (DSC thermogram, heat flow versus temperature). DSC signal processing and T were performed using TRIOS software version 5.0 provided by TA instruments. g Determination of.

[0251] Analysis of low molecular weight fractions by LC-MS

[0252] LC system: Agilent 1290 Infinity II; Detector No. 1: Agilent 1290 Infinity IIPDA; Detector No. 2: Agilent iFunnel 6550Q-TOF-MS.

[0253] LC-MS analysis of the low molecular weight fraction was performed using the following procedure. A solution of approximately 100 mg / kg of material in methanol was prepared gravimetrically and stirred. 0.5 μl of this solution was injected into a UPLC equipped with ESI-TOF-MS detection. The column used was a 100 × 2.1 mm, 1.8 μm, Waters HSS T3 C18 column operated at 40°C. The flow rate was 0.5 ml / min. -1 . The solvent used is 10mM NH4CH3COO aqueous solution (eluent A), acetonitrile (B) and THF (C) set to pH 9.0 with NH3. Two binary gradients from 80 / 20A / B to 1 / 99A / B and from 1 / 99A / B to 1 / 49 / 50A / B / C in 10 minutes are applied, after which the starting condition (80 / 20A / B) is applied. Assuming that all components have linear MS responses in all response ranges and that the ionization efficiency of all components is equal, the total ion current signal is integrated. In the case of coelution, the extracted ion chromatogram of the specific species is integrated. The integral signal of the specific low molecular weight peak is divided by the total integral sample signal to produce the score of the low molecular weight substance.

[0254] MALDI-ToF-MS

[0255] All MALDI-ToF-MS spectra are obtained using Bruker Ultraflextreme MALDI-ToF mass spectrometer. The instrument is equipped with an Nd:YAG laser and a collision cell (not used for these samples) emitted at 1064nm. Use a reflectron, use the highest resolution mode (scope of 60-7000m / z) providing accurate mass to obtain spectrum in positive ion mode. Use cesium triiodide (scope of 0.3-3.5kDa) to carry out mass calibration (calibration method: IAV molecular characterization, code MC-MS-05). The laser energy is 20%. Sample is dissolved in THF with approximately 50mg / mL. The matrix used is: DCTB (trans 2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene] malononitrile), CAS number 300364-84-5. Prepare matrix solution by dissolving 20mg in 1mL THF.

[0256] Sodium iodide (NaI, CAS No. 7681-82-5) was used as the salt; 10 mg was dissolved in 1 ml of THF and one drop of MeOH was added. The sample:matrix:salt ratio was 10:200:10 (μl). After mixing, 0.5 μl was spotted onto a MALDI plate and air-dried. The peak measured in the MALDI spectrum is the sodium adduct of the polyaziridine compound, and in the context of this specification, the molecular weight (MW) of the polyaziridine compound corresponds to MW = observed [M + M 阳离子 ]–M 阳离子 , where the observed [M+M 阳离子 ] is a MALDI-TOF MS peak, and M 阳离子 is the exact mass of the cation used to prepare the adduct (in this case, M of sodium 阳离子 = 23.0 Da). Polyaziridine compounds can be identified by comparing the MW to the exact molecular mass of the theoretical structure (ie the sum of the non-isotopic average atomic masses of its constituent atoms), using a maximum deviation of 0.6 Da.

[0257] Genotoxicity testing

[0258] pass Genotoxicity is assessed using the ToxTracker assay (Toxys, Leiden, the Netherlands). The ToxTracker assay is a panel of several validated green fluorescent protein (GFP)-based mouse embryonic stem (mES) reporter cell lines that can be used to identify the bioactivity and potential carcinogenicity of newly developed compounds in a single test. The method uses a two-step approach.

[0259] In a first step, dose-range finding was performed using wild-type mES cells (line B4418). 20 different concentrations of each compound were tested, starting with 10 mM in DMSO as the highest concentration, and 19 serial 2-fold dilutions.

[0260] Next, genotoxicity was assessed using specific genes linked to reporter genes for detecting DNA damage; the specific genes were Bscl2 (as described by US9695481B2 and EP2616484B1) and Rtkn (Hendriks et al., Toxicol. Sci. 2015, 150, 190-203) biomarkers. Genotoxicity was assessed at 10%, 25%, and 50% cytotoxicity in the absence and presence of a metabolic system based on rat S9 liver extract (aroclor1254-induced rats, Moltox, Boone, NC, USA). Independent cell lines were seeded into 96-well cell culture plates, and fresh ES cell culture medium containing diluted test substances was added to the cells 24 hours after the cells were seeded into the 96-well plates. For each compound tested, five concentrations were tested at 2-fold dilutions. The highest sample concentration induced significant cytotoxicity (50-70%). In the case of no or low cytotoxicity, 10 mM or the maximum soluble mixture concentration was used as the maximum test concentration.Cytotoxicity was determined by counting cells after 24 hours of exposure using a Guava easyCyte 10HT flow cytometer (Millipore).

[0261] GFP reporter gene induction is always compared with vehicle control treatment. For specific compounds, the DMSO concentration in all wells is similar and never exceeds 1%. All compounds are tested in at least three completely independent repeated experiments. All experiments include a positive control treatment (DNA damage) using cisplatin. Metabolism is assessed by adding S9 liver extract. In the presence of S9 and required cofactors (RegenSysA+B, Moltox, Boone, NC, USA), cells are exposed to five concentrations of test compounds for 3 hours. After washing, cells are incubated in fresh ES cell culture medium for 24 hours. After 24 hours of exposure, the induction of GFP reporter gene is determined using Guava easyCyte 10HT flow cytometer (Millipore). Only GFP expression in complete single cells is determined. The average GFP fluorescence and cell concentration in each well are measured and used for cytotoxicity assessment. Data are analyzed using ToxPlot software (Toxys, Leiden, the Netherlands). Induction levels reported are at compound concentrations that induce 10%, 25% and 50% cytotoxicity after a 3-hour exposure and 24-hour recovery in the presence of S9 rat liver extract or alternatively a 24-hour exposure in the absence of S9 rat liver extract.

[0262] A positive induction level of a biomarker is defined as equal to or higher than a 2-fold induction at at least one of 10%, 25%, and 50% cytotoxicity in the absence or presence of a metabolic system rat S9 liver extract; a weak positive induction is defined as higher than a 1.5-fold and lower than a 2-fold induction at at least one of 10%, 25%, and 50% cytotoxicity in the absence or presence of a metabolic system rat S9 liver extract (but lower than a 2-fold induction at 10%, 25%, and 50% cytotoxicity), and a negative induction is defined as lower than or equal to a 1.5-fold induction at 10%, 25%, and 50% cytotoxicity in the absence or presence of a metabolic system based on rat S9 liver extract.

[0263] Components and abbreviations used:

[0264] Dimethylolpropionic acid (DMPA, CAS No. 4767-03-7) was obtained from Perstop Polyols.

[0265] Polypropylene glycol with an average Mn of 2000 Da and polypropylene glycol with an average Mn of 1000 Da (CAS No. 25322-69-4) were obtained from BASF.

[0266] IPDI (5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane, I, isophorone diisocyanate, CAS No. 4098-71-9) was obtained from Covestro.

[0267] DBTDL (dibutyltin dilaurate, CAS No. 77-58-7) was obtained from Reaxis.

[0268] Triethylamine (TEA, CAS No. 121-44-8) was obtained from Arkema.

[0269] Nonylphenol ethoxylate 9eo (CAS No. 68412-54-4) was obtained from Sigma-Aldrich.

[0270] Hydrazine (16% aqueous solution, CAS No. 302-01-2) was obtained from Honeywell.

[0271] 2-Methylaziridine (propylene imine, CAS No. 75-55-8) was obtained from Menadiona SL. (Palafolls, Spain).

[0272] n-Butyl glycidyl ether (CAS No. 2426-08-6) was obtained from Alfa Aesar (a subsidiary of Thermo Fisher Scientific).

[0273] Potassium carbonate (CAS No. 584-08-7) was obtained from Alfa Aesar (a subsidiary of Thermo Fisher Scientific).

[0274] Bismuth neodecanoate (CAS No. 34364-26-6) was obtained from TIB chemicals AG (Mannheim, Germany).

[0275] 2-Methyltetrahydrofuran (CAS No. 96-47-9) was obtained from Merck KgaA.

[0276] N3600, N3900, N3800 and N3400 was obtained from Covestro.

[0277] Acetone (CAS No. 67-64-1) was obtained from Sigma-Aldrich.

[0278] Maxemul TM 7101 was obtained from Croda Int. PLC.

[0279] Sodium lauryl sulfate (30% aqueous solution, CAS No. 73296-89-6) was obtained from BASF.

[0280] Methyl methacrylate (CAS No. 80-62-6) was obtained from Lucite Int.

[0281] n-Butyl acrylate (CAS No. 141-32-2) was obtained from Dow Chemical.

[0282] Methacrylic acid (CAS No. 79-41-4) was obtained from Lucite Int.

[0283] Ammonium persulfate (CAS No. 7727-54-0) was obtained from United Initiators.

[0284] Ammonia (25% aqueous solution, CAS No. 1336-21-6) was obtained from Merck.

[0285] Polytetrahydrofuran with an average Mn of 650 Da (pTHF650, polytetramethylene ether glycol with an OH value of 172 mg KOH / g) and polytetrahydrofuran with an average Mn of 1000 Da (pTHF1000, CAS No. 25190-06-1) were obtained from BASF.

[0286] 2-Methyl-1,3-propanediol (CAS No. 2163-42-0) was obtained from Lyondell.

[0287] Cyclohexanedimethanol (CAS No. 105-08-8) was obtained from Alfa Aesar (a subsidiary of Thermo Fisher Scientific).

[0288] TMP (1,1,1-tris(hydroxymethyl)propane, CAS No. 77-99-6) was obtained from Sigma-Aldrich (a subsidiary of Merck KGaA).

[0289] Isophthalic acid (CAS No. 121-91-5) was obtained from Alfa Aesar (a subsidiary of Thermo Fisher Scientific).

[0290] Sorbic acid (CAS No. 110-44-1) was obtained from Alfa Aesar (a subsidiary of Thermo Fisher Scientific).

[0291] Methyl ethyl ketone (MEK, 2-butanone, CAS No. 78-93-3) was obtained from Alfa Aesar (a subsidiary of Thermo Fisher Scientific).

[0292] Terephthalic acid (CAS No. 100-21-0) was obtained from Sigma-Aldrich (a subsidiary of Merck KGaA).

[0293] Decanediolic acid (sebacic acid, CAS No. 111-20-6) was obtained from Acros Organics (a subsidiary of Thermo Fisher Scientific).

[0294] Butylstannoic acid (CAS No. 2273-43-0) was obtained from Sigma-Aldrich (a subsidiary of Merck KGaA).

[0295] o-Xylene (CAS No. 95-47-6) was obtained from Alfa Aesar (a subsidiary of Thermo Fisher Scientific).

[0296] Maleic anhydride (CAS No. 108-31-6) was obtained from Alfa Aesar (a subsidiary of Thermo Fisher Scientific).

[0297] Dimethylethanolamine (CAS No. 108-01-0) was obtained from Sigma-Aldrich (a subsidiary of Merck KGaA).

[0298] Trimethylolpropane tris(2-methyl-1-aziridine propionate), CAS No. 64265-57-2, CX-100 was obtained from DSM.

[0299] Atlas TM G-5000 was obtained from Croda Int. PLC.

[0300] Atlas TM G-5002L-LQ was obtained from Croda Int. PLC.

[0301] Di(propylene glycol) dimethyl ether (Proglyde DMM, CAS No. 111109-77-4) was obtained from Dow Inc.

[0302] P84 (CAS No. 9003-11-6) was obtained from BASF.

[0303] PE9400 (CAS No. 9003-11-6) was obtained from BASF.

[0304] Sodium hydroxide (CAS No. 1310-73-2) was obtained from Merck.

[0305] N-Methylpiperidine (CAS No. 626-67-5) was obtained from Sigma-Aldrich (a subsidiary of Merck KGaA).

[0306] 1-Butanol (CAS No. 71-36-3) was obtained from Sigma-Aldrich (a subsidiary of Merck KGaA).

[0307] 2,2-Dimethylaziridine (CAS No. 2658-24-4) was obtained from Enamine LLC (Monmouth Jct., NJ, United States of America).

[0308] Toluene (CAS No. 108-88-3) was obtained from Sigma-Aldrich.

[0309] Dimethylformamide (CAS No. 68-12-2) was obtained from Acros Organics (a subsidiary of Thermo Fisher Scientific).

[0310] 1-(2-Hydroxyethyl)ethyleneimine) (CAS No. 1072-52-2) was obtained from Tokyo Chemical Industry Co., Ltd.

[0311] PE6800 (CAS No. 9003-11-6) was obtained from BASF.

[0312] T 1890 / 100, an isocyanurate based on isophorone diisocyanate (CAS No. 67873-91-0) was obtained from Evonik.

[0313] 1-Methoxy-2-propyl acetate (MPA, propylene glycol methyl ether acetate, CAS No. 108-65-6) was obtained from Shell Chemicals.

[0314] Polyethylene glycol monomethyl ether (CAS No.: 9004-74-4) with a number average molecular weight of 500 Da was obtained from Acros Organics (a subsidiary of Thermo Fisher Scientific).

[0315] XTJ-436 (CAS No. 118270-87-4) was obtained from Huntsman.

[0316] 2-Ethylhexyl glycidyl ether (CAS No. 2461-15-6) was obtained from Sigma-Aldrich (a subsidiary of Merck KGaA).

[0317] Cardura E10P (CAS No. 26761-45-5) was obtained from Hexion Inc.

[0318] H12MDI (4,4'-methylenebis(phenyl isocyanate, W, CAS No. 101-66-8) was obtained from Covestro.

[0319] Durez-ter S105-110 (polyester polyol with an OH value of 110 mg KOH / g based on adipic acid and hexanediol) was obtained from Sumitomo Bakelite.

[0320] Ymer TM N-120 was obtained from Perstorp.

[0321] Vestamin A-95 (CAS No. 34730-59-1) was obtained from Evonik.

[0322] Voranol CP450 (CAS No. 25791-96-2) was obtained from Dow Inc.

[0323] Bisphenol A diglycidyl ether (CAS No. 1675-54-3) was obtained from Tokyo Chemical Industry Co., Ltd.

[0324] Voranol TM P-400 was obtained from Dow Inc.

[0325] Tin 2-ethylhexanoate (CAS No. 301-10-0) was obtained from Sigma-Aldrich.

[0326] D3403 was obtained from Evonik.

[0327] 3-Methyl-1-phenyl-2-phosphole-1-oxide (CAS No. 707-61-9) was obtained from Sigma-Aldrich.

[0328] Toluene diisocyanate (TDI, CAS No. 26471-62-5) was obtained from Covestro.

[0329] Triton X-100 (CAS No. 9002-93-1) was obtained from Sigma-Aldrich.

[0330] Synthesis of waterborne polyurethane P1

[0331] A 1-liter flask (equipped with a thermometer and an overhead stirrer) was charged with 29.9 grams of dimethylolpropionic acid, 282.1 grams of polypropylene glycol (with a calculated average molecular weight (M) of 2000 Da and an OH number of 56 ± 2 mg KOH / g polypropylene glycol), 166.5 grams of polypropylene glycol (with a calculated average molecular weight (M) of 1000 Da and an OH number of 112 ± 2 mg KOH / g polypropylene glycol), and 262.8 grams of isophorone diisocyanate (the average molecular weight of each polyol in the polyols was calculated from its OH number according to the following equation: M = 2 * 56100 / [OH number in mg KOH / g polypropylene glycol]. The reaction mixture was placed under an N2 atmosphere and heated to 50°C, after which 0.07 grams of dibutyltin dilaurate was added to the reaction mixture. An exothermic reaction was observed; however, appropriate measures were taken to prevent the reaction temperature from exceeding 97°C. The reaction was maintained at 95°C for one hour. The resulting polyurethane P1' had an NCO content of 7.00% (theoretical 7.44%) based on solids, as determined according to the method described herein, and an acid number of 16.1 ± 1 mg KOH / g polyurethane P1'. Polyurethane P1' was cooled to 60° C., 18.7 g of triethylamine was added, and the resulting mixture was stirred for 30 minutes. Subsequently, an aqueous dispersion of polyurethane P1' (hereinafter referred to as P1) was prepared as follows: the mixture of polyurethane P1' thus prepared and triethylamine was added to a mixture of 1100 g of demineralized water, 19.5 g of nonylphenol ethoxylate (9 ethoxylate groups), and 4.0 g of triethylamine at room temperature over a period of 60 minutes. After the additions were complete, the mixture was stirred for an additional 5 minutes, after which 111.2 g of hydrazine (16 wt.% aqueous solution) was added to the mixture. The aqueous dispersion of polyurethane P1' thus prepared was stirred for an additional hour to obtain P1.

[0332] Example 1

[0333] A 1 L round-bottom flask equipped with a condenser was placed under a N atmosphere and charged with propylene imine (120 g), n-butyl glycidyl ether (189.0 g) and KCO (15.0 g) and heated to 80° C. over 30 minutes, after which the mixture was stirred for 21 hours at T = 80° C. After filtration, excess PI was removed in vacuo, followed by further purification by vacuum distillation to obtain a colorless, low-viscosity liquid.

[0334] 186.2 g of the resulting material (1-butoxy-3-(2-methylaziridin-1-yl)propan-2-ol) was placed in a reaction flask equipped with a thermometer along with 0.02 g of bismuth neodecanoate and 77.8 g of 2-methyltetrahydrofuran. The mixture was stirred with a mechanical overhead stirrer under a nitrogen atmosphere and heated to 50° C. A solution of 200 g of Desmodur N 3600 in 77.8 g of 2-methyltetrahydrofuran was then added dropwise to the reaction flask over 45 minutes, after which the mixture was further heated to 70° C. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 The solvent was removed in vacuo to obtain a clear, light yellow, high-viscosity liquid. The theoretical main component has a calculated molecular weight of 1065.74 Da and its chemical structure is shown below.

[0335]

[0336] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1088.74 Da; observed [M+Na+] = 1088.78 Da. The following components with masses less than 580 Da were determined and quantified by LC-MS:

[0337]

[0338] present in the composition at 0.21% by weight, and

[0339]

[0340] Present in less than 0.01 wt%.

[0341] Genotoxicity testing

[0342]

[0343] The results of the genotoxicity test showed that the crosslinker composition of Example 1 was non-genotoxic.

[0344] Subsequently, 15 g of the viscous liquid obtained in the previous step was mixed with 7.5 g of acetone and incubated at 50°C until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.5 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 15 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0345] Genotoxicity testing

[0346]

[0347] The results of the genotoxicity test showed that the dispersion of Example 1 was non-genotoxic.

[0348] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 2.0 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 1). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicates complete degradation of the film and a score of 5 indicates no visible damage):

[0349] Performance and stability testing

[0350]

[0351] The performance of the synthesized compounds as crosslinking agents was evaluated using a spot test on coating surfaces with different binder systems.

[0352] Aqueous acrylic adhesive 1 was synthesized as follows.

[0353] A 2 L, four-necked flask equipped with a thermometer and overhead stirrer was charged with sodium lauryl sulfate (30% solids in water, 18.6 g solution) and demineralized water (711 g). The reactor phase was placed under a nitrogen atmosphere and heated to 82°C. A mixture of demineralized water (112 g), sodium lauryl sulfate (30% solids in water, 37.2 g solution), methyl methacrylate (209.3 g), n-butyl acrylate (453.56 g), and methacrylic acid (34.88 g) was placed in a large feed funnel and emulsified with an overhead stirrer (monomer feed). Ammonium persulfate (1.75 g) was dissolved in demineralized water (89.61 g) and placed in a small feed funnel (initiator feed). Ammonium persulfate (1.75 g) was dissolved in demineralized water (10.5 g) and this solution was added to the reactor phase. Immediately thereafter, 5% by volume of the monomer feed was added to the reactor phase. The reaction mixture was then allowed to exotherm to 85°C and held at 85°C for 5 minutes. The remaining monomer feed and initiator feed were then fed to the reaction mixture over 90 minutes, maintaining the temperature at 85°C. After the feeds were complete, the monomer feed funnel was rinsed with demineralized water (18.9 g), and the reaction temperature was maintained at 85°C for 45 minutes. The mixture was then cooled to room temperature and adjusted to pH 7.2 with ammonia solution (6.25 wt% in demineralized water) and to 40% solids with additional demineralized water.

[0354] Aqueous acrylic adhesive 2 was synthesized as aqueous acrylic adhesive 1, but using 174.4 g of methyl methacrylate instead of 209.3 g, and 488.4 g of n-butyl acrylate instead of 453.56 g.

[0355] Aqueous acrylic adhesive 3 was synthesized as aqueous acrylic adhesive 1, but using 139.5 g of methyl methacrylate instead of 209.3 g, and 523.3 g of n-butyl acrylate instead of 453.56 g.

[0356] For further spot test, the additional crosslinker dispersion synthesized as described above was stored in an oven at 50°C for 4 weeks. Weekly, for each of the above-mentioned water-based acrylic adhesives 1, 2 and 3, 4.1 grams of aged crosslinker dispersions were mixed with 21 grams of adhesive under continuous stirring, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card (test 1-WA1, 1-WA2 and 1-WA3 for corresponding adhesives) using a 100 μm wire applicator. As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank-WA1, blank-WA2 and blank-WA3). The film was dried at 25°C for 1 hour, then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the film, and 5 indicates no visible damage):

[0357]

[0358] The waterborne polyurethane adhesive was synthesized as follows.

[0359] DMPA (12.9 g), pTHF650 (168.4 g) and IPDI (140.5 g) were charged into a 1 L flask equipped with a thermometer and an overhead stirrer. The reaction mixture was placed under an N2 atmosphere, heated to 50°C, and 0.03 g of bismuth neodecanoate was added. The mixture was allowed to exotherm and maintained at 90°C for 2.5 hours. The NCO content of the resulting urethane prepolymer was 8.00% (theoretically 8.80%) based on solids. The prepolymer was cooled to 75°C and TEA (8.73 g) was added, and the resulting mixture was stirred for 15 minutes. A dispersion of the resulting prepolymer was prepared by feeding 290 g of the prepolymer into demineralized water (686 g) at room temperature over 30 minutes. After the feeding was complete, the mixture was stirred for 5 minutes and hydrazine (16% aqueous solution, 51.0 g) was added. The dispersion was stirred for another 1 hour. Subsequently, the mixture was cooled to room temperature and brought to 30% solids with additional demineralized water.

[0360] For further spot testing, the additional crosslinker dispersion synthesized as described above was stored in an oven at 50°C for 4 weeks. Each week, 1.6 grams of the aged crosslinker dispersion was mixed with 21 grams of an aqueous polyurethane adhesive under constant stirring, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (Test 1-WU1). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (Test Blank-WU1). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the film, 5 indicates no visible damage):

[0361]

[0362] The water-based polyester adhesive was synthesized as follows.

[0363] 2-methyl-1,3-propanediol (795 g), 1,4-cyclohexanedimethanol (139 g), trimethylolpropane (10.4 g), isophthalic acid (288 g), terephthalic acid (859 g), decanedioic acid (189 g) and butyl stannoic acid (2.26 g) were loaded into a 3-liter flask equipped with a thermometer, an overhead stirrer and a fractionating column for distillation. The reaction mixture was placed under an N2 atmosphere and gradually heated to 240°C while removing water. The reaction was monitored by acid value and stopped when an acid value of 1.0 was reached. Subsequently, the reaction mixture was cooled to 120°C and the fractionating column was replaced with a Dean-Stark water trap. Next, 120 g of xylene was added to the reaction mixture, followed by 181 g of maleic anhydride. The mixture was then heated to 200°C, whereby the azeotropic mixture was refluxed to further remove water. During the reaction, further 2-methyl-1,3-propanediol was added to maintain a hydroxyl delta value of 11.0, and the reaction was continued until an acid value of 10.0 was reached. Subsequently, the reaction mixture was cooled to 160°C, and 85.2 g of sorbic acid was added in three doses over 30 minutes, causing the reaction to exotherm. The reaction temperature was maintained for 3 hours, after which the mixture was cooled to 80°C and 650 g of methyl ethyl ketone (MEK) was slowly added.

[0364] 300 g of the polyester solution obtained above was added to a 1-liter flask equipped with a thermometer, overhead stirrer, and condenser. The reaction mixture was placed under an N2 atmosphere and heated to 75°C. Then, under continuous stirring, 9.5 g of dimethylethanolamine (DMEA) was added over 10 minutes, followed by 500 g of demineralized water over 60 minutes. The reactor contents were then cooled to 50°C and the MEK removed under vacuum. Finally, the mixture was adjusted to pH 8.4 with DMEA and to a solids content of 30% with demineralized water, and then cooled to room temperature.

[0365] For further spot testing, the additional crosslinker dispersion synthesized as described above was stored in an oven at 50°C for 4 weeks. 4.5 grams of aged crosslinker dispersion were mixed with 10.5 grams of an aqueous polyester adhesive under constant stirring each week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (Test 1-WE1). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (Test Blank-WE1). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the film, 5 indicates no visible damage):

[0366]

[0367] Example 2

[0368] As in Example 1, where during the water addition step, 15 g of demineralized water adjusted to pH 9 with TEA were used instead of the demineralized water adjusted to pH 11 and the dispersion was set to pH 9 with TEA.

[0369] As described for Example 1, a spot test was performed on the coating surface using polymer P1 to assess the functional properties and stability of the crosslinker dispersion.

[0370] Performance and stability testing

[0371]

[0372]

[0373] Example 3

[0374] As in Example 1, wherein during the water addition step, 15 g of demineralized water adjusted to pH 8 with TEA were used instead of the demineralized water adjusted to pH 11 and the dispersion was set to pH 8 with TEA.

[0375] As described for Example 1, a spot test was performed on the coating surface using polymer P1 to assess the functional properties and stability of the crosslinker dispersion.

[0376] Performance and stability testing

[0377]

[0378] Comparative Example C1

[0379] For Comparative Example C1, the crosslinker CX-100—trimethylolpropane tris(2-methyl-1-aziridine propionate)—was used:

[0380]

[0381] Genotoxicity testing

[0382]

[0383] The results of the genotoxicity test showed that the cross-linking agent of Comparative Example 1 was genotoxic.

[0384] 7.5 g of this crosslinker was mixed with 3.75 g of acetone and incubated at 50°C until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine and then 0.75 g of molten Atlas TM G-5000 dispersant. Using IKA T25 Digital with S25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 7.5 grams of demineralized water adjusted to pH 11 with triethylamine (TEA) was gradually added to the mixture over 15 minutes. The mixer was continuously moved around the reaction vessel during this addition. After the addition was complete, the resulting mixture was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the mixture was adjusted to 11.

[0385] The functional performance and stability of the crosslinker mixture were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 0.8 grams of the aged crosslinker mixture was mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting coating composition was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test C1). As a reference, a film was also cast from the same composition lacking the crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and left on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicates complete degradation of the film and a score of 5 indicates no visible damage):

[0386] Performance and stability testing

[0387]

[0388] * The crosslinker mixture gelled during the first week of storage.

[0389] Comparative Example C2

[0390] As in Example C1, wherein during the water addition step, 7.5 g of demineralized water adjusted to pH 9 with TEA were used instead of demineralized water adjusted to pH 11, and the resulting mixture was set to pH 9 with TEA.

[0391] As described for Comparative Example C1, a spot test was performed on the coating surface using polymer P1 to evaluate the functional performance and stability of the crosslinker mixture.

[0392] Performance and stability testing

[0393]

[0394] * The crosslinker mixture gelled during the first week of storage.

[0395] Comparative Example C3

[0396] As in Example C1, wherein during the water addition step, 7.5 g of demineralized water adjusted to pH 8 with TEA were used instead of demineralized water adjusted to pH 11, and the resulting mixture was set to pH 8 with TEA.

[0397] As described for Comparative Example C1, a spot test was performed on the coating surface using polymer P1 to evaluate the functional performance and stability of the crosslinker mixture.

[0398] Performance and stability testing

[0399]

[0400] * The crosslinker mixture gelled during the first week of storage.

[0401] Example 4

[0402] As in Example 1, 1.5 g of Atlas TM G-5002L-LQ is used as a dispersant instead of Maxemul TM 7101.

[0403] As described for Example 1, a spot test was performed on the coating surface using polymer P1 to assess the functional properties and stability of the crosslinker dispersion.

[0404] Performance and stability testing

[0405]

[0406] Example 5

[0407] As in Example 1, the viscous crosslinker liquid was mixed with 7.5 g of Proglyde TM DMM instead of acetone, and use 2.0 g of P84 as dispersant instead of Maxemul TM 7101.

[0408] As described for Example 1, a spot test was performed on the coating surface using polymer P1 to assess the functional properties and stability of the crosslinker dispersion.

[0409] Performance and stability testing

[0410]

[0411] Example 6

[0412] The cross-linking agent was synthesized as in Example 1.

[0413] Subsequently, 15 g of the viscous liquid obtained in the previous step was mixed with 7.5 g of Proglyde TM DMM was mixed and incubated at 50°C until a homogeneous solution was obtained. To this solution was added 0.02 g of sodium hydroxide (NaOH) and then 2.0 g of Atlas TMG-5002L-LQ dispersant. Using IKA T25 Digital with S 25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. Agitation was then increased to 10,000 rpm, and 15 grams of demineralized water, adjusted to a pH of 11 with NaOH, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with NaOH.

[0414] As described for Example 1, a spot test was performed on the coating surface using polymer P1 to assess the functional properties and stability of the crosslinker dispersion.

[0415] Performance and stability testing

[0416]

[0417] Example 7

[0418] The cross-linking agent was synthesized as in Example 1.

[0419] Subsequently, 15 g of the viscous liquid obtained in the previous step was mixed with 7.5 g of acetone and incubated at 50°C until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.5 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S25N-18G head The obtained mixture was stirred at room temperature by a mixer at 2,000 rpm for 5 minutes. The stirring was then increased to 10,000 rpm, and 15 grams of demineralized water adjusted to pH 11 using triethylamine were gradually added to the mixture over 15 minutes. The mixer was continuously moved around the reaction vessel. After the addition was complete, the obtained dispersion was stirred for another 10 minutes at 5,000 rpm, and the pH of the dispersion was set to 11 with TEA. A rotary evaporator was then used to remove acetone from the dispersion, with water and TEA (adding aliquots after every 5 grams of distillate) added during this process to maintain solid and pH levels.

[0420] As described for Example 1, a spot test was performed on the coating surface using polymer P1 to assess the functional properties and stability of the crosslinker dispersion.

[0421] Performance and stability testing

[0422]

[0423] Example 8

[0424] As in Example 7, 7.5 g of methyl ethyl ketone (MEK) was used as solvent instead of acetone.

[0425] As described for Example 1, a spot test was performed on the coating surface using polymer P1 to assess the functional properties and stability of the crosslinker dispersion.

[0426] Performance and stability testing

[0427]

[0428] Example 9

[0429] The crosslinker was synthesized and dispersed as in Example 1. The functional properties and stability of the crosslinker dispersion were evaluated as in Example 1, except that 1.0 g instead of 2.0 g of aged crosslinker dispersion was mixed with 21 g of polymer P1 under constant stirring every week.

[0430] Performance and stability testing

[0431]

[0432] Example 10

[0433] As in Example 9, except that once a week 3.0 g instead of 1.0 g of the aged crosslinker dispersion were mixed with 21 g of polymer P1 under constant stirring.

[0434] Performance and stability testing

[0435]

[0436] Example 11

[0437] The cross-linking agent was synthesized as in Example 1.

[0438] Subsequently, 15 g of the viscous liquid obtained in the previous step was mixed with 7.5 g of acetone and incubated at 50°C until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.5 g of molten Maxemul TM7101 dispersant. The resulting mixture was stirred at room temperature at 500 rpm for 30 minutes using a three-blade propeller stirrer with a diameter of 50 mm. Then, the stirring was increased to 800 rpm, and 15 grams of demineralized water adjusted to pH 11 using triethylamine was gradually added to the mixture over 15 minutes. After the addition was complete, the resulting dispersion was stirred at 500 rpm for an additional 10 minutes, and the pH of the dispersion was set to 11 using TEA.

[0439] As described for Example 1, a spot test was performed on the coating surface using polymer P1 to assess the functional properties and stability of the crosslinker dispersion.

[0440] Performance and stability testing

[0441]

[0442] Example 12

[0443] The cross-linking agent was synthesized as in Example 1.

[0444] Subsequently, 14.4 g of the viscous liquid obtained in the previous step was mixed with 6.2 g of acetone and incubated at 50° C. until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA), followed by 3.0 g of molten PE9400 dispersant. Using IKA T25 Digital with S 25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 15 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0445] As described for Example 1, a spot test was performed on the coating surface using polymer P1 to assess the functional properties and stability of the crosslinker dispersion.

[0446] Performance and stability testing

[0447]

[0448] Example 13

[0449] The cross-linking agent was synthesized as in Example 1.

[0450] Subsequently, 15 g of the viscous liquid obtained in the previous step was mixed with 7.5 g of acetone and incubated at 50°C until a homogeneous solution was obtained. To this solution was added 0.3 g of N-methylpiperidine and then 1.5 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S 25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 15 grams of demineralized water was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 using N-methylpiperidine.

[0451] As described for Example 1, a spot test was performed on the coating surface using polymer P1 to assess the functional properties and stability of the crosslinker dispersion.

[0452] Performance and stability testing

[0453]

[0454] Example 14

[0455] A 2 L round-bottom flask equipped with a condenser was placed under a N atmosphere and charged with propylene imine (250 g), n-butyl glycidyl ether (380 g) and KCO (30.0 g) and heated to 80° C. over 30 minutes, after which the mixture was stirred at T = 80° C. for 24 hours. After filtration, excess PI was removed in vacuo, followed by further purification by vacuum distillation to obtain a colorless, low-viscosity liquid.

[0456] 530.6 g of the resulting material (1-butoxy-3-(2-methylaziridin-1-yl)propan-2-ol) was placed in a feed vessel. Separately, 570 g of Desmodur N 3600 was placed in a reaction flask equipped with a thermometer along with 0.05 g of bismuth neodecanoate. This mixture was stirred with a mechanical overhead stirrer under a nitrogen atmosphere and heated to 50° C. The solution in the feed vessel was then added dropwise to the reaction flask over a period of 90 minutes, and the mixture was then further heated to 70° C. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1The mixture was stirred for 1 h until no NCO stretching change was observed. Subsequently, 12 g of 1-butanol was added to the mixture, followed by further reaction until the NCO stretching peak completely disappeared. The solvent was removed in vacuo to obtain a high-viscosity liquid. The calculated molecular weight of the theoretical main component is 1065.74 Da, and the chemical structure is shown below.

[0457]

[0458] Subsequently, 3.85 g of the viscous liquid obtained in the previous step was mixed with 1.92 g of acetone and incubated at 50° C. until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.38 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S 25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. Agitation was then increased to 10,000 rpm, and 77.4 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 30 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0459] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 8.6 grams of aged crosslinker dispersion were mixed with 10.5 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100μm wire coater (test 14). As a reference, a film was also cast from the same composition lacking the crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and left on the film for 1 hour. After removal of EtOH and 60 minutes of recovery, the following results were obtained (score 1 indicates complete degradation of the membrane, 5 indicates no visible damage):

[0460] Performance and stability testing

[0461]

[0462] Example 15

[0463] Two 10 mL vials were placed under N2 atmosphere and each was charged with 2,2-dimethylaziridine (4.98 g), n-butyl glycidyl ether (5.96 g) and K2CO3 (0.3 g), sealed and heated to 65 ° C in a heating block, after which the mixture was stirred at 65 ° C for 23 h. Subsequently, the reaction mixtures were combined, diluted with 100 mL of toluene, and filtered to remove potassium carbonate. After filtration, the excess dimethylaziridine and toluene were removed in vacuo, and then further purified by vacuum distillation to obtain a light yellow, low-viscosity liquid.

[0464] 12.91 grams of the resulting material (1-butoxy-3-(2,2-dimethylaziridin-1-yl)propan-2-ol) were charged to a feed vessel. Subsequently, 42.5 grams of dimethylformamide were added to the feed vessel and the contents were homogenized by stirring. Separately, 12.90 grams of Desmodur N 3600 were placed in a reaction flask equipped with a thermometer together with 0.002 grams of bismuth neodecanoate and 85 grams of dimethylformamide. This mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere and heated to 50°C. The solution in the feed vessel was then added dropwise to the reaction flask over 30 minutes, and the mixture was then maintained at 50°C. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 The mixture was stirred for 2 hours until no NCO stretching was observed. The solvent was removed in vacuo to obtain a clear yellow liquid. The calculated molecular weight of the theoretical main component is 1107.79 Da, and the chemical structure is shown below.

[0465]

[0466] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1130.79 Da; observed [M+Na+] = 1130.86 Da. The following components with masses less than 580 Da were determined and quantified by LC-MS:

[0467]

[0468] present in the composition at less than 0.01% by weight, and

[0469]

[0470] Present in the composition at 0.89% by weight.

[0471] Genotoxicity testing

[0472]

[0473] The results of the genotoxicity test showed that the cross-linking agent of Example 15 was non-genotoxic.

[0474] Subsequently, 9.9 g of the clear liquid obtained in the previous step was mixed with 3.3 g of acetone and incubated at 50° C. until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.0 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S 25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. Agitation was then increased to 10,000 rpm, and 9.9 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0475] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 1.0 grams of aged crosslinker dispersion was mixed with 10.5 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 15). As a reference, a film was also cast from the same composition lacking the crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and left on the film for 1 hour. After removal of EtOH and 60 minutes of recovery, the following results were obtained (score 1 indicates complete degradation of the membrane, 5 indicates no visible damage):

[0476] Performance and stability testing

[0477]

[0478] Comparative Example C4

[0479] 13.0 grams of 1-(2-hydroxyethyl)ethyleneimine and 175 grams of dimethylformamide were charged into a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere. The mixture was then heated to 50°C, after which 0.03 grams of bismuth neodecanoate was charged into the reaction flask. Subsequently, a solution of 30.0 grams of Desmodur N3600 in 87.5 grams of dimethylformamide was added over 30 minutes. After the feed was complete, the reaction temperature was raised to 80°C. Samples were taken at regular intervals and the reaction progress was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 The solvent was removed in vacuo to obtain a clear, colorless, high-viscosity liquid. The theoretical main component has a calculated molecular weight of 765.47 Da and its chemical structure is shown below.

[0480]

[0481] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 788.46 Da; observed [M+Na+] = 788.31 Da.

[0482] Subsequently, 7.5 g of the colorless liquid obtained in the previous step was mixed with 2.5 g of methyl ethyl ketone and incubated at 50° C. until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.5 g of Atlas TM G-5002L-LQ dispersant. Using IKA T25 Digital with S 25N-18G head The obtained mixture was stirred at room temperature by a mixer at 2,000 rpm for 5 minutes. The stirring was then increased to 10,000 rpm, and 7.5 grams of demineralized water, adjusted to pH 11 using triethylamine, were gradually added to the mixture over 15 minutes. The mixer was continuously moved around the reaction vessel. After the addition was complete, the obtained dispersion was stirred for another 10 minutes at 5,000 rpm, and the pH of the dispersion was set to 11 with TEA. Within 4 hours after the preparation of this 1-(2-hydroxyethyl) ethyleneimine was completed, severe coagulation was observed. Therefore, no storage-stable dispersion was obtained.

[0483] Comparative Example C5

[0484] The crosslinking agent was synthesized as Comparative Example C4.

[0485] Subsequently, 7.5 g of the colorless liquid obtained in the previous step was mixed with 3.8 g of acetone and incubated at 50° C. until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 0.8 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S 25N-18G head The obtained mixture was stirred at room temperature by a mixer at 2,000 rpm for 5 minutes. The stirring was then increased to 10,000 rpm, and 7.5 grams of demineralized water, adjusted to pH 11 using triethylamine, were gradually added to the mixture over 15 minutes. The mixer was continuously moved around the reaction vessel. After the addition was complete, the obtained dispersion was stirred for another 10 minutes at 5,000 rpm, and the pH of the dispersion was set to 11 with TEA. Within 4 hours after the preparation of this 1-(2-hydroxyethyl) ethyleneimine was completed, severe coagulation was observed. Therefore, no storage-stable dispersion was obtained.

[0486] Comparative Example C6

[0487] The crosslinking agent was synthesized as Comparative Example C4.

[0488] Subsequently, 7.5 g of the colorless liquid obtained in the previous step was mixed with 2.5 g of Proglyde TM DMM was mixed and incubated at 50°C until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) followed by 1.5 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S 25N-18G head The obtained mixture was stirred at room temperature by a mixer at 2,000 rpm for 5 minutes. The stirring was then increased to 10,000 rpm, and 7.5 grams of demineralized water, adjusted to pH 11 using triethylamine, were gradually added to the mixture over 15 minutes. The mixer was continuously moved around the reaction vessel. After the addition was complete, the obtained dispersion was stirred for another 10 minutes at 5,000 rpm, and the pH of the dispersion was set to 11 with TEA. Within 4 hours after the preparation of this 1-(2-hydroxyethyl) ethyleneimine was completed, severe coagulation was observed. Therefore, no storage-stable dispersion was obtained.

[0489] Example 16

[0490] 20.0 g of Desmodur N 3600, 11.98 g of 1-(2-methylaziridin-1-yl)propan-2-ol, and 106 g of 2-methyltetrahydrofuran were placed in a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under a nitrogen atmosphere. The mixture was then heated to 50° C., held at this temperature for 15 minutes, and then further heated to 60° C. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until the peak at 2200-2300 cm -1 The solvent was removed in vacuo to obtain a clear, high-viscosity liquid. The theoretical main component has a calculated molecular weight of 849.57 Da and its chemical structure is shown below.

[0491]

[0492] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 872.57 Da; observed [M+Na+] = 872.53 Da. The following components with masses less than 580 Da were determined and quantified by LC-MS:

[0493]

[0494] Present in the composition at 0.06% by weight.

[0495] Genotoxicity testing

[0496]

[0497] The results of the genotoxicity test showed that the crosslinker composition of Example 16 was non-genotoxic.

[0498] Subsequently, 15 g of the viscous liquid obtained in the previous step was mixed with 7.5 g of methyl ethyl ketone and incubated at 50°C until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 3.0 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S 25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 15 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0499] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 1.6 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 16). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicates complete degradation of the film and a score of 5 indicates no visible damage):

[0500] Performance and stability testing

[0501]

[0502] Comparative Example C7

[0503] The cross-linking agent was synthesized as in Example 16.

[0504] Subsequently, 15 grams of the viscous liquid obtained in the previous step was mixed with 15 grams of acetone and incubated at 50°C until a homogeneous solution was obtained. To this solution, 15 grams of demineralized water was added, and the pH was adjusted to 11 using triethylamine. The resulting mixture (a clear solution without the dispersed phase) was stirred at 500 rpm for 30 minutes at room temperature using a three-blade propeller with a diameter of 50 mm. Finally, the pH of the solution was adjusted to 11 using TEA.

[0505] The functional performance and stability of the crosslinker solution were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 1.8 grams of aged crosslinker solution were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test C7). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicates complete degradation of the film and a score of 5 indicates no visible damage):

[0506] Performance and stability testing

[0507]

[0508] * The crosslinker mixture gelled during the second week of storage

[0509] Comparative Example C8

[0510] The cross-linking agent was synthesized as in Example 16.

[0511] Subsequently, 12.4 g of the high-viscosity liquid obtained in the synthesis was mixed with 10.1 g of acetone and incubated at 50°C until a homogeneous solution was obtained. To this solution, 7.5 g of demineralized water was added, and the pH was adjusted to 10 using triethylamine. The resulting mixture (a clear solution without the dispersed phase) was stirred at room temperature for 30 minutes at 500 rpm using a three-blade propeller with a diameter of 50 mm. Finally, the pH of the solution was adjusted to 10 using TEA.

[0512] The functional performance and stability of the crosslinker solution were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 1.4 grams of aged crosslinker solution were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test C8). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicates complete degradation of the film and a score of 5 indicates no visible damage):

[0513] Performance and stability testing

[0514]

[0515] * The crosslinker mixture gelled during the first week of storage.

[0516] Example 17

[0517] The cross-linking agent was synthesized as in Example 16.

[0518] Subsequently, 15 g of the viscous liquid obtained in the previous step was mixed with 5.0 g of methyl ethyl ketone (MEK) and incubated at 50°C until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA), followed by 3.0 g of molten PE6800 dispersant. Using IKA T25 Digital with S 25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 15 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0519] The crosslinker dispersion was evaluated for functional properties and stability as in Example 16.

[0520] Performance and stability testing

[0521]

[0522] Example 18

[0523] A 1 L round-bottom flask equipped with a condenser was placed under a N atmosphere and charged with propylene imine (80.0 g), n-butyl glycidyl ether (126.0 g) and KCO (10.00 g) and heated to 80° C. over 30 minutes, after which the mixture was stirred for 21 hours at T = 80° C. After filtration, excess PI was removed in vacuo, followed by further purification by vacuum distillation to obtain a colorless, low-viscosity liquid.

[0524] 46.54 g of the resulting material (1-butoxy-3-(2-methylaziridin-1-yl)propan-2-ol) and 28.63 g of 1-(2-methylaziridin-1-yl)propan-2-ol were placed in a reaction flask equipped with a thermometer, along with 0.02 g of bismuth neodecanoate and 32.54 g of 2-methyltetrahydrofuran. The mixture was stirred with a mechanical overhead stirrer under a nitrogen atmosphere and heated to 50° C. A solution of 100 g of Desmodur N 3600 in 32.54 g of 2-methyltetrahydrofuran was then added dropwise to the reaction flask over 45 minutes, and 10 g of 2-methyltetrahydrofuran was flushed into the reaction mixture through an addition funnel, which was then further heated to 70° C. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 The reaction mixture was stirred for 2 hours until no NCO stretching was observed. The solvent was removed in vacuo to obtain a light yellow, high-viscosity liquid. The calculated molecular weights of the theoretical main components are 849.57 Da (three methyl side groups), 921.63 Da (two methyl side groups, one butoxymethyl side group), 993.68 Da (one methyl side group, two butoxymethyl side groups), and 1065.74 Da (three butoxymethyl side groups). The chemical structures are shown below.

[0525]

[0526] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 872.57 Da; observed [M+Na+] = 872.59 Da.

[0527]

[0528] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 944.63 Da; observed [M+Na+] = 944.66 Da.

[0529]

[0530] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1016.68 Da; observed [M+Na+] = 1016.72 Da.

[0531]

[0532] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1088.74 Da; observed [M+Na+] = 1088.79 Da.

[0533] Subsequently, 15 g of the viscous liquid obtained in the previous step was mixed with 7.5 g of acetone and incubated at 50°C until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.5 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 15 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0534] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 1.8 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 18). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicates complete degradation of the film and a score of 5 indicates no visible damage):

[0535] Performance and stability testing

[0536]

[0537] Comparative Example C9

[0538] 13.6 grams of 1-(2-hydroxyethyl)ethyleneimine were placed in a reaction flask equipped with a thermometer along with 0.02 grams of bismuth neodecanoate and 147 grams of dimethylformamide. The mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere and heated to 50°C. A solution of 40.0 grams of Vestanat T1890 / 100 in 147 grams of dimethylformamide was then added dropwise to the reaction flask over 45 minutes, followed by rinsing with another 10.0 grams of dimethylformamide, and the mixture was then further heated to 70°C. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 The reaction mixture was stirred for 2 hours until no NCO stretching was observed. The solvent was removed in vacuo to obtain a whitish solid. The calculated molecular weight of the theoretical main component was 927.62 Da, and the chemical structure is shown below.

[0539]

[0540] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 950.61 Da; observed [M+Na+] = 950.50 Da.

[0541] Subsequently, 15 g of the whitish solid obtained in the previous step was mixed with 7.5 g of acetone and incubated at 50° C. until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.5 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S 25N-18G head The obtained mixture was stirred at room temperature by a mixer at 2,000 rpm for 5 minutes. The stirring was then increased to 10,000 rpm, and 15 grams of demineralized water, adjusted to pH 11 using triethylamine, were added to the mixture gradually over 15 minutes. The mixer was continuously moved around the reaction vessel. After the addition was complete, the obtained dispersion was stirred for another 10 minutes at 5,000 rpm, and the pH of the dispersion was set to 11 with TEA. Within 2 hours after the preparation of this 1-(2-hydroxyethyl) ethyleneimine was completed, the obtained dispersion coagulated, indicating an unstable crosslinking agent system and insufficient shelf life.

[0542] Example 19

[0543] 15.6 g of 1-(2-methylaziridin-1-yl)propan-2-ol were placed in a reaction flask equipped with a thermometer, along with 0.02 g of bismuth neodecanoate and 81.4 g of dimethylformamide. The mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere and heated to 50° C. A solution of 34.5 g of Vestanat T1890 / 100 in 200 g of dimethylformamide was then added dropwise to the reaction flask over a period of 45 minutes, after which the mixture was further heated to 70° C. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 The reaction mixture was stirred for 2 hours until no NCO stretching was observed. The solvent was removed in vacuo to obtain a whitish solid. The calculated molecular weight of the theoretical main component is 1011.71 Da, and the chemical structure is shown below.

[0544]

[0545] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1034.70 Da; observed [M+Na+] = 1034.66 Da.

[0546] Subsequently, 15 g of the whitish solid obtained in the previous step was mixed with 7.5 g of acetone and incubated at 50° C. until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.5 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S 25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 15 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0547] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 2.6 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 19). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the film, 5 indicates no visible damage):

[0548] Performance and stability testing

[0549]

[0550] Example 20

[0551] A 1 L round-bottom flask equipped with a condenser was placed under a N atmosphere and charged with propylene imine (80 g), n-butyl glycidyl ether (126.0 g) and KCO (10.00 g) and heated to 80° C. over 30 minutes, after which the mixture was stirred at T = 80° C. for 21 hours. After filtration, excess PI was removed in vacuo, followed by further purification by vacuum distillation to obtain a colorless, low-viscosity liquid.

[0552] 22.0 g of the resulting material (1-butoxy-3-(2-methylaziridin-1-yl)propan-2-ol) was placed in a reaction flask equipped with a thermometer along with 0.02 g of bismuth neodecanoate and 70.8 g of 2-methyltetrahydrofuran. The mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere and heated to 50° C. A solution of 30.0 g of Vestanat T1890 / 100 in 177 g of 2-methyltetrahydrofuran was then added dropwise to the reaction flask over 45 minutes, after which the mixture was further heated to 70° C. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 The reaction mixture was stirred for 2 hours until no NCO stretching was observed. The solvent was removed in vacuo to obtain a whitish solid. The calculated molecular weight of the theoretical main component is 1227.88 Da, and the chemical structure is shown below.

[0553]

[0554] Subsequently, 15 g of the whitish solid obtained in the previous step was mixed with 7.5 g of acetone and incubated at 50° C. until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.5 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S 25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 15 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0555] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 3.0 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 20). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicates complete degradation of the film and a score of 5 indicates no visible damage):

[0556] Performance and stability testing

[0557]

[0558] Example 21

[0559] The (1-butoxy-3-(2-methylaziridin-1-yl)propan-2-ol) intermediate was prepared as described in Example 1 and 32.8 grams were charged to a feed vessel. Subsequently, 8.30 grams of 1-methoxy-2-propyl acetate (MPA) were added to the feed vessel and the contents were homogenized by stirring. Separately, 45.0 grams of Desmodur N3600 were placed in a reaction flask equipped with a thermometer together with 0.02 grams of bismuth neodecanoate and 8.30 grams of MPA. This mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere and heated to 50°C. The solution in the feed vessel was then added dropwise to the reaction flask over 45 minutes and the mixture was then maintained at 50°C. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak value of 2200-2300 cm -1 The mixture was stirred for 1 h at room temperature until no NCO stretching change was observed. Subsequently, a solution of 24.3 grams of poly(ethylene glycol) monomethyl ether with an average Mn of 500Da in 8.30 grams of MPA was added to the mixture over 15 minutes, and the temperature of the mixture was thereafter raised to 80°C. The reaction mixture was then allowed to react further until the above-mentioned NCO-stretching peak completely disappeared. The solvent was removed in vacuo to obtain a clear light yellow viscous liquid. The calculated molecular weight of the theoretical main component is 1065.74Da (three aziridines), 1394.90Da (two aziridines, 11EG repeating units), 1438.92Da (two aziridines, 12EG repeating units) and 1482.95Da (two aziridines, 13EG repeating units), and the chemical structure is shown below.

[0560]

[0561] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1088.74 Da; observed [M+Na+] = 1088.67 Da.

[0562]

[0563] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1417.90 Da; observed [M+Na+] = 1417.81 Da.

[0564]

[0565] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1461.92 Da; observed [M+Na+] = 1461.84 Da.

[0566]

[0567] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1505.95 Da; observed [M+Na+] = 1505.86 Da. The following components with masses less than 580 Da were determined and quantified by LC-MS:

[0568]

[0569] present in the composition at 0.04% by weight, and

[0570]

[0571] Present at 0.05 wt%.

[0572] Genotoxicity testing

[0573]

[0574] The results of the genotoxicity test showed that the crosslinker composition of Example 21 was non-genotoxic.

[0575] Subsequently, 94 g of the viscous liquid obtained in the previous step was placed in a 300 mL cylindrical reactor with a corresponding spiral stirrer and stirred at 120 rpm at 50° C. 0.03 g of triethylamine (TEA) was added to the reactor, followed by 3.0 g of molten Maxemul TM 7101 dispersant was added and stirred until a homogeneous mixture was obtained. Then, 10.8 g of demineralized water was adjusted to pH 11 with triethylamine, added to the mixture and stirred for 1 hour. Subsequently, another 141.7 g of demineralized water was added over 70 minutes, adjusted to pH 11 with triethylamine, and the pH of the dispersion was set to 11 with TEA. Then, an IKA T25 Digital with S 25N-18G head was used. A mixer was used to stir 45 grams of the resulting dispersion at 5,000 rpm at room temperature. A solution of 3.0 grams of sodium lauryl sulfate (SLS) in 7.0 grams of demineralized water was added dropwise under continuous stirring. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes.

[0576] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 3.1 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 21). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicates complete degradation of the film and a score of 5 indicates no visible damage):

[0577] Performance and stability testing

[0578]

[0579] Example 22

[0580] A 1 L round-bottom flask equipped with a condenser was placed under a N atmosphere and charged with propylene imine (80.0 g), n-butyl glycidyl ether (126.0 g) and KCO (10.00 g) and heated to 80° C. over 30 minutes, after which the mixture was stirred for 21 hours at T = 80° C. After filtration, excess PI was removed in vacuo, followed by further purification by vacuum distillation to obtain a colorless, low-viscosity liquid.

[0581] 130 grams of Desmodur N 3600 were placed in a reaction flask equipped with a thermometer along with 0.02 grams of bismuth neodecanoate. The mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere and heated to 50°C. 94.7 grams of the mixture from the previous step were then added dropwise to the reaction flask over 10 minutes, and the mixture was then further heated to 70°C and maintained at that temperature for 90 minutes. Subsequently, 141.2 grams of Jeffamine XTJ-436 were added dropwise to the reaction vessel over 25 minutes. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1The mixture was stirred for 2 hours until no NCO stretching change was observed. Subsequently, 4.16 grams of 1-butanol were added to the mixture, and then further reacted to completely eliminate the above-mentioned NCO stretching peak. The product is a light yellow translucent liquid with high viscosity. The calculated molecular weights of the theoretical main components are 1065.74Da (three aziridines), 1852.33Da (two aziridines, 13PG repeating units) and 1910.37Da (two aziridines, 14PG repeating units), and the chemical structure is shown below.

[0582]

[0583] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1088.74 Da; observed [M+Na+] = 1089.03 Da.

[0584]

[0585] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1875.33 Da; observed [M+Na+] = 1875.31 Da.

[0586]

[0587] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1933.37 Da; observed [M+Na+] = 1933.30 Da.

[0588] Subsequently, 15 g of the viscous liquid obtained in the previous step was mixed with 7.5 g of acetone and incubated at 50°C until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.5 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 15 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0589] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 4.0 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 22). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicates complete degradation of the film and a score of 5 indicates no visible damage):

[0590] Performance and stability testing

[0591]

[0592] Example 23

[0593] A 1 L round-bottom flask equipped with a condenser was placed under a N atmosphere and charged with propylene imine (91.0 g), 2-ethylhexyl glycidyl ether (201.0 g) and KCO (10.00 g) and heated to 80° C., after which the mixture was stirred at T = 80° C. for 47 hours. After filtration, excess PI was removed in vacuo, followed by further purification by vacuum distillation to obtain a colorless, low-viscosity liquid.

[0594] 130 g of the resulting material was placed in a reaction flask equipped with a thermometer along with 0.02 g of bismuth neodecanoate and 668 g of dimethylformamide. The mixture was stirred with a mechanical overhead stirrer under a nitrogen atmosphere and heated to 50°C. A solution of 107.4 g of Desmodur N 3600 in 668 g of dimethylformamide was then added dropwise to the reaction flask over 45 minutes. 10 g of dimethylformamide was then flushed into the reaction mixture via an addition funnel, and the mixture was then further heated to 75°C. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 The solvent was removed in vacuo to obtain a highly viscous, colorless liquid. The theoretical main component has a calculated molecular weight of 1233.93 Da and its chemical structure is shown below.

[0595]

[0596] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1256.93 Da; observed [M+Na+] = 1256.86 Da. The following components with masses less than 580 Da were determined and quantified by LC-MS:

[0597]

[0598] present in the composition at 0.84% by weight, and

[0599]

[0600] Present at 0.16 wt%.

[0601] Genotoxicity testing

[0602]

[0603] The results of the genotoxicity test showed that the crosslinker composition of Example 23 was non-genotoxic.

[0604] Subsequently, 15 g of the viscous liquid obtained in the previous step was mixed with 7.5 g of acetone and incubated at 50°C until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.5 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 15 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0605] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 2.3 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 23). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicates complete degradation of the film and a score of 5 indicates no visible damage):

[0606] Performance and stability testing

[0607]

[0608] Example 24

[0609] A 1 L round-bottom flask equipped with a condenser was placed under a N atmosphere and charged with propylene imine (69.0 g), Cardura E10P (201.0 g) and K CO (7.30 g) and heated to 80° C., after which the mixture was stirred for 24 hours at T = 80° C. After filtration, excess PI was removed in vacuo to obtain a colorless, low-viscosity liquid.

[0610] 34.7 g of the resulting material (2-hydroxy-3-(2-methylaziridin-1-yl)propyl neodecanoate) was charged to a reaction flask equipped with a thermometer along with 0.05 g of bismuth neodecanoate and 400 g of dimethylformamide. The mixture was stirred with a mechanical overhead stirrer under a nitrogen atmosphere and heated to 50° C. A solution of 30 g of Desmodur N 3600 in 288 g of dimethylformamide was then added dropwise to the reaction flask over 45 minutes. After maintaining the temperature for 15 minutes, 16.2 g of poly(ethylene glycol) monomethyl ether having an average Mn of 500 Da was added to the reactor, rinsed with 10 mL of dimethylformamide, and the mixture was then further heated to 70° C. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1The reaction mixture was stirred for 2 hours until no NCO stretching was observed. The solvent was removed in vacuo to obtain a clear, high-viscosity liquid. The calculated molecular weights of the theoretical main components are 1359.96 Da (three aziridines) and 1591.04 Da (two aziridines, 11EG repeating units), and the chemical structures are shown below.

[0611]

[0612] Subsequently, 30 g of the viscous liquid obtained in the previous step was mixed with 15 g of acetone and incubated at 50°C until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 3.0 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 30 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0613] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 3.4 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 24). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicated complete degradation of the film and a score of 5 indicated no visible damage):

[0614] Performance and stability testing

[0615]

[0616] Example 25

[0617] The first crosslinker was synthesized by charging 15.0 g of Desmodur N 3600, 7.09 g of 1-(2-methylaziridin-1-yl)propan-2-ol, 8.21 g of poly(ethylene glycol) monomethyl ether having an average Mn of 500 Da, and 110 g of 2-methyltetrahydrofuran into a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under a nitrogen atmosphere. The mixture was then heated to 50° C., held at this temperature for 15 minutes, and then further heated to 60° C. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 The reaction mixture was stirred for 2 hours until no NCO stretching was observed. The solvent was removed in vacuo to obtain a clear, high-viscosity liquid. The calculated molecular weights of the theoretical main components are 849.57 Da (three aziridines), 1250.78 Da (two aziridines, 11EG repeating units), 1294.81 Da (two aziridines, 12EG repeating units), and 1338.84 Da (two aziridines, 13EG repeating units). The chemical structures are shown below.

[0618]

[0619] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 872.57 Da; observed [M+Na+] = 872.54 Da.

[0620]

[0621] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1273.78 Da; observed [M+Na+] = 1273.76 Da.

[0622]

[0623] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1317.81 Da; observed [M+Na+] = 1317.78 Da.

[0624]

[0625] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1361.84 Da; observed [M+Na+] = 1361.81 Da. The following components with masses less than 580 Da were determined and quantified by LC-MS:

[0626]

[0627] Present in the composition at 0.26% by weight.

[0628] Genotoxicity testing

[0629]

[0630] The results of the genotoxicity test showed that the crosslinker composition 25-1 was non-genotoxic.

[0631] The second cross-linking agent was synthesized by placing a 1 L round-bottom flask equipped with a condenser under a N atmosphere and charging it with propylene imine (69.0 g), Cardura E10P (201.0 g) and KCO (7.30 g) and then heating it to 80° C., after which the mixture was stirred at T = 80° C. for 24 hours. After filtration, the excess PI was removed in vacuo to obtain a colorless, low-viscosity liquid.

[0632] 32.3 grams of the resulting material (2-hydroxy-3-(2-methylaziridin-1-yl)propyl neodecanoate) was charged to a reaction flask equipped with a thermometer along with 0.02 grams of bismuth neodecanoate and 6.79 grams of 2-methyltetrahydrofuran. The mixture was stirred with a mechanical overhead stirrer under a nitrogen atmosphere and heated to 50° C. A solution of 22.7 grams of Desmodur N3600 in 6.79 grams of 2-methyltetrahydrofuran was then added dropwise to the reaction flask over 45 minutes, and 10 grams of 2-methyltetrahydrofuran was flushed into the reaction mixture through an inlet funnel, which was then further heated to 70° C. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 The solvent was removed in vacuo to obtain an opaque, high-viscosity liquid. The theoretical main component has a calculated molecular weight of 1359.96 Da and its chemical structure is shown below.

[0633]

[0634] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1382.95 Da; observed [M+Na+] = 1382.94 Da.

[0635] Genotoxicity testing

[0636]

[0637] The results of the genotoxicity test showed that the crosslinker composition 25-2 was non-genotoxic.

[0638] Subsequently, 1.5 g of the viscous liquid obtained in the first crosslinker synthesis was mixed with 13.5 g of the viscous liquid obtained in the second crosslinker synthesis, 7.5 g of acetone and incubated at 50° C. until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.5 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S 25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 15 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0639] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 2.8 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 25). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicates complete degradation of the film and a score of 5 indicates no visible damage):

[0640] Performance and stability testing

[0641]

[0642] Example 26

[0643] A 1 L round-bottom flask equipped with a condenser was placed under a N atmosphere and charged with propylene imine (80.0 g), n-butyl glycidyl ether (126.0 g) and KCO (10.00 g) and heated to 80° C. over 30 minutes, after which the mixture was stirred for 21 hours at T = 80° C. After filtration, excess PI was removed in vacuo, followed by further purification by vacuum distillation to obtain a colorless, low-viscosity liquid.

[0644] 20 g of Desmodur N 3400 and 0.02 g of bismuth neodecanoate were placed in a reaction flask equipped with a thermometer. The mixture was stirred with a mechanical overhead stirrer under a nitrogen atmosphere and heated to 50°C. 17.88 g of the product from the first step was then added dropwise to the reaction flask over 10 minutes, and the mixture was then further heated to 70°C. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 The mixture was stirred for 1 h until no NCO stretching peak was observed. Subsequently, 0.16 g of 1-butanol was added to the mixture, followed by further reaction until the NCO stretching peak completely disappeared. The product was a pale yellow, high-viscosity liquid. The theoretical main component had a calculated molecular weight of 710.49 Da, and its chemical structure is shown below.

[0645]

[0646] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 733.49 Da; observed [M+Na+] = 733.57 Da. The following components with masses less than 580 Da were determined and quantified by LC-MS:

[0647]

[0648] present in the composition at 0.2% by weight, and

[0649]

[0650] Present in less than 0.01 wt%.

[0651] Genotoxicity testing

[0652]

[0653]

[0654] The results of the genotoxicity test showed that the cross-linker composition of Example 26 had only weak positive induced genotoxicity.

[0655] Subsequently, 15 g of the viscous liquid obtained in the previous step was mixed with 7.5 g of acetone and incubated at 50° C. until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.5 g of Atlas TM G-5002L-LQ dispersant. Using IKA T25 Digital with S 25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 15 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0656] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 2.1 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 26). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the film, 5 indicates no visible damage):

[0657] Performance and stability testing

[0658]

[0659]

[0660] Example 27

[0661] The (1-butoxy-3-(2-methylaziridin-1-yl)propan-2-ol) intermediate was prepared as described in Example 1 and 9.6 grams of the intermediate was placed in a reaction flask equipped with a thermometer together with 0.02 grams of bismuth neodecanoate and 30 grams of 2-methyltetrahydrofuran. The mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere and heated to 50° C. A solution of 10 grams of Desmodur N 3900 in 30 grams of 2-methyltetrahydrofuran was then added dropwise to the reaction flask over 45 minutes, after which the mixture was further heated to 70° C. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 The mixture was stirred for 1 h until no NCO stretching change was observed. Subsequently, 0.33 g of 1-butanol was added to the mixture, followed by further reaction until the NCO stretching peak completely disappeared. The solvent was removed in vacuo to obtain a clear, light yellow, highly viscous liquid. The calculated molecular weight of the theoretical main component is 1065.74 Da, and the chemical structure is shown below.

[0662]

[0663] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1088.74 Da; observed [M+Na+] = 1088.81 Da. The following components with masses less than 580 Da were determined and quantified by LC-MS:

[0664]

[0665] present in the composition at 0.30% by weight, and

[0666]

[0667] Present at 0.02 wt%.

[0668] Genotoxicity testing

[0669]

[0670] The results of the genotoxicity test showed that the crosslinker composition of Example 27 was non-genotoxic.

[0671] Subsequently, 15 g of the viscous liquid obtained in the previous step was mixed with 7.5 g of acetone and incubated at 50°C until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.5 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 15 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0672] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 2.0 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 27). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the film, 5 indicates no visible damage):

[0673] Performance and stability testing

[0674]

[0675] Example 28

[0676] A 1 L round-bottom flask equipped with a condenser was placed under a N atmosphere and charged with propylene imine (80 g), n-butyl glycidyl ether (126.0 g) and KCO (10.00 g) and heated to 80° C. over 30 minutes, after which the mixture was stirred at T = 80° C. for 21 hours. After filtration, excess PI was removed in vacuo, followed by further purification by vacuum distillation to obtain a colorless, low-viscosity liquid.

[0677] 73.3 g of the resulting material (1-butoxy-3-(2-methylaziridin-1-yl)propan-2-ol) was placed in a reaction flask equipped with a thermometer along with 0.02 g of bismuth neodecanoate and 460 g of dimethylformamide. The mixture was stirred with a mechanical overhead stirrer under a nitrogen atmosphere and heated to 50° C. A solution of 162.6 g of Desmodur N 3800 in 460 g of dimethylformamide was then added dropwise to the reaction flask over 45 minutes, after which the mixture was further heated to 70° C. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 The solvent was removed in vacuo to obtain a clear, light yellow, high-viscosity liquid.

[0678] The calculated molecular weights of the theoretical main components are 1065.74 Da (three aziridine groups) and 1589.08 (four aziridine groups), and the chemical structures are shown below.

[0679]

[0680] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1088.74 Da; observed [M+Na+] = 1088.79 Da (three aziridine groups). Calculated [M+Na+] = 1612.07 Da; observed [M+Na+] = 1612.19 Da (four aziridine groups).

[0681] The following components with masses below 580 Da were determined and quantified by LC-MS:

[0682]

[0683] present in the composition at 0.31% by weight, and

[0684]

[0685] Present in less than 0.01 wt%.

[0686] Subsequently, 20 g of the viscous liquid obtained in the previous step was mixed with 10 g of Proglyde TM DMM was mixed and incubated at 50°C until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 2.7 g of P84 dispersant. Using IKA T25 Digital with S 25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 20 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0687] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 3.0 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 28). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicates complete degradation of the film and a score of 5 indicates no visible damage):

[0688] Performance and stability testing

[0689]

[0690] Example 29

[0691] A 1 L round-bottom flask equipped with a condenser was placed under a N atmosphere and charged with propylene imine (69.0 g), Cardura E10P (201.0 g) and K CO (7.30 g) and heated to 80° C., after which the mixture was stirred for 24 hours at T = 80° C. After filtration, excess PI was removed in vacuo to obtain a colorless, low-viscosity liquid.

[0692] A 500 mL round-bottom flask equipped with a thermometer and an overhead stirrer was placed under a N2 atmosphere and charged with Desmodur W (60.08 g) and 65.35 g of the product from the previous step. The resulting mixture was heated to 50°C, after which bismuth neodecanoate (0.05 g) was added. The mixture was allowed to exotherm, then further heated to 80°C and stirred at 80°C for 2.5 hours. pTHF650 (74.52 g) was then added to the mixture, and the mixture was stirred at 80°C for another hour. The solvent was removed in vacuo to obtain a colorless solid.

[0693] The calculated molecular weights of the theoretical main components are 832.63 Da (no pTHF650 repeating units), 1473.1.0 Da (one pTHF segment with 5 tetramethylene ether glycol repeating units), 1545.15 Da (one pTHF segment with 6 tetramethylene ether glycol repeating units) and 2257.68 Da (two pTHF segments with 6 tetramethylene ether glycol repeating units), and the chemical structures are shown below.

[0694]

[0695] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 855.63 Da; observed [M+Na+] = 855.66 Da.

[0696]

[0697] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1496.10 Da; observed [M+Na+] = 1496.16 Da.

[0698]

[0699] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1568.15 Da; observed [M+Na+] = 1568.21 Da.

[0700]

[0701] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 2280.68 Da; observed [M+Na+] = 2280.78 Da.

[0702] Subsequently, 15 g of the colorless solid obtained in the previous step was mixed with 7.5 g of acetone and incubated at 50° C. until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.5 g of molten Maxemul TM7101 dispersant. Using IKA T25 Digital with S25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 15 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0703] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 4.8 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 29). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicates complete degradation of the film and a score of 5 indicates no visible damage):

[0704] Performance and stability testing

[0705]

[0706] Example 30

[0707] A 1 L round-bottom flask equipped with a condenser was placed under a N atmosphere and charged with propylene imine (80.0 g), n-butyl glycidyl ether (126.0 g) and KCO (10.00 g) and heated to 80° C. over 30 minutes, after which the mixture was stirred for 21 hours at T = 80° C. After filtration, excess PI was removed in vacuo, followed by further purification by vacuum distillation to obtain a colorless, low-viscosity liquid.

[0708] A 500 mL round-bottom flask equipped with a thermometer and an overhead stirrer was placed under a N2 atmosphere and charged with Desmodur W (54.63 g) and 38.99 g of the product from the previous step. The resulting mixture was heated to 50°C, after which bismuth neodecanoate (0.05 g) was added. The mixture was allowed to exotherm, after which it was further heated to 80°C and stirred at 80°C for 1 hour. PPG1000 (106.33 g) was then added to the mixture, and the mixture was stirred at 80°C for an additional hour. The solvent was removed in vacuo to obtain a colorless solid.

[0709] Subsequently, 30 g of the colorless solid obtained in the previous step was mixed with 15 g of acetone and incubated at 50° C. until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 3 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 30 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0710] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 5.3 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 30). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicates complete degradation of the film and a score of 5 indicates no visible damage):

[0711] Performance and stability testing

[0712]

[0713] Example 31

[0714] The (1-butoxy-3-(2-methylaziridin-1-yl)propan-2-ol) intermediate was prepared as described in Example 1. A 500 mL round-bottom flask equipped with a thermometer and an overhead stirrer was placed under a N2 atmosphere and charged with Desmodur W (54.67 g) and 39.03 g of the (1-butoxy-3-(2-methylaziridin-1-yl)propan-2-ol) intermediate. The resulting mixture was heated to 50°C, after which bismuth neodecanoate (0.02 g) was added. The mixture was allowed to exotherm, after which it was further heated to 80°C and stirred at 80°C for 1 hour. Durez-Ter S 105-110 (106.26 g) was then added to the mixture, and the mixture was stirred at 80°C for an additional hour. Samples were then taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 The solvent was removed in vacuo to obtain a colorless solid.

[0715] Subsequently, 30 g of the colorless solid obtained in the previous step was mixed with 15 g of acetone and incubated at 50° C. until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 3 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. The stirring was then increased to 10,000 rpm, and 30 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0716] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 5.3 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 31). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (score 1 indicates complete degradation of the film, 5 indicates no visible damage):

[0717] Performance and stability testing

[0718]

[0719] Example 32

[0720] A 1 L round-bottom flask equipped with a thermometer and an overhead stirrer was placed under a N atmosphere and charged with the (1-butoxy-3-(2-methylaziridin-1-yl)propan-2-ol) intermediate (25.12 g) prepared as described in Example 1, Desmodur W (55.30 g), Ymer N120 (18.21 g), and 51.36 g of polytetrahydrofuran (pTHF650) with an average Mn of 650 Da. The resulting mixture was heated to 50° C., after which bismuth neodecanoate (0.02 g) was added. The mixture was allowed to exotherm, then further heated to 70° C. and stirred until a residual NCO level of 3.8% was reached. The mixture was then cooled to 60° C. and 50.0 g of acetone was added, followed by further cooling to 40° C. Vestamin A-95 (8.31 g) was then added to the mixture, rinsed with 15 g of demineralized water and 1.5 g of a 15% aqueous potassium hydroxide solution, and the mixture was heated to 50°C and stirred for a further 15 minutes. Then, 280 g of demineralized water and 9.5 g of a 10% aqueous sodium sulfate solution were added. The solvent was removed in vacuo to obtain a whitish dispersion. The dispersion was filtered, the solids content was adjusted to 34% using demineralized water, and the pH was adjusted to 11 using an aqueous potassium hydroxide solution.

[0721] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 7.2 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 32). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and left on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicates complete degradation of the film and a score of 5 indicates no visible damage):

[0722] Performance and stability testing

[0723]

[0724] Example 33

[0725] The (1-butoxy-3-(2-methylaziridin-1-yl)propan-2-ol) intermediate was prepared as described in Example 1. A 500 mL round-bottom flask equipped with a thermometer and an overhead stirrer was placed under a N2 atmosphere and charged with Desmodur W (88.03 grams) and 62.84 grams of the (1-butoxy-3-(2-methylaziridin-1-yl)propan-2-ol) intermediate. Bismuth neodecanoate (0.02 grams) was added at room temperature. The mixture was allowed to exotherm and then further heated to 60°C over a period of 1 hour. Voranol CP450 (49.13 grams) and 50.0 grams of acetone were then added to the mixture, and the mixture was stirred at 60°C for an additional 4 hours. Samples were then taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 This step produces a low-viscosity, slightly yellow solution.

[0726] Subsequently, 15.4 g of the low-viscosity, slightly yellow solution obtained in the previous step was mixed with 3.4 g of acetone and incubated at 50° C. until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.3 g of molten Maxemul TM7101 dispersant. Using IKA T25 Digital Ultra- The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. Agitation was then increased to 10,000 rpm, and 12.6 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0727] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 1.6 grams of aged crosslinker dispersion was mixed with 10.5 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 33). As a reference, a film was also cast from the same composition lacking the crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and left on the film for 1 hour. After removal of EtOH and 60 minutes of recovery, the following results were obtained (score 1 indicates complete degradation of the membrane, 5 indicates no visible damage):

[0728] Performance and stability testing

[0729]

[0730]

[0731] Example 34

[0732] A 2 L round-bottom flask equipped with a condenser was placed under a N2 atmosphere and charged with toluene (250 g), propylene imine (325 g), bisphenol A diglycidyl ether (387 g) and K2CO3 (10.0 g) and heated to 70°C over 30 min, after which the mixture was stirred for 19 h at T = 70°C. After filtration, excess PI was removed in vacuo, followed by further purification by vacuum distillation to obtain a whitish solid.

[0733] A 500 mL round bottom flask equipped with a thermometer and an overhead stirrer was placed under a N2 atmosphere and charged with the bisphenol A-PI intermediate from the first step (34.15 g), the (1-butoxy-3-(2-methylaziridin-1-yl)propan-2-ol) intermediate (25.32 g) prepared as described in Example 1, Desmodur W (39.41 g) and 22.83 g of acetone. The resulting mixture was heated to 50°C, after which bismuth neodecanoate (0.02 g) was added. The mixture was allowed to exotherm to 60°C and then stirred at 60°C for 2 hours. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 The reaction mixture was stirred for 1 h until no NCO stretching change was observed. Subsequently, 1.11 g of n-butanol was added to the reaction mixture. The reaction mixture was then allowed to react further until the NCO stretching peak completely disappeared. Finally, 32.00 g of acetone was added to produce a light yellow solution.

[0734] The calculated molecular weight and chemical structure of the theoretical main component are shown below:

[0735]

[0736] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1375.92 Da; observed [M+Na+] = 1375.91 Da.

[0737]

[0738] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 659.47 Da; observed [M+Na+] = 659.44 Da.

[0739] Subsequently, 27 g of the yellow solution obtained in the previous step was mixed with 3.6 g of methyl ethyl ketone (MEK) and incubated at 50° C. until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.8 g of molten Maxemul TM 7101 dispersant. Using IKA T25 Digital with S 25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. Agitation was then increased to 10,000 rpm, and 18.9 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0740] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 1.0 grams of aged crosslinker dispersion was mixed with 10.5 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 34). As a reference, a film was also cast from the same composition lacking the crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and left on the film for 1 hour. After removal of EtOH and 60 minutes of recovery, the following results were obtained (score 1 indicates complete degradation of the membrane, 5 indicates no visible damage):

[0741] Performance and stability testing

[0742]

[0743] Example 35

[0744] A 500 mL round bottom flask equipped with a thermometer and an overhead stirrer was placed under a N2 atmosphere and charged with the bisphenol A-PI intermediate prepared as described in Example 34 (31.74 g), the (1-butoxy-3-(2-methylaziridin-1-yl)propan-2-ol) intermediate prepared as described in Example 1 (18.73 g), Desmodur W (35.14 g) and 22.83 g of acetone. The resulting mixture was heated to 50°C, after which bismuth neodecanoate (0.02 g) was added. The mixture was allowed to exotherm to 60°C and then stirred at 60°C for 80 minutes. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until the peak value at 2200-2300 cm -1 The reaction mixture was stirred for 10 minutes until no NCO stretching change was observed. Subsequently, 14.39 g of Ymer N120 was added to the reaction mixture. The reaction mixture was then heated to 65°C and allowed to react further until the NCO stretching peak disappeared completely. 25.00 g of acetone was then added to dilute the reaction mixture. The mixture was then cooled to 40°C and 170 g of demineralized water was gradually added to obtain a blue dispersion. The acetone was then removed from the dispersion using a rotary evaporator, and finally, the pH of the dispersion was adjusted to 11 using triethylamine.

[0745] The calculated molecular weight and chemical structure of the theoretical main component are shown below:

[0746]

[0747] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1375.92 Da; observed [M+Na+] = 1375.88 Da.

[0748]

[0749] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 659.47 Da; observed [M+Na+] = 659.44 Da.

[0750]

[0751] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 2622.70 Da; observed [M+Na+] = 2622.54 Da.

[0752] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 1.8 grams of aged crosslinker dispersion were mixed with 21 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 35). As a reference, a film was also cast from the same composition lacking a crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour. After removing the EtOH and recovering for 60 minutes, the following results were obtained (a score of 1 indicates complete degradation of the film and a score of 5 indicates no visible damage):

[0753] Performance and stability testing

[0754]

[0755]

[0756] Example 36

[0757] A 500 mL round bottom flask equipped with a thermometer and an overhead stirrer was placed under a N2 atmosphere and charged with the bisphenol A-PI intermediate prepared as described in Example 34 (17.13 g), the (1-butoxy-3-(2-methylaziridin-1-yl)propan-2-ol) intermediate prepared as described in Example 1 (28.24 g), Desmodur W (39.55 g) and 25.00 g of acetone. The resulting mixture was heated to 60°C, after which bismuth neodecanoate (0.02 g) was added. The mixture was maintained at 60°C using a water bath throughout the exothermic reaction and then stirred at 60°C for 2 hours. Samples were taken at regular intervals and the progress of the reaction was monitored using a Bruker Alpha FT-IR spectrometer until a peak at 2200-2300 cm -1 The reaction mixture was stirred for 1 h until no NCO stretching change was observed. Subsequently, 15.08 g of Voranol P-400 was added to the reaction mixture. The reaction mixture was then allowed to react further until the NCO stretching peak completely disappeared. Finally, 20.00 g of acetone was added to produce a light yellow solution. The calculated molecular weight of the theoretical main component and its chemical structure are shown below:

[0758]

[0759] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 2062.40 Da; observed [M+Na+] = 2062.39 Da.

[0760]

[0761] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1375.92 Da; observed [M+Na+] = 1375.86 Da.

[0762]

[0763] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 659.47 Da; observed [M+Na+] = 659.41 Da.

[0764] The following components with masses below 580 Da were determined and quantified by LC-MS:

[0765]

[0766] present in the composition at less than 0.01% by weight, and

[0767]

[0768] Present in less than 0.01 wt%.

[0769] Genotoxicity testing

[0770]

[0771] The results of the genotoxicity test showed that the cross-linker composition of Example 36 had only weak positive induced genotoxicity.

[0772] Subsequently, 15 g of the yellow solution obtained in the previous step was mixed with 1.5 g of methyl ethyl ketone (MEK) and incubated at 50° C. until a homogeneous solution was obtained. To this solution was added 0.03 g of triethylamine (TEA) and then 1.1 g of Atlas TM G-5002L-LQ dispersant. Using IKA T25 Digital with S 25N-18G head The resulting mixture was stirred at 2,000 rpm for 5 minutes at room temperature. Agitation was then increased to 10,000 rpm, and 10.4 grams of demineralized water, adjusted to a pH of 11 with triethylamine, was gradually added to the mixture over 15 minutes. During this addition, the mixer was continuously moved around the reaction vessel. After the addition was complete, the resulting dispersion was stirred at 5,000 rpm for an additional 10 minutes, and the pH of the dispersion was adjusted to 11 with TEA.

[0773] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 1.2 grams of aged crosslinker dispersion were mixed with 10.5 grams of polymer P1 under continuous stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100 μm wire coater (test 36). As a reference, a film was also cast from the same composition lacking the crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and left on the film for 1 hour. After removal of EtOH and 60 minutes of recovery, the following results were obtained (score 1 indicates complete degradation of the membrane, 5 indicates no visible damage):

[0774] Performance and stability testing

[0775]

[0776] Comparative Example C10

[0777] Under a nitrogen atmosphere, 21.3 g of 1-propanol were added to 78.7 g of isophorone diisocyanate (IPDI) and 0.01 g of tin 2-ethylhexanoate at 20-25° C. while stirring over a period of 6 hours. After standing overnight, 196.3 g of IPDI, 74.1 g of Tegomer D3403, and 2.4 g of 3-methyl-1-phenyl-2-phosphole-1-oxide were added. The mixture was heated to 150° C. while stirring. The mixture was maintained at 150° C. until the NCO content reached 7.0% by weight. The mixture was cooled to 80° C. and 333 g of 1-methoxy-2-propyl acetate (MPA) were added. This gave a solution of an isocyanate-functional polycarbodiimide having a solids content of 50.6% by weight and an NCO content of 7.0% by weight based on the solids.

[0778] To 100 grams of this isocyanate-functional polycarbodiimide, 7.0 grams of 1-(2-hydroxyethyl)ethyleneimine were added. One drop of dibutyltin dilaurate was added. The mixture was heated to 80°C while stirring. The mixture was held at 80°C for 1 hour. FTIR analysis showed a small amount of residual isocyanate signal, which disappeared after a few days. The solution was further diluted with 8.0 grams of MPA to give a yellow solution with a solids content of 50.4% by weight. This aziridine-functional carbodiimide contains 3.2 meq of acid-reactive groups (i.e., aziridine and carbodiimide functionalities) per gram of solids.

[0779] The general structure of this carbodiimide is depicted below.

[0780]

[0781] wherein a, b and c represent repeating units.

[0782] MALDI-TOF-MS confirmed this structure, as shown below:

[0783]

[0784] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 2043.34 Da; observed [M+Na+] = 2043.32 Da.

[0785] Genotoxicity test results:

[0786]

[0787] The results of the genotoxicity test showed that the crosslinker composition of Comparative Example C10 was genotoxic.

[0788] Subsequently, 25.0 g of the yellow solution obtained in the previous step was stirred at 500 rpm at room temperature using a three-blade propeller stirrer with a diameter of 50 mm. Then, 25.0 g of demineralized water was gradually added to the mixture over 15 minutes. After the addition was complete, the resulting dispersion was stirred at 500 rpm for an additional 5 minutes.

[0789] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface, viscosity measurement, and particle size measurement based on a procedure from the DIN 68861-1 standard. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 5.1 grams of aged crosslinker dispersion were mixed with 10.5 grams of polymer P1 under constant stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100μm wire coater (test C10). As a reference, a film was also cast from the same composition lacking the crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and left on the film for 1 hour. After removal of EtOH and 60 minutes of recovery, the following results were obtained (score 1 indicates complete degradation of the membrane, 5 indicates no visible damage):

[0790] Performance and stability testing

[0791]

[0792] *The crosslinker mixture based on 1-(2-hydroxyethyl)ethyleneimine coagulated during the first week of storage

[0793] Comparative Example C11

[0794] A 1L round-bottom flask equipped with a thermometer and an overhead stirrer is placed under an N atmosphere and charged with 196.1 grams of polytetrahydrofuran (pTHF1000) with an average Mn of 1000Da and 200.0 grams of o-xylene. The resulting mixture is cooled to -10°C using ethanol and ice, after which a solution of 68.4 grams of toluene diisocyanate (TDI) in 50.0 grams of o-xylene is added. The mixture is allowed to exotherm, thereby reaching -1°C, and then gradually warmed to room temperature without increasing heating. The reaction is continued to complete conversion (residual NCO is 3.2%), and under an N atmosphere, the 200 grams of the resulting reaction mixture is transferred to a 500mL round-bottom flask equipped with a thermometer and an overhead stirrer. 14.5 grams of 1-(2-hydroxyethyl)ethyleneimine are then added to the mixture over 60 minutes, and a water bath is used to maintain room temperature. The mixture is then stirred at 25°C for 1 hour. Then, samples were taken at regular intervals and the reaction progress was monitored using a Bruker Alpha FT-IR spectrometer until the peak wavelength was between 2200 and 2300 cm -1 The solids content was set to 49% using additional o-xylene, resulting in a slightly turbid, low-viscosity solution.

[0795] The calculated molecular weight and chemical structure of the theoretical main component are shown below:

[0796]

[0797] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 1427.91 Da; observed [M+Na+] = 1428.02 Da.

[0798]

[0799] The molecular weight was confirmed by Maldi-TOF-MS: calculated [M+Na+] = 371.17 Da; observed [M+Na+] = 371.21 Da.

[0800] Subsequently, 18.0 grams of the low-viscosity solution obtained above was mixed with 1.5 grams of Triton X-100 and incubated at 50°C until a homogeneous solution was obtained. The resulting mixture was stirred at 500 rpm for 30 minutes at room temperature using a three-blade propeller with a diameter of 50 mm. Stirring was then increased to 800 rpm, and 15.0 grams of demineralized water was gradually added to the mixture over 15 minutes. After the addition was complete, the resulting dispersion was stirred at 500 rpm for an additional 10 minutes.

[0801] The functional performance and stability of the crosslinker dispersion were evaluated using a spot test on the coating surface based on a procedure from the DIN 68861-1 standard, and viscosity and particle size measurements. For these tests, the crosslinker dispersion was stored in a 50°C oven for 4 weeks. The viscosity and particle size of the crosslinker dispersion were measured weekly. In addition, 2.8 grams of aged crosslinker dispersion were mixed with 10.5 grams of polymer P1 under constant stirring every week, and the resulting mixture was further stirred for 30 minutes. This coating composition was filtered and applied to a Leneta test card using a 100μm wire coater (test C11). As a reference, a film was also cast from the same composition lacking the crosslinker dispersion (test blank). The film was dried at 25°C for 1 hour and then annealed at 50°C for 16 hours. Subsequently, a piece of cotton wool was immersed in 1:1 EtOH: demineralized water and left on the film for 1 hour. After removal of EtOH and 60 minutes of recovery, the following results were obtained (score 1 indicates complete degradation of the membrane, 5 indicates no visible damage):

[0802] Performance and stability testing

[0803]

[0804] * The crosslinker mixture gelled during the second week of storage

[0805] Reliable particle size measurements were not possible for this sample

Claims

1. A polyaziridine crosslinking agent composition, characterized in that The polyaziridine crosslinker composition is an aqueous dispersion having a pH range of 8 to 14 and comprises a polyaziridine compound in dispersed form, wherein The polyaziridine compound has: a. 2 to 6 of the following structural units A: in R1 is H, R2 and R4 are independently selected from H or an aliphatic hydrocarbon group containing 1 to 4 carbon atoms, R3 is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms, m is 1, R' and R" according to (1) or (2): (1) R' = H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms; and R"=aliphatic hydrocarbon group containing 1 to 14 carbon atoms, alicyclic hydrocarbon group containing 5 to 12 carbon atoms, aromatic hydrocarbon group containing 6 to 12 carbon atoms, CH2-O-(C=O)-R"', CH2-OR"" or CH2-(OCR""'HCR""'H) n -OR""", wherein R"' is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms and R"" is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms or an aromatic hydrocarbon group containing 6 to 12 carbon atoms, n is 1 to 35, R""' is independently H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, and R""" is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms, (2) R′ and R″ together form a saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms; b. one or more link chains, wherein each of these link chains links two structural units A in the structural unit A, wherein the link chain is the shortest chain of consecutive atoms linking two structural units A; and c. a molecular weight in the range of 500 Daltons to 10,000 Daltons, wherein the molecular weight is determined using MALDI-TOF mass spectrometry; as well as d. one or more linking groups, wherein each of these linking groups connects two structural units A in the structural unit A, wherein the linking group is composed of at least one functional group selected from the following items: an aliphatic hydrocarbon functional group, an alicyclic hydrocarbon functional group, an aromatic hydrocarbon functional group, an isocyanurate functional group, an iminooxadiazinedione functional group, an ether functional group, an ester functional group, an amide functional group, a carbonate functional group, a carbamate functional group, a urea functional group, a biuret functional group, an allophanate functional group, a uretdione functional group and any combination thereof.

2. The polyaziridine crosslinking agent composition according to claim 1, characterized in that R2 is H, R3 is C2H5 and R4 is H, or R2 is H, R3 is CH3 and R4 is CH3.

3. The polyaziridine crosslinking agent composition according to claim 1, characterized in that R2 is H, R3 is CH3 and R4 is H.

4. The polyaziridine crosslinker composition according to any one of claims 1 to 3, characterized in that The linker chain consists of 4 to 300 atoms, and the linker chain is a collection of covalently linked atoms consisting of i) carbon atoms, ii) carbon and nitrogen atoms, or iv) carbon, oxygen, and nitrogen atoms.

5. The polyaziridine crosslinker composition according to any one of claims 1 to 3, characterized in that The polyaziridine compound contains 2 or 3 structural units A.

6. The polyaziridine crosslinker composition according to any one of claims 1 to 3, characterized in that R' is H and R" = alkyl containing 1 to 4 carbon atoms, CH2-O-(C=O)-R"', CH2-OR"", wherein R"' is alkyl containing 3 to 12 carbon atoms and R"" is alkyl containing 1 to 14 carbon atoms.

7. The polyaziridine crosslinker composition according to any one of claims 1 to 3, characterized in that The linking group consists of at least one aliphatic hydrocarbon functional group and / or at least one alicyclic hydrocarbon functional group and an isocyanurate functional group.

8. The polyaziridine crosslinker composition according to any one of claims 1 to 3, characterized in that The linking group consists of at least one aliphatic hydrocarbon functional group and / or at least one alicyclic hydrocarbon functional group and an iminooxadiazinedione functional group.

9. The polyaziridine crosslinker composition according to any one of claims 1 to 3, wherein the polyaziridine compound comprises one or more linking groups, wherein each of the linking groups links two of the structural units A, wherein the linking group consists of (i) at least two aliphatic hydrocarbon functional groups and (ii) an isocyanurate functional group or an iminooxadiazinedione functional group, and wherein a pendant group is present on the linking group, wherein the pendant group has the following structural formula: in n' is the number of repeating units and is an integer from 1 to 50, X is O or NH, In each repeating unit, R7 and R8 are independently H or CH3, R9 is an aliphatic hydrocarbon group, and R 10 It is an aliphatic hydrocarbon group containing 1 to 20 carbon atoms, an alicyclic hydrocarbon group containing 5 to 20 carbon atoms, or an aromatic hydrocarbon group containing 6 to 20 carbon atoms.

10. The polyaziridine crosslinker composition according to any one of claims 1 to 3, characterized in that The number of consecutive C atoms and optionally O atoms between the N atom of a urethane group in a structural unit A and the next N atom which is present in the linking chain or is a N atom of a urethane group of another structural unit A is at most 9.

11. The polyaziridine crosslinker composition according to any one of claims 1 to 3, characterized in that The polyaziridine compound is obtained by reacting at least a polyisocyanate having aliphatic reactivity with a compound B having the following structural formula, wherein all isocyanate groups are directly bonded to aliphatic or alicyclic hydrocarbon groups, regardless of whether aromatic hydrocarbon groups are also present: wherein the molar ratio of compound B to polyisocyanate is 2 to 6, and wherein m, R′, R″, R1, R2, R3 and R4 are as defined in any one of claims 1 to 3.

12. The polyaziridine crosslinker composition according to any one of claims 1 to 3, characterized in that The molecular weight of the polyaziridine compound is 600 Dalton to 5000 Dalton.

13. The polyaziridine crosslinker composition according to any one of claims 1 to 3, characterized in that The aqueous dispersion comprises aziridinyl-functional molecules having a molecular weight of less than 580 Daltons in an amount less than 5 wt. %, based on the total weight of the aqueous dispersion, wherein the molecular weight is determined using LC-MS.

14. The polyaziridine crosslinker composition according to any one of claims 1 to 3, characterized in that The pH of the aqueous dispersion is at least 9.5 and at most 13.

15. The polyaziridine crosslinker composition according to any one of claims 1 to 3, characterized in that The amount of water in the aqueous dispersion is at least 15 wt% and at most 95 wt% based on the total weight of the aqueous dispersion.

16. The polyaziridine crosslinker composition according to any one of claims 1 to 3, characterized in that The amount of the polyaziridine compound in the aqueous dispersion is at least 5 wt % and at most 70 wt % based on the total weight of the aqueous dispersion.

17. The polyaziridine crosslinker composition according to any one of claims 1 to 3, characterized in that The solids content of the aqueous dispersion is at least 5% by weight and at most 70% by weight.

18. The polyaziridine crosslinker composition according to any one of claims 1 to 3, characterized in that The polyaziridine crosslinker composition comprises particles containing the polyaziridine compound, wherein the particles have an average hydrodynamic diameter based on scattered intensity of 30 nm to 650 nm, as measured using a method derived from the ISO 22412:2017 standard.

19. The polyaziridine crosslinker composition according to any one of claims 1 to 3, characterized in that The aqueous dispersion comprises a dispersant.

20. The polyaziridine crosslinker composition according to any one of claims 1 to 3, characterized in that The aqueous dispersion contains a single surface-active molecular component as a dispersant, and the amount of the single surface-active molecular component is in the range of 0.1 wt % to 20 wt % based on the total weight of the aqueous dispersion.

21. The polyaziridine crosslinker composition according to claim 20, characterized in that The dispersant is a polymer having a number average molecular weight of at least 2,000 Daltons and at most 1,000,000 Daltons, and the polymer is a polyether, wherein the number average molecular weight is determined using MALDI-ToF mass spectrometry.

22. Use of a polyaziridine crosslinker composition according to any one of claims 1 to 21 for crosslinking carboxylic acid-functional polymers dissolved and / or dispersed in an aqueous medium, wherein the carboxylic acid-functional polymer contains carboxylic acid groups and / or carboxylate groups, and the amount of aziridine groups and the amount of carboxylic acid groups and carboxylate groups are selected such that the stoichiometric amount of aziridine groups on the carboxylic acid groups and carboxylate groups is from 0.1 to 2.

0.

23. A two-component coating system comprising a first component and a second component, each of the first component and the second component being separate and distinct from each other, and characterized in that The first component comprises a carboxylic acid functional polymer dissolved and / or dispersed in an aqueous medium, wherein the carboxylic acid functional polymer contains carboxylic acid groups and / or carboxylate groups, and the second component comprises a polyaziridine crosslinker composition according to any one of claims 1 to 21.

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