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Patent Analysis of

Amino photo-reactive binder

Updated Time 12 June 2019

Patent Registration Data

Publication Number

US10000446

Application Number

US14/361433

Application Date

18 December 2012

Publication Date

19 June 2018

Current Assignee

ALLNEX BELGIUM S.A.

Original Assignee (Applicant)

ALLNEX BELGIUM S.A.

International Classification

C07C229/38,C07C229/12,C09D11/101,C09D133/14,C07C227/16

Cooperative Classification

C07C229/38,C07C227/16,C07C229/12,C09D11/101,C09D133/14

Inventor

GEVAERT, PAUL,CAPPELLE, STEVEN,VAN DEN BERGEN, HUGUES,GUPTA, RAM

Patent Images

This patent contains figures and images illustrating the invention and its embodiment.

US10000446 Amino photo-reactive binder 1 US10000446 Amino photo-reactive binder 2 US10000446 Amino photo-reactive binder 3
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Abstract

A compound obtained by reaction of one or more amines of the general formula NHR6R7 with a compound of the following general formula (IX):

wherein,

    • PI is a photoinitiator derivative,
    • G is linker comprising a number p′ of unreacted hydroxyl groups,
    • M is a group comprising a number z of (meth)acrylate groups equal to at least one, as well as inks, coating compositions and adhesives comprising the same.

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Claims

1. A compound having the formula, wherein: PI is a thioxanthone derivative, a benzophenone derivative, an anthraquinone derivative, or a 1,2-diketone derivative, M is a group comprising a number z of (meth)acrylate groups equal to at least one, Q is a linker, G is a linker comprising a number p of unreacted hydroxyl groups comprised between 0 and 9, the linker being a residue of a polyhydroxy compound having at least 4 and at most 12 hydroxyl groups,R1 and R2 either: together with the N to which they are attached form a 5-6 membered saturated or aromatic ring optionally fused with a phenyl, said 5-6 membered ring containing one or more carbon atoms, from one to three nitrogen atoms and up to one oxygen atom, orare independently selected from the group consisting of: H, C1-30 alkyl, C2-30 alkenyl, and 5-6 membered saturated or aromatic ring containing one or more carbon atoms, up to three nitrogen atoms and up to two oxygen atoms, said ring being optionally substituted by a C1-30 alkyl or by a C1-30 alkyloxy or by a hydroxyl or by a C1-6 alkyl substituted acyloxy, or being optionally fused with a phenyl,wherein each of said C1-30 alkyl and C2-30 alkenyl are independently optionally substituted with one or more substituents independently selected from the group consisting of: a 5-6 membered saturated or aromatic ring containing one or more carbon atoms, up to three nitrogen atoms and up to two oxygen atoms, a hydroxyl group, a C1-10 alkoxy group, and an amine of formula —NR3R4, wherein R3 and R4 are independently selected from the group consisting of H and C1-8 alkyl, and n is from 1 to 10, m is from 1 to 10, and x is from 1 to 10, with the proviso that if R1 is a hydrogen atom, then the carbon atom in R2 directly attached to the nitrogen must be attached to at least two carbon atoms.

2. The compound according to claim 1 wherein G is a residue of a polyhydroxy compound selected from the group consisting of polyhydroxy derivatives of aliphatic or aromatic polyethers, polyhydroxy derivatives of polyesters, polyhydroxy derivatives of polyamides, polyhydroxy derivatives of polyimides, polyhydroxy derivatives of polycarbonates, styrene allyl alcohols copolymers, di-trimethylolpropane, pentaerytritol, dipentaerytritol, C1-3 alkoxylated derivatives thereof and mixtures thereof.

3. The compound according to claim 1, wherein PI is selected from the group consisting of: wherein “*” indicates the point of attachment of PI in the compound, wherein R′ is selected from the group consisting of H and phenyl, and wherein the phenyl is optionally substituted with a group R′″, wherein R, R″ and R′″ are selected from the list group consisting of H, C1-8 alkyl, C1-10 alkoxy and halogen,wherein E is selected from the group consisting of a single bond, a group of formula —O—Y—, and a group of formula -w-O(CO)-J-, wherein Y and J are selected from the group consisting of C1-3 alkylene and C1-3 alkoxy C1-3 alkylene, and wherein w is a C1-3 alkylene.

4. The compound according to claim 3 wherein PI is selected from the list consisting of

5. The compound according to claim 4 having the formula

6. The compound of claim 5 wherein: Q is —C(O)—(CH2)2—.

7. A compound obtained by reaction of one or more amines of the formula NHR6R7 with a compound of the following formula (IX) wherein: PI is a thioxanthone derivative, a benzophenone derivative, an anthraquinone derivative, or a 1,2-diketone derivative,R6 and R7 either: together with the N to which they are attached form a 5-6 membered saturated or aromatic ring optionally fused with a phenyl, said 5-6 membered ring containing one or more carbon atoms, from one to three nitrogen atoms and up to one oxygen atom, orare independently selected from the group consisting of: H, C1-30 alkyl, C2-30 alkenyl, and 5-6 membered saturated or aromatic ring containing one or more carbon atoms, up to three nitrogen atoms and up to one oxygen atom, said ring being optionally substituted by a C1-30 alkyl or by a C1-30 alkyloxy or by a hydroxyl or by a C1-6 acyloxy, or being optionally fused with a phenyl,wherein each of said C1-30 alkyl and C2-30 alkenyl are independently optionally substituted with one or more substituents independently selected from the group consisting of: a 5-6 membered saturated or aromatic ring containing one or more carbon atoms, up to three nitrogen atoms and up to one oxygen atom, a hydroxyl group, a C1-10 alkoxy group, and an amine of formula —NR3R4, wherein R3 and R4 are independently selected from the group consisting of H and C1-8 alkyl, M is a group comprising a number z of (meth)acrylate groups equal to at least one, G is linker comprising a number p′ of unreacted reactive hydroxyl groups, the linker being a residue of a polyhydroxy compound having at least 4 and at most 12 hydroxyl groups, A is either H or CH3, n′ is from 1 to 11, m is from 1 to 11, and p′ is from 0 to 10; with the proviso that n′ is at least 2 when M comprises only one (meth)acrylate group.

8. The compound according to claim 7 wherein the amine NHR6R7 is selected from the list consisting of methylamine, ethylamine, propylamine, n-butylamine, sec-butylamine, pentylamine, hexylamine, 2-ethylhexylamine, cyclohexylamine, octylamine, tert-octylamine, 3-morpholinopropylamine, dodecylamine, fatty amines, ethoxylated fatty amines, monoethanolamine, aniline, N-alkyl aniline, 4-aminophenol, Ethyl-4-aminobenzoate, dicocoamine, diethylamine, diethanolamine, dipropylamine, dibutylamine, 2-(methylamino)ethanol, 2-methoxyethylamine, bis(2-hydroxypropylamine), dihexylamine, diisopropylamine, 1-methylpiperazine, 4-methylpiperidine, morpholine, piperidine, Bis(2-ethylhexyl)amine, 2-hydroxypropylamine, N-benzylmethylamine, Dipentylamine, 1,2,3,4-tetrahydroisoquinoline, dicyclohexylamine and dioctylamine.

9. The compound of claim 8 wherein M is the residue of (meth)acrylic acid.

10. An ink, a coating composition or an adhesive comprising the compound according to claim 9.

11. A substrate on which the ink, coating composition or adhesive of claim 10 has been applied.

12. The substrate according to claim 11 being a food packaging printed with the ink.

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Claim Tree

  • 1
    1. A compound having
    • the formula, wherein: PI is a thioxanthone derivative, a benzophenone derivative, an anthraquinone derivative, or a 1,2-diketone derivative, M is a group comprising a number z of (meth)acrylate groups equal to at least one, Q is a linker, G is a linker comprising a number p of unreacted hydroxyl groups comprised between 0 and 9, the linker being a residue of a polyhydroxy compound having at least 4 and at most 12 hydroxyl groups,R1 and R2 either: together with the N to which they are attached form a 5-6 membered saturated or aromatic ring optionally fused with a phenyl, said 5-6 membered ring containing one or more carbon atoms, from one to three nitrogen atoms and up to one oxygen atom, orare independently selected from the group consisting of: H, C1-30 alkyl, C2-30 alkenyl, and 5-6 membered saturated or aromatic ring containing one or more carbon atoms, up to three nitrogen atoms and up to two oxygen atoms, said ring being optionally substituted by a C1-30 alkyl or by a C1-30 alkyloxy or by a hydroxyl or by a C1-6 alkyl substituted acyloxy, or being optionally fused with a phenyl,wherein each of said C1-30 alkyl and C2-30 alkenyl are independently optionally substituted with one or more substituents independently selected from the group consisting of: a 5-6 membered saturated or aromatic ring containing one or more carbon atoms, up to three nitrogen atoms and up to two oxygen atoms, a hydroxyl group, a C1-10 alkoxy group, and an amine of formula —NR3R4, wherein R3 and R4 are independently selected from the group consisting of H and C1-8 alkyl, and n is from 1 to 10, m is from 1 to 10, and x is from 1 to 10, with the proviso that if R1 is a hydrogen atom, then the carbon atom in R2 directly attached to the nitrogen must be attached to at least two carbon atoms.
    • 2. The compound according to claim 1 wherein
      • G is a residue of a polyhydroxy compound selected from the group consisting of
    • 3. The compound according to claim 1, wherein
      • PI is selected from the group consisting of:
  • 7
    7. A compound obtained by reaction of one or more amines of the formula NHR6R7 with a compound of the following formula (IX) wherein
    • : PI is a thioxanthone derivative, a benzophenone derivative, an anthraquinone derivative, or a 1,2-diketone derivative,R6 and R7 either: together with the N to which they are attached form a 5-6 membered saturated or aromatic ring optionally fused with a phenyl, said 5-6 membered ring containing
    • 8. The compound according to claim 7 wherein
      • the amine NHR6R7 is selected from the list consisting of
  • 10
    10. An ink, a coating composition or an adhesive comprising
    • the compound according to claim 9.
    • 11. A substrate on which the ink, coating composition or adhesive of claim 10 has been applied.
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Description

TECHNICAL FIELD OF THE INVENTION

The present invention relates to the field of photo-reactive binders for the preparation of inks, coatings and adhesives particularly suitable for the food industry.

BACKGROUND OF THE INVENTION

UV curable inks (flexo, offset, screen and inkjet) that are used for food packaging applications must fulfill very low migration level. Part of migration originates from the photoinitiator, the co-initiator (also called synergist) and from products of photo cleavage. Benzophenone is the most widely used photoinitiator for ultraviolet (UV) cured overprint varnishes as it has good surface curing, low yellowing and good solubility and is cheap and widely available. However, benzophenone is also known for its relatively strong odor and its ability to migrate and get extracted from print into foodstuffs, even through packaging such as board and plastic wrappers (see EP 1 438 282 B1). This has been partially solved by using “polymeric photoinitiators”, i.e. photoinitiators with higher molecular weight. Most of the polymeric photoinitiators have solubility issues, poor reactivity and have a big impact on ink flow. When used in higher concentration to increase the reactivity, they often act as plasticizer which is detrimental for the mechanical properties of the cured ink.

There is thus a need to develop photo-reactive binders with no or low migration level of the photo-initiator and the synergist, along with a high UV reactivity and with low detrimental effect on ink flow and mechanical properties of the cured ink even when it is used in large concentration.

EP2130817 describes a molecule in which the nitrogen is integrated in the chain with a 1:1 mol ratio between nitrogen and type II photoinitiator. This way there is less flexibility to adapt the nitrogen content to a different stoichiometry. As amines play also a role in preventing oxygen inhibition, it can be advantageous to work with a mole ratio between nitrogen and type II photoinitiator higher than 1.

EP2161290 describes an aromatic amine blended with an acrylated type II photoinitiator. Amine synergists are not covalently bound to the type II photoinitiator compound. The nitrogen and photoinitiator mol % is limited compared with a molecule having both nitrogen and type II photoinitiator covalently bound on the same backbone.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a photo-reactive binder and more in particular a UV curable binder permitting the preparation of photo-reactive compositions showing good surface and deep curing while simultaneously having a very low migration level. This object has been realized by compounds according to the first and second aspect of the present invention.

In the first and second aspect of the present invention, the compounds may present one or more of the following advantages:

    • they permit a good surface and deep curing,
    • they may have a low yellowing,
    • they may have a good solubility with other components of a UV formulation (e.g. with (meth)acrylates),
    • they do not significantly act as plasticizers,
    • they may be halogen-free.

In a further aspect of the present invention, the compositions (e.g. the inks) comprising the compounds of the first or second aspect may present one or more of the following advantages:

    • they can be used in food packaging due to their very low migration properties,
    • they may have very good flow properties,
    • they have high UV reactivity,
    • they may have low yellowing,
    • they may have weak or no odor,
    • they may have good mechanical properties once cured (e.g. good scratch resistance).

The following terms are provided solely to aid in the understanding of the invention:

As used herein and unless otherwise stated, the term “C1-n alkyl” means straight, branched or cyclic (cycloalkyl) saturated hydrocarbon monovalent radicals having from 1 to n carbon atoms such as, for example, methyl, ethyl, propyl, n-butyl, 1-methylethyl (isopropyl), 2-methylpropyl (isobutyl), 1,1-dimethylethyl (ter-butyl), 2-methylbutyl, n-pentyl, dimethylpropyl, n-hexyl, cyclohexyl, 2-methylpentyl, 3-methylpentyl, n-heptyl and the like.

As used herein and unless otherwise stated, the term “C2-n alkenyl” designates straight, branched or cyclic hydrocarbon monovalent radicals having one or more ethylenic unsaturations and having from 2 to n carbon atoms such as, for example, vinyl, 1-propenyl, 2-propenyl (allyl), 1-butenyl, 2-butenyl, 2-pentenyl, 3-pentenyl, 3-methyl-2-butenyl, 3-hexenyl, 2-hexenyl, 2-heptenyl, 1,3-butadienyl, pentadienyl, hexadienyl, heptadienyl, heptatrienyl and the like, including all possible isomers thereof.

As used herein and unless otherwise stated, the term “C1-n alkylene” means the divalent hydrocarbon radical corresponding to the above defined C1-n alkyl.

As used herein with respect to a substituting radical, and unless otherwise stated, the term “aryl” designate any mono- or polycyclic aromatic monovalent hydrocarbon radical having from 6 up to 30 carbon atoms such as but not limited to phenyl, naphthyl, anthracenyl, phenantracyl, fluoranthenyl, chrysenyl, pyrenyl, biphenylyl, terphenyl, picenyl, indenyl, biphenyl, indacenyl, benzocyclobutenyl, benzocyclooctenyl and the like, including fused benzo-C4-8 cycloalkyl radicals (the latter being as defined above) such as, for instance, indanyl, tetrahydronaphtyl, fluorenyl and the like.

As used herein and unless otherwise stated, the term “C1-n alkoxy” or “C1-n alkyloxy” is intended to include those C1-n alkyl groups of the designated length in either a linear or branched or cyclic configuration linked through an ether oxygen having its free valence bond from the ether oxygen. Examples of linear alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy and hexoxy. Examples of branched alkoxy are isopropoxy, sec-butoxy, tert-butoxy, isopentoxy and isohexoxy. Example of cyclic alkoxy are cyclopropyloxy, cyclobutyloxy, cyclopentyloxy and cyclohexyloxy.

As used herein and unless otherwise stated, the term “C1-n alkoxy alkylene” refers to a C1-n alkylene as defined herein whereto is attached a C1-n alkoxy as defined herein, e.g. methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, amongst others.

As used herein and unless otherwise stated, the term “(meth)acrylic” covers both “methacrylic” and “acrylic”.

As used herein, the term “residue” when relating to a chemical compound, refers to the chemical structure remaining after that at least some of the reactive groups of the chemical compound have reacted. For instance, the term “residue of a polyhydroxy compound” refers to the chemical structure remaining after that at least some of the hydroxyl groups of the polyhydroxy compound have reacted (e.g. to form esters or urethanes).

As used herein and unless provided otherwise, the term “type II photoinitiator” relates to a Norrish type II photoinitiator able to generate radicals indirectly by hydrogen abstraction from a suitable synergist or co-initiator. Examples of typical Norrish type II photoinitiators are given infra. Aliphatic tertiary amines, aromatic amines and thiols are preferred examples of co-initiators for this type of photinitiators. In the context of the present invention amine synergists are preferred.

By an “amine synergist” is meant to designate an amine capable of acting as an electron or hydrogen donor with a type II photoinitiator (also called a Norrish type II photoinitiator) like the ones exemplified in the present invention. Type II photoinitiator systems can form an excited state upon irradiation, and then abstract an atom or electron from a donor molecule (synergist). The donor molecule then acts as the initiating species for polymerization. In the present invention the amine synergist is often also referred to as an “amine co-initiator”.

In a first aspect, the present invention relates to a compound linking covalently:

    • a type II photoinitiator (PI),
    • at least one polymerizable insaturation, and
    • an amine co-initiator for said type II photoinitiator (PI).

In an embodiment of the first aspect, said polymerizable insaturation may belong to a (meth)acrylate group, preferably to an acrylate group.

In an embodiment of the first aspect, the compound may have the general formula (I),

Wherein:

    • is a type II photoinitiator derivative,
    • M is a group comprising a number z of (meth)acrylate groups equal to at least one,
    • Q is a linker,
    • G is a linker comprising a number p of unreacted hydroxyl groups comprised between 0 and 100,
    • R1 and R2 either:
      • together with the N to which they are attached form a 5-6 membered saturated or aromatic ring optionally fused with a phenyl, said 5-6 membered ring containing one or more carbon atoms, from one to three nitrogen atom(s) and up to two oxygen atoms, or
      • are independently selected from the group consisting of:
        • H
        • C1-30 alkyl,
        • C2-30 alkenyl, and
        • 5-6 membered saturated or aromatic ring containing one or more carbon atoms, up to three nitrogen atoms and up to two oxygen atoms, said ring being optionally substituted by a C1-30 alkyl or by a C1-30 alkyloxy or by a hydroxyl or by a C1-6 alkyl substituted acyloxy or fused with a phenyl,
          • wherein each of said C1-30 alkyl and C2-30 alkenyl (as R1 or R2 group or as a substituent on a R1 or R2 group being a 5-6 membered saturated or aromatic ring) are independently optionally substituted with one or more substituents independently selected from: a 5-6 membered saturated or aromatic ring containing one or more carbon atoms, up to three nitrogen atoms and up to two oxygen atoms,
          • a hydroxyl group,
          • a C1-10 alkoxy group, and
          • an amine of formula NR3R4, wherein R3 and R4 are independently selected from the group consisting of H and C1-8 alkyl, and
    • m is from 1 to 100, and
    • x is from 1 to 100,

      with the proviso that if R1 (or R2) is a hydrogen atom, then the carbon atom in R2 (or R1) directly attached to the nitrogen (i.e. in alpha of the nitrogen) must be attached to at least two carbon atoms.

This compound is advantageously used in a coating (e.g. varnish), ink, or adhesive composition based on (meth)acrylics because it enables a very efficient curing of the (meth)acrylic composition while ensuring that few or no residual species prone to migration remains in the final product. The photoinitiator being of the type II, it does not lead to photocleavage products that can migrate upon curing. The photoinitiator being functionalized with at least one (meth)acrylic polymerizable function, it is incorporated in the polyacrylate network upon curing, thereby efficiently preventing migration. Furthermore, the compound comprises its own co-initiator (an amine synergist) which is also covalently bound to the compound. This permits a very efficient curing even in presence of oxygen while assuring that few or no residual species prone to migration remains in the final product. This ability to avoid migration is particularly advantageous in compositions for use in coatings (e.g. inks or varnishes) to be applied on food packaging.

Without being bound by theory, it is believed that a faster intramolecular hydrogen transfer can be obtained when the benzophenone derivative and the amine synergist are bound together.

In an embodiment, z can be an integer from 1 up to 8. In general z is at most 3, often at most 2. In a particular embodiment z is 1. In an embodiment, if z is 1 then n is at least 2.

In an embodiment, each one of the n M groups is independently selected from the list consisting of

    • R9 is a group comprising at least one (meth)acrylate group and the residue of a reactive group capable to react with an isocyanate,
    • R8 is a divalent hydrocarbon group having from 1 to 20 carbon atoms, and
    • A is either H or CH3.
      • The “*” indicates the point of attachment of the group to an oxygen atom on the linker G.

In an embodiment of the invention the group *—NR1R2 may originate from primary amines and/or secondary amines. Preferred in this category are often secondary amines though also a mix of one or more primary amines and one or more secondary amines may be used. Suitable primary amines you find further below (see the second aspect). Preferred in this category are monoethanolamine (2-aminoethanol), 2-ethylhexylamine, octylamine and/or cyclohexylamine and particularly preferred is octylamine. Examples of preferred secondary amines you find below. Particularly preferred in this category is dibutylamine.

In embodiments of the present invention, the molecular weight of the group *—NR1R2 is preferably of 30 g/mol or more, more preferably 36 g/mol or more and most preferably of 44 g/mol or more.

In embodiments of the present invention, the molecular weight of the group *—NR1R2 is preferably of 600 g/mol or less, more preferably 300 g/mol or less and most preferably of 250 g/mol or less.

In embodiments, R1 and/or R2 may be independently selected from alkyl and alkenyl groups independently comprising from 1 to 30 carbon atoms, preferably from 2 to 18 carbon atoms, optionally substituted by one or more hydroxyl groups.

In other embodiments, wherein R1 or R2 is an aromatic group, the group *—NR1R2 may originate from an aromatic amines such as aniline, N-alkyl substituted aniline, isomers of aminophenol, (methylamino)phenol, ethyl-4-aminobenzoate and methyl-4-(methylamino)benzoate, and possibly mixtures thereof.

In embodiments, the group *—NR1R2 may originate from secondary amines such as diethylamine, diethanolamine, dipropylamine, dibutylamine, 2-(methylamino)ethanol, 2-methoxyethylamine, Bis(2-hydroxypropyl)amine, diisopropylamine, dipentylamine, dihexylamine, bis(2-ethylhexyl)amine, 1,2,3,4-Tetrahydroisoquinoline, N-benzylmethylamine, diisopropylamine, morpholine, piperidine, dioctylamine, and di-cocoamine, and possibly mixtures thereof.

Preferred secondary amines are diethylamine, dipropylamine, dibutylamine, diethanolamine, dioctylamine, bis(2-ethylhexyl)amine, piperidine and morpholine. Most preferred are diethylamine, diethanolamine, dipropylamine, dibutylamine, dioctylamine and morpholine, and possibly mixtures thereof.

Examples of suitable non-aromatic primary amines may be sec-butylamine, isopropylamine and cyclohexylamine. Further suited primary amines are monoethanolamine (2-aminoethanol), 2-ethylhexylamine, octylamine and/or octylamine.

In other embodiments, wherein R1 or R2 is an aromatic group, the group *—NR1R2 may preferably originate from aromatic amines such as an optionally substituted aniline, optionally substituted N-alkylaniline, or an optionally substituted benzocaine (ethyl-4-aminobenzoate).

In an embodiment, the group *—NR1R2 may be selected from the list consisting of *—N((CH2)2CH3)2, *—N((CH2)3CH3)2, *—N((CH2)5CH3)2,

wherein “*” indicates the point of attachment of —NR1R2 to the linker Q.

Primary and secondary amines can add onto a meth(acrylic) reactive double bond via an Aza-Michael addition, permitting easy incorporation of one of the above amine synergists into a compound of the invention. By an “amine synergist” is meant to designate an amine capable of acting as an electron or hydrogen donor with a type II photoinitiator (also called a Norrish type II photoinitiator) like the one exemplified in the present invention. Type II photoinitiator systems can form an excited state upon irradiation, and then abstract an atom or electron from a donor molecule (synergist). The donor molecule then acts as the initiating species for polymerization. In the present invention the amine synergist is often also referred to as an “amine co-initiator”.

Tertiary amines can be incorporated into a compound of the invention via e.g. a transesterification process. Examples of suitable compounds are dialkylaminobenzoate esters, like e.g. a 4-dimethylaminobenzoic acid ethyl ester and/or a 4-dimethylaminobenzoic acid methyl ester.

Polymeric tertiary amines can also be blended with the compounds of the invention. The polymeric tertiary amines used for that purpose according to this variant often comprise at least one aromatic group. By “polymeric” is meant that the number average molecular weight (Mn) of the polymeric tertiary amine is preferably of 400 g/mol or more, more preferably of 500 g/mol or more and most preferably of 600 g/mol or more. Typically the molecular weight of these compounds is at most 5.000 g/mol more preferably at most 3.000 g/mol and most preferably at most 2.000 g/mol.

An example of suitable polymeric tertiary amines in this category: dialkyl aminobenzoate esters and more in particular dimethylaminobenzoate esters as described e.g. in U.S. Pat. No. 5,905,164. Both monoamines and diamines can be used, possibly a mixture of both.

An example of a suitable diamine compound in this category is polyethyleneglycol bis (p-dimethyl aminobenzoate) as disclosed in U.S. Pat. No. 5,905,164

These compounds typically exist in a mixture as described in U.S. Pat. No. 5,905,164 p 10, with n typically in the range of from 2 to 110, more preferably from 4 to 61, most preferably from 7 to 40.

Another example of a suitable diamine compound in this category is polytetrahydrofurane bis (p-dimethyl aminobenzoate)

with n typically in the range of from 2 to 65, more preferably from 3 to 40, most preferably from 4 to 25.

An example of a suitable monoamine compound in this category is 4-N,N′-dimethylaminobenzoyl polyethyleneglycol monomethylether as disclosed in U.S. Pat. No. 5,905,164

with n typically in the range of from 2 to 110, more preferably from 4 to 61, most preferably from 7 to 40.

Particularly preferred compounds in this category are Omnipol ASA from IGM (a Poly(ethyleneglycol) bis(p-dimethylamino benzoate) with number average molecular weight 488-532 g/mol), ESACURE™ A198 from Lamberti & Speedcure 7040 from Lambson (polymeric (mix 4+2)amine with number average molecular weight 1060 g/mol).

In embodiments of the present invention, PI may have the formula

PI′-E-* wherein PI′ is a type II photoinitiator derivative, wherein E is either a single bond, a group of general formula —O—Y— or a group of general formula -w-O(CO)-J- wherein Y and J are selected from the group consisting of C1-3 alkylenes and C1-3 alkoxy C1-3 alkylenes, and wherein w is selected from the group consisting of C1-3 alkylenes. Such a linker E has the advantage to be synthetically readily accessible and to be stable under processing and curing conditions.

In embodiments of the present invention, G may be a residue of a polyhydroxy compound having at least 3 hydroxyl groups, preferably at least 4 hydroxyl groups.

At least three hydroxyl groups permit the attachment of the linker to a PI derivative, to a M group (e.g. (meth)acrylate), and to an amine synergist (either via direct reaction on a hydroxyl group or via reaction on a (meth)acrylate of a meth(acrylating) compound M previously reacted on a hydroxyl). If x=i, at least i+3 hydroxyl groups permit to attach at least two M groups to the linker. For instance, if x=1, at least four hydroxyl groups permit to attach at least two M groups to the linker. This in turn improves the chances of integration of the compound in a poly(meth)acrylate network after curing of a composition comprising the compound.

In embodiments, the polyhydroxy compound used to prepare the compound according to the first aspect may have at most 200 hydroxyl groups, preferably at most 150 hydroxyl groups, more preferably at most 100 hydroxyl groups, still more preferably at most 50 hydroxyl group, still more preferably at most 32 hydroxyl groups, still more preferably at most 16 hydroxyl groups, yet still more preferably at most 12 hydroxyl groups and most preferably at most 6 hydroxyl groups. A small number of hydroxyl groups lead to compounds having a relatively smaller molecular weight which is advantageous for having good solubility and low impact on the viscosity of compositions comprising it.

In embodiments, the polyhydroxy compound used to prepare the compound according to the first aspect can be selected from polyhydroxy derivatives of aliphatic or aromatic polyethers, polyhydroxy derivatives of polyesters, polyhydroxy derivatives of polyamides, polyhydroxy derivatives of polyimides, polyhydroxy derivatives of polycarbonates, styrene allyl alcohols copolymers (commercially available from Lyondell like SAA 100 or SAA 101), trimethylolpropane, di-trimethylolpropane, pentaerytritol, dipentaerytritol, hyperbranched or dendritic polyols, as well as alkoxylated derivatives thereof (for instance oxypropylated and/or oxyethylated derivatives of any of the foregoing) and/or mixtures thereof.

In embodiments of the present invention, the polyhydroxy compound may have its hydroxyl groups modified into other reactive groups capable to react with a carboxylic acid or an activated carboxylic acid to form an ester. For instance, the polyhydroxy compound used to prepare the compound according to the first aspect may have some or all of its hydroxyl groups alkoxylated. The polyhydroxy compound may therefore have alkoxylated units, more preferably ethoxylated and/or propoxylated units.

The following alkoxylated polyhydroxy compounds are example of particularly suitable polyhydroxy compounds: Boltorn® H20; Boltorn® H2004; Boltorn® P1000; Boltorn® P500; polyol 3165, Polyol 3380, Polyol 4290; Polyol 4360; Polyol 4525; Polyol 4640, Polyol R3215, Polyol R3430; 6250 Polyol R4630; Polyol R4631; and 6430 Polyol R6405 from Perstorp.

In embodiments of the present invention, the polyhydroxy compound used to prepare the compound according to the first aspect may have a hydroxyl number between 100 and 1500 mg KOH/g, more preferably between 200 and 800 mg KOH/g, still more preferably between 200 and 600 mg KOH/g.

In embodiments of the present invention, the polyhydroxy compound used to prepare the compound according to the first aspect may have a number average molecular weight (Mn) between 100 and 5000 g/mol, more preferably between 300 and 3500 g/mol, still more preferably between 300 and 1300 g/mol.

The number average molecular weight of compounds is either calculated based on a target molecule representing the biggest fraction of the composition or measured by gel permeation chromatography (GPC) in case of higher molecular weight molecules. Therefore, a small portion of the oligomer is dissolved in tetrahydrofuran (THF) and injected in the liquid chromatograph after a preliminary filtration. The components of the sample are typically eluted by the mobile phase solvent (THF) at a flow rate of 1 ml/min and separated by a combination of polystyrene-divinylbenzene columns at a temperature of 40° C. Standards of polystyrene with known molecular weight and narrow polydispersity are used to generate a calibration curve.

Liquid polyhydroxy compounds are preferred as they may lead to liquid photo-reactive binders (which a.o. are more compatible and easy to handle and induce lower viscosity than solid photo-reactive binders).

The table below list examples of polyhydroxy compounds useful for use in the present invention:


Number
average
Hydroxy
Molecular
number mg
weight
Viscosity
functionality
KOH/g
(g/mol)
mPas, 23° C.
Polyol R2395
2
395
276
350
Polyol R 2490
2
490
220
170
Polyol 3165
3
165
1014
350
Polyol 3380
3
380
444
360
Polyol 3610
3
610
275
700
Polyol 3611
3
611
275
700
Polyol 3940
3
940
179
4000
Polyol 3990
3
990
170
4500
Polyol R3215
3
215
795
340
Polyol R3430
3
430
398
400
Polyol R3530
3
530
308
2000
Polyol R3540
3
540
311
550
Polyol R3600
3
600
275
700
Polyol 4290
4
290
797
450
Polyol 4360
4
360
629
1300
Polyol 4525
4
525
426
2600
Polyol 4640
4
640
355
1100
Polyol 4800
4
800
282
2200
Polyol R4630
4
630
350
1500
Polyol 4631
4
631
356
1500
Polyol R6405
6
405
827
1900
Boltorn P 1000
430-490
5000
Boltorn P 500
560-630
15000
Boltorn H 2004
105-125
3200
14000-20000
Boltorn H 20
16
490-530
2100
solid
PG17*
17
solid
PG33*
33
solid
PG83*
83
solid
PG179*
179
solid
*a hyperbranched polyglycidol (available from HYPERPOLYMERS GMBH, Freiburg, Germany);

It are in particular the ones with functionality of at least 3 that are suitable for use in the present invention.

In an embodiment of the first aspect, PI may be a thioxanthone derivative, a benzophenone derivative, an anthraquinone derivative, or a 1,2-diketone derivative (or a mixture thereof). Examples of 1,2-diketone derivative are camphorquinone derivatives and diphenylethanedione derivatives.

In an embodiment of the first aspect, PI may be selected from the list consisting of:

wherein “*” indicates the point of attachment of PI in the compound,

wherein R′, R″ are selected from the list consisting of H (preferred), C1-8 alkyl, C1-10 alkoxy and halogen and aryl (e.g. phenyl),

wherein Ar is an aryl group, and

wherein E is selected from a single bond, a group of general formula —O—Y— and a group of general formula -w-O(CO)-J- wherein Y and J are selected from the group consisting of C1-3 alkylene and C1-3 alkoxy C1-3 alkylene, wherein w is selected from the group consisting of C1-3 alkylene.

In an embodiment, Ar may be selected from

wherein R′ is selected from the list consisting of H and phenyl and wherein the phenyl is optionally substituted with a group R′″,

wherein R is selected from the list consisting of H, C1-8 alkyl, C1-10 alkoxy and halogen, and wherein the “*” indicates the point of attachment to the carbonyl.

In an embodiment of the first aspect, PI may be of the general formula:

In an embodiment of the first aspect, PI may be selected from the list consisting of

wherein R′″ is selected from the list consisting of H (preferred), C1-8 alkyl, C1-10 alkoxy and halogen,

In an embodiment of the first aspect, PI may be of formula (II) and E may be either in ortho or in para of the carbonyl in said formula (II), or PI may be of formula (III) and E may be either in ortho or in meta of the carbonyl in said formula (III), or PI may be of formula (IV) and E may be in meta of a first carbonyl and in para of a second carbonyl in said formula (IV), or PI may be of formula (VI) and E may be in para of the carbonyl in said formula (IV).

In an embodiment of the first aspect, PI may be selected from the list consisting of:

In a preferred embodiment, the compound of the first aspect may have the following general formula:

The phenyl bearing the R′ function may be attached to the benzophenone moiety in ortho, meta or para of its carbonyl function.

Preferably, the phenyl bearing the R′″ function may be attached to the benzophenone moiety in para of its carbonyl function.

Expressed differently, the compound of the first aspect may have the general formula.

Embodiments where R, R″ and R′″ may be independently selected from the group consisting of H, C1-8 alkyl and C1-10 alkoxy are advantageous because of the absence of halogens. This is more environment-friendly and preferred for food packaging applications.

Having the R′″ bearing phenyl in para of the carbonyl on the benzophenone has the advantage of a very rapid curing time both under air and under inert atmosphere.

The linker E may be attached at any position of the phenyl bearing the R″ function.

In a preferred embodiment, E may be a single bond. When E is a single bond, without being bound by theory it is believed that the distance between the type II photoinitiator (e.g. a benzophenone derivative) and the amine synergist is minimal, favoring an efficient hydrogen transfer. Furthermore, the absence of the linker E (i.e. it is a single bond) limit to a minimum the dilution of the compound's properties, the increase of its viscosity and eventual adverse plasticizing effects.

In this embodiment, the compound may have the general formula

Preferably, the linker E when being a single bond may be attached in ortho of the carbonyl of the type II photoinitiator (e.g. benzophenone moiety). For instance, when E is a single bond, the compound of the first aspect may have the general formula

These embodiments where E is a single bond have the further advantage to be easily synthetically accessible from carboxy substituted type II photoinitiator (e.g. benzophenone) derivatives.

R, R″ and R′″ may be at any position on their respective phenyl. R′″ is however preferably in para of its attachment point to the benzophenone.

Still more preferred is the family of compounds

Still more preferred is the family of compounds having the general formula

Q may for instance be selected from the list consisting of a C1-8 straight or branched alkylenoyl, a C4-10 cyclic alkylenoyl optionally substituted with a C1-4 straight or branched alkyl, and a phenylenoyl group optionally substituted with a C1-4 straight or branched alkyl, wherein the carbonyl of Q forms an ester with a hydroxyl of the linker G. Preferably, Q equals to —C(O)(CHA-CH2)— (as in formula VII). Most preferably A is a H atom.

In an embodiment, the compound may have the general formula (VII)

Having Q equal to —C(O)(CHA-CH2)— with A preferably being a H atom, is advantageous as it is a short linker having therefore a minimal negative impact on the performance of the compound and of the compositions comprising it. Furthermore, it is a stable linker in the conditions of cure and processing. A further advantage of this linker is that it permits an easy incorporation of the amine synergist by Aza-Michael addition of at least one primary amine and/or at least one secondary amine onto a meth(acrylic) reactive double bond.

In embodiments of the present invention, A is preferably a H atom due to the higher reactivity of acrylates compared to methacrylates.

As an example, the compound may have the following formula

wherein G is a linker as defined above.

A typical example is depicted below wherein G is a di-trimethylolpropane residue and wherein x and m=1, n=2 and p=0:

In an embodiment, the M group may be of the formula *—(CO)—NH—R8—NH—(CO)—R9.

In embodiments, the group *—(CO)NH—R8—NH(CO)—* in this formula may be the residue of a reacted diisocyanate.

In embodiments, R8 may be a divalent hydrocarbon group having from 1 to 20 carbon atoms selected from the list consisting of:

    • alkylenes (e.g. hexamethylene obtainable from hexamethylene diisocyanate),
    • cycloalkylenes optionally substituted by one or more alkyl groups (e.g. cyclohexylene obtainable from cyclohexylene diisocyanate),
    • arylenes (e.g. tolylene, a divalent tolidine radical or naphthylene each obtainable from their respective diisocyanate derivative), and
    • Combinations thereof (such as alkylene cycloalkylene (e.g. divalent isophorone radical obtainable from reaction of isophorone diisocyanate), alkylene arylene alkylene (e.g. xylylene obtainable from xylylene diisocyanate), alkylene cycloalkylene alkylene (e.g. hydrogenated xylylene obtainable from hydrogenated xylylene diisocyanate), cycloalkylene alkylene cycloalkylene (e.g. cyclohexylene methylene cyclohexylene obtainable from dicyclohexylmethane diisocyanate), arylene alkylene arylene (e.g. phenylene methylene phenylene obtainable from reaction of diphenylmethane diisocyanate), amongst others.)

In an embodiment, —R9 may be a residue of a meth(acrylating) compound of a first type.

(Meth)acrylating compounds of said first type are compounds that contain at least one reactive group capable to react with isocyanate groups and that contain at least one (meth)acryloyl group. Typically (meth)acrylating compounds of said first type are end-capping agents that contain at least one acryloyl and/or methacryloyl group and one (or essentially one) nucleophilic function capable of reacting with isocyanate groups, such as a hydroxyl group. Useful (meth)acrylating compounds of said first type include the esterification products of aliphatic and/or aromatic polyols with (meth)acrylic acid having a residual average hydroxyl functionality of about 1. The partial esterification products of (meth)acrylic acid with tri-, tetra-, penta- or hexahydric polyols or mixtures thereof are preferred. In this context, it is also possible to use reaction products of such polyols with ethylene oxide and/or propylene oxide. These modified or unmodified polyols are partly esterified with acrylic acid, methacrylic acid or mixtures thereof until the desired residual hydroxyl functionality is reached. (Meth)acrylating compounds of said first type obtained from the reaction of (meth)acrylic acid with aliphatic, cycloaliphatic or aromatic compounds bearing an epoxy functionality together with at least one (meth)acrylic functionality can be used as well. Other suitable (meth)acrylating compounds of said first type are the (meth)acrylic esters with linear and branched polyols in which at least one hydroxy functionality remains free, like hydroxyalkyl(meth)acrylates having 1 to 20 carbon atoms in the alkyl group. Preferred molecules in this category are hydroxymethyl(meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate and/or hydroxybutyl (meth)acrylate. Preferred examples of poly(meth)acryloyl hydroxylated compounds are compounds comprising at least two (meth)acryl functions such as glycerol diacrylate, trimethylolpropane diacrylate, glycerol diacrylate, pentaerythritol triacrylate, ditrimethylolpropane triacrylate, dipentaerythritol pentaacrylate and their (poly)ethoxylated and/or (poly)propoxylated equivalents.

In embodiments of the present invention, n may preferably be from 1 to 50, more preferably from 1 to 31, still more preferably from 1 to 10, yet still more preferably from 2 to 5, and most preferably from 3 to 5 in order to provide sufficiently high integration in a (meth)acrylate network.

In embodiments of the present invention, m may preferably be from 1 to 50, more preferably from 1 to 31, still more preferably from 1 to 10, yet still more preferably from 1 to 5.

In embodiments of the present invention, x may preferably be from 1 to 50, more preferably from 1 to 31, still more preferably from 1 to 10, yet still more preferably from 1 to 5.

For instance, n and m may be independently from 1 to 31, preferably from 2 to 5, x may be from 1 to 30, preferably from 1 to 5 and p may be from 0 to 30, preferably from 0 to 5.

In embodiments of the present invention, n+m+x+p may be from 3 to 400, preferably from 3 to 200, more preferably from 3 to 100 still more preferably from 3 to 50, still more preferably from 3 to 32 and most preferably from 3 to 15.

For instance, n may be from 1 to 31, m may be from 1 to 31, x may be from 1 to 30, and p may be from 0 to 30 while n+m+x+p may be from 3 to 32. This last embodiment keeps the molecular weight relatively low which is advantageous to keep the viscosity relatively low.

In embodiments of the present invention, the compound may be a liquid at 25° C. and 1 atm. This is advantageous as it permits a greater solubility in an ink, coating or adhesive composition.

In a second aspect, the present invention relates to a compound obtained (or obtainable) by reaction of one or more amines of the general formula NHR6R7 with a PI (e.g. benzophenone) derivative of the following general formula (VIII)

    • wherein
    • PI is a type II photoinitiator derivative,
    • R6 and R7 either:
      • together with the N to which they are attached form a 5-6 membered saturated or aromatic ring optionally fused with a phenyl, said 5-6 membered ring containing one or more carbon atoms, from one to three nitrogen atom(s) and up to two oxygen atoms, or
      • are independently selected from the group consisting of
        • H,
        • C1-30 alkyl,
        • C2-30 alkenyl, and
        • 5-6 membered saturated or aromatic ring containing one or more carbon atoms, up to three nitrogen atoms and up to one oxygen atom, said ring being optionally substituted by a C1-30 alkyl or by a C1-30 alkyloxy or by a hydroxyl or by a C1-6 acyloxy or fused with a phenyl,
      • wherein each of said C1-30 alkyl and C2-30 alkenyl (as R1 or R2 group or as a substituent on a R1 or R2 group being a 5-6 membered saturated or aromatic ring) are independently optionally substituted with one or more substituents independently selected from:
        • a 5-6 membered saturated or aromatic ring containing one or more carbon atoms, up to three nitrogen atoms and up to two oxygen atoms,
        • a hydroxyl group,
        • a C1-10 alkoxy group, and
        • an amine of formula —NR3R4, wherein R3 and R4 are independently selected from the group consisting of H and C1-8 alkyl,
    • M is as defined in any embodiment of the first aspect,
    • m and n are as defined in any embodiment of the first aspect,
    • G is linker comprising a number p′ of unreacted hydroxyl groups, and
    • p′ is from 0 to 200,

      with the proviso that n is at least 2 when M comprises only one (meth)acrylate group.

Although some of the compounds of this other aspect are already covered by the first aspect of the present invention and are described in a Markush formula (I) (the case when NHR6R7 is a secondary amine with neither R6 nor R7 being a hydrogen atom), and the case when NHR6R7 is a primary amine with R6 or R7 being bulky (e.g. having the carbon in alpha of the nitrogen bonded to at least two carbon atoms), other compounds obtainable by reaction of one or more amines of the general formula NHR6R7 with a PI (e.g. benzophenone) derivative of the general formula (IX) cannot be described in a general Markush formula. This is the case when NHR6R7 is a primary amine (except for bulky amines as described above) with either R6 or R7 being a hydrogen atom. In this case, the product obtained by the addition of NHR6R7 on a (meth)acrylate group of the PI (e.g. benzophenone) derivative of the general formula (IX) is, due to the remaining active hydrogen on the amine, still prone to react with a second (meth)acrylate group (e.g. belonging to a second PI (e.g. benzophenone) derivative of the general formula (IX)). This starts a chain reaction that can lead to the formation of oligomers of complex structures and to a structure distribution. The resulting product is nevertheless useful as a photo-reactive binder and possesses the same advantages as provided by the compounds of the first aspect of the present invention.

Examples of useful secondary amines NHR6R7 may be amines of formula NHR1R2 as described in the first aspect of the present invention. Examples of useful primary amines of formula NHR6R7 wherein either R6 or R7 is a hydrogen atom are: methylamine, ethylamine, propylamine, butylamine, Sec-butylamine, ter-butylamine, amylamine (pentylamine), hexylamine, 2-ethylhexylamine, cyclohexylamine, octylamine, ter-octylamine, 3-morpholinopropylamine, dodecylamine, fatty amines (such as cocoamine), ethoxylated fatty amines, monoethanolamine (2-aminoethanol), 2-methoxyethylamine, 2-hydroxypropylamine, and mixtures thereof.

Especially preferred primary amines are monoethanolamine (2-aminoethanol), 2-ethylhexylamine, octylamine and cyclohexylamine, and mixtures thereof.

Examples of fatty amines are octyl amine, 2-ethylhexylamine, lauryl amine, stearyl amine, oleyl amine, tallowamine, cetylamine, N-tetradecylamine, cocoamine, dicocoamine, hydrogenated tallowamine, alkyl(C16 and C18-unsaturated)amine, alkyl(C14-18)amine, alkyl(C16-22)amine, alkyl(C8-18 and C18-unsaturated)amine, alkyl(C12-18)amine, di(hydrogenated tallow)amine, dicocoalkyl amine, dialkyl(C14-18) amine, dialkyl(C12-18)amine, dialkyl(C16-22)amine, N-tridecyltridecanamine, N-methylstearylamine, distearyl amine, dialkyl(C8-20)amine, N-octadecylbenzylamine, N-isopropyloctadecylamine, and N-hexadecyloctadecylamine, and mixtures thereof.

Preferred fatty amines are cocoamine, di-cocoamine, octylamine, dodecylamine and 2-ethylhexylamine, and mixtures thereof.

G may be a residue of a polyhydroxy compound as defined in any embodiments of the first aspect of the present invention.

In embodiments, G may have at most 200 hydroxyl groups, preferably at most 150 hydroxyl groups, more preferably at most 100 hydroxyl groups, still more preferably at most 50 hydroxyl group, still more preferably at most 32 hydroxyl groups, still more preferably at most 16 hydroxyl groups, yet still more preferably at most 12 hydroxyl groups and most preferably at most 6 hydroxyl groups.

In embodiments, the equivalent weight of acrylic double bonds of the compound according to the first aspect of the present invention may be 1 meq/g or more, preferably 2 meq/g or more, most preferably 3 meq/g or more.

In embodiments, the equivalent weight of acrylic double bonds of the compound according to the first aspect of the present invention may be 11 meq/g or less, preferably 8 meq/g or less, most preferably 5 meq/g or less.

In another aspect, the present invention relates to a blend comprising an amine synergist, such as an amino(meth)acrylate, typically an aminoacrylate, and a compound according to any embodiment of the first aspect or of the second aspect of the present invention. The amine synergist used in the blend can also be one or more of the polymeric tertiary amines described above. Possibly a mix of at least one amino(meth)acrylate and at least one of these polymeric tertiary amines is being used. Other types of co-initiators that may be used in addition to or instead of the above include: aliphatic tertiary amines, aromatic amines and/or thiols.

In a further aspect, the present invention relates to a composition comprising the compound or blend according to any embodiment of the present invention. The composition can for instance be an ink, a coating composition (e.g. a varnish) or an adhesive. The compounds of the first and second aspect of the present invention are particularly useful in an ink for printing food packaging or in a varnish for coating food packaging. The compounds of the present invention having the ability to integrate covalently a (meth)acrylate network upon curing, (meth)acrylate based compositions comprising said compound are particularly safe to use for food packaging where migration must be avoided.

In embodiments, the compound of the present invention may be present in an amount of 0.1 wt % or more, preferably 5 wt % or more, and most preferably 10 wt % or more in the composition (e.g. ink or varnish).

In embodiments, the compound of the present invention may be present in an amount of 90 wt % or less, preferably 50 wt % or less and most preferably 35 wt % or less in the composition (e.g. ink or varnish).

In yet a further aspect, the present invention relates to a substrate coated or printed with a coating as described above. The coating may be cured or uncured but will typically be cured. Such substrates have the advantage to leach no or negligible amounts of initiator and amine synergist. Particularly advantageous are food packaging printed with an ink or coated with a varnish as described above. Food packaging must meet strict chemical migration requirements that the inks/varnishes as described above help to meet. Furthermore, inks/varnishes for food packaging preferably have good flow properties and high UV reactivity. Two features that the inks/varnishes as described above also help to meet. This is especially true when the compound of the first or second aspect present in said coatings is a liquid.

In yet a further aspect, the present invention relates to a process for the synthesis of a compound according to the first or second aspect of the present invention.

The synthesis may proceed by the reaction of:

    • a type II photoinitiator derivative PI bearing a reactive group capable to react with a hydroxyl group to form e.g. an ester,
    • a linker comprising from 3 to 400 hydroxyl groups,
    • a (meth)acrylating compound of a second type, and
    • an amine of the general formula NHR6R7 or Q′-NR1R2 wherein R6, R7, R1 and R2 are as defined above and wherein Q′ comprises a reactive group capable to react with a hydroxyl group to form e.g. an ester.

Combinations of different amines (e.g. some of formula NHR6R7 and some of formula Q′-NR1R2) can also be used.

The (meth)acrylating compound of a second type is a compound comprising at least one (meth)acrylate group and at least one reactive group capable to react with an hydroxyl group. Examples of such reactive group capable to react with a hydroxyl group are carboxylic acid, activated carboxylic acid, carboxylic acid esters or isocyanate groups. An example of (meth)acrylating compound is (meth)acrylic acid itself.

A (meth)acrylating compound of a second type can be obtained by the reaction of a (meth)acrylating compound of a first type and a linker comprising at least two reactive groups capable to react with an hydroxyl. Examples are polyisocyanates and polycarboxylic acids.

Examples of suitable diisocyanates and triisocyanates are:

wherein R8 is as described above. An example of polycarboxylic acid is HOOCR8COOH, activated versions thereof or transesterifiable ester thereof wherein R8 is as described above.

In an alternative embodiment, the synthesis may proceed by the reaction of 1) type II photoinitiator derivative PI bearing a reactive group capable to react with a hydroxyl group to form e.g an ester with 2) a linker comprising from 3 to 400 hydroxyl groups, 3) a linker comprising at least two reactive groups capable to react with an hydroxyl, 4) a (meth)acrylating compound of a first type, and 5) an amine of the general formula NHR6R7 or Q′-NR1R2 wherein R6, R7, R1 and R2 are as defined above and wherein Q′ comprises a reactive group capable to react with a hydroxyl group to form e.g. an ester. Combinations of different amines (e.g. some of formula NHR6R7 and some of formula Q′-NR1R2) can also be used.

In a preferred embodiment, the synthesis may proceed by the reaction of 1) a phenyl substituted benzophenone derivative bearing on its benzophenone moiety a reactive group capable to react with a hydroxyl group to form e.g. an ester with 2) a linker comprising from 3 to 400 hydroxyl groups, 3) a linker comprising at least two reactive groups capable to react with an hydroxyl, 4) a (meth)acrylating compound of a first type, and optionally 5) a primary or secondary amine of general formula NHR6R7 or a tertiary amine Q′-NR1R2. Combinations of different amines (e.g. some of formula NHR6R7 and some of formula Q′-NR1R2) can also be used.

The linker comprising from 3 to 400 hydroxyl groups may be a polyhydroxy compound as defined in any embodiment of the first aspect of the present invention.

Q′ may for instance comprise a carboxylic acid, an activated carboxylic acid or a transesterifiable ester group.

Q′ may for instance be selected from the list consisting of the following groups: a C1-8 straight or branched alkyl, a C4-10 cyclic alkyl optionally substituted with a C1-4 straight or branched alkyl, and a phenyl group optionally substituted with a C1-4 straight or branched alkyl, wherein said groups are substituted with one or more carboxylic acid, activated carboxylic acid or transesterifiable carboxylic ester groups.

This permits the carboxylic acid or ester group of Q′ to form an ester with a hydroxyl of the linker G. For instance, Q′ may be HO—C(O)(CH2)2— or may be CH3—O—C(O)—C6H6— or may be HO—C(O)C6H6—.

The type II photoinitiator derivative PI bearing a reactive group capable to react with a hydroxyl to form e.g. an ester may have the following general formula:

PI and E may be as defined in the first aspect of the present invention.

R5 is a reactive group capable to react with a hydroxyl group to form e.g. an ester. This group can for instance be a carboxylic acid group or a modified carboxylic acid group capable to react with a hydroxyl group to form an ester. Examples of modified carboxylic groups are methyl carboxylate and activated carboxylic acid groups such as an acyl halide group (e.g. an acyl chloride or acyl bromide group) or an anhydride group.

PI may for instance be a phenyl substituted benzophenone.

The phenyl-substituted benzophenone derivative can be for instance 2-(4-phenylbenzoyl)benzoic acid.

The preparation of 2-(4-phenylbenzoyl)benzoic acid is for example described in U.S. Pat. No. 1,814,145 from phthalic anhydride and biphenyl.

Other benzophenone derivatives may be prepared in an analogous way.

The preparation of carboxy substituted benzophenone is described for example in Journal of Chemical Research, Synopses, (10), 650-651; 2003 and in Journal of combinatorial chemistry 10(2), p 333-342, 2008

The preparation of carboxy substituted thioxanthones is described for example in Organic & Biomolecular Chemistry, 4(22), p 4101-4112; 2006.

The preparation of carboxy substituted anthraquinone is for example described Organic Preparations and Procedures International; Volume 13, Issue 5, p 368-71, 1981

The preparation of carboxy substituted 1-2 diketone is described for example in From Journal of Organic Chemistry, 53(7), 1353-6; 1988

Hydroxyl substituted PI can easily be transformed in carboxy substituted PI:

The preparation of hydroxyl substituted benzophenone is described for example in Tetrahedron, 67(3), 641-649; 2011. These can be reacted for example with chloroacetic acid to get a carboxy substituted benzophenone

The preparation of hydroxyl substituted thioxanthones is described for example in synthesis, Issue 17, p 2900-2904, 2004. These can be reacted for example with chloroacetic acid to get a carboxy substituted thioxanthones

The preparation of hydroxymethyl substituted anthraquinone is for example described. in Journal of Organic Chemistry, Volume 75, Issue 2, p 412-416; 2010. These can be reacted for example with chloroacetic acid to get a carboxy substituted anthraquinone

The preparation of hydroxyl substituted anthraquinone is for example described in Canadian Journal of Chemistry, Volume 61, Issue 9, p 1965-9, 1983. These can be reacted for example with chloroacetic acid to get a carboxy substituted anthraquinone

The linker comprising reactive groups capable to react with a carboxylic acid group or with an activated carboxylic acid group to form an ester may be a polyhydroxy compound as defined above or a polyhydroxy compound which hydroxyl groups have been modified into other reactive groups capable to react with a carboxylic acid or an activated carboxylic acid to form an ester (as also defined above).

In an embodiment, the PI derivative (e.g. a phenyl substituted benzophenone derivative) may be first reacted with said linker, and in a second step with said (meth)acrylating compound.

Alternatively, the PI derivative and the (meth)acrylating compound can be reacted together with the linker.

Alternatively, the (meth)acrylating compound of the second type may be first reacted with said linker, and in a second step the reaction product of the first step is then further reacted with a phenyl substituted benzophenone derivative as described above.

In embodiments, the PI derivative may be reacted with the reactive groups (e.g. hydroxyls groups) of the linker (e.g. polyhydroxy compound) by an esterification reaction with equivalent ratios of 0.05:1 or more, preferably of 0.1:1 or more and most preferably of 0.2:1 or more.

In embodiments, the PI derivative may be reacted with the reactive groups (e.g. hydroxyls groups) of the linker (polyhydroxy compound) by an esterification reaction with equivalent ratios of 0.95:1 or less, preferably of 0.75:1 or less and most preferably of 0.5:1 or less.

After reaction between the PI derivative and the linker, residual reactive groups on the linker (e.g. hydroxyl groups) may be further reacted partially or totally with a (meth)acrylicating compound.

In an embodiment, the process may further comprise reacting the reaction product of the linker, PI derivative and a (meth)acrylating compound with an amine of general formula NHR6R7 or Q′-NR1R2, thereby obtaining an amino photo-reactive binder. Combinations of different amines (e.g. some of formula NHR6R7 and some of formula Q′-NR1R2) can also be used

When a primary or secondary amine is reacted, it is preferably reacted after that the PI derivative, the (meth)acrylating compound and the linker have been reacted together.

In an embodiment of the present invention, the amino photo-reactive binder may be obtained by the reaction of at least one primary amine and/or at least one secondary amine with part of the (meth)acrylic unsaturations of the photo-reactive binder. It is advantageous to keep at least one (meth)acrylic unsaturation unreacted in order to insure that the obtained amino photo-reactive binder has at least one (meth)acrylic unsaturation for future integration in a (meth)acrylate network.

In an embodiment of the present invention, the amino photo-reactive binder may be prepared by performing an Aza-Michael addition of at least one primary amine and/or at least one secondary amine onto a (meth)acrylate function of the photo-reactive binders. An example of amino photo-reactive binder preparation is shown below:

Amines used to prepare “amino photo-reactive binders” of the present invention are generally selected from primary amines (R1—NH2) and/or secondary amines (R1—NH—R2) as described in the first and second aspect of the present invention.

In an embodiment, the amino photo-reactive binder may be prepared by an addition reaction of at least one primary amine and/or at least one secondary amine to (meth)acrylic double bonds with an equivalent ratio amine:(meth)acrylic double bonds of 0.05:1 or more, preferably 0.1:1 or more and most preferably 0.2:1 or more.

In an embodiment, the amino photo-reactive binder may be prepared by an addition reaction of at least one primary amine and/or at least one secondary amine to (meth)acrylic double bonds with an equivalent ratio amine:(meth)acrylic double bonds of 0.95:1 or less, preferably 0.75:1 or less and most preferably 0.5:1 or less.

In an embodiment, the amino photo-reactive binder may be prepared by an esterification or transesterification reaction between a) a tertiary amine bearing reactive groups capable to react with an hydroxyl to form an ester (e.g. carboxylic acid groups or the corresponding esters), and b) hydroxyl groups on the linker G.

Examples of tertiary amines that can be used are polymeric tertiary amines. By “polymeric” is meant that the number average molecular weight (Mn) of the polymeric tertiary amine is preferably of 400 g/mol or more, more preferably of 500 g/mol or more and most preferably of 600 g/mol or more. Typically the molecular weight of these compounds is at most 5.000 g/mol more preferably at most 3.000 g/mol and most preferably at most 2.000 g/mol.

An example of suitable polymeric tertiary amines in this category: dialkyl aminobenzoate esters and more in particular dimethylaminobenzoate esters as described e.g. in U.S. Pat. No. 5,905,164. Both monoamines and diamines can be used, possibly a mixture of both.

An example of a suitable diamine compound in this category is polyethyleneglycol bis (p-dimethyl aminobenzoate) as disclosed in U.S. Pat. No. 5,905,164

These compounds typically exist in a mixture as described in U.S. Pat. No. 5,905,164 p 10, with n typically in the range of from 2 to 110, more preferably from 4 to 61, most preferably from 7 to 40.

Another example of a suitable diamine compound in this category is polytetrahydrofurane bis (p-dimethyl aminobenzoate)

with n typically in the range of from 2 to 65, more preferably from 3 to 40, most preferably from 4 to 25.

An example of a suitable monoamine compound in this category is 4-N,N′-dimethylaminobenzoyl polyethyleneglycol monomethylether as disclosed in U.S. Pat. No. 5,905,164

with n typically in the range of from 2 to 110, more preferably from 4 to 61, most preferably from 7 to 40.

Particularly preferred compounds in this category are Omnipol ASA from IGM (a Poly(ethyleneglycol) bis(p-dimethylamino benzoate) with number average molecular weight 488-532 g/mol), ESACURE™ A198 from Lamberti & Speedcure 7040 from Lambson (polymeric (mix 4+2)amine with number average molecular weight 1060 g/mol).

In an embodiment, the amine(s) may be added in an amount such that the reaction product has a nitrogen content of 0.1% wt or more, preferably 0.2% wt or more and most preferably 0.3% wt or more.

In an embodiment, the amine(s) may be added in an amount such that the reaction product has a nitrogen content of 10% wt or less, preferably 5% wt or less and most preferably 3% wt or less.

In an embodiment, the residual (meth)acrylic content in the amine photo-reactive binder (e.g. after reaction of the amine(s) with the photo-reactive binder) is 0.5 meq/g or more, preferably 1 meq/g or more, most preferably 2 meq/g or more.

In an embodiment, the residual (meth)acrylic content in the amine photo-reactive binder (e.g. after reaction of the amine(s) with the photo-reactive binder) is 10 meq/g or less, preferably 8 meq/g or less, most preferably 5 meq/g or less.

In embodiments where the primary or secondary amine is an aromatic amine, an appropriate catalyst is preferably used to promote the Aza-Michael addition. For instance, the catalyst may be selected from Brønsted or Lewis acids or bases, yttrium trinitrate hexahydrate (Y(NO3)3.6H2O), ionic liquids, clays and other catalysts described in Tetrahedron Letters 47 (2006)7723-7726 and Catalysis Communications 9 (2008) 1189-1195 or glacial acetic acid as described in WO 2011/117591 A2 (Sun Chemical). This is advantageous since it permits to obtain good yield despite the lower nucleophilicity of aromatic amines when compared to alkyl or alkenyl amines.

Yet another aspect of the invention concerns products obtainable by a process according to the invention.

DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present invention will be described with respect to particular embodiments but the invention is not limited thereto.

Example 1: General Procedure for the Synthesis of a Compound PI1 (and for Compounds PI2 and PI3

To a 1 liter double jacketed reactor vessel connected to an oil bath and equipped with a stirrer, was added 100 g of polyhydroxy compound 4631 (polyhydroxy compound commercially available from Perstorp); “a” g of acrylic acid; “b” g of paratoluenesulfonic acid; “c” g of carboxy substituted benzophenone “d”; 1000 ppm of a phosphite type inhibitor; 600 ppm of a hydroquinone type inhibitor; 1250 ppm of a cupper type inhibitor and 116 g of toluene. The reaction mixture was stirred and heated under reflux until no more water was distilled. The reaction mixture was cooled down to 60° C. and diluted with 39 g of toluene. The reaction mixture was washed 3 times with an aqueous solution (15 wt %) of sodium sulphate. Water was then removed by azeotropic distillation under reduced pressure. Once no more water distilled, the organic mixture was filtered at 50° C. and toluene was removed by distillation under reduced pressure.

The table below gives the values for parameters “a”, “b”, “c” and “d”.


PI 1 (ex. 1.1)
PI 2 (ex. 1.2)
PI 3 (ex. 1.3)
“a”
86
86
66
“b”
 5
 5
 4
“c”
85
89
73
“d”
2-(4-
2-(4-
2-(4-
Phenylbenzoyl)-
Phenoxybenzoyl)benzoic
chlorobenzoyl)benzoic
benzoic acid
acid
acid

Precursors:

  • 2-(4-Phenylbenzoyl)benzoic acid precursor (example 1.1): X=Phenyl
  • 2-(4-Phenoxybenzoyl)benzoic acid precursor (example 1.2): X=Phenoxy
  • 2-(4-chlorobenzoyl)benzoic acid precursor (example 1.3): X=Cl

Example 2: Preparation of a Compound PI4 According to an Embodiment of the Present Invention: Reaction of a Secondary Amine with an Acrylated Carboxy Substituted Benzophenone Polyhydroxy Compound

1.65 g of diethylamine (secondary amine) was added to 20 g of the acrylated carboxy substituted benzophenone polyhydroxy compound (see example 1.1), homogenized and heated at 40° C. for 24 hours.

Example 3: Evaluation of the Photoreactivity of the Compound PI4


OPV 4
OPV 5
Wt %
Wt %
EBECRYL LEO ™ 10501
70
70
PI 4
30
PI 1
30
Graphite test m/min under air 4 microns
10
<1
ADR test 60 m/min (1x) under air 4 microns
4
0
ADR test 60 m/min (5x) under air 4 microns
30
1

ADR: acetone double rubs

Graphite Test:

This test is performed by placing some graphite on the coated surface, followed by rubbing said surface with a piece of cotton. If no black stain remain on the surface, the surface is considered cured.

“10 m/min” means that curing at 10 m/min was necessary to pass the graphite test.

Acetone Double Rubs Test:

The rubs are made with a piece of cotton rag saturated with acetone; one double rub is equal to a forward and backward stroke on the coated surface. The reported number is the number of double rubs required to break through the coating. “60” means that 60 doubles rubs are necessary to break through the coating.

The photo reactivity of the formulation based on photo-reactive binder PI 1 reacted with amine synergist 1 (diethylamine adduct) (PI 4) is significantly higher than the photo reactivity of a formulation based on the Photo-reactive binder without amine synergist (2-(4-Phenylbenzoyl)benzoic acid precursor PI 1) (OPV 5).

This shows that the amine synergist keeps its co-initiating role despite being covalently bound to the PI.

Example 4: Evaluation of the Photoreactivity of the Compound PI4 Compared with Commercially Available Polymeric Photoinitiators

Omnipol BP is a di-functional benzophenone photoinitiator specifically designed for use in inks and coatings requiring low migration and low volatility. It is particularly suited to use, in combination with amine synergists, in non-pigmented coatings as an alternative to benzophenone. Its chemical structure is Di-ester of carboxymethoxy-benzophenone and polytetramethylene glycol 250; molecular weight 730; CAS 515136-48-8

Omnipol 910 is a kind of photoinitiator with high activity, good compatibility, low odor and migration, and with low fragments releasing after curing. It is specifically designed for use in inks and coatings requiring low migration and low volatiles. Its chemical structure is Polyethylene Glycol di(β-4[4-(2-dimethylamino-2-benzyl)butaonylphenyl]piperazine) propionate, molecular weight 1032; CAS 886463-10-1

The following formulations were prepared and their cure-speed was assessed by curing film at 1.5 g/m2 under air using a UV lamp of 120 W/cm. Graphite test (m/min) gives the speed at which a stain free print is obtained; the higher the more reactive. The Total Energy dose (mJ/cm2) is the energy necessary to have a stain free print; the lower the more reactive


FI 4
FI 6
FI 8
FI 10
(comp)
FI 5
(comp)
FI 7
(comp)
FI 9
(comp)
FI 11
EBECRYL 452
26.5
26.5
18.9
18.9
19
19
EBECRYL LEO
10.8
10.8
10601
EBECRYL LEO
13.5
13.5
10501
ADDITOL S 130
0.4
0.4
0.35
0.35
0.35
0.35
0.45
0.45
Solspers 39000
0.8
0.8
1.75
1.75
1.3
1.3
2.25
2.25
(Lubrizol)
Solsperse 22000
0.3
0.3
(Lubrizol)
Solsperse 5000
0.35
0.35
(Lubrizol)
Yellow DGR
12
12
(Clariant)
Magenta pigment
14
14
4 BY (SUN)
Cyan pigment GLO
14
14
(Ciba-BASF)
Special Black 250
18
18
(Evonik)
EBECRYL 570
10
10
10
5
10
5
5
EBECRYL LEO
10
20
15
30
15
30
10
25
10501
EBECRYL LEO
30
30
30
30
10551
Ominpol BP
5
5
5
5
(IGM)
Omnipol 910
5
5
5
5
(IGM)
PI 4
30
30
30
30
100
100
100
100
100
100
100
100
Cure speed- under air - 1.5 g/m2 film - 120 W/cm
Graphite test
10
30
20
40
20
45
20
50
(m/min)
Total Energy dose
700
260
400
180
400
160
400
140
(mJ/cm2)

The photoreactivity of compound PI 4 was compared with a mixture of the two Omnipol BP and 910 polymeric photoinitiator in flexo inks (4 process colors). Overall, an addition of 30 wt % of compound of PI 4 leads to higher reactivity than comparative examples using commercial photoinitiators instead.

Example 8: Preparation of a Compound PI5 According to an Embodiment of the Present Invention Wherein: Reaction of a Primary (Octylamine) and Secondary Amine (Dibutylamine) with an Acrylated Carboxy Substituted Benzophenone Polyhydroxy Compound PI1

45.8 g of dibutylamine (secondary amine) and 30.5 g of octylamine (primary amine) were added to 750 g of the acrylated carboxy substituted benzophenone polyhydroxy compound (PI 1, see example 1.1), homogenized and heated at 40° C. for 24 hours. The nitrogen content is 1 wt %.

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Citation

Patents Cited in This Cited by
Title Current Assignee Application Date Publication Date
Radiation curable compositions AGFA GRAPHICS N.V. 09 September 2008 10 March 2010
一种二苯甲酮类光引发剂及其制备方法 长沙新宇高分子科技有限公司 17 January 2013 24 April 2013
二苯甲酮衍生物与其作为光引发剂的应用 惠州市华泓新材料有限公司 31 July 2012 07 November 2012
光反应性粘结剂 湛新比利时股份有限公司 18 December 2012 01 October 2014
反应型二苯甲酮光引发剂及其制备方法 常州华钛化学有限公司 03 February 2005 01 February 2006
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