Aziridine functional compounds

Abstract

The present application relates to aziridine-functional compounds with reduced genotoxicity and good cross-linking efficiency, which are useful for preparing, for example, coatings.

Description

[0001] The present invention relates to aziridine-functional compounds which can be used, for example, for crosslinking, for example, for crosslinking carboxylic acid-functional polymers dissolved and / or dispersed in an aqueous medium.

[0002] Over the years, there has been an increasing demand for coatings with improved resistance properties such as stain resistance and solvent resistance, improved mechanical properties, and improved bond strength. One or more of these properties can be improved to a higher level by means of crosslinking. Many crosslinking mechanisms have been investigated over the years, and for waterborne dispersions, the most useful crosslinking mechanisms include isocyanate crosslinking of hydroxyl functional dispersions, reactions between carbodiimides and carboxylic acids, epoxy crosslinking, and crosslinking using aziridine based crosslinking agents.

[0003] US-A-5133997 describes a coating composition comprising an aqueous dispersion of a linear aliphatic polyurethane resin, an anionic surfactant, and a crosslinking agent capable of promoting the curing of the resin. Trimethylolpropane tris (2-methyl-1-aziridine propionate), CAS No. 64265-57-2, is a multifunctional aziridine crosslinking agent used as a crosslinking agent, which is well-known and highly active for crosslinking carboxylic acid functional polymers. However, the crosslinking agent has unfavorable genotoxic characteristics. There is an industry need to improve the safety, health and environmental characteristics of adhesives, inks and coatings and materials used to prepare adhesives, inks and coatings. Genotoxicity describes the property of chemical or physical agents that cause any type of DNA damage, which may not always result in transmittable mutations. Mutagenicity refers to the induction of permanent transmittable DNA changes (as DNA components or chromosome structures) that are maintained in somatic cell divisions and passed on to progeny in germ cells. Genotoxicity should not be confused with mutagenicity. All mutagens are genotoxic, but not all genotoxic agents are mutagenic.

[0004] The object of the present invention is to provide aziridine-functional crosslinking compounds which have reduced genotoxicity compared to trimethylolpropane tris(2-methyl-1-aziridine propionate) and have good crosslinking efficiency.

[0005] This object was unexpectedly achieved by providing aziridines having:

[0006] a) One or two of the following structural units A:

[0007]

[0008] in

[0009] R1 is H;

[0010] R2 and R4 are independently selected from H or an aliphatic hydrocarbon group containing 1 to 4 carbon atoms;

[0011] R3 is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms;

[0012] R' and R" are based on (1) or (2):

[0013] (1) R'=H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms; and R"=H, an aliphatic hydrocarbon group containing 5 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 4 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,

[0014] (2) R' and R" together form a saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms,

[0015] R 11 is H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, preferably R 11 is H or methyl,

[0016] m is an integer from 1 to 6;

[0017] b) A structural unit B:

[0018]

[0019] in

[0020] p+q is an integer from 0 to 4;

[0021] r is an integer from 0 to 2;

[0022] X is NR, NH or O, wherein R contains up to 36 carbon atoms and optionally (herein the same as "optionally") contains one or more heteroatoms;

[0023] R5 and R6 independently contain 4 to 13 carbon atoms;

[0024] R7 is a divalent group;

[0025] c) optionally a structural unit C:

[0026]

[0027] in

[0028] Z is NR, NH or O, wherein R contains up to 36 carbon atoms and optionally contains one or more heteroatoms;

[0029] R8 is a monovalent group; and

[0030] d) structural formula ABA (i.e., the aziridine compound is a structural unit B connected to two structural units A) or structural formula ABC (i.e., the structural unit B of the aziridine compound is connected to one structural unit A and to a structural unit C);

[0031] e) a molecular weight of greater than 600 Daltons and at most 5000 Daltons; provided that the starting materials providing the structural units A, B and C are selected such that

[0032] f) the mathematical sum of the molar mass of the starting diisocyanate providing the carbodiimide functional groups in structural unit B + the molar mass of structural unit A + the molar mass of structural unit A is higher than 600 Daltons; and

[0033] g) if structural unit C is present (ie the aziridine compound is according to formula ABC), the mathematical sum of the molar mass of the starting diisocyanate providing the carbodiimide functionality in structural unit B + the molar mass of structural unit A + the molar mass of structural unit C is higher than 600 Daltons.

[0034] It was unexpectedly found that the compounds according to the present invention have reduced genotoxicity compared to trimethylolpropane tris (2-methyl-1-aziridine propionate). The compounds according to the present invention only show weak positive induced genotoxicity, or even they do not show genotoxicity, i.e. they show genotoxicity levels comparable to the naturally occurring background, while still having sufficient cross-linking efficiency. Compounds having at least one aziridine group and at least one carbodiimide group are further referred to herein as aziridine-functional carbodiimide compounds. Both aziridine and carbodiimide functional groups are reactive to carboxylate groups, and the acid-base interaction of aziridine with carboxylate groups inherently provides close proximity of both aziridine and carbodiimide groups, thereby enhancing cross-linking.

[0035] EP0507407 describes multifunctional water-dispersible crosslinkers which are oligomeric materials containing carbodiimide functions and reactive functional groups different from the carbodiimide functions. According to this patent publication, compounds having carbodiimide functions and aziridine functions are mutagenic and therefore genotoxic.

[0036] Genotoxicity can be determined by The measurements were performed using the Toxys® assay (Toxys, Leiden, the Netherlands). The assay can be applied to pure substances or to compositions that are direct products obtained in the preparation of the aziridine-functional carbodiimide compounds of the present invention. Positive induction of genotoxicity means that the induction level of the biomarkers Bscl2-GFP and Rtkn-GFP in the absence or presence of a metabolic system rat S9 liver extract is equal to or higher than 2 times at at least one of 10%, 25% and 50% cytotoxicity. Weak positive induction of genotoxicity means that the induction level of the biomarkers Bscl2-GFP and Rtkn-GFP in the absence or presence of a metabolic system based on rat S9 liver extract (aroclor1254-induced rats, Moltox, Boone, NC, USA) is higher than 1.5 times and lower than 2 times at at least one of 10%, 25% and 50% cytotoxicity (but lower than 2 times at 10%, 25% and 50% cytotoxicity). Genotoxicity comparable to the naturally occurring background means that the induction level of the biomarkers Bscl2-GFP and Rtkn-GFP in the absence and presence of a metabolic system based on rat S9 liver extract (aroclor1254-induced rats, Boone, NC, USA) is less than or equal to 1.5 times 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), the induction level of the genotoxicity reporter genes Bscl2-GFP and Rtkn-GFP is preferably less than or equal to 1.5 times at 10%, 25% and 50% cytotoxicity. Substances that show induction levels less than or equal to 1.5 times 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) are not genotoxic. The cross-linking efficiency of a cross-linking agent can be evaluated by assessing the chemical resistance determined as described below.

[0037] For all upper and / or lower boundaries of any range given herein, unless otherwise specifically indicated, 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.

[0038] In this specification, the term "coating composition" covers paints, coatings, varnishes, adhesives and ink compositions, but is not limited to this list. The term "aliphatic hydrocarbon group" refers to optionally branched alkyl, alkenyl and alkynyl groups. The term "alicyclic hydrocarbon group" refers to cycloalkyl and cycloalkenyl groups optionally substituted by at least one aliphatic hydrocarbon group. The term "aromatic hydrocarbon group" refers to a benzene ring optionally substituted by at least one aliphatic hydrocarbon group. These optional aliphatic hydrocarbon substituents are preferably alkyl groups. Examples of alicyclic hydrocarbon groups with 7 carbon atoms are cycloheptyl and methyl-substituted cyclohexyl. Examples of aromatic hydrocarbon groups with 7 carbon atoms are methyl-substituted phenyl. Examples of aromatic hydrocarbon groups with 8 carbon atoms are xylyl and ethyl-substituted phenyl.

[0039] The aziridine-functional carbodiimide compounds according to the invention are usually obtained in compositions in which, in addition to the aziridine-functional carbodiimide compounds, the remaining starting materials, by-products and / or solvents used in the preparation of the aziridine-functional carbodiimide compounds may be present. The composition may contain only one aziridine-functional carbodiimide compound according to the invention, but may also contain more than one aziridine-functional carbodiimide compound according to the invention. For example, when a mixture of diisocyanates is used as starting material to form the carbodiimide bonds in the structural unit B, a mixture of aziridine-functional carbodiimide compounds is obtained.

[0040] Although the two structural units A may independently have different R2, R3, R4, R', R", R 11 and / or m, if the aziridine-functional carbodiimide compound according to the invention has two structural units A, the structural units A are preferably identical to one another.

[0041] The aziridine-functional carbodiimide compounds according to the invention contain 1 or 2 structural units A, preferably 2 structural units A.

[0042] 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. R3 is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms, preferably an aliphatic hydrocarbon group containing 1 to 2 carbon atoms. In one embodiment of the present invention, R1 is H, R2 is H, R3 is C2H5 and R4 is H. In another and more preferred embodiment of the present invention, R1 is H, R2 is H, R3 is CH3 and R4 is CH3. In another and even more preferred embodiment of the present invention, R1 is H, R2 is H, R3 is CH3 and R4 is H.

[0043] m is an integer of 1 to 6, preferably m is 1 to 4, more preferably m is 1 or 2 and most preferably m is 1.

[0044] Preferably, R' and R" are according to (1) or (2):

[0045] (1) R'=H;

[0046] R"=H, an aliphatic hydrocarbon group containing 5 to 10 carbon atoms, CH2-O-(C=O)-R"', CH2-OR"" or CH2-(OCR""'HCR""'H)n-OR""", wherein R"' is an aliphatic hydrocarbon group containing 4 to 14 carbon atoms and R"" is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, n is 1 to 35, R""' is independently H or a methyl group and R""" is an alkyl group containing 1 to 4 carbon atoms;

[0047] (2) R' and R" together form a saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms,

[0048] R 11 is H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, preferably R 11 is H or methyl,

[0049] More preferably, R' is H and R" is an alkyl group containing 5 to 10 carbon atoms, CH2-O-(C=O)-R"', CH2-OR"" or CH2-(OCH2CH2)n-OCH3, wherein R"' is an alkyl group containing 4 to 12 carbon atoms, such as, for example, neopentyl or neodecyl. Most preferably, R"' is a branched C9 alkyl group. R"" is preferably an alkyl group containing 4 to 14 carbon atoms, more preferably 1 to 12 carbon atoms. Non-limiting examples of R"" are butyl and 2-ethylhexyl.

[0050] The aziridine-functional carbodiimide compound according to the invention contains 1 structural unit B connected to at least one structural unit A. The structural unit B present in the aziridine-functional carbodiimide compound according to the invention is connected to one structural unit A and to one structural unit C, or to two structural units A. If the structural unit B present in the aziridine-functional carbodiimide compound according to the invention is connected to 1 structural unit A and also to a structural unit C, i.e. the aziridine-functional carbodiimide compound has the configuration ABC, it has the following structural formula:

[0051]

[0052] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R 11 , R', R", X, Z, p, q, r and m as well as preferred characteristics thereof are as defined above.

[0053] If the structural unit B present in the aziridine-functional carbodiimide compound according to the invention is linked to two structural units A, ie the aziridine-functional carbodiimide compound has the configuration ABA, it has the following structural formula:

[0054]

[0055] Among them, R1, R2, R3, R4, R5, R6, R7, R 11 , R', R", X, p, q, r and m and preferred features thereof are as defined above. m and n are integers from 1 to 6, preferably m and n are independently selected from 1 to 4, more preferably m and n are independently selected from 1 or 2. m and n are preferably equal. Most preferably, both m and n are 1.

[0056] In one embodiment, the aziridine functional carbodiimide compound has the configuration ABA. In another embodiment, the aziridine functional carbodiimide compound has the configuration ABC.

[0057] Structural unit B

[0058]

[0059] P+q is an integer from 0 to 4, i.e., the aziridine functional carbodiimide compound has at least one carbodiimide functional group and at most 5 carbodiimide functional groups. Preferably, p+q is an integer from 0 to 3, i.e., the aziridine functional carbodiimide compound has at least one carbodiimide functional group and at most 4 carbodiimide functional groups. More preferably, p+q is an integer from 0 to 2, i.e., the aziridine functional carbodiimide compound has at least one carbodiimide functional group and at most 3 carbodiimide functional groups. Even more preferably, p+q is 0 or 1, i.e., the aziridine functional carbodiimide compound has at least one carbodiimide functional group and at most 2 carbodiimide functional groups. Most preferably, p+q is 1, i.e., the aziridine functional carbodiimide compound has 2 carbodiimide functional groups.

[0060] r is an integer from 0 to 2. Preferably, r is 0 or 1, more preferably r is 1. If r is 1, the aziridine functional carbodiimide compound is preferably according to the structural formula ABA. If r is 0, the aziridine functional carbodiimide compound is preferably according to the structural formula ABC.

[0061] X is NR, O or NH, preferably X is O. R contains up to 36 carbon atoms and optionally contains one or more heteroatoms in the chain. Preferably, R contains one or more heteroatoms in the chain. The heteroatom is preferably O. Preferably, R is a straight or branched chain group containing 1 to 36 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, or R is a cyclic group containing 3 to 8 carbon atoms.

[0062] R5 and R6 independently contain 4 to 13 carbon atoms. R5 and R6 are preferably independently selected from aliphatic hydrocarbon groups containing 4 to 13 carbon atoms, at least one alicyclic hydrocarbon group containing 5 to 15 carbon atoms, at least one aromatic hydrocarbon group containing 6 to 13 carbon atoms, and any combination thereof. More preferably, R5 and R6 are independently one or two alicyclic hydrocarbon groups containing 5 to 15 carbon atoms or an aromatic hydrocarbon group containing 6 to 13 carbon atoms. Preferably, R5=R6. Typically, R5 and R6 are hydrocarbon residues from diisocyanates used to form the carbodiimide functional group present in structural unit B.

[0063] R7 is a divalent group preferably comprising carbon atoms and hydrogen atoms and preferably also comprising one or more heteroatoms. R7 preferably comprises carbon, hydrogen and oxygen atoms. The average molecular weight of R7 is preferably 62 to 3000 Daltons. The average molecular weight of R7 is determined by the average molecular weight of HX-R7-XH, wherein X is as defined above. If both X are O, the average molecular weight of the diol HO-R7-OH is calculated by its OH-value according to the following equation: 2*56100 / [OH-value in mg KOH / g diol]. The OH value is determined according to ISO 14900 (2017) method A. If both X are NH or NR or one X is NH and the other X is NR, the average molecular weight of the diamine HX-R7-XH is calculated by the amine-value according to the following equation: 2*56100 / [amine-value in mg KOH / g diamine]. The amine value is determined according to ASTM method D6979-18 (2018).

[0064] Preferably, R7 contains a hydrophilic segment to improve the dispersibility of the aziridine compound in water. Preferably, R7 contains a poly(oxyalkylene) unit, preferably a poly(oxyethylene) unit. R7 is preferably a polyether having an average molecular weight of 106 to 3000 Daltons, more preferably 150 to 2000 Daltons, most preferably 194 to 1300 Daltons, and preferably contains more than 50% by weight of ethoxylated groups, more preferably more than 80% by weight of ethoxylated groups, most preferably more than 90% by weight of ethoxylated groups. The polyether may contain an acid residue or a sodium sulfonate residue. In another preferred embodiment, R7 is a residue of a diol or diamine or an alcoholamine having the formula HX-R7-XH (wherein both X are O or both X are NH or both X are NR or one X is NH and the other X is NR), wherein R7 contains carbon and hydrogen atoms and comprises a sulfonate group, such as sodium 2-[(2-aminoethyl)amino]ethanesulfonate. Preferred sodium sulfonate is sodium 2-[(2-aminoethyl)amino]ethanesulfonate.

[0065] Structural unit C

[0066] The aziridine-functional carbodiimide compounds according to the invention optionally contain a structural unit C having the following structural formula:

[0067]

[0068] in

[0069] Z is NR, O or NH, wherein R contains up to 36 carbon atoms and optionally contains one or more heteroatoms in the chain. Preferably, R contains one or more heteroatoms in the chain. The heteroatom is preferably O. Preferably, R is a straight or branched chain group containing 1 to 36 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, or R is a cyclic group containing 3 to 8 carbon atoms. Preferably, Z is NH or O, more preferably Z is NH.

[0070] R8 is a monovalent group, preferably a monovalent group comprising carbon atoms and hydrogen atoms. The average molecular weight of R8 is preferably 62 to 3000 Daltons. The average molecular weight of R8 is determined by the average molecular weight of HZ-R8, wherein Z is as defined above. If Z is O, the average molecular weight of the monoalcohol HO-R8 is calculated by its OH-value according to the following equation: 56100 / [OH-value in mg KOH / g monoalcohol]. The OH value is determined according to ISO 14900 (2017) method A. If Z is NH or NR, the average molecular weight of the monoamine H2N-R8 or HRN-R8 is calculated by the amine-value according to the following equation: 56100 / [amine value in mg KOH / g monoamine]. The amine value is determined according to ASTM method D6979-18 (2018).

[0071] The structural unit C is preferably derived from (i.e., HZ-R8 is) a linear or branched monofunctional monoalcohol or monoamine, such as, for example, 1-propanol, 2-propanol, butanol, pentanol, hexanol, heptanol, octanol and amine analogs thereof. Preferably, R8 contains a hydrophilic segment to improve the dispersibility of the aziridine compound in water. Preferably, R8 contains a poly(oxyalkylene) unit, preferably a poly(oxyethylene) unit. R8 is preferably a polyether having an average molecular weight of 106 to 3000 daltons, more preferably 200 to 3000 daltons, more preferably 350 to 2000 daltons, more preferably 350 to 2000 daltons, most preferably 500 to 1500 daltons, and preferably contains more than 50% by weight of ethoxylated groups, more preferably more than 80% by weight of ethoxylated groups, most preferably more than 90% by weight of ethoxylated groups. Examples are methoxypolyethylene glycol 350, 550, 750 and polyetheramines such as Jeffamine M-600, M-1000, M-2070.

[0072] The molecular weight of the aziridine functional carbodiimide compound according to the present invention is higher than 600 daltons and at most 5000 daltons. The molecular weight of the aziridine functional carbodiimide compound according to the present invention is preferably at most 4000 daltons, more preferably at most 3500 daltons, more preferably at most 3000 daltons. The molecular weight of the aziridine functional carbodiimide compound according to the present invention is preferably at least 700 daltons, more preferably at least 750 daltons, even more preferably at least 800 daltons and most preferably at least 1000 daltons. As used herein, the molecular weight of the aziridine functional carbodiimide compound is a calculated molecular weight. The calculated molecular weight is obtained by summing the atomic masses of all atoms present in the structural formula of the aziridine functional carbodiimide compound. If the aziridine functional carbodiimide compound is present in a composition comprising more than one aziridine functional carbodiimide compound according to the present invention, for example, when one or more starting materials in the starting materials for preparing the aziridine functional carbodiimide compound are a mixture, the molecular weight calculation can be performed for each compound present alone in the composition. The molecular weight of the aziridine functional carbodiimide compounds according to the present invention can be measured using MALDI-TOF mass spectrometry as described in the experimental section below.

[0073] If the desired structural formula of the aziridine functional carbodiimide compound is ABA, the aziridine functional carbodiimide compound is prepared without using the compound HZ-R8. The starting materials (or raw materials) providing the structural units A and B are selected so that the mathematical sum of the molar mass of the starting diisocyanate providing the carbodiimide functional group in the structural unit B + the molar mass of the structural unit A + the molar mass of the structural unit A is higher than 600 Daltons, preferably higher than 615 Daltons, more preferably higher than 700 Daltons. Therefore, the molar mass of the compound with the following structural formula (G) is higher than 600 Daltons, preferably higher than 615 Daltons, more preferably higher than 700 Daltons.

[0074]

[0075] Among them, R1, R2, R3, R4, R 11 , R', R", m and n and their preferred characteristics are as defined above. R 10 is R5 or R6 as defined above. Therefore, the mathematical sum of the molar mass of the starting diisocyanate providing the carbodiimide functional group in the structural unit B + the molar mass of the structural unit A + the molar mass of the structural unit A is equal to the molar mass of the compound of formula (G). The molar mass of the compound of formula (G) is determined using LC-MS as described below.

[0076] If the desired structural formula of the aziridine-functional carbodiimide compound is ABC, the compound HZ-R8 is preferably used to prepare the aziridine-functional carbodiimide compound. In this embodiment of the invention, the starting materials providing the structural units A and B are selected so that the mathematical sum of the molar mass of the starting diisocyanate providing the carbodiimide functional group in the structural unit B + the molar mass of the structural unit A + the molar mass of the structural unit A is higher than 600 Daltons, preferably higher than 615 Daltons, more preferably higher than 700 Daltons, and in addition, the starting materials providing the structural units A, B and C are selected so that the mathematical sum of the molar mass of the starting diisocyanate providing the carbodiimide functional group in the structural unit B + the molar mass of the structural unit A + the molar mass of the structural unit C is higher than 600 Daltons, preferably higher than 615 Daltons, more preferably higher than 700 Daltons. Thus, the molar mass of the compound of formula G as shown above is higher than 600 Daltons, preferably higher than 615 Daltons, more preferably higher than 700 Daltons, and furthermore the molar mass of the compound of formula (H) below is higher than 600 Daltons, preferably higher than 615 Daltons, more preferably higher than 700 Daltons.

[0077]

[0078] Among them, R1, R2, R3, R4, R11 , R', R", R8 and R 10 , m and n and their preferred characteristics are as defined above. 10 is R5 or R6 as defined above. Thus, the mathematical sum of the molar mass of the starting diisocyanate providing the carbodiimide functional group in structural unit B + the molar mass of structural unit A + the molar mass of structural unit C is equal to the molar mass of the compound of formula (H). The molar mass of the compound of formula (H) is determined using LC-MS as described below.

[0079] The aziridine equivalent weight (molecular weight of the aziridine functional carbodiimide compound divided by the number of aziridinyl groups present in the aziridine functional carbodiimide compound) of the aziridine functional carbodiimide compound according to the invention is preferably at least 300, more preferably at least 350, more preferably at least 400 and even more preferably at least 450 Daltons and preferably at most 5000, more preferably at most 3000, even more preferably at most 2500 Daltons and most preferably at most 2000 Daltons.

[0080] The aziridinyl group has the following structural formula:

[0081]

[0082] wherein R1, R2, R3 and R4 are as defined above.

[0083] The carbodiimide equivalent weight (molecular weight of the aziridine functional carbodiimide divided by the number of carbodiimide functional groups present in the compound) of the aziridine functional carbodiimide compounds according to the invention is preferably at least 300, preferably at least 350, more preferably at least 400, most preferably at least 600 Daltons and preferably at most 5000, preferably at most 2500, more preferably at most 2000 and most preferably at most 1500 Daltons.

[0084] The aziridine functional carbodiimide preferably contains at least 0.5 meq of acid-reactive groups (i.e., aziridine and carbodiimide functional groups) per gram solid, preferably at least 1.0 meq / g solid, more preferably 1.5 meq / g solid and at most 5 meq / g solid, preferably at most 4.5 meq / g solid, more preferably at most 4 meq / g solid.

[0085] Another aspect of the present invention is a process for the preparation of an aziridine-functional carbodiimide compound as defined above.

[0086] Methods for preparing structural unit A and derivatives are known in the art. For example, the synthesis of 1-(2-methylaziridine-1-yl) propan-2-ol is described in 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 in A.Baklien, MVLeeding, J.Kolm Aust.J.Chem.1968, 21, 1557-1570. Preferred aziridines for preparing structural unit A are propylene imine and ethyl aziridine. The synthesis of ethyl aziridine is described, for example, in EP0227461B1. The most preferred aziridine for preparing structural unit A is propylene imine.

[0087] The structural unit A present in the compounds according to the invention is preferably obtained by reacting at least one monoepoxide compound with an aziridine of the following formula (C):

[0088]

[0089] Wherein R1, R2, R3 and R4 and its preferred features are as defined above. Monoepoxide can be a mixture of different monoepoxides. Non-limiting examples of monoepoxides are 2-ethyl oxirane, 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 neodecanoic acid glycidyl ester. Monoepoxide is preferably selected from the group consisting of: n-butyl glycidyl ether (CAS number 2426-08-6), 2-ethylhexyl glycidyl ether (CAS number 2461-15-6), neodecanoic acid glycidyl ester (CAS number 26761-45-5) and any mixture thereof.

[0090] The structural unit A present in the compound according to the present invention can be obtained in a process comprising at least the following step (i): (i) contacting one equivalent of an epoxide compound with one equivalent of an aziridine of formula (C) at a temperature ranging from 20°C to 110°C, more suitably from 40°C to 95°C, even more suitably from 60°C to 85°C at atmospheric pressure. The aziridine of formula (C) is preferably acrylimine (CAS No. 75-55-8) or 2,2-dimethylaziridine (CAS No. 2658-24-4), more preferably the aziridine of formula (C) is acrylimine.

[0091] Methods for preparing building blocks B and derivatives thereof are known in the art, see for example EP507407 and WO2012 / 015295 describing the synthesis of carbodiimide functional groups starting from diisocyanates.

[0092] The structural unit B present in the compounds of the invention is preferably obtained by reacting a diisocyanate with the following structural formula (E) to form a polycarbodiimide functional group: O=C=NR 10 -N=C=O(E), where R 10 is R5 or R6 as described above, and optionally is a diol, diamine and / or hydroxylamine of formula HX-R7-XH (wherein X, R and R7 are as defined above) and optionally HZ-R8 (wherein Z, R and R8 are as defined above). The carbodiimide functional group is obtained by reacting a diisocyanate: 2O=C=NR 10 -N=C=O→O=C=NR 10 -N=C=NR 10 -N=C=O+CO2, where R 10 If the compound of the present invention has the structural formula ABC, the carbodiimide formation is achieved in the presence of a component having the formula HZ-R8, wherein Z and R8 are as defined above.

[0093] These components are usually heated and formed by using a catalyst, and the reaction is stopped when the desired NCO% by weight is achieved in the reaction mixture, and the remaining NCO groups are then reacted with the structural unit A and the optional structural unit C. The first step of the method (i.e., carbodiimide formation) occurs at a reaction temperature of 70-180°C, while carbon dioxide escapes and optionally hydroxyl or amine functional substances HX-R7-XH are incorporated into the main chain. Phosphorene, phosphorene oxide sulfide or phosphorene oxide can be used as a catalyst for carbodiimide formation. Typical catalysts are 2,5-dihydro-3-methyl-1-phenylphosphine alcohol-1-oxide or 1-methylphosphine-1-oxide. The reaction is continued until the desired NCO% by weight is reached in the reaction mixture. The desired NCO% by weight determines the chain length and functionality of the carbodiimide. After reducing the temperature, the remaining NCO groups are reacted with the hydroxyl functional forms of the structural units A and optionally the hydroxyl or amine functional forms of the structural units C at 20 to 110°C.

[0094] The compounds of the present invention are preferably obtained by reacting a compound of formula (D) (providing structural unit A):

[0095]

[0096] Where R', R", m, R1, R2, R3, R4 and R 11 is as defined above; and has the formula EO=C=NR 10 -N=C=O(E) diisocyanate, wherein R 10 is R5 or R6 as described above; and optionally a diol, diamine and / or hydroxylamine of formula F HX-R7-XH (F), wherein X, R and R7 are as defined above (providing structural unit B); and in the case of a compound of formula ABC, compound G HZ-R8 (G), wherein Z, R and R8 are as defined above (providing structural unit C). The compounds of formula (D), (E), (F) and (G) are selected such that the molar mass of the smallest compound that can be formed during the reaction is higher than 600 Daltons, preferably higher than 615 Daltons, more preferably higher than 700 Daltons, i.e. the compounds of formula (D), (E), (F) and (G) are selected such that the molar mass of the by-products inherently formed is higher than 600 Daltons, preferably higher than 615 Daltons, more preferably higher than 700 Daltons. The present invention further relates to a process for preparing the aziridine compounds according to the invention, which is carried out by reacting a compound of formula (D) (providing structural unit A) and a diisocyanate of formula (E) and optionally a diol, diamine and / or hydroxylamine of formula (F) and, in the case of a compound of formula ABC, a compound G of formula (G) (providing structural unit C).

[0097] With the formula EO=C=NR 10 -N=C=O(E) diisocyanate (where R 10R5 or R6 as described above) preferably 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 with similar compounds but based on polyisocyanates with aromatic reactivity, compounds based on polyisocyanates with aliphatic reactivity have a reduced tendency to yellow over time. The term "polyisocyanate with aromatic reactivity" refers to 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). More preferred polyisocyanates are isophorone diisocyanate IPDI, 4,4'-dicyclohexylmethane diisocyanate H12MDI and / or tetramethylxylene diisocyanate TMXDI (all isomers). The most preferred polyisocyanate is 4,4'-dicyclohexylmethane diisocyanate H12MDI.

[0098] In a preferred embodiment, the aziridine functional carbodiimide compound according to the present invention preferably contains polyoxyethylene (-O-CH2-CH2-) x Group, polyoxypropylene (-O-CHCH3-CH2-) x Groups and / or polytetrahydrofuran (-O-CH2-CH2-CH2-CH2) x The aziridine functional carbodiimide compound preferably contains at least 5% by weight, more preferably at least 10% by weight, more preferably at least 20% by weight and preferably less than 60% by weight, more preferably less than 45% by weight and most preferably less than 30% by weight. Preferably, the aziridine functional carbodiimide compound contains polyoxyethylene (-O-CH2-CH2-) x The amount of the aziridine functional carbodiimide compound is preferably at least 5 wt%, more preferably at least 10 wt%, more preferably at least 20 wt% and preferably less than 60 wt%, more preferably less than 45 wt% and most preferably less than 30 wt%. x represents the average number of moles of oxyethylene, and x is preferably an integer from 1 to 40, more preferably from 1 to 20 and even more preferably from 3 to 5.

[0099] The aziridine-functional carbodiimide compounds can, if desired, be stabilized with 0.1 to 1% by weight of a tertiary amine, preferably a beta-hydroxyamine such as, for example, Amietol M21 or Amietol M-12.

[0100] Another aspect of the present invention is a crosslinker composition comprising at least one aziridine-functional carbodiimide compound as defined above and further comprising at least one additional component, such as, for example, the remaining starting materials, by-products and / or solvents used to prepare the aziridine-functional carbodiimide compound according to the present invention. The crosslinker composition may contain only one aziridine-functional carbodiimide compound according to the present invention, but may also contain more than one aziridine-functional carbodiimide compound according to the present invention. For example, when a mixture of polyisocyanates is used as starting material to prepare the aziridine-functional carbodiimide, a mixture of aziridine-functional carbodiimide compounds is obtained. After obtaining the aziridine-functional carbodiimide compound according to the present invention, the aziridine-functional carbodiimide compound according to the present invention may be isolated, the reaction product may be used without further purification, or the solvent used to prepare the aziridine-functional carbodiimide may be removed from the composition obtained in the preparation of the aziridine-functional carbodiimide compound according to the present invention. The amount of the aziridine-functional carbodiimide compound according to the present invention in the crosslinker composition is generally at least 10 weight %, usually often at least 15 weight % and most often at least 25 weight % relative to the total amount of the composition. The amount of the aziridine-functional carbodiimide compound according to the present invention in the crosslinker composition is preferably at least 60 weight %, more preferably at least 80 weight % and most preferably at least 99 weight % relative to the total amount of the crosslinker composition. The molecular weight of the aziridine-functional carbodiimide compound in the crosslinker composition is higher than 600 dalton and 5000 dalton at the most. The preferred molecular weight is as described above and the molecular weight of the aziridine-functional carbodiimide compound is measured using the MALDI-TOF-MS described in the experimental part below. MALDI-TOF-MS refers to matrix-assisted laser desorption ionization time-of-flight mass spectrometry. The crosslinker composition preferably comprises at most 1 wt.-%, preferably at most 0.5 wt.-%, more preferably at most 0.1 wt.-% and most preferably at most 0.05 wt.-% and especially preferably at most 0.01 wt.-% of aziridinyl group-functional molecules having a molar mass below 600 Daltons, wherein the molar mass is determined using LC-MS as described below.

[0101] In view of the potential water sensitivity of the aziridine functional carbodiimide compound according to the present invention, the crosslinker composition preferably does not contain a significant amount of water, and more preferably does not contain water. Containing no significant amount of water means less than 15% by weight, preferably less than 5% by weight, more preferably less than 1% by weight and most preferably less than 0.1% by weight. In view of the potential water sensitivity of the aziridine functional carbodiimide compound according to the present invention, water is preferably added to the composition unintentionally (i.e., a small amount of water may be present in the compound used to prepare the aziridine functional carbodiimide compound according to the present invention). Alternatively, the aziridine functional carbodiimide compound according to the present invention is present in the crosslinker composition in a dispersed form, i.e., the crosslinker composition is an aqueous dispersion of particles comprising the aziridine functional carbodiimide compound according to the present invention. The pH of the aqueous dispersion is preferably at least 8.8, more preferably at least 10 and most preferably at least 10.5. Preferably, the pH is lower than 12, more preferably lower than 11.5. The average hydrodynamic diameter of the particles of the aziridine-functional carbodiimide compound based on scattered intensity is preferably from 5 to 700 nm, more preferably from 10 to 300 nm, even more preferably from 15 to 200 nm, most preferably from 15 to 150 nm.

[0102] The aziridine functional carbodiimide compound according to the present invention or a crosslinker composition comprising at least one aziridine functional carbodiimide compound as defined above can be advantageously used as a crosslinker for crosslinking carboxylic acid functional polymers, preferably a crosslinker for crosslinking carboxylic acid functional polymers dissolved in and / or dispersed in an aqueous medium. The carboxylic acid functional polymer contains carboxylic acid groups and / or carboxylate groups. 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 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 at least partially carboxylate groups neutralized with 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 crosslinked undergo 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.

[0103] Another aspect of the invention is a two-component system comprising a first component and a second component, which are separate and distinct from each other, wherein the first component comprises a carboxylic acid functional polymer dissolved and / or dispersed in an aqueous medium and wherein the second composition comprises an aziridine functional carbodiimide compound as defined above or a crosslinker composition comprising at least one aziridine functional carbodiimide compound as defined above, wherein the first component and the second component are stored separately because the crosslinking reaction between the crosslinker and the polymer to be crosslinked can start immediately after mixing the crosslinker with the aqueous composition of the polymer to be crosslinked. Non-limiting examples of crosslinkable carboxylic acid functional polymers are vinyl polymers such as styrene-acrylic acid, (meth)acrylic acid copolymers, vinyl acetate (co)polymers such as, for example, vinyl acetate vinyl chloride ethylene polymers, ethylene acrylic acid polymers, polyurethanes, condensation polymers such as polyesters, polyamides, polycarbonates, and hybrids of any of these polymers, wherein at least one of the two polymers has a carboxylic acid functional group. The present invention further relates to a coating composition obtained by mixing a first component and a second component of a two-component system just before applying the coating composition, wherein the coating composition comprises aziridinyl groups, carbodiimide groups and carboxylic acid groups in amounts such that the stoichiometric amount (SA) of aziridinyl groups and carbodiimide groups relative to carboxylic acid groups is preferably from 0.1 to 2.0, more preferably from 0.2 to 1.1, even more preferably from 0.25 to 0.95, most preferably from 0.3 to 0.8. 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 carboxylic acid functional polymer to be crosslinked.

[0104] The present invention also relates to a substrate with a coating obtained by (i) applying a coating composition as described above to a substrate, and (ii) drying the coating composition by evaporating volatiles. The drying of the coating composition is preferably carried out at a temperature below 160°C, preferably at a temperature below 90°C, more preferably at a temperature below 50°C and most preferably at ambient temperature. The coating composition according to the present invention can be applied to any kind of substrate, such as wood, leather, concrete, textiles, plastics, vinyl flooring, glass, metal, ceramics, paper, wood-plastic composites, glass fiber reinforced materials. The thickness of the dry coating on the substrate is preferably 1 micron to 200 microns, more preferably 5 microns to 150 microns, most preferably 15 microns to 90 microns. In the case where the coating composition is an ink, primer or overcoat coating composition applied by a printing technique for graphic arts, the thickness of the dry coating is preferably 0.005 to 35 microns, more preferably 0.05 to 25 microns and most preferably 4 to 15 microns.

[0105] The present invention is further defined by a set of exemplary embodiments as listed below. Unless otherwise stated herein or if it is obvious to a skilled person that it is not technically feasible, any of the embodiments, aspects and preferred features or ranges as disclosed in this application may be combined in any combination.

[0106] [1] An aziridine compound having:

[0107] a) One or two of the following structural units A:

[0108]

[0109]

[0110] in

[0111] R1 is H;

[0112] R2 and R4 are independently selected from H or an aliphatic hydrocarbon group containing 1 to 4 carbon atoms;

[0113] R3 is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms;

[0114] R' and R" are based on (1) or (2):

[0115] (1) R'=H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms; and

[0116] R"=H, an aliphatic hydrocarbon group containing 5 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 4 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,

[0117] (2) R' and R" together form a saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms,

[0118] R 11 is H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, preferably R 11 is H or methyl,

[0119] m is an integer from 1 to 6;

[0120] b) A structural unit B:

[0121]

[0122] in

[0123] p+q is an integer from 0 to 4;

[0124] r is an integer from 0 to 2;

[0125] X is NH or O or NR, wherein R contains up to 36 carbon atoms and optionally contains one or more heteroatoms in the chain, preferably R contains one or more heteroatoms (preferably O) in the chain, R is preferably a straight or branched chain group containing 1 to 36 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms or R is a cyclic group containing 3 to 8 carbon atoms;

[0126] R5 and R6 independently contain 4 to 13 carbon atoms;

[0127] R7 is a divalent group; and

[0128] c) optionally a structural unit C:

[0129]

[0130] in

[0131] Z is NH or O or NR, wherein R contains up to 36 carbon atoms and optionally contains one or more heteroatoms in the chain, preferably R contains one or more heteroatoms (preferably O) in the chain, R is preferably a straight or branched chain group containing 1 to 36 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms or R is a cyclic group containing 3 to 8 carbon atoms;

[0132] R8 is a monovalent group; and

[0133] d) Structural formula ABA or structural formula ABC;

[0134] e) a molecular weight greater than 600 Daltons and up to 5000 Daltons; provided that

[0135] f) the mathematical sum of the molar mass of the starting diisocyanate providing the carbodiimide functional groups in structural unit B + the molar mass of structural unit A + the molar mass of structural unit A is higher than 600 Daltons; and

[0136] g) if structural unit C is present, the mathematical sum of the molar mass of the starting diisocyanate providing the carbodiimide functions in structural unit B + the molar mass of structural unit A + the molar mass of structural unit C is higher than 600 Daltons.

[0137] [2] The aziridine compound according to embodiment [1], wherein R1 is H, R2 is H, R3 is CH3 and R4 is H.

[0138] [3] The aziridine compound according to embodiment [1], wherein R1 is H, R2 is H, R3 is CH3 and R4 is CH3.

[0139] [4] The aziridine compound according to any one of the preceding embodiments, wherein m is 1.

[0140] [5] An aziridine compound according to any one of the preceding embodiments, wherein R' is H and R" = an alkyl group containing 5 to 10 carbon atoms, CH2-O-(C=O)-R"', CH2-OR"" or CH2-(OCH2CH2) n -OCH3, wherein R'' is an alkyl group containing 4 to 12 carbon atoms and R"" is an alkyl group containing 1 to 12 carbon atoms.

[0141] [6] The aziridine compound according to any one of the preceding embodiments, wherein p+q is an integer from 0 to 3, more preferably from 0 to 2, even more preferably 0 or 1 and even more preferably 1.

[0142] [7] The aziridine compound according to any one of the preceding embodiments, wherein r is 0 or 1, more preferably r is 1.

[0143] [8] An aziridine compound according to any one of the preceding embodiments, wherein R5 and R6 are independently selected from an aliphatic hydrocarbon group containing 4 to 13 carbon atoms, at least one alicyclic hydrocarbon group containing 5 to 15 carbon atoms, at least one aromatic hydrocarbon group containing 6 to 13 carbon atoms, and any combination thereof.

[0144] [9] An aziridine compound according to any one of the preceding embodiments, wherein R5 and R6 are independently one alicyclic hydrocarbon group containing 5 to 15 carbon atoms, two alicyclic hydrocarbon groups containing 5 to 15 carbon atoms, or one aromatic hydrocarbon group containing 6 to 13 carbon atoms.

[0145]

[10] The aziridine compound according to any one of the preceding embodiments, wherein R5=R6.

[0146]

[11] The aziridine compound according to embodiment 10, wherein R5 and R6 are hydrocarbon residues derived from diisocyanate, and the diisocyanate is used to form the carbodiimide functional group present in structural unit B.

[0147]

[12] An aziridine compound according to any one of the preceding embodiments, wherein R7 is a divalent group having an average molecular weight of 62 to 3000 Daltons, preferably comprising carbon atoms and hydrogen atoms and preferably further comprising one or more heteroatoms, preferably at least oxygen atoms.

[0148]

[13] An aziridine compound according to any one of the preceding embodiments, wherein R7 is a polyether having an average molecular weight of 106 to 3000 Daltons, more preferably 150 to 2000 Daltons, most preferably 194 to 1300 Daltons, and preferably contains more than 50 wt% ethoxylated groups, more preferably more than 80 wt% ethoxylated groups, most preferably more than 90 wt% ethoxylated groups.

[0149]

[14] An aziridine compound according to any one of the preceding embodiments, wherein X is O and Z is O, preferably X is O and Z is NH.

[0150]

[15] An aziridine compound according to any one of the preceding embodiments, wherein R8 is a monovalent group having an average molecular weight of 106 to 3000 Daltons, preferably comprising carbon atoms and hydrogen atoms and preferably further comprising one or more heteroatoms, preferably at least oxygen atoms.

[0151]

[16] An aziridine compound according to any one of the preceding embodiments, wherein R8 is a polyether having an average molecular weight of 200 to 3000 Daltons, more preferably 350 to 2000 Daltons, most preferably 500 to 1500 Daltons, and preferably contains more than 50 wt% ethoxylated groups, more preferably more than 80 wt% ethoxylated groups, most preferably more than 90 wt% ethoxylated groups.

[0152]

[17] An aziridine compound having:

[0153] a) One or two of the following structural units A:

[0154]

[0155] in

[0156] R1 is H;

[0157] R2 and R4 are independently selected from H or an aliphatic hydrocarbon group containing 1 to 4 carbon atoms;

[0158] R3 is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms;

[0159] R' and R" are based on (1) or (2):

[0160] (1) R'=H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms; and

[0161] R"=H, an aliphatic hydrocarbon group containing 5 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 4 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,

[0162] (2) R' and R" together form a saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms,

[0163] R 11 is H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, preferably R 11 is H or methyl,

[0164] m is an integer from 1 to 6;

[0165] b) A structural unit B:

[0166]

[0167] in

[0168] p+q is an integer from 0 to 4;

[0169] r is an integer from 0 to 2;

[0170] X is NH or O or NR, wherein R contains up to 36 carbon atoms and optionally contains one or more heteroatoms (preferably O) in the chain, preferably R is a straight or branched chain group containing 1 to 36 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms and optionally contains one or more heteroatoms (preferably O) in the chain, optionally a branched or cyclic group containing 3 to 8 carbon atoms;

[0171] R5 and R6 independently contain 4 to 13 carbon atoms;

[0172] R7 is a divalent group having an average molecular weight preferably of 106 to 3000 Daltons; and

[0173] c) optionally a structural unit C:

[0174]

[0175] in

[0176] Z is NH or O or NR, wherein R contains up to 36 carbon atoms and optionally contains one or more heteroatoms (preferably O) in the chain, preferably R is a straight or branched chain group containing 1 to 36 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms and optionally contains one or more heteroatoms (preferably O) in the chain, optionally a branched or cyclic group containing 3 to 8 carbon atoms;

[0177] R8 is a monovalent group having an average molecular weight preferably of 62 to 3000 Daltons; and

[0178] d) Structural formula ABA or structural formula ABC;

[0179] The prerequisite is

[0180] The molar mass of the compound of the following formula (G) is higher than 600 Daltons, preferably higher than 615 Daltons, more preferably higher than 700 Daltons.

[0181]

[0182] Among them, R1, R2, R3, R4, R 11 , R', R", R 10 , m and n and their preferred characteristics are as defined above. 10 is R5 or R6 as defined above, and

[0183] If the structural unit C is present, the molar mass of the compound of the following formula (H) is higher than 600 Daltons, preferably higher than 615 Daltons, more preferably higher than 700 Daltons.

[0184]

[0185] Among them, R1, R2, R3, R4, R 11 , R', R", R8 and R 10 , m and n and their preferred characteristics are as defined above.

[0186]

[18] An aziridine compound according to any one of the preceding embodiments, wherein the mathematical sum of the molar mass of the starting diisocyanate providing the carbodiimide functional group in structural unit B + the molar mass of structural unit A + the molar mass of structural unit A is higher than 615 Daltons, more preferably higher than 700 Daltons.

[0187]

[19] An aziridine compound according to any of the preceding embodiments, wherein, if structural unit C is present (i.e., the aziridine compound is according to structural formula ABC), the mathematical sum of the molar mass of the starting diisocyanate providing the carbodiimide functional group in structural unit B + the molar mass of structural unit A + the molar mass of structural unit C is higher than 615 Daltons, more preferably higher than 700 Daltons.

[0188]

[20] An aziridine compound according to any one of the preceding embodiments, wherein the molecular weight of the aziridine compound is at most 4000 Daltons, more preferably at most 3500 Daltons, more preferably at most 3000 Daltons, and the molecular weight of the compound is at least 700 Daltons, more preferably at least 750 Daltons, even more preferably at least 800 Daltons and most preferably at least 1000 Daltons.

[0189]

[21] An aziridine compound according to any of the preceding embodiments, wherein the aziridine equivalent weight (molecular weight of the compound divided by the number of aziridine functional groups present in the compound) of the aziridine compound is at least 350, more preferably at least 400 and even more preferably at least 450 Daltons and preferably at most 5000, more preferably at most 3000, even more preferably at most 2500 Daltons and most preferably at most 2000 Daltons.

[0190]

[22] An aziridine compound according to any of the preceding embodiments, wherein the carbodiimide equivalent weight (molecular weight of the compound divided by the number of carbodiimide functional groups present in the compound) of the aziridine compound is at least 300, preferably at least 350, more preferably at least 400, most preferably at least 600 Daltons and preferably at most 5000, more preferably at most 2500, more preferably at most 2000 and most preferably at most 1500 Daltons.

[0191]

[23] An aziridine compound according to any one of the preceding embodiments, wherein the aziridine compound contains at least 0.5 meq of acid-reactive groups (i.e., aziridine and carbodiimide functional groups) / gram of solid, preferably at least 1.0 meq / g, more preferably 1.5 meq / g and at most 5 meq / g, preferably at most 4.5 meq / g, more preferably at most 4 meq / g.

[0192]

[24] An aziridine compound according to any one of the preceding embodiments, wherein the structural unit A is obtained by reacting at least one monoepoxide compound with an aziridine having the following structural formula:

[0193]

[0194] wherein R1, R2, R3 and R4 are as defined in any one of embodiments 1 to 3.

[0195]

[25] According to the aziridine compound described in embodiment

[24] , the monoepoxide compound is selected from the group consisting of: 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), neodecanoic acid glycidyl ester and any mixture thereof.

[0196]

[26] According to the aziridine compound described in embodiment

[24] , the monoepoxide compound is selected from the group consisting of: n-butyl glycidyl ether (CAS No. 2426-08-6), 2-ethylhexyl glycidyl ether (CAS No. 2461-15-6), neodecanoic acid glycidyl ester (CAS No. 26761-45-5) and any mixture thereof.

[0197]

[27] An aziridine compound according to any one of embodiments

[24] to

[26] , wherein the aziridine is propylene imine (CAS No. 75-55-8) or 2,2-dimethylaziridine (CAS No. 2658-24-4), and more preferably the aziridine is propylene imine.

[0198]

[28] An aziridine compound according to any one of the preceding embodiments, wherein the structural unit B is obtained by reacting a diisocyanate having the formula:

[0199] O=C=NR 10 -N=C=O, where R 10 is R5 or R6 as described in any of the preceding embodiments; and optionally a diol, diamine and / or hydroxylamine having the formula HX-R7-XH, wherein X and R7 are defined as described in any of the preceding embodiments; and optionally HZ-R8, wherein Z and R8 are defined as described in any of the preceding embodiments.

[0200]

[29] An aziridine compound according to any one of the preceding embodiments, wherein the aziridine compound is obtained by reacting: a compound having the following structural formula (D) (providing structural unit A)

[0201]

[0202] Among them, R', R", R 11 , m, R1, R2, R3 and R4 are as defined above, and have the formula EO=C=NR 10 -N=C=O(E) diisocyanate, wherein R 10is R5 or R6 as defined in any one of the above embodiments; and optionally has a diol, diamine and / or hydroxylamine of formula F HX-R7-XH (F), wherein X, R and R7 are as defined in any one of the above embodiments (providing structural unit B); and in the case where the compound has the structural formula ABC, compound G HZ-R8 (G), wherein Z, R and R8 are as defined in any one of the embodiments (providing structural unit C).

[0203]

[30] The aziridine compound according to embodiment

[29] , wherein the compound has the formula EO=C=NR 10 The diisocyanate of -N=C=O(E) has aliphatic reactivity.

[0204]

[31] According to the aziridine compound described in embodiment

[29] or

[30] , the diisocyanate having aliphatic reactivity is 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 and / or tetramethylxylene diisocyanate TMXDI (all isomers).

[0205]

[32] An aziridine compound according to any of the preceding embodiments, wherein if r is 1, the aziridine functional carbodiimide compound has the structural formula ABA.

[0206]

[33] An aziridine compound according to any one of embodiments [1] to

[31] , wherein if r is 0, the aziridine functional carbodiimide compound has the structural formula ABC.

[0207]

[34] An aziridine compound according to any one of embodiments [1] to

[33] , wherein the molar mass of the compound having the following structural formula (G) is greater than 600 Daltons, preferably greater than 615 Daltons, and more preferably greater than 700 Daltons.

[0208]

[0209] Among them, R1, R2, R3, R4, R 11 , R', R", R 10 , m and n and their preferred characteristics are as defined above. 10 is R5 or R6 as defined above.

[0210]

[35] An aziridine compound according to any one of embodiments [1] to

[34] , wherein if structural unit C is present, the molar mass of the compound having the following structural formula (H) is higher than 600 Daltons, preferably higher than 615 Daltons, and more preferably higher than 700 Daltons.

[0211]

[0212] Among them, R1, R2, R3, R4, R 11 , R', R", R8 and R 10 , m and n and their preferred characteristics are as defined above.

[0213]

[36] A crosslinker composition comprising at least one aziridine compound according to any one of the preceding embodiments and further comprising at least one additional component.

[0214]

[37] A crosslinker composition according to embodiment

[36] , wherein the crosslinker composition preferably comprises at most 1 wt. %, preferably at most 0.5 wt. %, more preferably at most 0.1 wt. % and most preferably at most 0.05 wt. % and particularly preferably at most 0.01 wt. % of aziridine group-functional molecules having a molar mass of less than 600 Daltons.

[0215]

[38] The crosslinker composition according to any one of embodiments

[36] to

[37] , wherein the composition is an aqueous dispersion of particles comprising the aziridine compound according to any one of embodiments 1 to

[35] .

[0216]

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

[36] to

[38] , wherein the average hydrodynamic diameter of the particles present in the dispersion based on the scattered intensity is preferably 5 to 700 nm, more preferably 10 to 300 nm, even more preferably 15 to 200 nm, most preferably 15 to 150 nm.

[0217]

[40] A crosslinker composition according to embodiment

[39] , wherein the pH of the aqueous dispersion is at least 8.8, more preferably at least 10 and most preferably at least 10.5.

[0218]

[41] A crosslinker composition according to embodiment

[39] or

[40] , wherein the pH of the aqueous dispersion is lower than 12, preferably lower than 11.5.

[0219]

[42] Use of the aziridine compound according to any one of embodiments [1] to

[35] or the crosslinker composition according to any one of embodiments

[36] to

[41] for crosslinking a carboxylic acid functional polymer dissolved and / or dispersed in an aqueous medium.

[0220]

[43] A two-component system comprising a first component and a second component, each of which is separate and different from each other, and wherein the first component comprises a carboxylic acid functional polymer dissolved and / or dispersed in an aqueous medium and the second component comprises an aziridine compound according to any one of embodiments [1] to

[35] or a crosslinker composition according to any one of embodiments

[36] to

[40] .

[0221]

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

[42] to a substrate, and (ii) drying the coating composition by evaporating volatiles.

[0222] The present invention is further defined by a set of exemplary embodiments as listed below. Unless otherwise stated herein or if it is obvious to a skilled person that it is not technically feasible, any of the embodiments, aspects and preferred features or ranges as disclosed in this application may be combined in any combination.

[0223] The invention will now be illustrated by reference to the following examples. Unless otherwise indicated, all parts, percentages and ratios are by weight.

[0224] Components and abbreviations used:

[0225] n-Butyl glycidyl ether (CAS No. 2426-08-6) was obtained from Alfa Aesar (a division of Thermo Fisher Scientific).

[0226] Di(propylene glycol) dimethyl ether (Proglyde DMM, CAS No. 111109-77-4) was obtained from Dow Inc.

[0227] Polyethylene glycol monomethyl ether (CAS No. 9004-74-4) with a number average molecular weight of 500 Da and a number average molecular weight of 750 Da were obtained from Acros Organics (a division of Thermo Fisher Scientific).

[0228] Potassium carbonate (CAS No. 584-08-7) was obtained from Alfa Aesar (a division of Thermo Fisher Scientific).

[0229] Cardura E10P (CAS No. 26761-45-5) was obtained from Hexion Inc.

[0230] H12MDI (4,4'-methylenebis(phenyl isocyanate, W, CAS number 101-66-8) was from Covestro.

[0231] Trimethylolpropane tris(2-methyl-1-aziridine propionate), CAS No. 64265-57-2, CX-100 was obtained from DSM.

[0232] 2-Methylaziridine (propylene imine, PI, CAS No. 75-55-8) was obtained from Menadiona SL (Palafolls, Spain).

[0233] 1,3-Bis(2-isocyanatopropan-2-yl)benzene (m-tetramethylxylene diisocyanate, TMXDI, CAS No. 2778-42-9) was obtained from Allnex

[0234] IPDI (5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane, I, isophorone diisocyanate, CAS No. 4098-71-9) was obtained from Covestro.

[0235] Bismuth neodecanoate (CAS No. 34364-26-6) was obtained from TIB chemicals AG (Mannheim, Germany).

[0236] 1-Methyl-2-propanol acetate (propylene glycol methyl ether acetate, CAS No. 108-65-6) was obtained from Shell Chemicals.

[0237] Hydrazine (16% aqueous solution, CAS No. 302-01-2) was obtained from Honeywell.

[0238] Dimethylolpropionic acid (DMPA, CAS No. 4767-03-7) was obtained from Perstop Polyols.

[0239] Triethylamine (TEA, CAS No. 121-44-8) was obtained from Arkema

[0240] Sodium lauryl sulfate (30% aqueous solution, CAS No. 73296-89-6) was obtained from BASF.

[0241] Methyl methacrylate (CAS No. 80-62-6) was obtained from Lucite Int.

[0242] n-Butyl acrylate (CAS No. 141-32-2) was obtained from Dow Chemical.

[0243] Methacrylic acid (CAS No. 79-41-4) was obtained from Lucite Int.

[0244] Ammonium persulfate (CAS No. 7727-54-0) was obtained from United Initiators.

[0245] Ammonia (25% aqueous solution, CAS No. 1336-21-6) was obtained from Merck.

[0246] Dipropylene glycol dimethyl ether (CAS No. 34590-94-8) was obtained from Dow Chemical.

[0247] 1-Propanol (CAS No. 71-23-8) was obtained from Sigma-Aldrich.

[0248] Tin 2-ethylhexanoate (CAS No. 301-10-0) was obtained from Sigma-Aldrich.

[0249] Dibutyltin dilaurate (CAS No. 77-58-7) was obtained from Sigma-Aldrich (a division of Merck KGaA).

[0250] D3403 was obtained from Evonik.

[0251] 1-(2-Hydroxyethyl)ethyleneimine (CAS No. 1072-52-2) was obtained from TCI Europe

[0252] Polypropylenes with a number average molecular weight of 1000 Da and a number average molecular weight of 2000 Da were obtained from BASF.

[0253] 3-Methyl-1-phenyl-2-phosphene-1-oxide (CAS No. 707-61-9) was obtained from Sigma-Aldrich.

[0254] LC-MS

[0255] LC-MS analysis was performed to determine the concentration and accurate mass of the low molecular weight fraction using the following program:

[0256] LC system: Agilent 1290 Infinity II; Detector #1: Agilent 1290 Infinity IIPDA; Detector #2: Agilent iFunnel 6550 Q-TOF-MS

[0257] About 2000mg / kg of ethanol solution of material was prepared gravimetrically and stirred. 1μl of this solution was injected into a UPLC equipped with ESI-TOF-MS detection. The column used was 100x2.1mm, 1.8um, WatersHSS T3 C18 running at 40°C. The flow rate was 0.5ml.min-1. The solvent used was 10mM NH4CH3COO in water (set to pH 9.0 with NH3. Eluent A), acetonitrile (B) and THF (C). Two binary gradients were applied, from 95 / 5A / B to 0 / 100A / B in 20 minutes and from 100 / 0BC to 5050B / C in 1 minute, and from 50 / 50BC to 100 / 0BC in 1 minute, after which the starting conditions (95 / 5A / B) were applied. Assuming that all components have a linear MS response 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 that specific species is integrated. Calibration is performed using diluted EtOH-IPDI-EtOH standards.

[0258] MALDI-ToF-MS

[0259] All MALDI-ToF-MS spectra are obtained using Bruker Ultraflextreme MALDI-ToF mass spectrometer. The instrument is equipped with a Nd:YAG laser and a collision cell (not used for these samples) emitted at 1064nm. Use a reflector, use the highest resolution mode (scope of 60-7000m / z) providing accurate mass to obtain spectrum in positive ion mode. Cesium triiodide (scope 0.3-3.5kDa) is used for mass calibration (calibration method: IAV molecular characterization, encoding MC-MS-05). The laser energy is 20%. Sample is dissolved in THF with about 50mg / mL. The matrix used is: DCTB (trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenyl] malononitrile), CAS number 300364-84-5. Prepare matrix solution by dissolving 20mg in 1mL THF.

[0260] The peak measured in the MALDI spectrum is the sodium adduct of the aziridine compound, and in the context of this specification, the molecular weight (MW) of the aziridine functional carbodiimide compound corresponds to MW = observed value [M + M 阳离子 ]–M 阳离子 , where the observed value [M+M 阳离子 ] is the MALDI-TOF MS peak and M 阳离子 is the exact mass of the cation used to make the adduct (in this case the cation with M阳离子 = 23.0 Da of sodium). Aziridine functional carbodiimide compounds can be identified by comparing the MW to the exact molecular mass of the theoretical structure (ie, the non-isotopic average - the atomic masses of its constituent atoms) using a maximum deviation of 0.6 Da.

[0261] Genotoxicity testing

[0262] pass The genotoxicity of the Examples and Comparative Examples was evaluated using the ToxTracker assay (Toxys, Leiden, the Netherlands). The ToxTracker assay is a set of several validated green fluorescent protein (GFP) based mouse embryonic stem (mES) reporter cell lines that can be used to identify the bioreactivity and potential carcinogenic properties of newly developed compounds in a single test. The method uses a two-step approach.

[0263] 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 nineteen serial 2-fold dilutions.

[0264] Next, the genotoxicity of the embodiments and comparators was evaluated using specific genes linked to reporter genes for detecting DNA damage; i.e., Bscl2 (as explained by US9695481B2 and EP2616484B1) and Rtkn (Hendriks et al. Toxicol. Sci. 2015, 150, 190-203) biomarkers. Genotoxicity was evaluated 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 inoculated 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 inoculated into the 96-well plates. For each compound tested, five concentrations were tested at 2-fold dilution. The highest sample concentration will induce significant cytotoxicity (50-70%). In case of no or low cytotoxicity, 10 mM or the maximum soluble mixture concentration was used as the maximum tested concentration.Cytotoxicity was determined by cell counting after 24 hours of exposure using a Guava easyCyte 10HT flow cytometer (Millipore).

[0265] 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 were tested in at least three completely independent repeated experiments. All experiments included positive control treatment (DNA damage) using cisplatin. Metabolism was assessed by adding S9 liver extract. In the presence of S9 and required cofactors (RegenSysA+B, Moltox, Boone, NC, USA), cells were exposed to five concentrations of test compounds for 3 hours. After washing, cells were incubated in fresh ES cell culture medium for 24 hours. After 24 hours of exposure, the induction of GFP reporter gene was determined using Guava easyCyte 10HT flow cytometer (Millipore). Only GFP expression in complete single cells was determined. The average GFP fluorescence and cell concentration in each well were measured, and the average GFP fluorescence and cell concentration were used for cytotoxicity assessment. ToxPlot software (Toxys, Leiden, the Netherlands) was used to analyze data. Induction levels reported are at compound concentrations that induce 10%, 25% and 50% cytotoxicity after 3 hours of exposure in the presence of S9 rat liver extract and 24 hours of recovery or alternatively after 24 hours of exposure in the absence of S9 rat liver extract.

[0266] 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 1.5-fold and lower than 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 2-fold 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.

[0267] Solid content

[0268] The solid content is determined on a Mettler Toledo HB43-S Compact halogen moisture analyzer. At the start of the measurement, the moisture analyzer determines the weight of the sample, then the sample is heated to 130°C by the integrated halogen heating module and the volatile compounds evaporate. During the drying process, the instrument continuously measures the weight of the sample. Once drying has been completed, the solid content of the sample is displayed as the final result.

[0269] Particle size measurement

[0270] The average hydrodynamic diameter of the particles based on the scattered intensity was determined using a method derived from ISO22412:2017 using a Zetasizer Nano S90DLS instrument operating under the following conditions: as a material, polystyrene latex was defined as having an RI of 1,590 at 25°C and, using, its absorption rate (absorption) was 0,10 for a demineralized water continuous medium with a viscosity of 0,8812 cP and an RI of 1,332. The measurements were carried out in a DTS0012 disposable cuvette obtained from Malvern Instruments (Malvern, Worcestershire, United Kingdom). The measurements were carried out at a backscattering angle of 173° as an average of 3 measurements after a 120 second equilibration consisting of 10-15 sub-runs (optimized by the machine itself). The focus of the laser was at a fixed position of 4,65 cm and the data were analyzed using a general purpose data fitting process. The sample was prepared by diluting 0,05 g (1 drop) of the sample dispersion in approximately 5 mL of demineralized water. If the sample still looks turbid, dilute it further with distilled water until it becomes almost clear. This method is suitable for determining particle sizes from 2 nm to 3 μm.

[0271] Chemical resistance

[0272] Chemical resistance test based on DIN 68861-1:2011-01

[0273] Synthesis of Cardura E-10 / PI adduct:

[0274] A 1 L round-bottom flask equipped with a condenser was placed under a N2 atmosphere, and propylene imine (69.0 g), Cardura E10P (201.0 g) and K2CO3 (7.30 g) were charged therein 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.

[0275] Synthesis of BGE / PI adducts:

[0276] A 1 L round bottom flask equipped with a condenser was placed under a N2 atmosphere, and propylene imine (80.0 g), n-butyl glycidyl ether (126.0 g) and K2CO3 (10.00 g) were charged therein and heated to 80°C within 30 min, 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 via vacuum filtration to obtain a colorless, low-viscosity liquid.

[0277] Comparative Example 1

[0278] Comparative Example 1 is CX-100, trimethylolpropane tris(2-methyl-1-aziridine propionate).

[0279] The chemical structure is shown below.

[0280]

[0281] Genotoxicity test results:

[0282]

[0283] The results of the genotoxicity test showed that the crosslinker of Comparative Example 1 was genotoxic.

[0284] Comparative Example 2 (Example 5 EP0507407B1)

[0285] Under nitrogen atmosphere, 21.3 g (0.354 mole) of 1-propanol was added to 78.7 g of isophorone diisocyanate (IPDI) and 0.01 g of 2-ethylhexanoate tin over a period of 6 hours at 20-25° C. while stirring. After standing overnight, 196.3 g (0.883 mole) of IPDI, 74.1 g (0.0628 mole) of Tegomer D3403 and 2.4 g of 3-methyl-1-phenyl-2-phosphene-1-oxide were added. The mixture was heated to 150° C. with stirring. The mixture was kept at 150° C. until the NCO content was 7.0 wt %. The mixture was cooled to 80° C. and 333 g of methoxypropyl acetate was added. A solution of isocyanate functional polycarbodiimide was obtained with a solid content of 50.6 wt % and an NCO content of 7.0 wt % on the solid.

[0286] To 100 g of this isocyanate functional polycarbodiimide was added 7.0 g of 1-(2-hydroxyethyl)ethyleneimine (0.08 mole). One drop of dibutyltin dilaurate was added. The mixture was heated to 80° C. with stirring. The mixture was kept at 80° C. for 1 hour. FTIR showed a small residual isocyanate signal which disappeared after a few days. The solution was further diluted with 8.0 g of methoxyacetate to give a yellow solution with a solids content of 50.4% by weight. The aziridine functional carbodiimide contained 3.2 meq of acid reactive groups (i.e., aziridine and carbodiimide functionalities) / gram of solids.

[0287] The smallest inherently formed aziridine functional by-product compound is the reaction product of 1-(2-hydroxyethyl)ethyleneimine / IPDI / 1-propanol and its calculated molar mass is 369.26 and the structure is shown below:

[0288]

[0289] Another inherently formed aziridine functional byproduct compound is the reaction product of 1-(2-hydroxyethyl)ethyleneimine / IPDI / 1-(2-hydroxyethyl)ethyleneimine having a calculated molar mass of 396.27 and the structure is shown below:

[0290]

[0291] The chemical representation of aziridine functional carbodiimide can be shown as follows:

[0292]

[0293] wherein a, b and c indicate repeating units.

[0294] The general structure was confirmed by MALDI-TOF-MS, an example is shown below:

[0295]

[0296] The molecular weight was confirmed by Maldi-TOF-MS: calculated value [M+Na+] = 2043.34 Da; observed value [M+Na+] = 2043.32 Da.

[0297] Genotoxicity test results:

[0298]

[0299] The results of the genotoxicity test showed that the crosslinker of Comparative Example 2 was genotoxic.

[0300] Example 1

[0301] Under nitrogen atmosphere, a mixture of 46.7g (0.210 mole) of isophorone diisocyanate (IPDI), 25.3g (0.0214 mole) of Tegomer D3403 and 0.02g of bismuth neodecanoate was heated to 65°C under stirring. After reacting at 65°C for 1 hour, 0.47g of 3-methyl-1-phenyl-2-phosphene-1-oxide was added to the mixture. The mixture was heated to 150°C under stirring. The mixture was kept at 150°C until the NCO content was 8.6% by weight. The mixture was cooled to 80°C and 60.4g of methoxypropyl acetate was added and stirred until uniform. 30g of Cardura E-10 / propylene imine adduct (0.105 mole) and 1 drop of dibutyltin dilaurate were added to the reaction mixture. The mixture was kept at 65°C for 5 hours under stirring. FTIR did not show isocyanate signals. 30g of methoxyacetate was added. A yellow solution with a solid content of 50.0% by weight is obtained. The reaction product is a mixture containing a series of compounds having the structure according to claim 1.

[0302] The aziridine functional carbodiimide contains 1.2 meq / gram solid of aziridine groups and 1.2 meq / gram solid of carbodiimide groups, resulting in a total of 2.4 meq of acid-reactive groups (i.e., aziridine and carbodiimide functional groups) / gram solid. The aziridine functional compound with the smallest (calculated) molar mass is the reaction product of propylene imine-Cardura E10 / IPDI / Cardura E10-propylene imine, with a molar mass of 792.6.

[0303] The structure of the smallest intrinsically formed aziridine functional byproduct compound is shown below:

[0304]

[0305] The calculated molecular weight of the theoretical main component was confirmed using MALDI-ToF-MS and its structure is shown below:

[0306]

[0307] Calculated value [M+Na+] = 993.73 Da; observed value [M+Na+] = 993.68 Da.

[0308]

[0309] Calculated value [M+Na+] = 1171.88 Da; observed value [M+Na+] = 1171.89 Da.

[0310]

[0311] Calculated value [M+Na+] = 2334.60 Da; observed value [M+Na+] = 2334.60 Da.

[0312] The following components with masses below 600 Da were determined and quantified by LC-MS:

[0313]

[0314] Present in the composition at 0.81 wt%.

[0315] Genotoxicity test results:

[0316]

[0317] All values ​​in this table show negative induction levels of biomarkers below 1.5-fold induction at 10%, 25% and 50% cytotoxicity in the absence and presence of a rat S9 liver extract based metabolic system and show that the cross-linker of Example 1 is non-genotoxic.

[0318] Example 2

[0319] Under nitrogen atmosphere, a mixture of 25.0 g (0.102 mole) of m-tetramethylxylene diisocyanate (TMXDI), 25.0 g (0.095 mole) of dicyclohexylmethane-4,4'-diisocyanate (H12MDI), 21.42 g (0.0182 mole) of Tegomer D3403 and 0.02 g of bismuth neodecanoate was heated to 65°C under stirring. After reacting at 65°C for 1 hour, 0.50 g of 3-methyl-1-phenyl-2-phosphene-1-oxide was added to the mixture. The mixture was heated to 150°C under stirring. The mixture was kept at 150°C until the NCO content was 7.2 wt%. The mixture was cooled to 80°C and 65.8 g of methoxypropyl acetate was added and stirred until uniform. 19.2 g of butyl glycidyl ether / propylene imine adduct (0.103 mol) and 1 drop of dibutyltin dilaurate were added to the reaction mixture. The mixture was kept at 65° C. for 5 hours under stirring. FTIR showed no isocyanate signal. 19.1 g of methoxyacetate was added. A yellow solution with a solid content of 50.0% by weight was obtained.

[0320] The reaction product is a mixture containing a series of compounds having the structure according to claim 1.

[0321] The aziridine functional carbodiimide contains 1.2 meq / gram solid of aziridine groups and 1.4 meq / gram solid of carbodiimide groups, resulting in a total of 2.6 meq of acid reactive groups (i.e., aziridine and carbodiimide functional groups) / gram solid. The aziridine functional compound with the smallest (calculated) molar mass is the reaction product of butyl glycidyl ether-propylene imine / TMXDI / butyl glycidyl ether-propylene imine with a molar mass of 618.44.

[0322] The structure of the smallest intrinsically formed aziridine functional byproduct compound is shown below:

[0323]

[0324] The calculated molecular weight of the theoretical main component was confirmed using MALDI-ToF-MS and its structure is shown below:

[0325]

[0326] Calculated value [M+Na+] = 841.56 Da; observed value [M+Na+] = 841.55 Da.

[0327]

[0328] Calculated value [M+Na+] = 859.60 Da; observed value [M+Na+] = 859.66 Da.

[0329]

[0330] Calculated value [M+Na+] = 877.65 Da; observed value [M+Na+] = 877.70 Da.

[0331]

[0332] Calculated value [M+Na+] = 1550.90 Da; observed value [M+Na+] = 1550.92 Da.

[0333] The following components with masses below 600 Da were determined and quantified by LC-MS:

[0334]

[0335] Present in the composition at 0.01 wt%.

[0336] Genotoxicity testing

[0337]

[0338] All values ​​in this table show negative induction levels of biomarkers below 2.0-fold induction at 10%, 25% and 50% cytotoxicity in the absence and presence of the rat S9 liver extract-based metabolic system and indicate that the cross-linker of Example 2 shows very weak positive induction of genotoxicity.

[0339] Example 3

[0340] 58.0 g (0.221 mole) of dicyclohexylmethane-4,4'-diisocyanate (H12MDI) and 0.58 g of 3-methyl-1-phenyl-2-phosphene-1-oxide were heated to 150° C. under stirring under a nitrogen atmosphere. The mixture was kept at 150° C. until the NCO content was 16.4% by weight. The mixture was cooled to 80° C. and 53.04 g of methoxypropyl acetate was added and stirred until homogeneous. 27.35 g of butyl glycidyl ether / propylene imine adduct (0.146 mole) and 1 drop of dibutyltin dilaurate were added to the reaction mixture. The mixture was kept at 65° C. for 1 hour under stirring. 21.43 g (0.0286 mole) of poly(ethylene glycol) methyl ether with an average Mn 750 (MPEG 750) and a drop of dibutyltin dilaurate were added to the reaction mixture. The mixture was kept at 65° C. for 5 hours under stirring. FTIR showed no isocyanate signal. 48.8 g of methoxyacetate were added. A yellow solution with a solids content of 50.0% by weight was obtained.

[0341] The reaction product is a mixture containing a series of compounds having the structure according to claim 1.

[0342] The aziridine functional carbodiimide contains 1.4 meq / gram solid of aziridine groups and 1.2 meq / gram solid of carbodiimide groups, resulting in a total of 2.6 meq of acid-reactive groups (i.e., aziridine and carbodiimide functional groups) / gram solid. The aziridine functional compound with the smallest (calculated) molar mass is the reaction product of butyl glycidyl ether-propylene imine / H12MDI / butyl glycidyl ether-propylene imine with a molar mass of 636.48.

[0343] The structure of the smallest intrinsically formed aziridine functional byproduct compound is shown below:

[0344]

[0345] The calculated molecular weight of the theoretical main component was confirmed using MALDI-ToF-MS and its structure is shown below:

[0346]

[0347] Calculated value [M+Na+] = 877.65 Da; observed value [M+Na+] = 877.64 Da.

[0348]

[0349] Calculated value [M+Na+] = 1294.86 Da; observed value [M+Na+] = 1294.88 Da.

[0350]

[0351] Calculated value [M+Na+] = 1513.04 Da; observed value [M+Na+] = 1513.08 Da.

[0352]

[0353] Calculated value [M+Na+] = 1731.22 Da; observed value [M+Na+] = 1731.23 Da.

[0354] The following components with masses below 600 Da were determined and quantified by LC-MS:

[0355]

[0356] Present in the composition at 0.01 wt%.

[0357] Genotoxicity testing

[0358]

[0359] All values ​​in this table show negative induction levels of biomarkers below 2.0-fold induction at 10%, 25% and 50% cytotoxicity in the absence and presence of the rat S9 liver extract-based metabolic system and indicate that the cross-linker of Example 3 shows very weak positive induction of genotoxicity.

[0360] Example 4

[0361] 58.0 g (0.221 mole) of dicyclohexylmethane-4,4'-diisocyanate (H12MDI) and 0.58 g of 3-methyl-1-phenyl-2-phosphene-1-oxide were heated to 150°C under stirring under a nitrogen atmosphere. The mixture was kept at 150°C until the NCO content was 16.4% by weight. The mixture was cooled to 80°C and 53.04 g of methoxypropyl acetate was added and stirred until homogeneous. 27.95 g of butyl glycidyl ether / propylene imine adduct (0.149 mole) and 1 drop of dibutyltin dilaurate were added to the reaction mixture. The mixture was kept at 65°C for 1 hour under stirring. 25.0 g (0.025 mole) of M-1000 (obtained from Huntsman) was added to the reaction mixture. The mixture was kept at 65° C. for 15 minutes under stirring. FTIR showed no isocyanate signal. 53.0 g of methoxyacetate was added. A yellow solution with a solid content of 50.0% by weight was obtained.

[0362] The reaction product is a mixture containing a series of compounds having the structure according to claim 1.

[0363] The aziridine functional carbodiimide contains 1.4 meq / gram solid of aziridine groups and 1.1 meq / gram solid of carbodiimide groups, resulting in a total of 2.5 meq acid reactive groups (i.e., aziridine and carbodiimide functional groups) / gram solid. The aziridine functional compound with the smallest (calculated) molar mass is the reaction product of butyl glycidyl ether-propylene imine / H12MDI / butyl glycidyl ether-propylene imine with a molar mass of 636.48, the structure of which is shown in Example 3.

[0364] The calculated molecular weight of the theoretical main component was confirmed using MALDI-ToF-MS and its structure is shown below:

[0365]

[0366] Calculated value [M+Na+] = 877.65 Da; observed value [M+Na+] = 877.65 Da.

[0367]

[0368] Calculated value [M+Na+] = 1762.17 Da; observed value [M+Na+] = 1762.20 Da.

[0369] The following components with masses below 600 Da were determined and quantified by LC-MS:

[0370]

[0371] Present in the composition at 0.01 wt%.

[0372] Genotoxicity testing

[0373]

[0374] The results of the genotoxicity test showed that the cross-linker composition of Example 4 had only weak positive induced genotoxicity.

[0375] Example 5

[0376] Under nitrogen atmosphere, a mixture of 80.4 g (0.306 mole) of dicyclohexylmethane-4,4'-diisocyanate (H12MDI), 33.4 g (0.0668 mole) of poly(ethylene glycol) methyl ether average Mn 500 (MPEG 500) and 0.02 g of bismuth neodecanoate was heated to 65°C with stirring. After reacting at 65°C for 1 hour, 0.80 g of 3-methyl-1-phenyl-2-phosphene-1-oxide was added to the mixture. The mixture was heated to 150°C with stirring. The mixture was kept at 150°C until the NCO content was 2.7 wt%. The mixture was cooled to 80°C and 11.4 g of butyl glycidyl ether / propylene imine adduct (0.061 mole) and 1 drop of dibutyltin dilaurate were added to the reaction mixture. The mixture was kept at 80°C for 1 hour with stirring. 177.8 g of water are slowly added to the mixture with stirring. The mixture is cooled to RT. 2.5 g of a 15% by weight solid potassium hydroxide solution are added. A slightly turbid, low-viscosity dispersion with a solids content of 39.3% by weight is obtained.

[0377] The reaction product is a mixture containing a series of compounds having the structure according to claim 1.

[0378] The aziridine functional carbodiimide contains 0.5 meq aziridine groups / gram solids and 2.1 meq carbodiimide groups / gram solids, resulting in a total of 2.6 meq acid reactive groups (i.e. aziridine and carbodiimide functional groups) / gram solids. The aziridine functional compound with the smallest (calculated) molar mass is the reaction product of butyl glycidyl ether-propylene imine / H12MDI / butyl glycidyl ether-propylene imine with a molar mass of 636.48, the structure of which is shown in Example 3.

[0379] The calculated molecular weight of the theoretical main component was confirmed using MALDI-ToF-MS and its structure is shown below:

[0380]

[0381] Calculated value [M+Na+] = 877.65 Da; observed value [M+Na+] = 877.64 Da.

[0382]

[0383] Calculated value [M+Na+] = 1074.73 Da; observed value [M+Na+] = 1074.72 Da.

[0384] The following components with masses below 600 Da were determined and quantified by LC-MS:

[0385]

[0386] Present in the composition at 0.01 wt%.

[0387] Genotoxicity testing

[0388]

[0389] The results of the genotoxicity test showed that the crosslinker composition of Example 5 was non-genotoxic.

[0390] Crosslinker test results

[0391] Synthesis of Waterborne Polyurethane P1

[0392] A one-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 having a calculated average molecular weight (M) of 2000 Da and an OH value of 56±2 mg KOH / g polypropylene glycol), 166.5 grams of polypropylene glycol having a calculated average molecular weight (M) of 1000 Da and an OH value of 112±2 mg KOH / g polypropylene glycol, and 262.8 grams of isophorone diisocyanate (the average molecular weight of each polyol was calculated from its OH value according to the following equation: M=2*56100 / [in mg KOH / g polypropylene glycol]. The reaction mixture was placed under a N2 atmosphere, heated to 50°C and subsequently 0.07 g of dibutyltin dilaurate was added to the reaction mixture. An exothermic reaction was observed; however, due care was taken so that the reaction temperature did not exceed 97°C. The reaction was kept at 95°C for one hour. The polyurethane P1' obtained had an NCO content of 7.00% based on solids, as determined according to ISO 14896 Method A (2009) (theoretical 7.44%) and an acid number of 16.1±1 mg KOH / g polyurethane P1'. Polyurethane P1' is cooled to 60 ° C and 18.7 grams of triethylamine are added, and the resulting mixture is stirred for 30 minutes. Subsequently, polyurethane P1' (the aqueous dispersion of polyurethane P1' is further referred to as P1) is prepared as follows: the mixture of polyurethane P1' and triethylamine prepared in this way is fed to a mixture of 1100 grams of demineralized water, 19.5 grams of nonylphenol ethoxylate (9 ethoxylate groups) and 4.0 grams of triethylamine at room temperature over a period of 60 minutes. After the feeding is completed, the mixture is stirred for another 5 minutes, and then 111.2 grams of hydrazine (16% by weight aqueous solution) is added to the mixture. The aqueous dispersion of polyurethane P1' prepared in this way is stirred for another 1h and P1 is obtained.

[0393] Synthesis of Water-Based Acrylic Adhesive A1

[0394] A 2L four-necked flask equipped with a thermometer and an overhead stirrer was charged with sodium dodecyl sulfate (30% solids in water, 18.6 grams of solution) and demineralized water (711 grams). The reactor phase was placed under an N2 atmosphere and heated to 82°C, and a mixture of demineralized water (112 grams), sodium dodecyl sulfate (30% solids in water, 37.2 grams of solution), methyl methacrylate (174.41 grams), n-butyl acrylate (488.44 grams), and methacrylic acid (34.88 grams) was placed in a large feed funnel and emulsified with an overhead stirrer (monomer feed). Ammonium persulfate (1.75 grams) was dissolved in demineralized water (89.61 grams) and placed in a small feed funnel (initiator feed). Ammonium persulfate (1.75 grams) was dissolved in demineralized water (10.5 grams) and this solution was added to the reactor phase. Immediately thereafter, 5% by volume of monomer feed was added to the reactor phase. The reaction mixture was then exothermed to 85° C. and maintained at 85° C. for 5 minutes. The remaining monomer feed and initiator feed were then fed to the reaction mixture over 90 minutes, maintained at a temperature of 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. Subsequently, the mixture was cooled to room temperature and adjusted to pH=7.2 with ammonia solution (6.25 wt. % in demineralized water), and further adjusted to 40% solids with demineralized water and A1 was obtained.

[0395] The adhesive and cross-linking agent are combined in a stoichiometric ratio ranging from 0.25 to 1.0 stoichiometric amounts, which is the total amount of carboxylic acid reactive groups (i.e., aziridine and carbodiimide functional groups) versus the amount of carboxylic acid groups. The cross-linking agent is diluted with water 50 / 50 and then added to the adhesive. The effect of adding the cross-linking agent is evaluated by using a spot test on the coating surface, based on the procedure of the DIN68861-1:2011 standard. The coating composition is filtered and applied to a Leneta test piece using a 100 μm wire applicator. The film is then dried according to the conditions described below. Subsequently, a piece of cotton wool is immersed in 1:1 EtOH: demineralized water and placed on the film for 1 hour and 4 hours. Similarly, the water spot test is placed on the film for 16 hours. After the cotton wool spot liquid is removed and recovered for 60 minutes, the following results are obtained (0 score indicates that the film is completely decomposed, and 5 score indicates that there is no visible damage):

[0396] Test results after drying for 1 day at 23±2°C (stoichiometric amount of acid-reactive group crosslinker compared to acid group binder is 0.93):

[0397]

[0398] Test results after drying at 23±2°C for 1 day, annealing at 80°C overnight and further drying at 23±2°C for 1 day (stoichiometric amount of acid-reactive group crosslinker compared to acid group binder is 0.93):

[0399]

Claims

1. An aziridine compound having: a) One or two 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; R' and R" are based on (1) or (2): (1) R'=H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms; and R" = an aliphatic hydrocarbon group containing 5 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 4 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, R 11 is H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, m is an integer from 1 to 6; b) A structural unit B: in p+q is an integer from 0 to 4; r is an integer from 0 to 2; X is NH or O or NR, wherein R contains up to 36 carbon atoms and optionally contains one or more heteroatoms in the chain; R5 and R6 independently contain 4 to 13 carbon atoms; R7 is a divalent group; and c) optionally a structural unit C: in Z is NH or O or NR, wherein R contains up to 36 carbon atoms in the chain and optionally contains one or more heteroatoms; R8 is a monovalent group; and d) Structural formula ABA or structural formula ABC; e) a molecular weight greater than 600 Daltons and at most 5000 Daltons as determined using MALDI-TOF mass spectrometry; provided that f) the mathematical sum of the molar mass of the starting diisocyanate providing the carbodiimide functional groups in said structural unit B + the molar mass of the structural unit A + the molar mass of the structural unit A is higher than 600 Daltons; and g) if structural unit C is present, the mathematical sum of the molar mass of the starting diisocyanate providing the carbodiimide functions in said structural unit B + the molar mass of structural unit A + the molar mass of structural unit C is higher than 600 Daltons.

2. The aziridine compound according to claim 1, wherein R1 is H, R2 is H, R3 is CH3 and R4 is H.

3. The aziridine compound according to claim 1, wherein R 11 It is H or methyl. 4 . The aziridine compound according to claim 1 , wherein m is 1. 5 . 5 . The aziridine compound according to claim 1 , wherein p+q is an integer from 0 to 2. 6 . The aziridine compound according to claim 1 , wherein r is 0 or 1. 7 .

7. The aziridine compound according to any one of claims 1 to 3, wherein R5 and R6 are hydrocarbon residues from a diisocyanate used to form the carbodiimide functional group present in structural unit B, and R5 = R6. The aziridine compound according to any one of claims 1 to 3, X is O, and Z is NH or O.

9. The aziridine compound according to any one of claims 1 to 3, wherein R7 is a polyether having an average molecular weight of 194 to 1300 Daltons and containing more than 80% by weight of ethoxylated groups.

10. The aziridine compound according to any one of claims 1 to 3, wherein R8 is a polyether having an average molecular weight of 500 to 1500 Daltons and containing more than 80% by weight of ethoxylated groups.

11. The aziridine compound according to any one of claims 1 to 3, wherein the mathematical sum of the molar mass of the starting diisocyanate providing the carbodiimide functional group in the structural unit B + the molar mass of the structural unit A + the molar mass of the structural unit A is higher than 615 Daltons, and if the structural unit C is present, the mathematical sum of the molar mass of the starting diisocyanate providing the carbodiimide functional group in the structural unit B + the molar mass of the structural unit A + the molar mass of the structural unit C is higher than 615 Daltons.

12. The aziridine compound according to any one of claims 1 to 3, wherein the molecular weight of the aziridine compound is at most 3000 Daltons, and the molecular weight of the compound is at least 700 Daltons.

13. A compound according to any one of claims 1 to 3, wherein the aziridine compound has an aziridine equivalent weight of at least 350 Daltons and at most 5000 Daltons, wherein the aziridine equivalent weight is defined as the molecular weight of the aziridine compound divided by the number of aziridinyl functional groups present in the aziridine compound.

14. The aziridine compound according to any one of claims 1 to 3, wherein the structural unit A is obtained by reacting at least one monoepoxide compound with an aziridine having the following structural formula: wherein R1, R2, R3 and R4 are as defined in any one of claims 1 to 3.

15. The aziridine compound according to claim 14, wherein the monoepoxide compound is selected from the group consisting of n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, neodecanoic acid glycidyl ester, and any mixture thereof.

16. A method for preparing an aziridine compound according to any one of claims 1 to 3, wherein the aziridine compound is obtained by reacting the following: a compound having the following structural formula (D): Among them, R', R", R 11 , m, R1, R2, R3 and R4 are as described in the above claims, and have the formula O=C=NR 10 -N=C=O diisocyanate, where R 10 R5 or R6 as described in the above claims, and optionally a diol, diamine and / or hydroxylamine of the formula HX-R7-XH, wherein X and R7 are as described in the above claims, and a compound G of the formula HZ-R8, in which Z and R8 are as described in the above claims, when the compound has the structural formula ABC. 17 . The method according to claim 16 , wherein the diisocyanate is any one of isomers of isophorone diisocyanate IPDI, 4,4′-dicyclohexylmethane diisocyanate H12MDI and / or tetramethylxylene diisocyanate TMXDI.

18. A crosslinker composition comprising at least one aziridine compound according to any one of claims 1 to 15 or obtained using a process according to claim 16 or 17 and comprising up to 1% by weight of aziridinyl-functional molecules having a molar mass below 600 Daltons. 19 . The crosslinker composition according to claim 18 , wherein the composition is an aqueous dispersion comprising particles of the aziridine compound according to any one of claims 1 to 15 or the aziridine compound obtained using the method according to claim 16 or 17 .

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