PARTICLES OF (AZIRIDINYL HYDROXY)-FUNCTIONAL ORGANIC COMPOUNDS

Abstract

The invention relates to particles comprising a particular (aziridinyl hydroxy)-functional organic component. The invention further relates to mixtures comprising said particles. The invention further relates to aqueous dispersions comprising said particles. The invention further relates to aqueous compositions comprising said particles. The invention further relates to coating compositions comprising said particles. The invention further relates to aqueous coating compositions comprising said particles. The invention further relates to particles obtained by a process comprising—amongst others—the steps of providing an aqueous dispersion comprising a particular (aziridinyl hydroxy)-functional organic component. The invention further relates to a kit-of-parts comprising in one of its parts an aqueous dispersion comprising a particular (aziridinyl hydroxy)-functional organic component. The invention further relates to cured forms of the various particles, mixtures, aqueous dispersions, aqueous compositions, coating compositions, and aqueous coating compositions. The invention further relates to articles comprising the particles and/or said mixtures, and/or said aqueous dispersions and/or aqueous compositions and/or said cured forms. The invention further relates to various uses of the particles and/or said mixtures, and/or said aqueous dispersions and/or aqueous compositions and/or said cured forms.

Claims

1.-19. (canceled)

20. Particles comprising an (aziridinyl hydroxy)-functional organic component (AZ-component), wherein the particles have a scatter intensity-based average hydrodynamic diameter (D.sub.H) determined via dynamic light scattering according to the description, of at least 2 and at most 3000, preferably at least 10 and at most 2000, more preferably at least 30 and at most 1000, most preferably at least 40 and at most 1000, for example at least 50 and at most 1000, for example at least 40 and at most 800, for example at least 50 and at most 800, for example at least 50 and at most 600, for example at least 50 and at most 500, for example at least 70 and at most 1000, for example at least 70 and at most 800, for example at least 70 and at most 600, for example at least 70 and at most 500, for example at least 90 and at most 500 nm, and wherein the (aziridinyl hydroxy)-functional organic component (AZ-component) is selected from the group consisting of i) to vi): i) (aziridinyl hydroxy)-functional organic compound AZ1 of Formula A1 having only two aziridine rings (AZ1-compound), ii) (aziridinyl hydroxy)-functional organic compound AZ2 of Formula A2 having only three aziridine rings (AZ2-compound), iii) (aziridinyl hydroxy)-functional organic compound AZ3 of Formula A3 having only four aziridine rings (AZ3-compound), iv) (aziridinyl hydroxy)-functional organic compound AZ4 of Formula A4 having only five aziridine rings (AZ4-compound), v) (aziridinyl hydroxy)functional organic compound AZ5 of Formula A5 having only six aziridine rings (AZ5-compound), and vi) mixtures thereof, ##STR00059## wherein X.sub.1 is a bivalent aliphatic organic radical or a bivalent aromatic organic radical, preferably X.sub.1 is a bivalent aliphatic organic radical; X.sub.2 is a trivalent aliphatic organic radical or a trivalent aromatic organic radical, preferably X.sub.2 is a trivalent aliphatic organic radical; X.sub.3 is a quadrivalent aliphatic organic radical or a quadrivalent aromatic organic radical, preferably X.sub.3 is a quadrivalent aliphatic organic radical; X.sub.4 is a pentavalent aliphatic organic radical or a pentavalent aromatic organic radical, preferably X.sub.4 is a pentavalent aliphatic organic radical; X.sub.5 is a hexavalent aliphatic organic radical or a hexavalent aromatic organic radical, preferably X.sub.5 is a hexavalent aliphatic organic radical; and wherein each of the X.sub.1 to X.sub.5 consists of a collection of atoms covalently connected in a configuration that comprises—preferably consists of—linear and/or branched and/or ring structures, which collection of atoms is selected from the group consisting of i) to x): i) carbon and hydrogen atoms, ii) carbon, hydrogen and oxygen atoms, iii) carbon, hydrogen and nitrogen atoms, iv) carbon, hydrogen and sulphur atoms, v) carbon, hydrogen, oxygen and nitrogen atoms, vi) carbon, hydrogen, nitrogen and sulphur atoms, vii) carbon, hydrogen, oxygen and sulphur atoms, viii) carbon, hydrogen, oxygen, nitrogen and sulphur, atoms, ix) carbon, hydrogen and silicon atoms, and x) carbon, hydrogen, oxygen and silicon atoms and xi) any combination of ix) and/or x) with any one or all of the iii) to viii), and wherein each of the X.sub.1 to X.sub.5 has carbon atoms and hydrogen atoms, and wherein each of the X.sub.1 to X.sub.5 has optionally oxygen atoms and/or nitrogen atoms and/or sulphur atoms and/or silicon atoms, and wherein the X.sub.1, and/or the X.sub.2 and/or the X.sub.3 and/or the X.sub.4 and/or the X.sub.5 may optionally comprise an ionic functional group, and wherein Y is a monovalent organic radical selected from the group consisting of: i) monovalent (aziridinyl hydroxyisopropyl) organic radical of Formula B 1, ii) monovalent (aziridinyl hydroxycyclohexane) organic radical of Formula B2, and iii) monovalent (aziridinyl hydroxycyclohexane) organic radical of Formula B3, preferably Y is a monovalent (aziridinyl hydroxyisopropyl) organic radical of Formula B1, ##STR00060## and wherein R.sub.1 is selected from the group consisting of hydrogen and methyl; and R.sub.2 is selected from the group consisting of hydrogen, methyl, and C.sub.2-C.sub.5 alkyl; and R.sub.3 is selected from the group consisting of methyl, and C.sub.2-C.sub.4 alkyl; and R.sub.4 is selected from the group consisting of hydrogen, methyl, and C.sub.2-C.sub.4 alkyl; and wherein the Y in each of the compounds A1 to A5 may be the same or different to each other, and wherein each of the single covalent bonds between the Y and each one of the X.sub.1 to X.sub.5 is selected from the group consisting of carbon-carbon single bond, carbon-oxygen single bond and carbon-nitrogen single bond, preferably carbon-oxygen single bond and carbon-nitrogen single bond, more preferably carbon-oxygen single bond, and wherein each of the AZ1- to AZ5-compound has a molecular weight determined via MALDI-TOF MS according to the description, of at least 600 and at most 10000, preferably at least 600 and at most 8000, more preferably at least 600 and at most 6000, most preferably at least 600 and at most 5000, especially at least 600 and at most 4000, more especially at least 600 and at most 3500, most especially at least 600 and at most 3200, for example at least 600 and at most 3000, for example at least 600 and at most 2500 Da.

21. The particles according to the claim 20, wherein the X.sub.1 is a bivalent aliphatic organic radical or a bivalent aromatic organic radical other than a bivalent radical of bisphenol A.

22. The particles according to claim 20, wherein the X.sub.1, and/or the X.sub.2 and/or the X.sub.3 and/or the X.sub.4 and/or the X.sub.5 comprises at least one structural unit or a combination of structural units selected from the group consisting of unit 1, unit 2, unit 3, unit 4, unit 5, unit 6, unit 7, unit 8, unit 9, unit 10, and unit 11, as the units 1 to 11 are depicted below: ##STR00061## ##STR00062## wherein R′ is selected from the group consisting of hydrogen and methyl; and j is an integer ranging from 1 to 5, preferably from 1 to 3; and n is an integer ranging from and including 2 up to and including 50.

23. The particles according to claim 20, wherein the aggregate number of carbon atoms in R.sub.1, and R.sub.2 and R.sub.3 and R.sub.4 is at most 9, preferably at most 4, more preferably at most 2, for example at most 1.

24. The particles according to claim 20, wherein the X.sub.1 and/or the X.sub.2 and/or the X.sub.3 and/or the X.sub.4 and/or the X.sub.5 does not contain one or any combination of the following structural units BP1, BP2, BP3, and BS ##STR00063##

25. The particles according to claim 20, wherein the X.sub.1 is the bivalent aliphatic organic radical of Formula A1a′ ##STR00064## wherein R′ is selected from the group consisting of hydrogen and methyl; and j is an integer ranging from 1 to 5, preferably from 1 to 3; and n is an integer ranging from and including 2 up to and including 50.

26. The particles according to claim 20, wherein the AZ-component is selected from the group consisting of i) to v): i) (aziridinyl hydroxy)-functional organic compound AZ1 of Formula A1 (AZ1-compound), ii) (aziridinyl hydroxy)-functional organic compound AZ2 of Formula A2 (AZ2-compound), iii) (aziridinyl hydroxy)-functional organic compound AZ3 of Formula A3 (AZ3-compound), iv) (aziridinyl hydroxy)-functional organic compound AZ5 of Formula A5 (AZ5-compound), and vi) mixtures thereof, and wherein the AZ1-compound is selected from the group consisting of compounds having the Formula A1a, and compounds having the Formula Alb, as each of these Formulae A1a-A1d is described below ##STR00065## wherein each of the n in Formula A1a is independently selected, and each of the n in Formula A1a is an integer ranging from and including 2 up to and including 20; and ##STR00066## wherein the R in Formula Alb is a C.sub.3-C.sub.10 saturated hydrocarbylene, and wherein each of the n in Formula Alb is independently selected and each of the n in Formula A1a is an integer ranging from and including 2 up to and including 20; and ##STR00067## wherein each of the n in Formula A1c is independently selected, and each of the n in Formula A1b is an integer ranging from and including 2 up to and including 20; and ##STR00068## wherein the R in Formula A1d is a C.sub.3-C.sub.10 saturated hydrocarbylene, and wherein each of the n in Formula A1d is independently selected, and each of the n in Formula A1b is an integer ranging from and including 2 up to and including 20; and wherein the AZ2-compound is selected from the group consisting of compounds having the Formula A2a, compounds having the Formula A2b, compounds having the Formula A2c, compounds having the Formula A2d, compounds having the Formula A2e, as each of these Formulae A2a-A2e is described below ##STR00069## wherein the n in Formula A2a is an integer ranging from and including 2 up to and including 20; and ##STR00070## wherein each of the n in Formula A2b is independently selected, and each of the n in Formula A2b is an integer ranging from and including 2 up to and including 20; and ##STR00071## wherein each of the n in Formula A2c is independently selected, and each of the n in Formula A2c is an integer ranging from and including 2 up to and including 20; and ##STR00072## and wherein the AZ3-compound is selected from the group consisting of compounds having the Formula A3a ##STR00073## wherein each of the n in Formula A3a is independently selected, and each of the n in Formula A3a is an integer ranging from and including 2 up to and including 20; and wherein the AZ5-compound is selected from the group consisting of compounds having the Formula A5a ##STR00074## wherein each of the n in Formula A5a is independently selected, and each of the n in Formula A5a is an integer ranging from and including 2 up to and including 40.

27. The particles according to claim 20, wherein the AZ-component is selected from the group consisting of AZ1-compound and wherein the AZ1-compound is the compound of the following formula, ##STR00075##

28. The particles according to claim 20, wherein the AZ-component is selected from the group consisting of AZ2-compound and wherein the AZ2-compound is the compound of the following formula, ##STR00076##

29. The particles according to claim 20, wherein the AZ-component is selected from the group consisting of AZ2-compound and wherein the AZ2-compound is the compound of the following formula, ##STR00077##

30. The particles according to claim 20, wherein the AZ-component is selected from the group consisting of AZ2-compound and wherein the AZ2-compound is the compound of the following formula, ##STR00078##

31. The particles according to claim 20, wherein the AZ-component is selected from the group consisting of AZ1-compound, AZ2-compound and mixtures thereof, and wherein the AZ1-compound is the compound of the following formula, ##STR00079## and wherein the AZ2-compound is selected from the group consisting of compounds of the following formulae, ##STR00080##

32. An aqueous dispersion having a pH determined according to the ISO 976:2013 and according to the description, of at least 7.5 and at most 14.0, preferably at least 8.0 and at most 14.0, for example at least 8.5 and at most 13.5, for example at least 9.0 and at most 13.0, for example at least 9.2 and at most 12.5, for example at least 9.4 and at most 12.0, for example at least 9.6 and at most 11.6, for example at least 10.5 and at most 11.5, and wherein the aqueous dispersion comprises: i) water, and ii) the particles according to claim 20 dispersed in the water.

33. Particles obtained by a process comprising the steps of: i) providing the aqueous dispersion according to the claim 32; and ii) removing the water—and any organic solvent if present—from the aqueous dispersion, preferably by spray-drying or freeze-drying or distillation under vacuum in order to obtain the particles; iii) collecting the particles, iv) optionally further drying the particles; and v) optionally applying means, e.g. grinding, that transform the collected particles into any form that a solid material may exist at standard conditions.

34. An aqueous composition comprising: i) the aqueous dispersion according to the claim 32, and ii) a polymer which has an acid value determined according to the ASTM D1639-90(1996)el in the range from 5 to 300, preferably from 8 to 200, more preferably from 10 to 150 mg KOH/g and wherein the polymer may optionally comprise ionic functional groups.

35. A kit-of-parts comprising parts A and B which are physically separated from each other, wherein: i) the part A comprises the aqueous dispersion according to claim 32, and ii) the part B comprises a polymer which has an acid value determined according to the ASTM D1639-90(1996)el in the range from 5 to 300 mg KOH/g, and wherein the polymer may optionally comprise ionic functional groups, and wherein the part A does not comprise the polymer of the part B, and the part B does not comprise the aqueous dispersion of the part A.

36. A cured form of the particles according to claim 20.

37. A cured form of the aqueous dispersion according to the claim 32.

38. A cured form of the particles according to claim 33.

39. A cured form of the aqueous composition according to claim 34.

40. An article comprising: i) particles according to claim 20, and/or ii) an aqueous dispersion, and/or iii) particles a and/or iv) an aqueous composition, and/or v) a cured form.

41. Any one or any combination of the following: i) particles according to claim 20; ii) an aqueous dispersion; iii) particles; iv) an aqueous composition; v) a kit-of-parts; vi) a cured form; vii) an article; for use in coatings, paints, inks, varnishes, lubricants, adhesives, additive manufacturing, 3D-printing, textiles, waxes, fuels, photography, plastics, medical compositions, medical devices.

Description

EXAMPLES

[0264] The invention is explained in more detail with reference to the following non-limiting examples.

[0265] All the Examples shown in this section were carried out in a controlled laboratory environment at standard conditions (as these are defined in the specification), a relative humidity of 50±1% and an airflow of 0.1 m/s, unless otherwise explicitly specified.

1.1 Chemicals, Raw Materials and Other Materials

[0266] Triethylamine (purity 99.7%) was supplied by ARKEMA. Propylene imine (purity 99.0%) was supplied by Menadiona. Anhydrous potassium carbonate (K.sub.2CO.sub.3; purity 99.0%) was supplied by Alfa Aesar. The trimethylolpropane tris(2-methyl-1-aziridinepropionate) (CAS No. 64265-57-2; see structure in Example 1C) was supplied by DSM (commercial product name ‘crosslinker CX-100’). The NeoCryl® B-300 is a methacrylic copolymer of methyl methacrylate (MMA) and butyl-methacrylate (BMA) (acid value lower than 1 mg KOH/g, T.sub.g: 45° C., theoretical molecular weight 16000 Da, density at 20° C.: 1.14 g/cm.sup.3, viscosity at 25° C. (40 wt % in 1,6-hexanediol diacrylate (HDDA)): 0.8-1.0 Pa.Math.s; form at 25° C.: white solid) supplied by DSM. The DESMODUR® N 3600 is a low viscosity aliphatic polyisocyanate (trimer) based on hexamethylene diisocyanate (HDI) (NCO content: 23.0±0.5% (M105- ISO 11909); viscosity at 23° C.: 1200±300 mPa.Math.s (M014-1S03219/A.3); color value (Hazen): 40 (M017-EN 1557); monomeric HDI: ≤0.25% (M106-1S0 10283); equivalent weight: approx. 183; flash point: approx. 159° C. (DIN 53213/1); density at 20° C.: approx. 1.16 g/ml (DIN EN ISO 2811), supplied by Covestro. The DESMODUR® N 3900 is a low viscosity aliphatic polyisocyanate based on hexamethylene diisocyanate (HDI) (NCO content: 23.0±0.5% (M105- ISO 11909); viscosity at 23° C.: 730±100 mPa.Math.s (M014-1S0 3219/A.3); color value (Hazen): 40 (M017-EN 1557); monomeric HDI: 0.25% (M106-1S0 10283); equivalent weight: approx. 179; flash point: approx. 203° C. (DIN 53213/1); density at 20° C.: approx. 1.15 g/ml (DIN EN ISO 2811), supplied by Covestro. The ERISYS® GE-36 is a triglycidyl ether of propoxylated glycerine (see Scheme 1) (EEW: 620-680 g/eq; viscosity: 200-320 cps at 25° C.; hydrolysable chloride: <0.10%; flash point: >93° C., residual epichlorohydrin: <20 ppm) was supplied by CVC Thermoset Specialties (now HUNTSMAN). The ERISYS® GA-240 (see Scheme 2) is glycidyl amine of m-xylelenediamine (CAS No. 63738-22-7) (epoxy equivalent weight (EEW): 95-110 g/eq; specific gravity at 25° C.: 1.14-1.16 g/ml; flash point: >215° C.; colour (Gardner): max. 5; viscosity at 25° C.: 1600-3000 cP) supplied by CVC Thermoset Specialties (now HUNSTMAN). The Cardolite® NC-514S is a di-functional glycidyl ether epoxy resin (see Scheme 3) [reddish brown liquid; color (Gardner): (ASTM D1544); viscosity at 25° C.: 1000-3000 cP (ASTM D2196); epoxy equivalent weight (EEW): 320-420 (ASTM D1652-97); hydrolysable chlorine (%): 0.5 (ASTM D1726-11); volatile loss (% wt): 0.5 (ASTM D2369-98); density at 25° C.: 1.026 Kg/L (ASTM D1475); flash point: >205° C. (ASTM D93)] was supplied by Cardolite Corporation. The EPPALOY® 9000 is tris hydroxyl phenyl ethane (CAS No. 87093-13-8) (see Scheme 4) [average epoxy functionality: 3.0; epoxy equivalent weight (EEW): 160-180 g/eq; viscosity at 72° C.: 5500-6500 cP; colour (Gardner): max. 2) supplied by CVC Thermoset Specialties (now HUNSTMAN]. The bisphenol A diglycidyl ether (CAS No. 1675-54-3) was supplied from Tokyo Chemical Industry Co., Ltd. The N,N-diglycidyl-4-glycidyloxyaniline (CAS No. 5026-74-4) was supplied by Sigma-Aldrich. The ATLAS™ G-5000 (non-ionic dispersant) is a polyalkylene glycol ether (colour: cream; solidification point: approx. 30 (DGF method III 46 (57); relative density at 25° C.: approx. 1.0; hydrophilic-lipophilic balance (HLB) value: 16.9; form at 25° C.: waxy solid; acid value: max. 0.3 mg KOH/g; hydroxyl value: 18-22 mg KOH/g) supplied by Croda. The ATLAS™ G-5002L-LQ (non-ionic dispersant) is a block copolymer of ethylene oxide and propylene oxide, terminated by a butoxy group (cloud point: 60.6; form at 25° C.: liquid; acid value: max. 0.3 mg KOH/g; hydroxyl value: 13-16 mg KOH/g; colour (Gardner) max. 4), supplied by Croda. Mehtylethylketone was supplied by Sigma-Aldrich. The polypropylene glycol with a calculated number average molecular weight (M.sub.e) of 2000 Da and an OH-value of 56±2 mg KOH/g polypropylene glycol), and the polypropylene glycol with a calculated number average molecular weight (M.sub.n) of 1000 Da and an OH-value of 112±2 mg KOH/g polypropylene glycol, were supplied by DOW. Any other chemical that is not explicitly mentioned in this paragraph and used in the Examples section (and unless otherwise stated in the specification) has been supplied by Sigma-Aldrich.

##STR00044##

##STR00045##

##STR00046##

##STR00047##

1.2 Preparation of the Polyurethane a and its Aqueous Dispersion (the Latter is Abbreviated as ‘Polyurethane A-AQD’)

[0267] A one-litre flask (equipped with a thermometer and an overhead stirrer), was charged with 29.9 grams of dimethylol propionic acid, 282.1 grams of polypropylene glycol with a calculated number average molecular weight (MO of 2000 Da and an OH-value of 56±2 mg KOH/g polypropylene glycol), 166.5 grams of polypropylene glycol with a calculated number average molecular weight (M.sub.n) of 1000 Da and an OH-value of 112±2 mg KOH/g polypropylene glycol, and 262.8 grams of isophorone diisocyanate (the number average molecular weight of each of the polyols is calculated from its OH-value according to the equation: M.sub.n=2*56100/[OH-value in mg KOH/g polypropylene glycol). The reaction mixture was placed under N.sub.2 atmosphere, heated to 50° C. and subsequently, 0.07 g dibutyltin dilaurate were added to the reaction mixture. An exothermic reaction was observed; however, proper care was taken in order for the reaction temperature not to exceed 97° C. The reaction was maintained at 95° C. for an hour. The NCO content of the resultant polyurethane A was 7.00% on solids determined according to the ISO 14896 Method A (year 2009) (theoretically 7.44%), and the acid value of the polyurethane A was 16.1±1 mg KOH/g polyurethane A. The polyurethane A was cooled down to 60° C., and 18.7 grams of triethylamine were added, and the resulting mixture was stirred for 30 minutes. Subsequently, an aqueous dispersion of the polyurethane A (abbreviated as ‘polyurethane A-AQD’) was prepared as follows: the thus prepared mixture of the polyurethane A and triethylamine was fed—at room temperature over a time period of 60 minutes—to a mixture of 1100 grams of demineralized water, 19.5 grams of nonylphenol ethoxylate (9 ethoxylate groups), and 4.0 grams of triethylamine. After the feed was completed, the mixture was stirred for additional 5 minutes, and subsequently, 111.2 grams of hydrazine (16 wt % solution in water) were added to the mixture. The aqueous dispersion of the polyurethane A thus prepared was stirred for an additional 1 h.

1.3 Determination of the Molecular Weight of the AZ1- to AZ5-Compounds and of the Component T (Matrix-Assisted Laser Desorption/Ionization on a Time-of-Flight Mass Spectrometry; MALDI-TOF MS)

[0268] All MALDI-ToF-MS spectra were acquired using a Bruker UltrafleXtreme™ MALDI-ToF mass spectrometer. The instrument is equipped with a Nd:YAG laser emitting at 1064 nm and a collision cell (not used for these samples). Spectra were acquired in the positive-ion mode using the reflectron, using the highest resolution mode providing accurate masses (range 60-7000 m/z). Cesium Tri-iodide (range 0.3-3.5 kDa) was used for mass calibration (calibration method: IAV Molecular Characterization, code MC-MS-05). The laser energy was 20%. The samples were dissolved in THF at approx. 50 mg/mL. The matrix used was: DCTB (trans-2-[3-(4-tertbutylphenyl)-2-methyl-2-propenylidene]malononitrile), CAS Number 300364-84-5. The matrix solution was prepared by dissolving 20 mg in 1 mL of THF. Potassium trifluoroacetate (KTFA, CAS Number: 2923-16-2) or alternatively sodium iodide was used as salt (NaI, CAS Number 7681-82-5); 10 mg was dissolved in 1 ml THF with a drop of MeOH added. Ratio sample:matrix:salt=10:200:10 (μL), after mixing, 0.5 μL was spot on MALDI plate and 20 allowed to air-dry. Reported signals are the major peaks within 0.5 Da of the calculated mass of the multi-aziridine compounds which are theoretically present in the composition in the largest amounts. In all cases, the reported peaks are the sodium or potassium adducts of the measured ions. The MALDI-TOF MS signals reported correspond to the major peaks of the sodium or potassium adducts of the measured ions of the theoretical formula of a multi-aziridine compound (the sodium and potassium cations. The theoretical formula of a multi-aziridine compound may be determined via analytical techniques well-known to one skilled in the art of analytical chemistry, e.g. NMR spectroscopy and/or liquid chromatography-mass spectroscopy (LC-MS), and/or liquid chromatography-mass spectroscopy-mass spectroscopy (LCMS-MS), and/or theoretically from its method of preparation (if reactants and conditions are known); once the theoretical formula of a multi-aziridine compound is determined, then its theoretical molecular weight may also be determined.

[0269] The multi-aziridine compounds are identified by comparing the molecular weight which is defined just below (MW), with the exact molecular mass (i.e. the sum of the non-isotopically averaged atomic masses of its constituent atoms) of a theoretical structure, using a maximum deviation of 0.5 Da. In the context of this specification, the molecular weight (MW) attributed to a multi-aziridine compound is calculated from the following equation:

MW=Obs.[M+M.sub.cation]=[M.sub.cation]

wherein
the M.sub.cation is the exact molar mass of the sodium (22.99 Da), or potassium cation (38.96 Da) (depending on which cation was used in the MALDI-TOF MS method), and
the Obs.+[M.sub.cation] is the MALDI-TOF MS signal (peak) which corresponds to the theoretical formula of the multi-aziridine compound.

1.4 Determination of the Scatter Intensity-Based Average Hydrodynamic Diameter of the Particles (Dynamic Light Scattering-DLS′)

[0270] The scatter intensity-based average hydrodynamic diameter (D.sub.H) of the particles was determined using a method derived from the ISO 22412:2017 standard with a Malvern Zetasizer Nano S90 DLS instrument that was operated under the following settings. As material, a polystyrene latex was defined with a RI 1.590 and absorption of 0.10 with a continuous of a medium of demineralized water with a viscosity of 0.8812 cP and a RI of 1.332 at 25° C. Measurements were performed in DTS0012 disposable cuvettes, obtained from Malvern Instruments (Malvern, Worcestershire, United Kingdom). The measurements were performed under a 173° C. back-scatter angle as an average of 3 measurements after 120 seconds equilibration, consisting of 10-15 sub-runs optimized by the machine itself. The focus point of the laser was at a fixed position of 4.65 cm, and data were analyzed using a general-purpose data fitting process. Samples were prepared by diluting 0.05 g sample (aqueous dispersion) in approximately 5 mL of demineralized water. If the sample still looks hazy, it is further diluted with distilled water until it becomes almost transparent.

1.5 Assessment of the Chemical Resistance

[0271] The starting and end chemical resistance of a film (cured coating) was tested based on the DIN 68861-1:2011-01.

[0272] The film was prepared as follows: an amount of a sample of an aqueous dispersion and an amount of the polyurethane A-AQD were mixed together under continuous stirring; these amounts were calculated on the basis that the molar ratio of the mol of aziridine rings present in the organic compound (or a mixture of organic compounds) bearing aziridine ring(s), e.g. AZ-component to the mol of carboxylic acid functional groups present in the polyurethane A was equal to 0.9. Upon completion of the mixing, the resulting mixture was stirred for additional 30 minutes to thus produce an aqueous coating composition. This aqueous coating composition was filtered and subsequently applied onto Leneta test cards using a 100 μm wire rod applicator. The film was subsequently dried for 1 h at 25° C. and then annealed at 50° C. for 16 h.

[0273] Cotton wool pads (1×1 cm) were soaked in a solution of ethanol: demineralized water (1:1). They were then placed on the films and covered with Petri dishes for 1 h. Afterwards, the pads and the Petri dishes were removed; after 1h the coatings were visually inspected for damages; the extent of damages was assessed according to the following rating scheme: [0274] 5: no visible changes [0275] 4: hardly noticeable changes in shine or colour [0276] 3: slight changes in shine or colour; the structure of the test surface has not changed [0277] 2: heavy changes noticeable; however, the structure of the test surface has remained more or less undamaged. [0278] 1: heavy changes noticeable; the structure of the test surface has changed. [0279] 0: the tested surface was heavily changed or destroyed.

[0280] In the context of this specification, the above integers 0-5 are mentioned as ‘ranking points’.

[0281] The chemical resistance of a reference film (prepared from only polyurethane A-AQD) was poor (this applies for all examples inventive and comparatives shown in the Examples).

1.6 Assessment of the Storage Stability and Crosslinking Efficiency

[0282] The storage stability of organic compounds bearing aziridine ring(s) in aqueous compositions[or equally the storage stability of aqueous dispersions comprising organic compounds bearing aziridine ring(s)] was assessed by viscosity measurements (starting and end viscosities) and determination of the chemical resistance (starting and end chemical resistance) as both are explained in the specification.

[0283] The crosslinking efficiency of organic compounds bearing aziridine ring(s) in aqueous compositions [or equally the crosslinking efficiency of aqueous dispersions comprising organic compounds bearing aziridine ring(s)] was assessed by determining the end chemical resistance of films (cured coatings).

[0284] Step 1: An aqueous dispersion comprising organic compounds bearing aziridine ring(s) was prepared, and its starting viscosity was determined as described in the specification.

[0285] In addition, the starting chemical resistance of said aqueous dispersion was also determined as described in the specification.

[0286] Step 2: Afterwards, the aqueous dispersion was stored in an oven at 50° C. for 4 weeks. Upon the expiration of this time period, the aqueous dispersion was removed from the oven and left to cool down to room temperature.

[0287] Subsequently: [0288] i) the end viscosity of the aqueous dispersion was determined as described in the specification, and [0289] ii) the end chemical resistance of the aqueous dispersion was determined as described in the specification.

[0290] For obvious reasons, an entity that gels during storage for a prolonged time period and at elevated temperature is deemed not to have enhanced storage stability because it is deemed not to have a workable viscosity.

[0291] For obvious reasons, an entity that gels during storage for a prolonged time period and at elevated temperature is deemed to have poor crosslinking efficiency.

1.7 Determination of the Apparent Viscosity

[0292] The starting and end apparent viscosities (or equally the starting and end viscosities) were measured at room temperature at 60 rpm, according to ISO 2555-2018 on a Brookfield DVE-LV viscometer (single-cylinder geometry). The spindle was selected from the spindles S62, S63 or S64, using the lowest-numbered spindle (i.e. the largest spindle) that yields a reading between 10% and 100% torque.

1.8 Determination of the pH

[0293] The pH of a sample was determined according to the ISO 976:2013. Samples were measured at room temperature using a Metrohm 691 pH-meter equipped with a combined glass electrode and a PT-1000 temperature sensor. The pH-meter was calibrated using buffer solutions of pH 7.00 and 9.21 prior to use.

1.9 Determination of the Acid Value

[0294] The acid value of a polymer is determined according to the ASTM D1639-90(1996)e1. According to the procedure, the sample was dissolved in a good solvent, was titrated with alcoholic potassium hydroxide solution of a known concentration (KOH). The difference in titration volume between the sample and a blank is the measure of the acid value on solids, according to the following formula:

AV=[(V.sub.blank−V.sub.sample)*N.sub.KOH*56.1]/(W*S/100)

where
AV is the acid number on solids in mg KOH/g solid material, V.sub.blank is the volume of KOH solution used in the blank, V.sub.sample is the volume of KOH solution used in the sample, N.sub.KOH is the normality of the KOH solution, W is the sample weight in grams and S is the solids content of the sample in %. Measurements are performed in duplicate using a potentiometric endpoint on a Metrohm 702SM Titrino titrator (accepting the measurement if the difference between duplicates is <0.1 mg KOH/g solid material).

1.10 Determination of the NCO Content

[0295] The NCO content of a sample is determined based on the ASTM D2572-19. In the procedure, the sample is reacted with excess n-dibutylamine. The excess of n-dibutylamine is subsequently back-titrated with standard 1N hydrochloric acid (HCl). The difference in titration volume between the sample and a blank is the measure of the isocyanate content on solids, according to the following formula:

% NCO.sub.solids=[(V.sub.b−V.sub.m)*N*4.2]/(A*s/100)

where
% NCO.sub.solids is the isocyanate content on solids, V.sub.b is the volume of HCl used in the blank, V.sub.m is the volume of HCl used in the sample, N is the normality of the HCl solution, A is the sample weight in grams and s is the solids content of the sample in %. Measurements are performed in duplicate using a potentiometric endpoint on a Metrohm 702SM Titrino titrator (accepting the measurement if the difference between duplicates is <0.1%.sub.NCO).
1.11 Determination of the Amount of Component T [Liquid Chromatography Coupled with Mass Spectroscopy (LC-MS)]

[0296] The amount of component T (as the latter is defined in the specification including the claims; wt % on the total weight of the AZ-compound) was determined via liquid chromatography coupled with mass spectroscopy (LC-MS). Initially, a 0.01 wt % solution of sample in methanol was prepared. Subsequently, 0.5 μL of this solution was injected into an Agilent 1290 Infinity II Ultra High Pressure Liquid Chromatography (UHPLC) system equipped with: a) a High Strength Silica (HSS) technology C.sub.18 type T3 column supplied by Waters® [100×2.1 mm (length×diameter); 1.8 micron average particle size of the stationary phase] operating at 40° C., and b) an Agilent 6550 iFunnel QTOF detector [ElectroSpray Ionization-Time-of-Flight Mass Spectrometer (ESI-TOF-MS) detector]. Once the sample was injected, then a gradient of a mobile phase [from 80/20 v/v A/B to 1/99 v/v A/B, wherein A was 10 mM CH.sub.3COO.sup.−NH.sub.4.sup.+ (set to pH 9.0 with NH.sub.3) and B was acetonitrile; A and B making up the mobile phase], at a flow rate of 0.5 mL/min, for 10 min, was used to separate the various ingredients of the sample. Subsequently, a gradient of a mobile phase [from 1/99 v/v A/B to 1/49/50 A/B/C, wherein A was 10 mM CH.sub.3COO.sup.−NH.sub.4.sup.+ (set to pH 9.0 with NH.sub.3), B was acetonitrile and C was tetrahydrofuran (THF); A, B and C making up the mobile phase] at a flow rate of 0.5 mL/min, for 5 min was applied to purge the column. Assuming a linear MS response of all the ingredients of the sample over all response ranges and an equal ionization efficiency for all the ingredients of the sample, the signals of the: [0297] total ion current, and [0298] extracted ion chromatograms of the component T,
were integrated.

[0299] The data acquisition was carried out via the MassHunter Build 10.1.48 software supplied by Agilent, while the data processing was carried out via the Qualitative Analysis Build 10.0.10305.0 software, also supplied by Agilent.

[0300] The amount of component T (wt % on the total weight of the AZ-compound) was determined by dividing the integrals of the extracted ion chromatograms of the component T by the integrals of the total ion current, multiplied by 100.

1.12 Determination of the Amount of Chloride

[0301] The amount of chloride in an aqueous dispersion was determined according to the ASTM D1726-11(2019).

2. INVENTIVE EXAMPLES

Example 1

[0302] 100 grams of ERISYS® GE-36, 26.5 grams of propylene imine and 5 grams of potassium carbonate were charged to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). The mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere. The mixture was then heated to 80° C. Samples were taken at regular intervals, and the reaction progress was monitored using a .sup.1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. The reaction mixture was diluted with toluene and filtered. The solvent and the excess of propylene imine were removed from the filtrate in vacuo to obtain from the filtrate was removed in vacuo to obtain a clear highly viscous liquid. The theoretical formula of the thus prepared (aziridinyl hydroxy)functional organic compound is shown below (wherein x+y+z=33), and the theoretical molecular weight was calculated to be 2346.68 Da.

##STR00048##

The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 2346.50 Da (=Obs. [M+M.sub.Na+]).

[0303] Subsequently, 15 grams of the (aziridinyl hydroxy)-functional organic compound obtained above was mixed with 3.2 grams of methylethylketone and incubated at 50° C. until a homogeneous solution was obtained. 0.03 grams of triethylamine (TEA) and 3 grams of molten ATLAS™ G-5000 (dispersant) were added to the solution. The resulting mixture was stirred for 5 minutes at room temperature using an IKA T25 Digital Ultra-Turrax® mixer with S 25 N-18G head at 2000 rpm. Then, stirring was increased to 10000 rpm and 15 grams of demineralized water and triethylamine, were added gradually to the mixture over 15 minutes in order to adjust the pH to 11. During this addition process, the mixer was moved around the reaction vessel continuously. After completion of the addition, the resulting dispersion was stirred at 5000 rpm for 10 more minutes, and the pH of the dispersion was again adjusted to 11 with triethylamine. The aqueous dispersion thus prepared contained the inventive particles (which were dispersed in the water).

[0304] The inventive particles had a scatter intensity-based average hydrodynamic diameter (D.sub.H) of 275 nm.

Assessment of Storage Stability and Crosslinking Efficiency

[0305] Starting viscosity (spindle S62): 260 mPa.Math.s
End viscosity (spindle S62): 320 mPa.Math.s
The end viscosity was 1.23 times higher (end viscosity/starting viscosity=1.23) than the starting viscosity.
Thus, the aqueous dispersion had a workable viscosity.
The starting chemical resistance was very good.
The end chemical resistance was very good.
The end chemical resistance was equal to the starting chemical resistance.
The crosslinking efficiency was very good.
Given the above results, the inventive particles and/or the inventive aqueous dispersion comprising the inventive particles had surprisingly enhanced storage stability for a prolonged time period and at elevated temperature (4 weeks at 50° C.) because: [0306] i) they had a workable viscosity, and [0307] ii) the end chemical resistance was equal to the starting chemical resistance,
at the same time maintained very good crosslinking efficiency because the end chemical resistance was very good.

Example 2

[0308] 30.0 grams of Cardolite® NC-514S, 19.2 grams of propylene imine, 30 grams of toluene and 3 grams of potassium carbonate were charged to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). The mixture was stirred with a mechanical stirrer under a nitrogen atmosphere. The mixture was then heated to 70° C. Samples were taken at regular intervals, and the reaction progress was monitored using a .sup.1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. After 20 hours of reaction, the mixture was diluted with toluene and filtered. The solvent and the excess of propylene imine were removed from the filtrate in vacuo to obtain a highly viscous brownish oil. The theoretical formula of the thus prepared (aziridinyl hydroxy)-functional organic compound is shown below, and the theoretical molecular weight was calculated to be 622.47 Da.

##STR00049##

The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 622.43 Da (=Obs. [M+M.sub.Na+]−[M.sub.Na+]).

[0309] Subsequently, 18.4 grams of the (aziridinyl hydroxy)-functional organic compound obtained above was mixed with 9.2 grams of methylethylketone and incubated at 50° C. until a homogeneous solution was obtained. 0.03 grams of triethylamine (TEA) and 3.7 grams of molten ATLAS™ G-5000 (dispersant) were added to the solution. The resulting mixture was stirred for 5 minutes at room temperature using an IKA T25 Digital Ultra-Turrax® mixer with S 25 N-18G head at 2000 rpm. Then, stirring was increased to 10000 rpm and 27.5 grams of demineralized water and triethylamine, were added gradually to the mixture over 15 minutes in order to adjust the pH to 11. During this addition process, the mixer was moved around the reaction vessel continuously. After completion of the addition, the resulting dispersion was stirred at 5000 rpm for 10 more minutes, and the pH of the dispersion was again adjusted to 11 with triethylamine. The aqueous dispersion thus prepared, contained the inventive particles (which were dispersed in the water).

[0310] The inventive particles had a scatter intensity-based average hydrodynamic diameter (D.sub.H) of 181 nm.

Assessment of Storage Stability and Crosslinking Efficiency

[0311] Starting viscosity (spindle S62): 132 mPa.Math.s
End viscosity (spindle S62): 138 mPa.Math.s
The end viscosity was 1.05 times higher (end viscosity/starting viscosity=1.05) than the starting viscosity.
Thus, the aqueous dispersion had a workable viscosity.
The starting chemical resistance was good.
The end chemical resistance was good.
The end chemical resistance was equal to the starting chemical resistance.
The crosslinking efficiency was good.
Given the above results, the inventive particles and/or the inventive aqueous dispersion comprising the inventive particles had surprisingly enhanced storage stability for prolonged time period and at elevated temperature (4 weeks at 50° C.) because: [0312] i) they had a workable viscosity, and [0313] ii) the end chemical resistance was equal to the starting chemical resistance,
at the same time maintained good crosslinking efficiency because the end chemical resistance was good.

Example 3

[0314] 30.0 grams of Cardolite® NC-514S, 19.2 grams of propylene imine, 30 grams of toluene and 3 grams of potassium carbonate were charged to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). The mixture was stirred with a mechanical stirrer under a nitrogen atmosphere. The mixture was then heated to 70° C. Samples were taken at regular intervals, and the reaction progress was monitored using a .sup.1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. After 20 hours of reaction, the mixture was diluted with toluene and filtered. The solvent and the excess of propylene imine were removed from the filtrate in vacuo to obtain a highly viscous brownish oil. The theoretical formula of the thus prepared (aziridinyl hydroxy)-functional organic compound is shown below, and the theoretical molecular weight was calculated to be 622.47 Da.

##STR00050##

The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 622.43 Da (=Obs. [M+M.sub.Na+]−[M.sub.Na+]).

[0315] Subsequently, 18.7 grams of the (aziridinyl hydroxy)-functional organic compound obtained above was mixed with 9.6 grams of acetone and incubated at 50° C. until a homogeneous solution was obtained. 0.03 grams of triethylamine (TEA) and 3.8 grams of Atlas™ G-5002L-LQ (dispersant) were added to the solution. The resulting mixture was stirred for 5 minutes at room temperature using an IKA T25 Digital Ultra-Turrax® mixer with S 25 N-18G head at 2000 rpm. Then, stirring was increased to 10000 rpm and 24.0 grams of demineralized water and triethylamine, were added gradually to the mixture over 15 minutes in order to adjust the pH to 11. During this addition process, the mixer was moved around the reaction vessel continuously. After completion of the addition, the resulting dispersion was stirred at 5000 rpm for 10 more minutes, and the pH of the dispersion was again adjusted to 11 with triethylamine. The aqueous dispersion thus prepared contained the inventive particles (which were dispersed in water).

[0316] The inventive particles had a scatter intensity-based average hydrodynamic diameter (D.sub.H) of 153 nm.

Assessment of Storage Stability and Crosslinking Efficiency

[0317] Starting viscosity (spindle S62): 1178 mPa.Math.s
End viscosity (spindle S62): 1212 mPa.Math.s
The end viscosity was 1.03 times higher (end viscosity/starting viscosity=1.03) than the starting viscosity.
Thus, the aqueous dispersion had a workable viscosity.
The starting chemical resistance was good.
The end chemical resistance was good.
The end chemical resistance was equal to the starting chemical resistance.
The crosslinking efficiency was good.
Given the above results, the inventive particles and/or the inventive aqueous dispersion comprising the inventive particles had surprisingly enhanced storage stability for prolonged time period and at elevated temperature (4 weeks at 50° C.) because: [0318] i) they had a workable viscosity, and [0319] ii) the end chemical resistance was equal to the starting chemical resistance,
at the same time maintained good crosslinking efficiency because the end chemical resistance was good.

Example 4

[0320] 30.0 grams of Cardolite® NC-514S, 19.2 grams of propylene imine, 30 grams of toluene and 3 grams of potassium carbonate were charged to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). The mixture was stirred with a mechanical stirrer under a nitrogen atmosphere. The mixture was then heated to 70° C. Samples were taken at regular intervals, and the reaction progress was monitored using a .sup.1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. After 20 hours of reaction, the mixture was diluted with toluene and filtered. The solvent and the excess of propylene imine were removed from the filtrate in vacuo to obtain a highly viscous brownish oil. The theoretical formula of the thus prepared (aziridinyl hydroxy)-functional organic compound is shown below, and the theoretical molecular weight was calculated to be 622.47 Da.

##STR00051##

[0321] The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 622.43 Da (=Obs. [M+M+M.sub.Na+]−[M.sub.Na+]).

[0322] Subsequently, 25.4 grams of the (aziridinyl hydroxy)-functional organic compound obtained above was mixed with 12.7 grams of methylethylketone and incubated at 50° C. until a homogeneous solution was obtained. 0.03 grams of triethylamine (TEA) and 5.1 grams of molten ATLAS™ G-5000 (dispersant) were added to the solution. The resulting mixture was stirred for 5 minutes at room temperature using an IKA T25 Digital Ultra-Turrax® mixer with S 25 N-18G head at 2000 rpm. Then, stirring was increased to 10000 rpm and 38.0 grams of demineralized water and triethylamine, were added gradually to the mixture over 15 minutes in order to adjust the pH to 11. During this addition process, the mixer was moved around the reaction vessel continuously. After completion of the addition, the resulting dispersion was stirred at 5000 rpm for 10 more minutes, and the pH of the dispersion was further adjusted to 12.5 with potassium hydroxide. The aqueous dispersion thus prepared contained the inventive particles (which were dispersed in water).

[0323] The inventive particles had a scatter intensity-based average hydrodynamic diameter (D.sub.H) of 176 nm.

Assessment of Storage Stability and Crosslinking Efficiency

[0324] Starting viscosity (spindle S62): 182 mPa.Math.s
End viscosity (spindle S62): 220 mPa.Math.s
The end viscosity was 1.21 times higher (end viscosity/starting viscosity=1.21) than the starting viscosity.
Thus, the aqueous dispersion had a workable viscosity.
The starting chemical resistance was good.
The end chemical resistance was good.
The end chemical resistance was equal to the starting chemical resistance.
The crosslinking efficiency was good.
Given the above results, the inventive particles and/or the inventive aqueous dispersion comprising the inventive particles had surprisingly enhanced storage stability for prolonged time period and at elevated temperature (4 weeks at 50° C.) because: [0325] i) they had a workable viscosity, and [0326] ii) the end chemical resistance was equal to the starting chemical resistance,
at the same time maintained good crosslinking efficiency because the end chemical resistance was good.

Example 5

[0327] 30.0 grams of Cardolite® NC-514S, 19.2 grams of propylene imine, 30 grams of toluene and 3 grams of potassium carbonate were charged to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). The mixture was stirred with a mechanical stirrer under a nitrogen atmosphere. The mixture was then heated to 70° C. Samples were taken at regular intervals, and the reaction progress was monitored using a .sup.1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. After 20 hours of reaction, the mixture was diluted with toluene and filtered. The solvent and the excess of propylene imine were removed from the filtrate in vacuo to obtain a highly viscous brownish oil. The theoretical formula of the thus prepared (aziridinyl hydroxy)-functional organic compound is shown below, and the theoretical molecular weight was calculated to be 622.47 Da.

##STR00052##

The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 622.43 Da (=Obs. [M+M.sub.Na+]−[M.sub.Na+]).

[0328] In a separate reaction, 75 grams of EPALLOY® 9000 was dissolved in 75 mL of toluene and charged to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). Next, 55 grams of propylene imine and 5 grams of potassium carbonate were added to the flask. The mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere. The mixture was than heated to 80° C. Samples were taken at regular intervals and the reaction progress was monitored using a .sup.1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. After 22 hours of reaction, the mixture was filtered. The solvent and excess of propylene imine from the filtrate was removed in vacuo to obtain an off-white solid. The theoretical formula of the thus prepared (aziridinyl hydroxy)-functional organic compound is shown below and the theoretical molecular weight was calculated to be 645.38 Da.

##STR00053##

The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 645.37 Da (=Obs. [M+M.sub.Na+]−[M.sub.Na+]).

[0329] Subsequently, 2.3 grams of the (aziridinyl hydroxy)-functional organic compound with theoretical molecular weight 645.38 Da obtained above, and 6.4 grams of the (aziridinyl hydroxy)-functional organic compound with theoretical molecular weight 622.47 Da obtained above, were mixed with 2.4 grams of toluene and 2.0 grams of methylethylketone and incubated at 50° C. until a homogeneous solution was obtained. 0.03 grams of triethylamine (TEA) and 1.8 grams of molten ATLAS™ G-5000 (dispersant) were added to the solution. The resulting mixture was stirred for 5 minutes at room temperature using an IKA T25 Digital Ultra-Turrax® mixer with S 25 N-18G head at 2000 rpm. Then, stirring was increased to 10000 rpm and 45.5 grams of demineralized water and triethylamine, were added gradually to the mixture over 15 minutes in order to adjust the pH to 11. During this addition process, the mixer was moved around the reaction vessel continuously. After completion of the addition, the resulting dispersion was stirred at 5000 rpm for 10 more minutes, and the pH of the dispersion was further adjusted to 11 with triethylamine. The aqueous dispersion thus prepared contained the inventive particles (which were dispersed in water).

[0330] The inventive particles had a scatter intensity-based average hydrodynamic diameter (D.sub.H) of 397 nm.

Assessment of Storage Stability and Crosslinking Efficiency

[0331] Starting viscosity (spindle S62): 14 mPa.Math.s
End viscosity (spindle S62): 41 mPa.Math.s
The end viscosity was 2.93 times higher (end viscosity/starting viscosity=2.93) than the starting viscosity.
Thus, the aqueous dispersion had a workable viscosity.
The starting chemical resistance was good.
The end chemical resistance was good.
The end chemical resistance was equal to the starting chemical resistance.
The crosslinking efficiency was good.
Given the above results, the inventive particles and/or the inventive aqueous dispersion comprising the inventive particles had surprisingly enhanced storage stability for prolonged time period and at elevated temperature (4 weeks at 50° C.) because: [0332] i) they had a workable viscosity, and [0333] ii) the end chemical resistance was equal to the starting chemical resistance,
at the same time maintained good crosslinking efficiency because the end chemical resistance was good.

Example 6

[0334] 180 grams of DESMODUR® N 3900 was dissolved in 150 grams of toluene, charged to a reaction flask equipped with a thermometer and heated to 50° C. Next, 0.05 grams of triethylamine was added to the flask and over the course of 150 minutes 74 grams of glycidol was slowly added to the reaction mixture, while making sure that the reaction temperature stayed constant between 55-58° C. After stirring for another 60 minutes at this temperature, the mixture was cooled down to room temperature and stirred for 18 hours at room temperature. The solvent was removed in vacuo and the resulting yellowish oil was transferred to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). Next, 250 grams of toluene, 175 grams of propylene imine and 10 grams of potassium carbonate were added to the flask. The mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere. The mixture was then heated to 60° C. Samples were taken at regular intervals, and the reaction progress was monitored using a .sup.1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. After 18 hours of reaction, the mixture was filtered. The solvent and the excess of propylene imine were removed from the filtrate in vacuo to obtain a high viscous liquid. The theoretical formula of the thus prepared (aziridinyl hydroxy)-functional organic compound is shown below and the theoretical molecular weight was calculated to be 897.55 Da.

##STR00054##

The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 897.56 Da (=Obs. [M+M.sub.Na+]−[M.sub.Na+]).

[0335] Subsequently, 4.2 grams of NeoCryl® B-300 was dissolved in 4.2 grams of methylethylketone. In parallel, 4.2 grams of the (aziridinyl hydroxy)-functional organic compound obtained above was mixed with 2.1 grams of methylethylketone. Both solutions were mixed and incubated at 50° C. until a homogeneous mixture was obtained. 0.03 grams of triethylamine (TEA) and 2.5 grams of molten ATLAS™ G-5000 (dispersant) were added to the solution. The resulting mixture was stirred for 5 minutes at room temperature using an IKA T25 Digital Ultra-Turrax® mixer with S 25 N-18G head at 2000 rpm. Then, stirring was increased to 10000 rpm and 15.4 grams of demineralized water and triethylamine, were added gradually to the mixture over 15 minutes in order to adjust the pH to 11. During this addition process, the mixer was moved around the reaction vessel continuously. After completion of the addition, the resulting dispersion was stirred at 5000 rpm for 10 more minutes. Afterwards, the solvent was removed using a rotary evaporator, replenishing with an equal amount of demineralized water, and the pH of the dispersion was again adjusted to 11 with triethylamine. The aqueous dispersion thus prepared contained the inventive particles (which were dispersed in water).

[0336] The inventive particles had a scatter intensity-based average hydrodynamic diameter (D.sub.H) of 100 nm.

Assessment of Storage Stability and Crosslinking Efficiency

[0337] Starting viscosity (spindle S62): 39 mPa.Math.s
End viscosity (spindle S62): 40 mPa.Math.s
The end viscosity was 1.03 time higher (end viscosity/starting viscosity=1.03) than the starting viscosity.
Thus, the aqueous dispersion had a workable viscosity.
The starting chemical resistance was good.
The end chemical resistance was good.
The end chemical resistance was equal to the starting chemical resistance.
The crosslinking efficiency was good.
Given the above results, the inventive particles and/or the inventive aqueous dispersion comprising the inventive particles had surprisingly enhanced storage stability for prolonged time period and at elevated temperature (4 weeks at 50° C.) because: [0338] i) they had a workable viscosity, and [0339] ii) the end chemical resistance was equal to the starting chemical resistance,
at the same time maintained good crosslinking efficiency because the end chemical resistance was good.

3. COMPARATIVE EXAMPLES

Example 1C

[0340] The trimethylolpropane tris(2-methyl-1-aziridinepropionate) (commercial product name ‘crosslinker CX-100’) has the following structure:

##STR00055##

and the theoretical molecular weight was calculated to be 467.30 Da.

[0341] 7.5 grams of trimethylolpropane tris(2-methyl-1-aziridinepropionate) were mixed with 3.75 grams of acetone and incubated at 50° C. until a homogeneous solution was obtained. Subsequently, 0.03 grams of triethylamine and 0.75 grams of molten Atlas™ G-5000 dispersant were added to the solution. The resulting mixture was stirred for 5 minutes at room temperature using an IKA T25 Digital Ultra-Turrax® mixer with S 25 N-18G head at 2000 rpm. Then, stirring was increased to 10000 rpm and 7.5 grams of demineralized water, an amount of triethylamine to adjust the pH to 10, were added gradually to the mixture over 15 minutes. During this addition process, the mixer was moved around the reaction vessel continuously. After completion of the addition, the mixture was stirred at 5000 rpm for additional 10 minutes, and the pH of the mixture was set to 10 by using triethylamine. This resulted in a homogenous solution which did not contain any particles.

Assessment of Storage Stability and Crosslinking Efficiency

[0342] Starting viscosity (spindle S62): 178 mPa.Math.s
End viscosity (spindle S62): not possible to measure because the aqueous composition gelled during the 2.sup.nd week of storage
Thus, the aqueous composition did not have a workable viscosity.
The starting chemical resistance was excellent.
The end chemical resistance was not possible to measure because the aqueous composition gelled during the 2.sup.nd week of storage.
Thus, the crosslinking efficiency was poor.
Given the above results, the trimethylolpropane tris(2-methyl-1-aziridinepropionate) and/or its solution failed to provide for enhanced storage stability for a prolonged time period and at elevated temperature (4 weeks at 50° C.) because they did not have a workable viscosity, and at the same time failed to maintain good crosslinking efficiency.

Example 2C

[0343] 299 grams of bisphenol A diglycidyl ether, 250 grams of toluene, 255 grams of propylene imine and 10 grams of potassium carbonate were charged to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). The mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere. The mixture was than heated to 70° C. Samples were taken at regular intervals and the reaction progress was monitored using a .sup.1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. After 19 hours of reaction, the mixture was filtered. The solvent and excess of propylene imine from the filtrate was removed in vacuo to obtain a highly viscous liquid. The theoretical formula of the thus prepared multi-aziridine compound is shown below and the theoretical molecular weight was calculated to be 454.28 Da.

##STR00056##

The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 454.26 Da (=Obs. [M+M.sub.Na+]−[M.sub.Na+]).

[0344] 6.95 grams of the multi-aziridine compound obtained above were mixed with 5.00 grams of methylethylketone (MEK) and incubated at 50° C. until a homogeneous solution was obtained. Subsequently, 0.03 grams of triethylamine and 1.20 grams of molten Atlas™ G-5000 dispersant were added to the solution. The resulting mixture was stirred for 5 minutes at room temperature using an IKA T25 Digital Ultra-Turrax® mixer with S 25 N-18G head at 2000 rpm. Then, stirring was increased to 10000 rpm and 7.5 grams of demineralized water were added gradually to the mixture over 15 minutes. During this addition process, the mixer was moved around the reaction vessel continuously. After completion of the addition, the resulting mixture was stirred at 5000 rpm for additional 10 minutes. The aqueous dispersion thus prepared contained particles (which were dispersed in water).

[0345] The particles had a scatter intensity-based average hydrodynamic diameter (D.sub.H) of 517 nm.

Assessment of Storage Stability and Crosslinking Efficiency

[0346] Starting viscosity (spindle S62): 10 mPa.Math.s
End viscosity (spindle S62): not possible to measure because the aqueous composition gelled during the 1.sup.st week of storage
Thus, the aqueous composition did not have a workable viscosity.
The starting chemical resistance was good.
The end chemical resistance was not possible to measure because the aqueous composition gelled during the 1.sup.st week of storage.
Thus, the crosslinking efficiency was poor.
Given the above results, this multi-aziridine compound obtained above and/or its aqueous dispersion failed to provide for enhanced storage stability for prolonged time period and at elevated temperature (4 weeks at 50° C.) because they did not have a workable viscosity, and at the same time failed to maintain a good crosslinking efficiency.

Example 3C

[0347] 24.0 grams of N,N-diglycidyl-4-glycidyloxyaniline, 42.0 grams of propylene imine, 30 grams of toluene and 3 grams of potassium carbonate were charged to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). The mixture was stirred with a mechanical stirrer under a nitrogen atmosphere. The mixture was than heated to 70° C. Samples were taken at regular intervals and the reaction progress was monitored using a .sup.1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. After 24 hours of reaction, the mixture was diluted with toluene and filtered. The solvent and excess of propylene imine from the filtrate was removed in vacuo to obtain a highly viscous yellow material. The theoretical formula of the thus prepared multi-aziridine compound is shown below and the theoretical molecular weight was calculated to be 448.30 Da.

##STR00057##

[0348] The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 448.29 Da (=Obs. [M+M.sub.Na+]−[M.sub.Na+]).

[0349] This compound was disclosed in U.S. Pat. No. 3,329,674 in cl. 2, II. 29-39.

[0350] 9.80 grams of the multi-aziridine compound obtained above were mixed with 4.90 grams of acetone and incubated at 50° C. until a homogeneous solution was obtained. Subsequently, 0.03 grams of triethylamine and 1.03 grams of molten Atlas™ G-5000 dispersant were added to the solution. The resulting mixture was stirred for 5 minutes at room temperature using an IKA T25 Digital Ultra-Turrax® mixer with S 25 N-18G head at 2000 rpm. Then, stirring was increased to 10000 rpm and 9.90 grams of demineralized water were added gradually to the mixture over 15 minutes. During this addition process, the mixer was moved around the reaction vessel continuously. After completion of the addition, the mixture was stirred at 5000 rpm for additional 10 minutes, and the pH of the mixture was set to 10 by using triethylamine. This resulted in a homogenous solution which did not contain any particles.

Assessment of Storage Stability and Crosslinking Efficiency

[0351] Starting viscosity (spindle S62): 52 mPa.Math.s
End viscosity (spindle S62): not possible to measure because the solution gelled during the 1.sup.st week of storage.
Thus, the solution did not have a workable viscosity.
The starting chemical resistance was very good.
The end chemical resistance was not possible to measure because the solution gelled during the 1.sup.st week of storage.
Thus, the crosslinking efficiency was poor.
Given the above results, the multi-aziridine compound obtained above and/or its solution failed to provide for enhanced storage stability for a prolonged time period and at elevated temperature (4 weeks at 50° C.) because they did not have a workable viscosity, and at the same time failed to maintain good crosslinking efficiency.

Example 4C

[0352] 75 grams of ERISYS® GA-240, 80 grams of propylene imine and 5 grams of potassium carbonate were charged to a reaction flask equipped with a thermometer and a condenser connected to a cryostat (3° C.). The mixture was stirred with a mechanical upper stirrer under a nitrogen atmosphere. The mixture was than heated to 71° C. Samples were taken at regular intervals and the reaction progress was monitored using a .sup.1H-NMR until no signal (chemical shifts) correlated to the epoxide protons from the multifunctional epoxide was observed. After 22 hours of reaction, the mixture was diluted with toluene and filtered. The solvent and excess of propylene imine from the filtrate was removed in vacuo to obtain a clear, transparent solid. The theoretical formula of the AZ-component is shown below and the theoretical molecular weight was calculated to be 588.44 Da.

##STR00058##

The molecular weight as defined and determined via MALDI-TOF MS—as this is defined and described in the specification—was 588.48 Da (=Obs. [M+M.sub.Na+]−[M.sub.Na+]).

[0353] 9.68 grams of the transparent solid described above were mixed with 4.90 grams of acetone and incubated at 50° C. until a homogeneous solution was obtained. Subsequently, 0.03 grams of triethylamine and 0.96 grams of molten Atlas™ G-5000 dispersant were added to the solution. The resulting mixture was stirred for 5 minutes at room temperature using an IKA T25 Digital Ultra-Turrax® mixer with S 25 N-18G head at 2000 rpm. Then, stirring was increased to 10000 rpm and 9.65 grams of demineralized water were added gradually to the mixture over 15 minutes. During this addition process, the mixer was moved around the reaction vessel continuously. After completion of the addition, the mixture was stirred at 5000 rpm for additional 10 minutes, and the pH of the mixture was set to 10 by using triethylamine. This resulted in a homogenous solution which did not contain any particles.

Assessment of Storage Stability and Crosslinking Efficiency

[0354] Starting Viscosity (Spindle S62): 64 mPa.Math.s
End viscosity (spindle S62): not possible to measure because the solution gelled during the 1.sub.st week of storage.
Thus, the solution did not have a workable viscosity.
The starting chemical resistance was very good.
The end chemical resistance was not possible to measure because the solution gelled during the 1.sup.st week of storage.
Thus, the crosslinking efficiency was poor.
Given the above results, the multi-aziridine compound obtained above and/or its solution failed to provide for enhanced storage stability for a prolonged time period and at elevated temperature (4 weeks at 50° C.) because they did not have a workable viscosity, and at the same time failed to maintain good crosslinking efficiency.

4. CONCLUSION

[0355] The U.S. Pat. No. 3,329,674 to Thiokol Chemical Corporation (prior art), as explained in detail in the specification, did neither disclose any particles—let alone any particles of compounds bearing aziridine group(s), let alone that these compounds had a molecular weight of at least 600 and at most 10000 Da—, nor any aqueous dispersions comprising particles which particles comprised an (aziridinyl hydroxy)-functional organic component. The U.S. Pat. No. 3,329,674 failed to provide for the combination of enhanced storage stability (at elevated temperature and for a prolonged time period; 4 weeks at 50° C.) of aqueous dispersions comprising organic compounds bearing aziridine ring(s), maintaining at least good crosslinking efficiency (the crosslinking efficiency was poor). Evidence for that is the Example 3C shown in the specification.

[0356] Upon comparing the results of the inventive Examples 1 to 6 and those of the comparative Examples 1C to 4C (that includes an example taken from the prior art and in particular from the U.S. Pat. No. 3,329,674 (Example 3C herein), it is evident that only the particles of the invention (and the aqueous dispersions of the invention) were able to provide for aqueous dispersions comprising organic compounds bearing aziridine ring(s) that had enhanced storage stability for a prolonged time period and at elevated temperature (4 weeks at 50° C.), and at the same time maintained at least good crosslinking efficiency.