Aziridine functional compounds

Abstract

The present invention relates to a compound (I) comprising at least one functional group A and at least one functional group B, wherein the functional group A has a structural formula A: wherein R 1 For H, R 2 , R 3 and R 4 independently selected from H, methyl or ethyl, m is 1 to 6; and the functional group B has the structural formula B: R 5 is H or methyl, X is O or NH, Z' is a polyalkoxy group or an ω-alkoxy polycaprolactone group, Y' is a collection of atoms covalently linked in a linear or branched configuration, n" is 0 or 1, and m' is an integer from 1 to 6; provided that the total number of functional groups A and the number of functional groups B in compound (I) is 2 to 13; and the molecular weight range of the compound is 800 to 10000 Daltons.

Description

[0001] The present invention relates to aziridinyl-functional compounds and to the use of such compositions as adhesion promoters or reactive diluents in free-radically curable compositions. The present invention further relates to the field of free-radically curable compositions comprising at least one compound containing at least two free-radically copolymerizable ethylenically unsaturated groups and at least one such aziridinyl-functional compound.

[0002] There is a global trend to use printed packaging to protect food (instead of ordinary packaging with printed adhesive labels). Most of this packaging involves flexible plastic packaging. Preferably, packaging manufacturers want to be able to print directly onto the packaging substrate. Therefore, it is necessary that the ink adheres firmly to the flexible substrate. The current technical field uses solvent-based inks. The disadvantage of using solvents in the application of coatings is that the solvent must evaporate during the coating process. The evaporated solvent must be captured and not allowed to be discharged into the environment because the typical solvents used have properties that are not conducive to the environment. The coating process must therefore include a solvent capture system that increases the cost of the process. In addition, the evaporation of the solvent is not a very fast process and the energy consumed limits the coating speed. Converters want to print as quickly as possible to shorten production time. Therefore, solvent-based systems have serious environmental pollution problems, as well as the disadvantages of long drying and curing times or high curing temperatures. In addition, in shrink sleeve applications using heat-sensitive substrates (capable of shrinking the sleeve around the bottle in the later stages of the process), the advantage of using an energy-curable system is that no heating is required to evaporate the solvent and dry the ink. In view of this, if it can be changed to a radiation-curable printing ink, there are several economic and technical advantages. However, the market share of radiation curable ink in flexographic printing is still very low. The main reason for this situation is that the current UV curable ink does not show a combination of good adhesion, high curing reaction, non-genotoxicity and low migration properties, that is, there is no possible component with migration to packaged food. The fast drying UV curable system in the current technical field of food packaging shows poor adhesion with flexible plastic substrates for them. The common solution for poor adhesion is to add low molecular weight monomers as diluents / adhesion promoters, but because there is no low-functional monomer that can be used for potential migration reasons, this limits the use of UV curable systems in printing and packaging applications. Therefore, UV curable formulations cannot be used in many graphic arts applications in the best way and the share in printing flexible packaging is relatively low. Therefore, the development of UV curable systems that meet these requirements is highly needed and can promote the radiation curable system to further market share in the printing flexible packaging industry. And, for the coating industry, adhesion to hard plastic substrates is also important. This is generally related to hard plastic substrates such as used for automotive applications, furniture, and household appliances. Also for coating applications on rigid plastics, the adhesion of UV curable resins tends to be insufficient, requiring the use of solvent based primers to ensure adequate adhesion. There is a clear need to eliminate these solvent based primers from a SHE perspective.

[0003] Another solution to improve adhesion to substrates is to treat the substrate with aziridine functional compounds, after which the coating or ink is applied to the substrate. Trimethylolpropane tris (2-methyl-1-aziridine propionate), CAS number 64265-57-2, a multifunctional aziridine crosslinker, is a well-known and very active adhesion promoter. This is described, for example, in US5057371. However, the compound has an unfavorable genotoxicity characteristic. The industry needs to improve the safety, health and environmental characteristics of adhesives, inks and coatings and materials for preparing adhesives, inks and coatings. Genotoxicity describes the characteristics of chemical or physical agents that cause any type of DNA damage, which may not always lead to transmissible mutations. Mutagenicity refers to inducing permanent transmissible DNA changes (as DNA constituents or chromosome structures), which are maintained in somatic cell divisions and passed down to offspring in reproductive cells. Genotoxicity must not be confused with mutagenicity. All mutagens are genotoxic, and not all genotoxic substances are mutagenic.

[0004] It is an object of the present invention to provide aziridinyl-functional compounds which can be used as adhesion promoters or reactive diluents in free-radically curable compositions and which have reduced genotoxicity compared to at least trimethylolpropane tris(2-methyl-1-aziridinium propionate).

[0005] This goal is unexpectedly achieved by providing:

[0006] A compound (I) comprising at least one functional group A and at least one functional group B, wherein:

[0007] The functional group A has a structural formula A:

[0008]

[0009] in

[0010] R 1 For H,

[0011] R 2 , R 3 and R 4 independently selected from H, methyl or ethyl,

[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

[0014] R"=H, an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, an alicyclic hydrocarbon group containing 5 to 12 carbon atoms, an aromatic hydrocarbon group containing 6 to 12 carbon atoms, CH 2-O-(C=O)-R"', CH 2 -OR”” or CH 2 -(OCR””'HCR””'H) n -OR""", wherein R"' is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms and R"" is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms or an aromatic hydrocarbon group containing 6 to 12 carbon atoms, n is 1 to 35, R""' is independently H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms and R""" is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms,

[0015] (2) R' and R" together form a saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms; and

[0016] The functional group B has the structural formula B:

[0017]

[0018] R 5 is H or methyl,

[0019] X is O or NH,

[0020] Z' is a polyalkoxy group or an ω-alkoxy polycaprolactone group,

[0021] Y' is a collection of atoms covalently linked in a linear or branched configuration consisting of: i) carbon and hydrogen atoms, ii) carbon, hydrogen, and oxygen atoms, iii) carbon, hydrogen, and nitrogen atoms, or iv) carbon, hydrogen, oxygen, and nitrogen atoms,

[0022] n" is 0 or 1, and

[0023] m' is an integer from 1 to 6;

[0024] Provided that the total number of functional groups A and the number of functional groups B in compound (I) is from 2 to 13; and

[0025] The molecular weight of compound (I) ranges from 600 Daltons to 10,000 Daltons.

[0026] It was unexpectedly found that the compounds according to the invention have reduced genotoxicity compared to trimethylolpropane tris(2-methyl-1-aziridine propionate). The compounds according to the invention show only weakly positive induced genotoxicity, or even they do not show genotoxicity, i.e. they show genotoxicity levels comparable to the naturally occurring background.

[0027] 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 which are direct products obtained in the preparation of the polyaziridine compounds of the present invention. Positive induced 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 least one of 10%, 25% and 50% cytotoxicity. Weak positive induced 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 levels 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) are 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 levels of the genotoxicity reporter genes Bscl2-GFP and Rtkn-GFP are 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.

[0028] The compounds according to the invention improve the adhesion of coatings or inks to substrates. Preferred substrates are plastic substrates, particularly low surface free energy plastic substrates and substrates from wood plastic composites. Examples of low surface free energy plastic substrates are biaxially oriented polypropylene (BOPP), polyethylene (PE) and polyethylene terephthalate (PET). Other substrates include PETG (polyethylene terephthalate), OPS (oriented polystyrene), PVC and PLA (polylactic acid polylactide) (all for shrink sleeve applications) and melamine-coated substrates. Examples of rigid plastics include PVC, ABS, PP, PE, PS, EPDM, PC (polycarbonate), PA (polyamide) and combinations thereof. In addition, very surprising and unexpected observations are that improved adhesion is observed not only for (corona discharge) pretreated plastic substrates, but also for untreated plastic substrates. This allows the use of untreated plastic substrates, but is also beneficial when using pretreated plastic substrates. The effect of the corona or plasma treatment is reduced in due course due to the surface reorganization, which means that the surface tension is reduced in due course. This can mean that the previously treated plastic has to be treated again before the primer is applied in order to obtain sufficient adhesion. The fact that the compounds of the invention also adhere to untreated plastics eliminates the need for this additional treatment step. This makes the coating system necessarily more robust, since there is no need to check whether the previously treated plastic still has a surface free energy that is high enough to facilitate proper adhesion.

[0029] US3523750, US5359005, US5164467 and CN108084870 describe aziridine compounds which do not contain a functional group having the structural formula B.

[0030] 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.

[0031] 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.

[0032] Functional Group A

[0033] The compounds (I) of the present invention contain at least one functional group A.

[0034] Functional group A has the structural formula A:

[0035]

[0036] in

[0037] R 1 For H,

[0038] R 2 , R 3 and R 4 independently selected from H, methyl or ethyl,

[0039] R' and R" are based on (1) or (2):

[0040] (1) R′=H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, and

[0041] R"=H, an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, an alicyclic hydrocarbon group containing 5 to 12 carbon atoms, an aromatic hydrocarbon group containing 6 to 12 carbon atoms, CH 2 -O-(C=O)-R"', CH 2 -OR”” or CH 2 -(OCR””'HCR””'H) n -OR""", wherein R"' is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms and R"" is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms or an aromatic hydrocarbon group containing 6 to 12 carbon atoms, n is 1 to 35, R""' is independently H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms and R""" is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms,

[0042] (2) R' and R" together form a saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms,

[0043] If the compounds (I) according to the invention contain more than one functional group A, the functional groups A present in the compounds (I) according to the invention may independently have different R 2 , R 3 , R 4 , R', R" and / or m. However, the functional groups A present in compound (I) are preferably identical to each other.

[0044] The compound (I) according to the present invention is usually obtained in a composition in which, following the compound (I), there may be other starting materials, by-products and / or solvents for the preparation of the compound (I). The composition may contain only one compound (I) according to the present invention, but also more than one compound (I) according to the present invention. For example, when a mixture of polyisocyanates is used as starting material, a mixture of compound (I) is obtained.

[0045] The compounds (I) according to the present invention contain at least one functional group A, preferably 1 to 3 functional groups A, more preferably 1 or 2 functional groups A, most preferably 1 functional group A.

[0046] In a preferred embodiment of the present invention, R 2 For H, R 3 C 2 H 5 And R 4 is H. In another and more preferred embodiment of the present invention, R 2 For H, R 3 CH 3 And R 4 CH 3 In another even more preferred embodiment of the present invention, R 2 For H, R 3 CH 3 And R 4 For H.

[0047] 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.

[0048] Preferably, R' is H or an alkyl group containing 1 to 2 carbon atoms. Most preferably, R' is H.

[0049] R" is preferably H, an aliphatic hydrocarbon group containing 1 to 4 carbon atoms, CH 2 -O-(C=O)-R"', CH 2 -OR”” or CH 2 -(OCR””'HCR””'H) n-OR""", wherein R"' is an aliphatic hydrocarbon group containing 1 to 12 carbon atoms and R"" is an aliphatic hydrocarbon group containing 1 to 12 carbon atoms or an aromatic hydrocarbon group containing 6 to 12 carbon atoms, n is 1 to 35, preferably 6 to 20, R""' is independently H or methyl and R""" is an alkyl group having 1 to 4 carbon atoms, or R' and R" can be part of the same saturated cycloaliphatic hydrocarbon group containing 5 to 8 carbon atoms. More preferably, R"=H or an alkyl group containing 1 to 4 carbon atoms. Even more preferably, R"=alkyl group containing 1 to 4 carbon atoms. Even more preferably, R" is methyl.

[0050] Preferably, R' is H and R" is methyl.

[0051] The functional group A is preferably introduced into the compound (I) according to the present invention by using as a starting material a compound A' having the following structural formula:

[0052]

[0053] Methods for preparing compound 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, 24 1336-1340. 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 aziridine compounds for preparing compound A' are propylene imine and ethyl aziridine. The synthesis of ethyl aziridine is described, for example, in EP0227461B1. The most preferred aziridine compound for preparing compound A' is propylene imine.

[0054] Compound A' is preferably obtained by reacting at least one monoepoxide compound with an aziridine compound having the following structural formula (C):

[0055]

[0056] Where R 1 , R 2 , R 3 and R 4And its preferred form is as defined above. Monoepoxide can be a mixture of different non-OH functional monoepoxides. Non-limiting examples of monoepoxides are ethylene oxide, propylene oxide, 2-ethyl ethylene oxide, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, 4-tert-butylphenyl 2,3-epoxypropyl ether (=tert-butylphenyl glycidyl ether), cresol glycidyl ether (ortho or para) and neodecanoic acid glycidyl ester. Monoepoxide is preferably selected from the group consisting of: propylene oxide, 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.

[0057] Compound A' can also be obtained by reacting at least one diepoxide compound with an aziridine compound having the structural formula (C) as given above. The epoxide is preferably selected from the group consisting of bisphenol A diglycidyl ether (CAS No. 1675-54-3), neopentyl glycol diglycidyl ether (CAS No. 17557-23-2), butanediol diglycidyl ether (CAS No. 2425-79-8), ethylene glycol diglycidyl ether (CAS No. 2224-15-9), 1,6-hexanediol diglycidyl ether (CAS No. 16096-31-4), polypropylene glycol diglycidyl ether (CAS No. 26142-30-3), poly(ethylene glycol)) diglycidyl ether (CAS No. 72207-80-8) and any mixture thereof.

[0058] Compound A' is obtained, for example, in a process comprising at least the following steps: (i) by carrying out, for example, by contacting one equivalent of an epoxide compound with one equivalent of an aziridine compound at a temperature in the range of 20°C to 110°C, more suitably 40°C to 95°C, even more suitably 60°C to 85°C at atmospheric pressure. The aziridine compound is preferably acryleneimine (CAS No. 75-55-8) or 2,2-dimethylaziridine (CAS No. 2658-24-4), more preferably the aziridine is acryleneimine.

[0059] Functional group B

[0060] The compound (I) of the present invention comprises at least one functional group B, preferably at least two functional groups B, more preferably two functional groups B.

[0061] Functional group B has the structural formula B:

[0062]

[0063] in

[0064] R 5 is H or methyl,

[0065] X is O or NH,

[0066] Z' is a polyalkoxy group or an ω-alkoxy polycaprolactone group,

[0067] Y' is a collection of atoms covalently linked in a linear or branched configuration consisting of: i) carbon and hydrogen atoms, ii) carbon, hydrogen, and oxygen atoms, iii) carbon, hydrogen, and nitrogen atoms, or iv) carbon, hydrogen, oxygen, and nitrogen atoms,

[0068] n" is 0 or 1, and

[0069] m' is an integer of 1 to 6.

[0070] If the compound (I) according to the invention contains more than one functional group (B), the functional groups (B) present in the compound (I) according to the invention may independently have different R 5 , X, Z', Y', n" and / or m'. However, the functional groups (B) present in compound (I) are preferably identical to each other.

[0071] R 5 Preferably it is H, resulting in compound (I) having acryloyl groups as free radical curable groups.

[0072] X is preferably O, resulting in compound (I) having a (meth)acryloyl ester group as a free radical curable group.

[0073] Preferably, R 5 is H, and X is O, resulting in compound (I) having an acryloyl ester group as a free radical curable group.

[0074] Z' is a polyalkoxy group or an ω-alkoxy polycaprolactone group. The polyalkoxy group preferably has 1 to 10 alkoxy repeating units, more preferably 3 to 6 alkoxy repeating units, and the alkoxy repeating units are preferably ethoxy, propoxy or butoxy repeating units. The ω-alkoxy polycaprolactone group preferably has 2 to 6 repeating units, more preferably 3 to 6 repeating units.

[0075] n" is 0 or 1.

[0076] m' is an integer from 1 to 6. In one embodiment, m' is 1. In this embodiment, the number of functional groups B is preferably 1 or 2 and the number of functional groups A is preferably 1 or 2; more preferably, the number of functional groups B is 2 and the number of functional groups A is 1. In another and more preferred embodiment, m' is 2 to 6. In this embodiment, the number of functional groups B is preferably 1 and the number of functional groups A is preferably 1 or 2, more preferably the number of functional groups A is 1.

[0077] Preferably, Y' is a collection of atoms covalently linked in a linear or branched configuration, the collection of atoms consisting of: i) carbon and hydrogen atoms, ii) carbon, hydrogen and oxygen atoms, or iii) carbon, hydrogen, oxygen and nitrogen atoms. Preferably, Y' consists of up to 100 atoms,

[0078] The functional group B is preferably introduced into the compound (I) according to the present invention by using as a starting material a compound B' having the following structural formula:

[0079]

[0080] Non-limiting examples of compounds B' that can be used in the present invention for chemical incorporation into the functional group B in compound (I) are hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, pentaerythritol tri(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, di(trimethylolpropane) tri(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents. equivalents, dipentaerythritol penta(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, glycerol diacrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, polycaprolactone (meth)acrylate, polypropylene glycol acrylate, aminoethanol Michael adducts of optionally alkoxylated trimethylolpropane tri(meth)acrylate, aminoethanol Michael adducts of glycerol propoxylated tri(meth)acrylate and aminoethanol Michael adducts of pentaerythritol tetra(meth)acrylate and mixtures thereof. Preferred compounds B' are hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and mixtures thereof as well as trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, dipentaerythritol penta(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, di(trimethylolpropane) tri(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, polycaprolactone (meth)acrylate, polypropylene glycol acrylate, optionally alkoxylated aminoethanol Michael adducts of trimethylolpropane tri(meth)acrylate, aminoethanol Michael adducts of glycerol propoxylated tri(meth)acrylate and aminoethanol Michael adducts of pentaerythritol tetra(meth)acrylate and mixtures thereof. Non-limiting examples of polypropylene glycol acrylates are Bisomer PPA6 (polypropylene glycol monoacrylate), CAS No. 50858-51-0, available from Geo specialty chemicals, such as Bisomer PPM5 polypropylene glycol (5) methacrylate, Bisomer PEA6 polyethylene glycol (6) acrylate, and Bisomer PEM6 polyethylene glycol (6) methacrylate. Non-limiting examples of polycaprolactone (meth)acrylates obtained by reacting hydroxyethyl acrylate HEA or hydroxyethyl methacrylate HEMA with caprolactone are available from Daicel, such as Placcel FM series (based on HEMA) and Placcel FA series (based on HEA).Another suitable example of polycaprolactone acrylate is Sartomer 495B, available from Arkema (reaction product of HEA and caprolactone (2-Oxepanone, homopolymer, 2-[(1-oxo-2-propen-1-yl)oxy]ethyl ester, Cas nr 110489-05-9)). 5 If R is methyl, an example of compound B' is the methacrylate variant of the above mentioned compound. 5 If is H, then examples of compound B' are acrylate modifications of the compounds mentioned above.

[0081] In the embodiment where m' is 1, compound B' is preferably hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and mixtures thereof. In the embodiment where m' is 2 to 6, compound B' is preferably trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, dipentaerythritol penta(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, di(trimethylolpropane) tri(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, polycaprolactone (meth)acrylate, polypropylene glycol acrylate, aminoethanol Michael adducts of trimethylolpropane tri(meth)acrylate, optionally alkoxylated, aminoethanol Michael adducts of glycerol propoxylated tri(meth)acrylate and aminoethanol Michael adducts of pentaerythritol tetra(meth)acrylate and mixtures thereof.

[0082] The compound (I) of the present invention preferably has the structural formula (A) p -W-(B) q, wherein functional groups A and B are as defined above, p and q are independently an integer of at least 1, p+q is an integer of 2 to 13 and W is preferably composed of a collection of atoms covalently linked in a straight or branched configuration, the collection of atoms consisting of: i) carbon and hydrogen atoms, ii) carbon, hydrogen and oxygen atoms, iii) carbon, hydrogen and nitrogen atoms, iv) carbon, hydrogen, oxygen and nitrogen atoms, or v) carbon, hydrogen and sulfur atoms. More preferably, W is a collection of atoms covalently linked in a straight or branched configuration, the collection of atoms consisting of: i) carbon and hydrogen atoms, ii) carbon, hydrogen and oxygen atoms, iii) carbon, hydrogen and nitrogen atoms, or iv) carbon, hydrogen, oxygen and nitrogen atoms, p is preferably 1 or 2. In one embodiment, in formula (B) m' is 1. In this embodiment, q is preferably 1 or 2 and p is preferably 1 or 2. More preferably, q is 1 and p is 2. In another and more preferred embodiment, in formula (B) m' is 2 to 6. In this embodiment, q is preferably 1 and p is preferably 1 or 2, more preferably p is 1.

[0083] Even more preferably, W is preferably composed of at least one functional group selected from the group consisting of an aliphatic hydrocarbon functional group (preferably containing 1 to 8 carbon atoms), an alicyclic hydrocarbon functional group (preferably containing 4 to 10 carbon atoms), an aromatic hydrocarbon functional group (preferably containing 6 to 12 carbon atoms), an isocyanurate functional group, an iminooxadiazinedione functional group, an ether functional group, an ester functional group, an amide functional group, a carbonate functional group, a carbamate functional group, a urea functional group, a biuret functional group, an allophanate functional group, a uretdione functional group and any combination thereof. Even more preferably, W is composed of at least one functional group selected from the group consisting of aliphatic hydrocarbon functional groups (preferably containing 1 to 8 carbon atoms), alicyclic hydrocarbon functional groups (preferably containing 4 to 10 carbon atoms), aromatic hydrocarbon functional groups (preferably containing 6 to 12 carbon atoms), isocyanurate functional groups, iminooxadiazinedione functional groups, ether functional groups, carbamate functional groups, urea functional groups, biuret functional groups and any combination thereof. W preferably contains isocyanurate functional groups, iminooxadiazinedione functional groups, biuret functional groups, allophanate functional groups or uretdione functional groups. More preferably, W contains isocyanurate functional groups or iminooxadiazinedione functional groups. For the sake of clarity, the compounds (I) of the present invention can be obtained from the reaction product of one or more suitable compounds A' and B' and a hybrid isocyanurate (such as, for example, HDI / IPDI isocyanurate), resulting in a compound having a linking group consisting of a series of the following consecutive functional groups: a linear C 6 H 12 (i.e., an aliphatic hydrocarbon functional group having 6 carbon atoms), an isocyanurate functional group (a cyclic C 3 N 3 O 3)as well as

[0084]

[0085] (ie, an alicyclic hydrocarbon functional group having 9 carbon atoms and an aliphatic hydrocarbon functional group having 1 carbon atom).

[0086] The aziridinyl group has the following structural formula:

[0087]

[0088] The isocyanurate functional group is defined as

[0089] The iminooxadiazinedione functional group is defined as

[0090] The allophanate functional group is defined as

[0091] The uretdione functional group is defined as

[0092] The biuret functional group is defined as

[0093] In a preferred embodiment of the present invention, W is composed of the following functional groups: at least one aliphatic hydrocarbon functional group and / or at least one alicyclic hydrocarbon functional group and optionally at least one aromatic hydrocarbon functional group and optionally isocyanurate functional group or imino oxadiazinedione functional group or allophanate functional group or uretdione functional group. Preferably, W is composed of the following functional groups: at least one aliphatic hydrocarbon functional group and / or at least one alicyclic hydrocarbon functional group and optionally at least one aromatic hydrocarbon functional group and optionally isocyanurate functional group or imino oxadiazinedione functional group. More preferably, W is composed of the following: at least one aliphatic hydrocarbon functional group and / or at least one alicyclic hydrocarbon functional group and isocyanurate functional group or imino oxadiazinedione functional group.

[0094] The group W is preferably introduced into the compound (I) according to the invention by using as starting material a compound W′ which is at least one polyisocyanate and / or at least one isocyanate-terminated polyurethane (urea).

[0095] The polyisocyanates preferably have aliphatic reactivity. The term "polyisocyanates with aliphatic reactivity" refers to compounds in which all isocyanate groups are directly bonded to aliphatic or cycloaliphatic hydrocarbon groups, regardless of whether aromatic hydrocarbon groups are also present. The polyisocyanates with aliphatic reactivity may be a mixture of polyisocyanates with aliphatic reactivity. Compounds based on polyisocyanates with aliphatic reactivity have a reduced tendency to yellow over time when compared to similar compounds but based on polyisocyanates with aromatic reactivity. The term "polyisocyanates 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, p-tetramethylxylene diisocyanate (p-TMXDI) and their meta-isomers, and also higher molecular weight variants such as, for example, their isocyanurates or iminooxadiazinediones or allophanates or uretdiones. More preferred polyisocyanates with aliphatic reactivity are 4,4′-dicyclohexylmethane diisocyanate H12MDI, m-TMXDI, isocyanurates of 1,6-hexamethylene diisocyanate or iminooxadiazinediones or allophanates or uretdiones and isocyanurates of 1,5-pentamethylene diisocyanate. Suitable iminooxadiazinedione trimers containing HDI are available from Covestro N3900. Suitable HDI-containing allophanates are available from Covestro XP2860. Suitable uretdione containing HDI is available from Covestro N3400. Suitable HDI-based isocyanurate trimers are available, for example, from Covestro ( N3600), Vencorex (TolonateTM HDT LV), Asahi Kasei (DuranateTM TPA-100), Evonik ( HT 2500 / LV) and Tosoh( HXR LV) was obtained.

[0096] The NCO / OH ratio of the isocyanate-terminated polyurethane (urea) is higher than 1 and preferably lower than 1.6, more preferably lower than 1.4, even more preferably lower than 1.2 and most preferably lower than 1.15 and is obtained by reacting at least one polyol with at least one polyisocyanate. Preferred polyisocyanates are as described above. The polyol is preferably selected from the group consisting of: polyether polyols, polythioether polyols, polyester polyols, polycarbonate polyols, polyacetal polyols, polyethylene polyols, polysiloxane polyols and any mixture thereof. More preferably, the polyol is selected from the group consisting of: polyether polyols and any mixture thereof. Preferred polyether polyols are polytetrahydrofuran, polyethylene oxide, polypropylene oxide or any mixture thereof.

[0097] The molecular weight of compound (I) according to the present invention is 600 to 5000 daltons. The molecular weight of compound (I) according to the present invention is preferably at most 3800 daltons, more preferably at most 3600 daltons, more preferably at most 3000 daltons, more preferably at most 1600 daltons. The molecular weight of compound (I) 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 compound (I) according to the present invention is determined using MALDI-TOF mass spectrometry as described in the following experimental section.

[0098] The total number of functional groups A and the number of functional groups B in compound (I) is 2 to 13. The total number of functional groups A and the number of functional groups B is preferably 3 to 10, more preferably 3 to 7, and even more preferably 3. In the embodiment in which the total number of functional groups A and the number of functional groups B is 3, structural formula (A) p -W-(B) q p and q in and m' in structural unit B are preferably according to the following terms:

[0099] (i) p is 1 and q is 2 and m' is 1, or

[0100] (ii) p is 1 and q is 1 and m' is 2, or

[0101] (iii) p is 2 and both q and m' are 1.

[0102] In this embodiment, the compound (I) has one functional group A and two (meth)acryloyl functional groups or the compound has two functional groups A and one (meth)acryloyl functional group.

[0103] The compound (I) according to the present invention is preferably obtained in a process comprising reacting compound A', compound B' and compound W' at a temperature in the range of 20°C to 110°C, more suitably 40°C to 95°C, even more suitably 60°C to 85°C at atmospheric pressure. The type and amount of compounds A', B' and W' are selected so as to obtain the desired amount of functional group A, the desired amount of functional group B and the desired amount of (meth)acryloyl functional group in the functional group B.

[0104] The compounds (I) according to the invention can also be obtained in a process comprising reacting compound A' with an isocyanate-terminated polyurethane having (meth)acryloyl functional groups.

[0105] The present invention further relates to a crosslinker composition comprising at least one compound (I) as defined above and generally further comprising at least one additional component, such as, for example, the remaining starting materials, by-products and / or solvents used to prepare the compound (I) according to the present invention. The crosslinker composition may contain only one compound (I) according to the present invention, but may also contain more than one compound (I) according to the present invention. For example, when a mixture of polyisocyanates is used as a starting material to prepare compound (I), a mixture of compounds (I) is obtained. After obtaining the compound (I) according to the present invention, the compound (I) according to the present invention may be separated, and the reaction product may be used without further purification, or the solvent used to prepare the compound (I) may be removed from the composition obtained in the preparation of the compound (I) according to the present invention. The amount of the compound (I) according to the present invention in the crosslinker composition is generally at least 10% by weight relative to the total amount of the crosslinker composition, generally often at least 15% by weight and most often at least 25% by weight. The amount of the compound (I) according to the present invention in the crosslinker composition is preferably at least 60% by weight relative to the total amount of the crosslinker composition, more preferably at least 80% by weight and most preferably at least 99% by weight. The molecular weight of compound (I) in the crosslinker composition ranges from 600 Daltons to 10000 Daltons. The preferred molecular weight is as described above and the molecular weight of compound (I) is determined using MALDI-TOF-MS as described in the experimental section below. MALDI-TOF-MS refers to matrix-assisted laser desorption ionization time-of-flight mass spectrometry.

[0106] The amount of aziridinyl group functional molecules present in the crosslinker composition according to the invention and having a molecular weight below 250 Daltons, more preferably below 350 Daltons, even more preferably below 450 Daltons, even more preferably below 550 Daltons and even more preferably below 580 Daltons is preferably below 5 wt.-%, more preferably below 2 wt.-%, more preferably below 1 wt.-%, more preferably below 0.5 wt.-% and most preferably below 0.1 wt.-%, relative to the total amount of the crosslinker composition, wherein the molecular weight is determined using LC-MS as described in the experimental part below.

[0107] The invention further relates to a composition which is curable by free radical polymerization and contains at least one aziridine-functional compound as adhesion promoter, which has reduced genotoxicity compared to trimethylolpropane tris(2-methyl-1-aziridine propionate). Aziridine-functional compounds show only weak positive induced genotoxicity, or even they do not show genotoxicity, i.e. they show genotoxicity levels comparable to the naturally occurring background. In addition, it was unexpectedly found that the composition according to the invention shows improved adhesion, while the amount of components (further referred to as migrateables) which have the possibility of migrating from the composition and in particular from the cured composition is not increased and preferably even reduced.

[0108] The present invention therefore further relates to a composition curable by free radical polymerization comprising:

[0109] at least one aziridinyl-functional compound (I) having a molecular weight of 600 to 10,000 daltons and having at least one functional group A and having no or at least one functional group B, wherein the functional groups A and B are as defined above,

[0110] Provided that the total number of functional groups A and the number of functional groups B in compound (I) is from 2 to 13, preferably from 3 to 10, more preferably from 3 to 7, even more preferably 3, and

[0111] At least one compound (II) comprising at least two free-radically copolymerizable ethylenically unsaturated groups.

[0112] In one embodiment of the present invention, the free radical polymerization curable composition comprises an aziridinyl-functional compound (I) having 3 to 6 functional groups A and no functional groups B. In this embodiment, the aziridinyl-functional compound (I) preferably has 3 functional groups A. The aziridinyl-functional compound (I) having 3 functional groups A can be obtained by reacting at least compound A' and compound W'.

[0113] The free radical polymerization curable composition preferably comprises

[0114] at least one compound (II) comprising at least two free-radically copolymerizable ethylenically unsaturated groups, and

[0115] At least one aziridine-functional compound (I) having a molecular weight of 600 to 10,000 Daltons and having at least one functional group A and having at least one functional group B, wherein functional group A and functional group B are as defined above, with the proviso that the total amount of the number of functional groups A and the number of functional groups B in compound (I) is 2 to 13. The total amount of the number of functional groups A and the number of functional groups B in compound (I) is preferably 3 to 10, more preferably the total amount of the number of functional groups A and the number of functional groups B in compound (I) is 3 to 7, even more preferably 3.

[0116] Compounds (II) comprising at least two free-radically copolymerizable ethylenically unsaturated groups preferably have an average number of at least two unsaturated monomeric (C═C) groups which, under the influence of radiation (optionally in combination with the presence of photoinitiators), can undergo crosslinking by free-radical copolymerization.

[0117] The composition of the present invention is preferably radiation curable. Radiation curable means that radiation is required to initiate crosslinking of the composition. Optionally, a photoinitiator (PI) can be added to the radiation curable composition of the present invention to assist radiation curing, especially when curing is performed by UV radiation. However, if curing is to be achieved by, for example, an electron beam (EB), PI may not be required. Preferably, the radiation curable composition of the present invention comprises a photoinitiator and UV-radiation is applied to obtain a cured coating. Therefore, the composition is preferably UV radiation curable. More preferably, the composition is 100% radiation curable (substantially free of water and volatile organic solvents, particularly solvents having an initial boiling point of less than or equal to 250° C. at a standard atmospheric pressure of 101.3 kPa). Most preferably, the composition is 100% UV radiation curable. A 100% radiation curable composition refers to a composition substantially free of water and volatile organic solvents, which preferably must be removed before complete curing is achieved. Substantially free of water and volatile organic solvents means that water and volatile organic solvents are not intentionally added to the composition, however, the presence of small amounts of water and / or volatile organic solvents cannot be excluded because small amounts of water and / or volatile organic solvents may be present in raw materials and additives added to the composition. As used herein, substantially free of water and volatile organic solvents (also referred to as the absence of a large amount of water and volatile organic solvents) means that the composition contains less than 5% by weight of water and volatile organic solvents, preferably less than 3% by weight of water and volatile organic solvents, and more preferably less than 1% by weight of water and volatile organic solvents, based on the weight of the solid content of the composition of the present invention. The present invention also relates to a 100% radiation curable composition comprising at least one compound (II) comprising at least two free-radically copolymerizable ethylenically unsaturated groups, wherein the composition comprises at least one aziridinyl-functional compound (I) as described above and wherein the composition contains less than 5% by weight of water and volatile organic solvents, preferably less than 3% by weight of water and volatile organic solvents, more preferably less than 1% by weight of water and volatile organic solvents, based on the weight of the solids content of the composition of the invention.

[0118] The free radical copolymerizable ethylenically unsaturated group of compound (II) is preferably a (meth)acryloyl ester group, a (meth)acrylamide group and any combination thereof. More preferably, the free radical copolymerizable ethylenically unsaturated group of compound (II) is a (meth)acryloyl ester group. Even more preferably, the free radical copolymerizable ethylenically unsaturated group of compound (II) is an acryloyl ester group.

[0119] The one or more compounds (II) in which the free radical copolymerizable ethylenically unsaturated groups are (meth)acryloyl ester groups may comprise at least one (meth)acrylated oligomer. (Meth)acrylate oligomers are usually composed of only a few monomer units, such as dimers, trimers, tetramers, etc. It is also possible to use one or more (meth)acrylate polymers.

[0120] Examples of suitable compounds (II) wherein the free radical copolymerizable ethylenically unsaturated groups are (meth)acryloyl ester groups include those selected from the group consisting of polyester (meth)acrylates, polyether (meth)acrylates, epoxy (meth)acrylates, amino (meth)acrylates, polycarbonate (meth)acrylates, (poly)urethane (meth)acrylates, (meth)acrylated (meth)acrylic acids or mixtures thereof. Preferred are polyester (meth)acrylates, polyether (meth)acrylates and / or epoxy (meth)acrylates. Most preferred are urethane (meth)acrylates, polyester (meth)acrylates and / or epoxy (meth)acrylates. "(Meth)acrylates" is intended to mean acrylates, methacrylates or mixtures thereof. Acrylates are generally preferred because they have higher UV reactivity.

[0121] Polyester (meth)acrylate oligomers are well known. These (meth)acrylated polyesters can be obtained by reacting a hydroxyl-containing polyester backbone with (meth)acrylic acid or by reacting a carboxyl-containing polyester backbone with a hydroxyalkyl (meth)acrylate (such as, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate or 3-hydroxypropyl acrylate, etc.) or a glycidyl (meth)acrylate. The polyester backbone can be obtained in a conventional manner by polycondensation of at least one polyhydroxy alcohol (such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexylene glycol, trimethylolpropane, bisphenol A, pentaerythritol, etc. and ethoxylates and / or propoxylates thereof) with at least one polycarboxylic acid or anhydride thereof (such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, etc.). Polyesters carrying (meth)acrylic acid and ethylenically unsaturated substances in the polymer chain can be obtained by using unsaturated monomer compounds for polyester synthesis, such as, for example, fumaric acid, maleic acid, itaconic acid, etc. In addition, polylactones and / or polylactides can be used as the polyester backbone. For example, poly(ε-caprolactone), polylactide and / or poly(lactide, caprolactone) can be obtained by ring-opening polymerization of ε-caprolactone and / or lactide, optionally in the presence of one or more polyhydroxy alcohols. Examples of suitable polyester (meth)acrylates include AgiSyn, available from DSM. TM 705. AgiSyn TM 707AgiSyn TM 716、AgiSynTM 720、AgiSyn TM 730、AgiSyn TM 740、NeoRad TM P-11, NeoRad TM P50, NeoRad TM P-56.

[0122] Polyether (meth) acrylate oligomers can be prepared by esterifying hydroxyl functional polyethers with (meth) acrylic acid. Hydroxy functional polyethers can be obtained by ring opening homopolymerization or copolymerization of cyclic ethers such as tetrahydrofuran, ethylene oxide and / or propylene oxide, or can be prepared by reacting polyhydric alcohols with ethylene oxide and / or propylene oxide.

[0123] Polycarbonate (meth)acrylate oligomers are also well known. They can be prepared by esterifying hydroxy-functional polycarbonates with (meth)acrylic acid.

[0124] (Poly)urethane (meth)acrylate oligomers can be prepared by reacting diisocyanates and / or polyisocyanates (such as hexamethylene-diisocyanate, isophorone-diisocyanate, toluene-diisocyanate) with hydroxyl-functional (meth)acrylates. Hydroxy-functional (meth)acrylates alone can be used, such as those mentioned above, but for chain extension, mono- or polyhydric alcohols such as those mentioned above for the synthesis of hydroxyl-containing polyesters, polyethers or polycarbonates can also be added. Examples of suitable urethane (meth)acrylates include AgiSyn, all available from DSM, TM 230T1, AgiSyn TM 230A2, AgiSyn TM 230S1-B85, NeoRad TM U-10-15T, NeoRad TM U-20-12H, NeoRad TM Examples of suitable aromatic urethane (meth)acrylates: AgiSyn TM 670T1, NeoRad TM U60, NeoRad TM U-61, all obtained from DSM.

[0125] Epoxy (meth) acrylate oligomers are intended to mean (meth) acrylates of epoxides, preferably polyepoxides, i.e. compounds containing at least one, preferably at least two, epoxide functional groups. Epoxy (meth) acrylate oligomers are usually obtained by the esterification of (meth) acrylic acid with epoxides. Epoxides are usually selected from epoxidized olefins, glycidyl esters of saturated or unsaturated carboxylic acids, glycidyl ethers of aromatic or aliphatic alcohols or polyols, and alicyclic polyepoxides. Preferred epoxides are diglycidyl ethers of aromatic and aliphatic diols and alicyclic diepoxides, such as diglycidyl ethers of bisphenol-A, diglycidyl ethers of bisphenol-F, diglycidyl ethers of poly(ethylene oxide-co-propylene oxide), diglycidyl ethers of polypropylene oxide, diglycidyl ethers of hexanediol, diglycidyl ethers of butanediol. Particularly preferred are diglycidyl ethers of bisphenol-A. Epoxidized natural oils or epoxidized phenol-formaldehyde copolymers can also be used. Examples of natural oils include soybean oil, linseed oil, perilla oil, fish oil, dehydrated castor oil, tung oil, coconut oil, corn oil, cottonseed oil, olive oil, palm oil, palm kernel oil, peanut oil, sunflower oil, safflower oil, castor oil. Examples of suitable epoxy (meth) acrylates include AgiSyn, all available from DSM. TM 1010、AgiSyn TM 1030、AgiSyn TM 1050、AgiSyn TM 2020, AgiSyn TM 3050、AgiSyn TM 3051.

[0126] (Meth)acrylated (meth)acrylic oligomers can be obtained by first preparing a (meth)acrylic copolymer by copolymerizing a (meth)acrylate monomer such as butyl acrylate with a monomer containing a pendant carboxylic acid, anhydride, hydroxyl, glycidyl or isocyanate group and then reacting this copolymer with a monomer containing at least one (meth)acrylate functional group and at least one carboxylic acid, anhydride, hydroxyl, glycidyl or isocyanate reactive group. For example, a glycidyl-containing copolymer can be prepared by first copolymerizing a functionalized monomer such as glycidyl (meth)acrylate with other (meth)acrylate monomers, which polymer containing glycidyl groups is typically reacted with (meth)acrylic acid in a second step. When the functionalized monomer is (meth)acrylic acid, the carboxyl-containing polymer is typically reacted with glycidyl (meth)acrylate in a second step. Examples of suitable (meth)acrylated (meth)acrylic acids are AgiSyn, all available from DSM. TM 9790、NeoRad TM A-20.

[0127] Amino (meth) acrylates may also be added to the composition of the invention. Amino (meth) acrylates may be obtained by addition reaction of (meth) acrylates with amines. Examples of suitable amino (meth) acrylates include AgiSyn, all available from DSM. TM 701、AgiSyn TM 701P、AgiSyn TM 703. AgiSyn TM 002. AgiSyn TM 003. NeoRad TM P-85.

[0128] The compound (II) wherein the free-radically copolymerizable ethylenically unsaturated group is a (meth)acryloyl ester group is generally a poly(meth)acrylate containing 2 to 10 (meth)acryloyl groups per mol. "(Meth)acryloyl group" means an acryloyl group, a methacryloyl group or a mixture of the two. Acryloyl groups are preferred herein.

[0129] Compounds (II) in which the free-radically copolymerizable ethylenically unsaturated groups are (meth)acryloyl ester groups typically comprise 2 to 6 and most typically 2 to 4 (meth)acryloyl ester groups. Acryloyl ester groups are preferred in this context.

[0130] Preferably, the number average molecular weight (Mn) of compound (II) is at least 300 daltons and more preferably at least 500 daltons. Typically, their Mn is at least 1000 daltons. Typically, the Mn of compound (II) is at most 20000 daltons, preferably at most 10000 daltons, more preferably at most 9000 daltons and even more preferably at most 8000 daltons. The number average molecular weight is determined herein by MALDI-ToF-MS.

[0131] The one or more compounds (II) may also include at least one reactive monomer or diluent as is known in the art. Typically, the one or more compounds (II) include at least one (trimethylolpropane) acrylated oligomer and at least one (meth) acrylated monomer. In an embodiment, the (meth) acrylated monomer may be a monofunctional, difunctional or trifunctional, tetrafunctional, pentafunctional or hexafunctional (meth) acrylate monomer. Representative examples of such monomers include, but are not limited to, (meth)acrylic acid, ethylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, isosorbide di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate and di(meth)acrylates, alkyl (such as isobornyl, isodecyl, isobutyl, n-butyl, tert-butyl, methyl, ethyl, tetrahydrofurfuryl, cyclohexyl, n-hexyl, iso-octyl, 2-ethylhexyl, n-dodecyl, octyl or decyl) or hydroxyalkyl (such as 2-hydroxyethyl and hydroxypropyl) esters of acrylic or methacrylic acid, phenoxyethyl (meth)acrylate, nonylphenol ethoxylate mono(meth)acrylate, 2-(-2-ethoxyethoxy)ethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, butanediol di(meth)acrylate and tri(meth)acrylate, tripropylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylates, 1,6-hexanediol di(meth)acrylate, ethoxylated and / or propoxylated hexanediol di(meth)acrylates, tricyclodecane di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dipentaerythritol hexaacrylate (DPHA), propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated and / or propoxylated neopentyl glycol di(meth)acrylate, hexamethylene glycol di(meth)acrylate, 4,4′-bis(2-acryloyloxyethoxy)diphenylpropane, di-trimethylolpropane tetra(meth)acrylate and ethoxylated or / and propoxylated derivatives thereof, phenyl glycidyl ether (meth)acrylate, (meth)acrylates obtained by (meth)acrylic acid esterification with aliphatic glycidyl ethers, glycerol triacrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents and any mixtures thereof and any combinations thereof.

[0132] In a preferred embodiment, the one or more compounds (II) further comprise at least one reactive monomer or diluent, preferably selected from the group consisting of trimethylolpropane tri(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, di-trimethylolpropane tetra(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, glycerol tri(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, and any mixtures thereof. In another preferred embodiment, the one or more compounds (II) are preferably selected from the group consisting of trimethylolpropane tri(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, di-trimethylolpropane tetra(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, glycerol tri(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, and any mixtures thereof.

[0133] The free-radically copolymerizable ethylenically unsaturated groups of compound (II) are preferably acryloyl ester groups and compound (I) present in the composition of the invention preferably contains acryloyl ester groups.

[0134] The amount of compound (I) in the composition of the present invention is preferably at least 2% by weight, more preferably at least 5% by weight, relative to the total amount of the composition. The amount of compound (I) in the composition of the present invention is preferably at most 40% by weight, more preferably at most 30% by weight, even more preferably at most 20% by weight, relative to the total amount of the composition. The amount of compound (II) in the composition of the present invention is at least 60% by weight, preferably at least 70% by weight, more preferably at least 80% by weight, and at most 90% by weight, preferably at most 95% by weight and more preferably at most 98% by weight, relative to the total amount of the composition.

[0135] The compound (I) has an aziridinyl group having the following structural formula

[0136] The molar ratio to the ethylenically unsaturated bonds is preferably in the range of 1:5 to 1:1, more preferably 1:3 to 1:1.

[0137] The ethylenically unsaturated bond concentration of the curable composition preferably ranges from 0.5 to 6 milliequivalents / gram of curable composition.As used herein, the amount of C=C bonds present in the composition is determined by adding the radiation curable C=C functional groups from the components used to prepare the composition.

[0138] The composition of the present invention is preferably used for coating substrates or for printing patterns on substrates. The present invention therefore further relates to a coating composition or to an ink composition comprising a radiation curable composition as described above. The substrate to which the composition is applied preferably contains wood, paper, metal, plastic, textile, leather, glass, concrete, packaging film or any combination thereof. More preferably, the substrate is selected from the group consisting of: wood, metal, plastic, tarpaulin, concrete, glass and any combination thereof. Even more preferably, the substrate is a flexible plastic, preferably biaxially oriented polypropylene, polyethylene and polyethylene terephthalate. The substrate to which the composition is applied can advantageously be used for food packaging.

[0139] Preferably, the composition of the present invention is applied to an ink composition, which is preferably a UV inkjet ink composition, an offset ink composition or a flexographic ink composition.

[0140] 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.

[0141] [1] A compound (I) comprising at least one functional group A and at least one functional group B, wherein:

[0142] The functional group A has a structural formula A:

[0143]

[0144] in

[0145] R 1 For H,

[0146] R 2 , R 3 and R 4 independently selected from H, methyl or ethyl,

[0147] m is 1 to 6,

[0148] R' and R" are based on (1) or (2):

[0149] (1) R′=H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, and

[0150] R"=H, an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, an alicyclic hydrocarbon group containing 5 to 12 carbon atoms, an aromatic hydrocarbon group containing 6 to 12 carbon atoms, CH 2 -O-(C=O)-R"', CH 2 -OR”” or CH 2-(OCR””'HCR””'H) n -OR""", wherein R"' is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms and R"" is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms or an aromatic hydrocarbon group containing 6 to 12 carbon atoms, n is 1 to 35, R""' is independently H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms and R""" is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms,

[0151] (2) R' and R" together form a saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms; and

[0152] The functional group B has the structural formula B:

[0153]

[0154] R 5 is H or methyl,

[0155] X is O or NH,

[0156] Z' is a polyalkoxy group or an ω-alkoxy polycaprolactone group,

[0157] Y' is a collection of atoms covalently linked in a linear or branched configuration consisting of: i) carbon and hydrogen atoms, ii) carbon, hydrogen, and oxygen atoms, iii) carbon, hydrogen, and nitrogen atoms, or iv) carbon, hydrogen, oxygen, and nitrogen atoms,

[0158] n" is 0 or 1, and

[0159] m' is an integer from 1 to 6;

[0160] Provided that the total number of functional groups A and the number of functional groups B in compound (I) is from 2 to 13; and

[0161] The molecular weight of the compounds ranges from 600 Daltons to 10,000 Daltons.

[0162] [2] The compound according to embodiment [1], wherein R 2 For H, R 3 C 2 H 5 And R 4 For H.

[0163] [3] The compound according to embodiment [1], characterized in that R 2 For H, R 3 CH 3 And R 4 For H.

[0164] [4] The compound according to embodiment [1], wherein R2 For H, R 3 CH 3 And R 4 CH 3 .

[0165] [5] The compound according to any one of embodiments [1] to [4], wherein m is 1.

[0166] [6] The compound according to any one of embodiments [1] to [5], wherein

[0167] R' and R" are based on (1) or (2):

[0168] (1) R′=H or an alkyl group containing 1 to 2 carbon atoms;

[0169] R"=H, an aliphatic hydrocarbon group containing 1 to 4 carbon atoms, CH2-O-(C=O)-R"', CH2-OR"" or CH2-(OCR""'HCR""'H)n-OR""", wherein R"' is an alkyl group containing 1 to 14 carbon atoms and R"" is an alkyl group containing 1 to 14 carbon atoms, n is 1 to 35, R""' is independently H or a methyl group and R""" is an alkyl group containing 1 to 4 carbon atoms;

[0170] (2) R' and R" together form a saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms,

[0171] [7] The compound according to any one of embodiments [1] to [6], wherein

[0172] R' is H and R" = alkyl containing 1 to 4 carbon atoms, more preferably R" is methyl.

[0173] [8] A compound according to any one of embodiments [1] to [7], wherein R 5 For H.

[0174] [9] The compound according to any one of embodiments [1] to [8], wherein X is O.

[0175]

[10] A compound according to any one of embodiments [1] to [9], wherein Z' is a polyalkoxy group having 1 to 10 alkoxy repeating units, more preferably 3 to 6 alkoxy repeating units, and the alkoxy repeating units are preferably ethoxy, propoxy or butoxy repeating units.

[0176]

[11] The compound according to any one of embodiments [1] to

[10] , wherein Z′ is an ω-alkoxy polycaprolactone group preferably having 2 to 6 repeating units, preferably 3 to 6 repeating units.

[0177]

[12] A compound according to any one of embodiments [1] to

[11] , wherein the compound has structural formula (A) p -W-(B) q , wherein p and q are independently an integer of at least 1, p+q is an integer from 2 to 13 and W consists of a collection of atoms covalently linked in a linear or branched configuration consisting of: i) carbon and hydrogen atoms, ii) carbon, hydrogen, and oxygen atoms, iii) carbon, hydrogen, and nitrogen atoms, iv) carbon, hydrogen, oxygen, and nitrogen atoms, or v) carbon, hydrogen, and sulfur atoms.

[0178]

[13] A compound according to any one of embodiments [1] to

[11] , wherein the compound has structural formula (A) p -W-(B) q , p and q are independently an integer of at least 1, p+q is an integer from 2 to 13 and W consists of a collection of atoms covalently linked in a linear or branched configuration consisting of: i) carbon and hydrogen atoms, ii) carbon, hydrogen, and oxygen atoms, iii) carbon, hydrogen, and nitrogen atoms, or iv) carbon, hydrogen, oxygen, and nitrogen atoms.

[0179]

[14] The compound according to embodiment

[11] or

[12] , wherein m′ in structural formula (B) is 1, q is 1 or 2, and p is 1 or 2.

[0180]

[15] The compound according to embodiment

[11] or

[12] , wherein m′ in structural formula (B) is 1, q is 1, and p is 2.

[0181]

[16] The compound according to embodiment

[11] or

[12] , wherein m' in formula (B) is 2 to 6, q is 1, and p is 1 or 2, preferably p is 1.

[0182]

[17] A compound according to any one of embodiments

[11] to

[16] , wherein W is composed of at least one functional group selected from the group consisting of an aliphatic hydrocarbon functional group (preferably containing 1 to 8 carbon atoms), an alicyclic hydrocarbon functional group (preferably containing 4 to 10 carbon atoms), an aromatic hydrocarbon functional group (preferably containing 6 to 12 carbon atoms), an isocyanurate functional group, an iminooxadiazinedione functional group, an ether functional group, an ester functional group, an amide functional group, a carbonate functional group, a carbamate functional group, a urea functional group, a biuret functional group, an allophanate functional group, a uretdione functional group, and any combination thereof.

[0183]

[18] A compound according to any one of embodiments

[11] to

[16] , wherein W is composed of at least one functional group selected from the group consisting of: an aliphatic hydrocarbon functional group (preferably containing 1 to 8 carbon atoms), an alicyclic hydrocarbon functional group (preferably containing 4 to 10 carbon atoms), an aromatic hydrocarbon functional group (preferably containing 6 to 12 carbon atoms), an isocyanurate functional group, an iminooxadiazinedione functional group, an ether functional group, a carbamate functional group, a urea functional group, a biuret functional group, and any combination thereof.

[0184]

[19] A compound according to any one of embodiments

[11] to

[16] , wherein W consists of: at least one aliphatic hydrocarbon functional group and / or at least one alicyclic hydrocarbon functional group and optionally at least one aromatic hydrocarbon functional group and optionally an isocyanurate functional group or an iminooxadiazinedione functional group.

[0185]

[20] A compound according to any one of embodiments

[11] to

[16] , wherein W contains an isocyanurate functional group or an iminooxadiazinedione functional group.

[0186]

[21] A compound according to any one of embodiments

[11] to

[16] , wherein W consists of: at least one aliphatic hydrocarbon functional group and / or at least one alicyclic hydrocarbon functional group and an isocyanurate functional group or an iminooxadiazinedione functional group.

[0187]

[22] A compound according to any one of embodiments

[11] to

[21] , wherein W introduced into compound (I) by using compound W' as a raw material is at least one polyisocyanate and / or at least one isocyanate-terminated polyurethane.

[0188]

[23] Compounds according to embodiment

[22] , wherein the polyisocyanate has aliphatic reactivity and is preferably 1,5-pentamethylene diisocyanate PDI, 1,6-hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, 4,4′-dicyclohexylmethane diisocyanate H12MDI, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, p-tetramethylxylene diisocyanate (p-TMXDI) and their meta-isomers, and / or higher molecular weight variants such as, for example, their isocyanurates or iminooxadiazinediones or allophanates or uretdione.

[0189]

[24] A compound according to embodiment

[22] , wherein the polyisocyanate has aliphatic reactivity and is preferably 4,4′-dicyclohexylmethane diisocyanate H12MDI, m-TMXDI, isocyanurate of 1,6-hexamethylene diisocyanate or iminooxadiazinedione or allophanate or uretdione and / or isocyanurate of 1,5-pentamethylene diisocyanate.

[0190]

[25] A compound according to any one of embodiments [1] to

[24] , wherein the molecular weight ranges from 600 Daltons to 5000 Daltons, preferably at least 700 Daltons, more preferably the molecular weight is at least 800 Daltons and preferably at most 3800 Daltons, more preferably at most 3600 Daltons, more preferably at most 3000 Daltons, more preferably at most 1600 Daltons.

[0191]

[26] Use of a compound according to any one of embodiments [1] to

[25] as an adhesion promoter or reactive diluent in a free radical curable composition, preferably a 100% UV radiation curable composition.

[0192]

[27] A 100% radiation curable composition comprising

[0193] at least one aziridinyl-functional compound (I) according to any one of embodiments [1] to

[25] , and

[0194] At least one compound (II) comprising at least two free-radically copolymerizable ethylenically unsaturated groups.

[0195]

[28] According to the composition of embodiment

[27] , the total number of functional groups A and the number of functional groups B in compound (I) is preferably 3 to 10, more preferably the total number of functional groups A and the number of functional groups B in compound (I) is 3 to 7, and even more preferably 3.

[0196]

[29] The composition according to embodiment

[27] or

[28] , wherein the free radical copolymerizable ethylenically unsaturated group of compound (I) is a (meth)acryloyl ester group, a (meth)acrylamide group, and any combination thereof.

[0197]

[30] The composition according to any one of embodiments

[27] to

[29] , wherein the free radical copolymerizable ethylenically unsaturated group of compound (I) is a (meth)acryloyl ester group.

[0198]

[31] A composition according to any one of embodiments

[27] to

[30] , wherein compound (II) comprises at least one urethane (meth)acrylate, at least one polyester (meth)acrylate, at least one epoxy (meth)acrylate, at least one (meth)acrylated monomer, or any mixture thereof.

[0199]

[32] A composition according to any one of embodiments

[27] to

[31] , wherein compound (II) comprises a (meth)acrylated monomer selected from the group consisting of trimethylolpropane tri(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, di-trimethylolpropane tetra(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, glycerol tri(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, and any mixture thereof.

[0200]

[33] A composition according to any one of embodiments

[27] to

[31] , wherein compound (II) is a (meth)acrylated monomer selected from the group consisting of trimethylolpropane tri(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, di-trimethylolpropane tetra(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, glycerol tri(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, and any mixture thereof.

[0201]

[34] A composition according to any one of embodiments

[27] to

[33] , wherein the amount of compound (I) is at least 2 wt%, preferably at least 5 wt% and at most 40 wt%, preferably at most 30 wt%, more preferably at most 20 wt%, relative to the total amount of the composition.

[0202]

[35] A composition according to any one of embodiments

[27] to

[34] , wherein the amount of compound (II) is at least 60 wt %, preferably at least 70 wt %, more preferably at least 80 wt % and at most 90 wt %, preferably at most 95 wt % and more preferably at most 98 wt % relative to the total amount of the composition.

[0203]

[36] A composition according to any one of embodiments

[27] to

[35] , wherein the aziridinyl group in compound (I) has the following structural formula

[0204] The molar ratio to ethylenically unsaturated bonds ranges from 1:5 to 1:1, more preferably from 1:3 to 1:1.

[0205]

[37] A composition according to any one of embodiments

[27] to

[36] , wherein the ethylenically unsaturated bond concentration of the curable composition ranges from 0.5 to 6 milliequivalents / g of curable composition.

[0206]

[38] The composition according to any one of embodiments

[27] to

[37] , wherein the composition is UV curable.

[0207]

[39] A composition according to embodiment

[38] , wherein the composition comprises a photoinitiator.

[0208] 40. An ink composition comprising the composition according to any one of embodiments

[39] to

[36] .

[0209]

[41] A substrate having a coating obtained by (i) applying the composition according to any one of embodiments

[27] to

[39] to a substrate and (ii) curing the composition.

[0210]

[42] A substrate according to embodiment

[41] , wherein the substrate is a flexible plastic, preferably biaxially oriented polypropylene, polyethylene and polyethylene terephthalate.

[0211]

[43] A food package comprising the substrate according to embodiment

[42] .

[0212] The invention will now be illustrated by reference to the following examples. Unless otherwise indicated, all parts, percentages and ratios are by weight.

[0213] pH Measurement

[0214] The pH of the samples was determined based on ISO 976:2013 standard. The samples were measured at 23°C 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 before use.

[0215] NCO determination

[0216] The NCO content of the sample is determined based on the ASTM D2572-19 standard. In the procedure, the sample is reacted with an excess of di-n-butylamine. The excess di-n-butylamine is then back-titrated with standard 1N hydrochloric acid (HCl). The difference in titration volume between the sample and the blank is a measure of the isocyanate content on the solid according to the following equation: % NCO 固体 =[(Vb–Vm)*N*4.2] / (A*s / 100), where %NCO 固体is the isocyanate content on the solid, Vb is the volume of HCl used for the blank, Vm is the volume of HCl used for the sample, N is the normality of the HCl solution, A is the sample weight in grams and s is the solid content of the sample in %. The measurements were performed in duplicate using a potentiometric endpoint on a Metrohm 702SM Titrino titrator (if the difference between the two replicates was < 0.1% NCO , the measured value is accepted).

[0217] AV determination

[0218] The solid matter acid value (AV) of the sample is determined based on the ASTM D1639-90 (1996) e1 standard. In the procedure, a sample dissolved in a good solvent is titrated with a known concentration of potassium hydroxide alcohol solution (KOH). The difference in titration volume between the sample and the blank is a measure of the solid acid value obtained according to the following equation: AV = [(V blank - V sample) * N KOH *56.1] / (W*S / 100), where AV is the solid acid value in mg KOH / g solid matter, Vblank is the volume of KOH solution used for blank, Vsample is the volume of KOH solution used for sample, and N KOH is the normality of the KOH solution, W is the sample weight in grams and S is the solid content of the sample in %. The measurements were performed in duplicate on a Metrohm 702SM Titrino titrator using a potentiometric endpoint (the measurement was accepted if the difference between the two replicates was <0.1 mg KOH / g solid matter).

[0219] Low molecular weight fraction by LC-MS

[0220] LC system: Agilent 1290 Infinity II; Detector #1: Agilent 1290 Infinity II PDA; Detector #2: Agilent iFunnel 6550Q-TOF-MS.

[0221] LC-MS analysis of the low molecular weight fraction was performed using the following procedure: A solution of approximately 100 mg / kg of the material in methanol was prepared gravimetrically and stirred. 0.5 μl of this solution was injected into a UPLC equipped with ESI-TOF-MS detection. The column used was a 100x2.1 mm, 1.8 um, Waters HSS T3 C18 running at 40°C. The flow rate was 0.5 ml.min -1 The solvent used was NH 3 10 mM NH in water set to pH 9.0 4 CH 3COO (eluent A), acetonitrile (B) and THF (C). Two binary gradients from 80 / 20A / B to 1 / 99A / B in 10 minutes and from 1 / 99A / B to 1 / 49 / 50A / B / C in 5 minutes were applied, followed by the starting condition (80 / 20A / B). Assuming that all components have linear MS responses in all response ranges and that the ionization efficiency of all components is equal, the total ion current signal is integrated. In the case of co-elution, the extracted ion chromatogram of the specific species is integrated. The integrated signal of the specific low molecular weight peak is divided by the total integrated sample signal to produce the score of the low molecular weight substance.

[0222] MALDI-ToF-MS

[0223] 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.

[0224] Sodium iodide was used as salt (NaI, CAS No. 7681-82-5); 10 mg was dissolved in 1 ml THF, to which a drop of MeOH was added. The ratio of sample: matrix: salt = 10:200:10 (μl), after mixing, 0.5 μl was spotted onto a MALDI plate and air-dried. The peak measured in the MALDI spectrum is the sodium adduct of the aziridine-functional compound (I), and in the context of this specification, the molecular weight (MW) of the aziridine-functional compound (I) 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, M of sodium 阳离子= 23.0 Da). Aziridinyl-functional compounds (I) can be identified by comparing the MW to the exact molecular mass of the theoretical structure (ie the sum of the non-isotopic average atomic masses of its constituent atoms) using a maximum deviation of 0.6 Da.

[0225] Genotoxicity testing

[0226] pass The ToxTracker assay (Toxys, Leiden, the Netherlands) assesses genotoxicity. 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 bioactivity and potential carcinogenic properties of newly developed compounds in a single test. The method uses a two-step approach.

[0227] 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.

[0228] Next, genotoxicity was assessed 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 assessed at 10%, 25% and 50% cytotoxicity in the absence and presence of a metabolic system based on rat S9 liver extract (aroclor1254-induced rats, Moltox, Boone, NC, USA). Independent cell lines were 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 dilutions. The highest sample concentration will induce significant cytotoxicity (50-70%). In the absence or low cytotoxicity, 10mM or the maximum soluble mixture concentration was used as the maximum test concentration. Cytotoxicity was determined by counting cells using a GuavaeasyCyte 10HT flow cytometer (Millipore) after 24 h of exposure.

[0229] 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 exposure for 24 hours, 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.

[0230] 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.

[0231]

[0232] Table 1 lists the substrates tested.

[0233] Table 1: Overview of tested flexible plastic substrates

[0234]

[0235] In the case of corona treatment, the total amount of energy applied was 0.35 kW.The surface tension of the foil was measured using an Arcotest BLUE surface tensiometer.

[0236] Ink Application

[0237] The ink was repeatedly printed on the (treated) foil using an IGT C1-5 test press, a rubber pad and a 300 N printing force. The target for printing the foil was a coating weight of 1.0 and 1.6 g / m 2 and a color density between 1.3 and 1.6, as measured using an X-Rite DensiEye 700.

[0238] Curing conditions

[0239] The printed ink was cured by UV dryer, medium pressure Hg lamp, 5 passes. The total UV curing energy, dose and intensity were measured using an EIT UV Power Puck II with 4 UV light sensitive units (Table 2).

[0240] Table 2: The intensity of the UV light used

[0241]

[0242]

[0243] Ink Adhesion Test:

[0244] Ink adhesion was tested by applying 5 cm long strips of 3M Scotch 600 tape (4.4 N / cm adhesion to steel) and TESA 4124 tape (3.2 N / cm adhesion to steel) to the flexible plastic substrate while being thoroughly manually compressed into place to avoid any air bubbles. The adhesive tape was then removed in an oscillating backward motion at an angle of approximately 60°. Adhesion was determined in %, which represents the amount of ink still present on the substrate after the tape was removed.

[0245] Examples and Comparative Examples

[0246] Compounds are named according to the chemical structure based on the molar ratio between the acrylate bond and the aziridine group. As an example, mono-Az-di-Ac represents a compound having one aziridine (Az) group and two acrylate (Ac) groups. Agisyn 2836 is ethoxylated (3) trimethylolpropane triacrylate (CAS Nr. 28961-43-5), and Agisyn 2837 is propoxylated (3) glycerol triacrylate (CAS Nr. 52408-84-1). Agisyn 230A2 is an aliphatic urethane acrylic oligomer available from DSM. Agisyn 2816 is 1,6-hexanediol diacrylate (CAS Nr. 13048-33-4). Agisyn 2824 is propoxylated pentaerythritol triacrylate (CAS Nr. 145611-81-0). Agisyn 2858 is ethoxylated (9) trimethylolpropane triacrylate (CAS No. 28961-43-5). N3600 was obtained from Covestro. n-Butyl glycidyl ether (CAS No. 2426-08-6) and potassium carbonate (CAS No. 584-08-7) were obtained from AlfaAesar (a division of Thermo Fisher Scientific). 2-Methylaziridine (propylene imine, PI, CAS No. 75-55-8) was obtained from Menadiona SL (Palafolls, Spain). Butylated hydroxytoluene (CAS No. 128-37-0) and phenothiazine (CAS No. 92-84-2) were obtained from Sigma-Aldrich. The synthesis of 1-(2-methyl-aziridine-1-yl)propan-2-ol is described in S. Lesniak, M. Rachwalski, S. Jarzynski, E. Obijalska Tetrahedron Asymm. 2013, 241336-1340.

[0247] Synthesis of Aziridine-Functional UV Curable Compounds (I)

[0248] A reaction product having a main component of mono-Az-di-Ac (this reaction product is further referred to as mono-Az-di-Ac (I)) was prepared by placing 1-(2-methyl-aziridin-1-yl)-propan-2-ol (30.9 g), 2-hydroxyethyl acrylate (62.2 g), butylated hydroxytoluene (0.4 g), phenothiazine (0.04 g) and a reactive diluent (propoxylated glycerol triacrylate, GTPA, 98 g) in a flask and heating the mixture to 50° C. under gentle stirring. In a dropping funnel, GTPA (98 g) and N3600 (160 g) was added to the mixture. Next, bismuth neodecanoate (0.02 g) was added to the reaction mixture and the mixture was added in a dropping funnel over 40 minutes. Next, GTPA (20 g) was added to the reaction mixture and the temperature was raised to 70°C. The progress of the reaction was monitored by IR to determine the disappearance of the NCO group.

[0249] The calculated molecular weight of the theoretical main component was confirmed using MALDI-ToF-MS and is shown below:

[0250]

[0251] Calculated value [M+Na+] = 874.45 Da; observed value [M+Na+] = 874.32 Da.

[0252] Genotoxicity test results:

[0253]

[0254] The results of the genotoxicity test showed that the reaction product obtained above was non-genotoxic.

[0255] Synthesis of Aziridine-Functional UV Curable Compounds (II)

[0256] According to the same procedure, a reaction product having a main component of di-Az-mono-Ac (this reaction product is further referred to as di-Az-mono-Ac (II)) was prepared using adjusted amounts of 1-(2-methyl-aziridin-1-yl)-propan-2-ol and 2-hydroxyethyl acrylate.

[0257] The calculated molecular weight of the theoretical main component was confirmed using MALDI-TOF-MS and is shown below:

[0258]

[0259] Calculated value [M+Na+] = 873.51 Da; observed value [M+Na+] = 873.33 Da.

[0260] Synthesis of Tri-Ac Compound (III)

[0261] According to the same procedure, only use Compound tri-Ac was prepared using N3600 and 2-hydroxyethyl acrylate and without 1-(2-methyl-aziridin-1-yl)-propan-2-ol.

[0262] The calculated molecular weight of the theoretical main component was confirmed using MALDI-TOF-MS and is shown below:

[0263]

[0264] Calculated value [M+Na+] = 875.40 Da; observed value [M+Na+] = 875.33 Da.

[0265] Ink preparation

[0266] The compositions of the pigment concentrate and initiator mixture are listed in Table 3.

[0267] Table 3. Overview of Pigment Concentrates and Initiator Mixtures

[0268]

[0269]

[0270] The ink formulations are given in Table 4 and the test results are given in Tables 5 and 6.

[0271] Table 4. Comparative Experiment 1 (C1) and Ink Formulations of Examples 1 to 6

[0272]

[0273] Adhesion results

[0274] The adhesion of comparative experiment C1 and examples 1 to 6 on corona treated foils is shown in Table 5 and the adhesion to untreated foils is shown in Table 6. In the test series, two adhesive tapes were used to evaluate the adhesion.

[0275] Table 5. Comp Ex 1 and Ex 1-6 adhesion to corona treated foils.

[0276]

[0277] Table 6. Comp Ex 1 and Ex 1-6 adhesion to untreated foil.

[0278]

[0279]

[0280] Tables 5 and 6 show that UV curable compositions containing aziridine groups provide excellent adhesion to corona treated and untreated flexible plastic foils compared to UV curable compositions not containing aziridine groups. The results also show that aziridine groups are necessary to obtain good adhesion (Example C1 does not provide good adhesion).

[0281]

[0282] The polypropylene PP used was supplied by Simona and had a surface tension of <34 mNm before corona treatment and >60 mN / m after treatment. In the case of corona treatment, the total amount of energy applied was 1.0 kW. The surface tension of the foil was measured using an Arcotest BLUE surface tensiometer.

[0283] Application conditions

[0284] The coating was applied through a 24 μm wire and cured through a UV dryer, medium pressure Hg lamp, 3 passes. The total UV curing energy, dose and intensity were measured using an EIT UV Power Puck II with four UV light sensitive units and are listed in Table 7.

[0285] Table 7. The intensity of the UV light used

[0286]

[0287] Ink Adhesion

[0288] Adhesion test method is derived from ISO 2409:2007. Deviation from the standard is as follows: Using a BYK 5126 cross-cut tester, cross cuts are made on the cured film. A 20 mm wide and 40 mm long tape strip is applied to the test surface and manually compressed in place to avoid air bubbles. The tape used is TESA 4104 (adhesion to steel is 2.3 N / cm). The adhesive tape is then removed at an angle of approximately 60° in a single backward motion. Adhesion data are reported according to ISO2409 specifications (5 = poor adhesion, 0 = good adhesion).

[0289] Ink preparation

[0290] The preparation is shown in Table 8:

[0291] Table 8. Ink preparation

[0292]

[0293] The adhesion results are shown in Table 9:

[0294] Table 9. Adhesion of Examples Comp Ex 2 and Examples 7-8 to corona treated rigid PP.

[0295] C2(comp) 7 8 Total aziridine content (mol / kg) 0.000 0.265 0.525 TESA4104 5 2 2

[0296] The adhesion of the ink composition containing aziridine groups is significantly improved compared to the ink composition without aziridine groups.

[0297] Comparative experiments of aziridine-functional UV-curable compounds showing genotoxic responses

[0298] Comp Ex 3: TMP(9EO)TA (AgiSyn 2858) was functionalized with 0.5 eq.PI via Michael addition to produce a compound without functional groups having structural unit A

[0299] 710.7g TMP (9EO) TA AgiSyn 2858 and 0.38g phenothiazine were loaded into a stainless steel reactor. Reactor contents were heated to 35°C. When the reactor contents reached a temperature of 35°C, 87.8g propylene imine and 87.8g water were added to the reactor. The duration of addition was 1 hour. After the addition of propylene imine / water mixture was completed, the reactor contents were heated to 45°C for 20 hours. The sample of the reaction mixture was analyzed to determine the free PI content. It was found that it was less than 1ppm of free PI. The reactor contents were then discharged. The reaction mixture was transferred to a separate glass reactor and the water in the reaction mixture was removed by heating the mixture to 50°C and by reducing the pressure to 50 bar. Water was distilled during 2 hours under these conditions to produce the final product. C4 and C5 were synthesized according to a similar procedure for adjusting the amount of propylene imine reflecting stoichiometry.

[0300] The following aziridine-functionalized multifunctional acrylate compounds were tested to compare their adhesion properties:

[0301] Comparative experiment 3: TMP9EOTA (trimethylolpropane triacrylate with 9 ethoxylate groups) was functionalized with 0.5 eq. PI by Michael addition to produce a compound without functional groups with structural unit A

[0302] Genotoxicity test results:

[0303]

[0304] The results of the genotoxicity test showed that the reaction product obtained above was genotoxic.

[0305] preparation

[0306] Comp Ex 3 has been formulated with the ingredients listed in Table 10. Adhesion data are listed in Table 11. Resins refer to the amounts of Comparative Example 3.

[0307] Table 10. Preparation C3

[0308]

[0309] Adhesion was tested according to the adhesion test for flexible plastic substrates described previously. The results are listed in Table 11.

[0310] Table 11. Adhesion test data C3

[0311]

[0312] The results in the table indicate that the adhesion of the ink containing the aziridine functionalized polyacrylate was good (almost no peeling). However, this comparative experiment indicated genotoxic activity as determined by the Toxys test as described above.

[0313] migrate

[0314] Test Method

[0315] Analysis of extractables was performed using gradient elution and PDA / CAD / ESI-TOF-MS detection.

[0316] LC system: Agilent 1290Infinity II

[0317] Detector #1: Agilent 1290 Infinity II PDA

[0318] Detector #2: Agilent 1260ELSD

[0319] Detector #3: Agilent iFunnel 6550Q-TOF-MS

[0320] Column: Waters C18 T3,100*2.1,1.8um

[0321] Injection volume: 1 μL

[0322] gradient:

[0323] A=H 2 O (10 mM NH4CH3COO, pH 9.0), B = acetonitrile, C = THF

[0324] The samples were extracted with acetonitrile for 1 week. Standards were prepared in acetonitrile (4-point calibration curve). Only the amount of aziridine-functional polyfunctional acrylic acid was measured. No other migratables were analyzed.

[0325] Ink preparation

[0326] The formulations used are listed below in Table 12. C4 is a comparative experiment without aziridine, while inks 9 and 10 are examples according to the invention.

[0327] Table 12. Formulations for migration testing

[0328]

[0329]

[0330] result

[0331] Table 13 lists the amounts of extractables.

[0332] Table 13. Amount of extractables (mg / kg) as measured by HPLC.

[0333]

[0334] *: The blank sample contained a small amount of tri-acrylic acid, which is most preferably due to the presence of contamination between the sample made using tri-Ac and the blank BOPP sheet.

[0335] The results show that the aziridine functionalized multifunctional acrylates exhibit substantially less migration than the non-aziridine functionalized multifunctional acrylates.

[0336] Synthesis of BGE-PI adducts:

[0337] A 1 L round-bottom flask equipped with a condenser was placed under N 2 atmosphere, and charged with propylene imine (80.0 g), n-butyl glycidyl ether (126.0 g) and K 2 CO 3 (10.00 g) and heated to 80°C over 30 min, after which the mixture was stirred at T = 80°C for 21 h. After filtration, excess PI was removed in vacuo, followed by further purification via vacuum filtration to yield a colorless, low-viscosity liquid.

[0338] Synthesis of Aziridine-Functional UV Curable Compounds (IV)

[0339] A reaction product having main components of mono-Az-di-Ac and mono-Az-hexa-Ac (the reaction product is further referred to as compound (IV)) was prepared by placing BGE-PI adduct (12.0 g), Agisyn 2824 (42.4 g), butylated hydroxytoluene (0.06 g), phenothiazine (0.01 g) and a reactive diluent (Agisyn 2837, 15 g) in a flask and heating the mixture to 50° C. under gentle stirring. In a dropping funnel, Agisyn 2837 (5 g) and N3600 (25.6 g) was added to the mixture. Next, bismuth neodecanoate (0.02 g) was added to the reaction mixture and the mixture was added in a dropping funnel over 30 minutes. Thereafter, the mixture was stirred at 50°C and the progress of the reaction was monitored by IR to determine the disappearance of the NCO group.

[0340] The calculated molecular weight of the theoretical main component was confirmed using MALDI-TOF-MS and is shown below:

[0341]

[0342] In this structure d 1 +d 2 +d 3 +d 4 =5

[0343] Calculated value [M+Na+] = 1489.89 Da; observed value [M+Na+] = 1489.83 Da.

[0344]

[0345] In this structure d 1 +d 2 +d 3 +d 4 +d 5 +d 6 +d 7 +d 8 =10

[0346] Calculated value [M+Na+] = 1891.05 Da; observed value [M+Na+] = 1890.90 Da.

[0347] The following components with masses below 580 Da were determined and quantified by LC-MS:

[0348]

[0349] Present in the composition at less than 0.01% by weight.

[0350] Genotoxicity test results:

[0351]

[0352] 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 Compound IV shows very weak positive induction of genotoxicity.

[0353] Ink properties of aziridine-functional UV-curable compounds (IV)

[0354] Preparation of formulations

[0355] Pigment paste:

[0356] The ingredients listed in Table 14 were added to a HDPP jar and mixed thoroughly for 2 minutes at 3500 rpm using a speed mixer (DAC 150.1 FV, Hauschield GmbH). Next, a grinding step by a three-roll mill (Exact 80, Exact GmbH) was employed until the fineness was <1 μm, as determined by Hegman Gage according to ASTM D1210.

[0357] Table 14

[0358] preparation: %w / w Producer NeoRad P-50 10.4 DSM NV AgiSyn 2836P 10.1 DSM NV Solsperse S 39000 2.2 Lubrizol Corp Genorad 16 0.1 Rahn AG Irgalith Rubine D4240 17.2 BASF SE 100.0

[0359] Initiator mixture:

[0360] The ingredients listed in Table 15 were added to a HDPP jar and heated to approximately 60°C for one hour or longer if necessary to dissolve all solid particles. Once all ingredients were dissolved, the mixture was thoroughly mixed using a speed mixer (DAC150.1FV, Hauschield GmbH) at 3500 rpm for 2 minutes.

[0361] Table 15:

[0362] preparation: %w / w Producer Omnipol ASA 46.0 IGM Resins BV Omnipol TX 33.0 IGM Resins BV Omnipol TPO-L 20.0 IGM Resins BV Genorad 16 1.0 Rahn AG 100.0

[0363] Next:

[0364] The ingredients listed in Table 16 were added to a HDPP jar and mixed thoroughly using a speed mixer (DAC 150.1 FV, Hauschield GmbH) at 3500 rpm for 2 minutes.

[0365] Table 16:

[0366]

[0367] Application of the preparation:

[0368] The obtained formulations were applied by a C1-5 printer (IGT Testing Systems Inc) onto commercially available foils; CDC 28 (BOPP ex Treofan GmbH) and Mylar 813 (PET ex DuPont Teijin Films Ltd) with a color density range between 1.3 and 1.5 measured by DensiEye 700 (ex X-Rite Inc) according to ATSM D7305.

[0369] Curing of the preparation:

[0370] Within 1 minute of application, the formulations were cured on a UVio curing unit with a conveyor speed of 30 m / min, equipped with a Light Hamer 10 Mark II, equipped with an H-bulb (Heraeus Inc, Hg-doped UV lamp generating 394 mJ / cm 2 and 4276mW / cm 2 Total dose of combined UVA, UVB, UVC and UVV as determined using an arm Power Puck II (EIT Inc)).

[0371] Testing of Cured Formulations:

[0372] Adhesion was determined 24 hours after printing, similar to ASTM D3359, but without the use of a scraper or cross-hatch marking. The tape used was TESA 57341 and the test was repeated. The given score was obtained by visual determination as % adhesion, rounded to the 5% level, and the average of the repeated measurements is reported in Table 17.

[0373] Table 17

[0374]

Claims

1. A compound (I) comprising at least one functional group A and at least one functional group B, in: The functional group A has a structural formula A: in R 1 For H, R 2 , R 3 and R 4 independently selected from H, methyl or ethyl, m is 1 to 6, 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"=H, an aliphatic hydrocarbon group containing 1 to 14 carbon atoms, an alicyclic hydrocarbon group containing 5 to 12 carbon atoms, an aromatic hydrocarbon group containing 6 to 12 carbon atoms, CH 2 -O-(C=O)-R"', CH 2 -OR”” or CH 2 -(OCR””'HCR””'H) n -OR""", wherein R"' is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms and R"" is an aliphatic hydrocarbon group containing 1 to 14 carbon atoms or an aromatic hydrocarbon group containing 6 to 12 carbon atoms, n is 1 to 35, R""' is independently H or an aliphatic hydrocarbon group containing 1 to 14 carbon atoms and R""" is an aliphatic hydrocarbon group containing 1 to 4 carbon atoms, (2) R' and R" together form a saturated alicyclic hydrocarbon group containing 5 to 8 carbon atoms; and The functional group B has the structural formula B: R 5 is H or methyl, X is O, Z' is a polyalkoxy group, Y' is a collection of atoms covalently linked in a linear or branched configuration consisting of: i) carbon and hydrogen atoms, ii) carbon, hydrogen, and oxygen atoms, iii) carbon, hydrogen, and nitrogen atoms, or iv) carbon, hydrogen, oxygen, and nitrogen atoms, n" is 0 or 1, and m' is an integer from 1 to 3; Provided that the total number of functional groups A and the number of functional groups B in compound (I) is from 2 to 13; and The molecular weight of the compounds ranges from 600 Daltons to 10,000 Daltons, where the molecular weight is determined using MALDI-TOF mass spectrometry.

2. The compound according to claim 1, Features R 2 For H, R 3 CH 3 And R 4 For H.

3. The compound according to any one of claims 1 to 2, wherein m is 1; R' is H and R" = alkyl containing 1 to 4 carbon atoms.

4. A compound according to any one of claims 1 to 2, wherein R 5 For H.

5. The compound according to any one of claims 1 to 2, wherein Z' is a polyalkoxy group having 1 to 10 alkoxy repeating units. 6 . The compound according to claim 1 , wherein the total number of functional groups A and the number of functional groups B in compound (I) is 3 to 10.

7. The compound according to any one of claims 1 to 2, wherein the compound has the structural formula (A) p -W-(B) q , wherein p and q are independently an integer of at least 1, p+q is an integer from 2 to 13 and W consists of a collection of atoms covalently linked in a linear or branched configuration, the collection of atoms consisting of composition: i) carbon and hydrogen atoms, ii) carbon, hydrogen and oxygen atoms, iii) carbon, hydrogen and nitrogen atoms, or iv) carbon, hydrogen, oxygen and nitrogen atoms.

8. The compound according to any one of claims 1 to 2, wherein the molecular weight ranges from 600 Daltons to 5000 Daltons.

9. A 100% radiation curable composition comprising at least one compound (II) comprising at least two free-radically copolymerizable ethylenically unsaturated groups, wherein the composition comprises at least one aziridinyl-functional compound (I) according to any one of claims 1 to 8, and wherein the composition contains less than 5% by weight of water and volatile organic solvents, based on the weight of the solids content of the composition.

10. The composition according to claim 9, wherein the free radical copolymerizable ethylenically unsaturated group of compound (II) is a (meth)acryloyl ester group.

11. The composition of claim 9 or 10, wherein compound (II) comprises at least one urethane (meth)acrylate, at least one polyester (meth)acrylate, at least one epoxy (meth)acrylate, at least one (meth)acrylated monomer, or any mixture thereof.

12. A composition according to any one of claims 9 to 10, wherein compound (II) comprises a (meth)acrylated monomer selected from the group consisting of trimethylolpropane tri(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, di-trimethylolpropane tetra(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, glycerol tri(meth)acrylate and its (poly)ethoxylated and / or (poly)propoxylated equivalents, and any mixtures thereof.

13. The composition according to claim 9, wherein the free radical copolymerizable ethylenically unsaturated group of compound (II) is an acryloyl ester group.

14. The composition according to any one of claims 9 to 10, wherein the amount of compound (I) is at least 2% by weight relative to the total amount of the composition, and the amount of compound (II) is at least 60% by weight relative to the total amount of the composition.

15. A composition according to any one of claims 9 to 10, wherein the aziridine group has the following structural formula The molar ratio of ethylenically unsaturated bonds to the compound (I) is in the range of 1:5 to 1:

1.

16. The composition of any one of claims 9 to 10, wherein the composition is UV curable.

17. An ink composition comprising the composition according to any one of claims 9 to 16.

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