Photoinitiator package containing special bisacylphosphine oxide photoinitiators and optical brightener sensitizers

Abstract

A photoinitiator package comprising one or more bisacylphosphine oxide photoinitiators and one or more optical brightener sensitizers, a photopolymerizable composition comprising the photoinitiator package and a suitable polymerizable compound, a method for polymerizing the photopolymerizable composition, and the use of the photoinitiator package in photopolymerization applications.

Description

[Technical field]

[0001] The present invention relates to a photoinitiator package comprising one or more bisacylphosphine oxide photoinitiators and one or more optical brightener sensitizers, a photopolymerizable composition comprising the photoinitiator package and a suitable polymerizable compound, a method of polymerizing the photopolymerizable composition, and the use of the photoinitiator package in photopolymerization applications. [Background technology]

[0002] Photoinitiators that promote the radical polymerization of ethylenically unsaturated compounds may be classified as either Norrish Type I, in which an electronically excited photoinitiator decomposes to form free radicals that act to initiate radical polymerization, or Norrish Type II, in which an electronically excited photoinitiator abstracts a hydrogen radical from an additional molecule to form a free radical from said additional molecule that acts to initiate radical polymerization. Type II photoinitiators require the presence of certain additives / co-initiators, which are not typically required for Type I photoinitiators.

[0003] The development of new type I photoinitiators is an important area of ​​research in the field of resin curing. In addition to offering new type I photoinitiators, type I photoinitiator packages are also offered in which the activity of the type I photoinitiator is enhanced by the presence of other compounds, such as photosensitizers. These compounds absorb light at a different wavelength than the photoinitiator itself and transfer the energy to the photoinitiator, improving the energy absorption by the photoinitiator.

[0004] Phosphine oxides are a well-known family of Type I photoinitiators that offer excellent activity due to the highly reactive phosphinoyl radicals formed upon fragmentation. Phosphine oxides are excellent photoinitiators for deep cure systems, but are notoriously much less effective at achieving surface cure. Therefore, blends of phosphine oxide photoinitiators with other photoinitiators known to be effective for surface cure are often used to ensure complete cure. Summary of the Invention [Problem to be solved by the invention]

[0005] The extent to which different type I photoinitiators interact with sensitizers is difficult to predict and often depends on the photoinitiator structure and energy levels. Providing a highly active photoinitiator package is desirable because it would improve photopolymerization without the need to develop new photoinitiators. In particular, improving the surface-cure ability of phosphine oxide photoinitiators would allow these powerful photoinitiators to be more widely applied. [Means for solving the problem]

[0006] The present disclosure is based on the observation that the combination of a sensitizer and a particular bisacylphosphine oxide photoinitiator unexpectedly possesses superior photoinitiator properties, including surface cure capability.

[0007] Thus, in a first aspect, the present invention provides a method for producing a method for treating a cancer a) one or more bisacylphosphine oxide photoinitiators, each having the structure of Formula (I): [ka] wherein each instance of R is independently selected from the group consisting of 1 ~C 4 is selected from the group consisting of alkyl, X is a direct single bond, O, S, NR 3 , -CH 2 CO 2 - and -CH 2 CH 2 CO 2 - selected from the group consisting of R 1 is C 1 ~C 40 Alkyl and one or more O or C 3 ~C 8 Cycloalkylene Interrupted C 2 ~C 40 alkyl, 1 ~C 40Alkyl or interrupted C 2 ~C 40 Alkyl is unsubstituted or is selected from the group consisting of OH and R 2 and optionally substituted with one or more groups selected from R 2 teeth, [ka] and R 3 is hydrogen, (CO)R 4 , Phenyl, C 1 ~C 12 Alkyl and C interrupted by one or more O 2 ~C 12 Alkyl, C 3 ~C 12 cycloalkyl; 1 ~C 12 Alkyl or interrupted C 2 ~C 12 Alkyl is unsubstituted or has one or more C 3 ~C 7 cycloalkyl, OH or NCO substituted, 3 ~C 12 Cycloalkyl is unsubstituted or has one or more C 1 ~C 4 Alkyl, C 1 ~C 4 alkoxy, OH or NCO substituted; R 4 is C 1 ~C 12 Alkyl and C interrupted by one or more O 2 ~C 12 alkyl, 1 ~C 12 Alkyl or interrupted C 2 ~C 12 Alkyl is unsubstituted or has one or more C 3 ~C 7 cycloalkyl, OH, NCO or phenyl, wherein the phenyl is substituted with NCO, C 3 ~C 12 Cycloalkyl, C2 ~C 10 Alkenyl, C 6 ~C 14 aryl-substituted, 2 ~C 10 Alkenyl is unsubstituted or has one or more C 1 ~C 4 Alkyl, OH or C 1 ~C 4 alkoxy, and the above C 6 ~C 14 Aryl is unsubstituted or C 1 ~C 12 Alkyl, C 1 ~C 12 Alkoxy, NCO or NCO substituted C 1 ~C 12 substituted with alkyl. b) one or more optical brightener sensitizers; The present invention is directed to a photoinitiator package comprising:

[0008] In a second aspect, the present invention provides a method for producing a method for the treatment of a pulmonary arthritis, comprising: a) one or more ethylenically unsaturated free radically polymerizable compounds; b) a photoinitiator package according to the first aspect; The present invention is directed to a photopolymerizable composition comprising:

[0009] In a third aspect, the present invention provides a method of photocuring photopolymerizable compositions, coatings, adhesives and inks, comprising: a) coating or printing the photopolymerizable composition according to the second aspect onto a substrate; b) photopolymerizing the composition coated or printed on the substrate with a light source; In one embodiment, the method includes, in a given order:

[0010] In a final aspect, the present invention is directed to the use of a photoinitiator package according to the first aspect in the manufacture of printing inks, screen printing inks, gravure printing inks, solder masks, etch offset printing inks, flexographic printing inks, gravure printing inks, inkjet inks, resist materials, insulators, encapsulants, image recording materials, solder masks, passivation layers, protective coatings, 3D printed objects and moulds, holographic applications, optical fibre coatings, wave guides and lenses, overprint varnishes, wood, vinyl, metal and plastic coatings. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] definition As used herein, unless otherwise indicated, the expressions "alkyl" or "alkyl group" mean a straight or branched saturated alkyl chain containing the given number of carbon atoms and include all possibilities for each number of carbon atoms in the alkyl group, i.e., n-propyl and i-propyl for three carbon atoms, n-butyl, i-butyl, s-butyl and t-butyl for four carbon atoms, and similarly for other numbers of carbon atoms.

[0012] The term "aryl" or "aryl group" includes substituted or unsubstituted aryl groups, such as, for example, substituted or unsubstituted phenyl groups, substituted or unsubstituted naphthyl groups, anthracenyl groups, indenyl groups, fluorenyl groups, and the like.

[0013] The terms "heteroaryl" or "heteroaryl group" include substituted or unsubstituted heteroatom-containing aromatic ring systems, such as, for example, pyridine, pyrrole, furan, triazine, indole, quinolone, thiophene, and the like.

[0014] "C interrupted by one or more oxygen 1 ~C 40 The term "alkyl" means that when two or more oxygen atoms are present, the oxygen atoms are separated from one another by at least one methylene group, i.e., the oxygen atoms are non-consecutive. Examples include -OCH2 OCH 3 ,-OCH 2 CH 2 OCH 2 CH 3 ,-O[CH 2 CH 2 O] v CH 3 ,-O[CH 2 CH 2 O] v OH,-O[CH 2 CH 2 O] v CH 2 CH 3 ,-CH 2 O[CH 2 CH 2 O] v CH 3 (v = 1~19),-O[CH 2 CH 2 CH 2 O] p OH,-O[CH 2 CH 2 CH 2 O] p CH 3 ,-O[CH 2 CH 2 CH 2 O] p CH 2 CH 3 ,-CH 2 O[CH 2 CH 2 CH 2 O] p CH 3 (p = 1~12) are exemplified.

[0015] Where a group is substituted, the term "substituted" means that said group has one or more substituents, said substituents being preferably selected from halogen atoms, alkyl, cycloalkyl, alkoxy, alkylamino, dialkylamino, alkylthio or arylthio groups, heterocyclic groups, more preferably methyl, ethyl, isopropyl, tert-butyl, phenyl, trifluoromethyl, cyano, acetyl, ethoxycarbonyl, carboxyl, carboxylate, amino, methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, diisopropylamino, cyclohexylamino, dicyclohexylamino, acetylamino, piperidino, pyrrolidinyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, phenoxy, hydroxyl, acetoxy, -PO 3 It is selected from H, methylthio, ethylthio, i-propylthio, n-propylthio, phenylthio, mercapto, acetylthio, thiocyano, methylsulfinyl, methylsulfonyl, dimethylsulfonyl, a sulfonate group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, trimethylsilyl, pentamethyldisilyl, triethylsilyl, trimethylstannyl, furyl, thienyl, pyridyl and morpholino.

[0016] The phrase "direct bond" means that there is no linking group and that a direct bond joins the two moieties on either side.

[0017] The methylene group is sp linked to two hydrogen groups. 3 Hybrid orbital carbon, i.e. -CH 2 R, whereas the methanetriyl group is a sp 3 Hybrid orbital carbon, i.e. -CHR 2 Refers to...

[0018] Photoinitiators may be classified as either Norrish Type I, in which an electronically excited photoinitiator decomposes to form free radicals that act to initiate radical polymerization, or Norrish Type II, in which an electronically excited photoinitiator abstracts a hydrogen radical from a further molecule to form a free radical from the further molecule that acts to initiate radical polymerization, as is well understood by those skilled in the art.

[0019] The term "photopolymerization package" refers to a combination of one or more photoinitiators and any components, such as synergists and / or sensitizers, that interact with the photoinitiators to affect the photoinitiator properties of the photopolymerization package. The term "photopolymerization package" does not include any further additives that do not affect the photopolymerizable monomers or the photoinitiator properties of the photopolymerization package, such as fillers, pigments, antistatic agents, wetting agents or flow enhancers, adhesion enhancers and / or plasticizers that are present to adjust the properties of the polymerizable composition (e.g., the flow properties of the polymerizable composition) or the mechanical properties or appearance of the resulting cured composition. Furthermore, the term "photopolymerization package" in the context of the present invention means that the components of the package are provided together as a blend, preferably in the form of a blend that is liquid at 25°C and standard pressure.

[0020] In the context of the present invention, in order for a blend to be called a "liquid", the blend must be a single-phase liquid, i.e. a blend that is a suspension having a solid and a liquid phase would not be classified as a "liquid" in the context of the present invention, nor would an emulsion, which has multiple immiscible liquid phases.

[0021] Bisacylphosphine oxide photoinitiator One essential feature of the photoinitiator package of the present invention is one or more bisacylphosphine oxide photoinitiators.

[0022] The one or more bisacylphosphine oxide photoinitiators each have the structure of Formula (I). [ka] wherein each instance of R is independently selected from the group consisting of 1 ~C 4 is selected from the group consisting of alkyl, X is a direct single bond, O, S, NR 3 , -CH 2 CO 2 - and -CH 2 CH 2 CO 2 is selected from the group consisting of R 1 is C 1 ~C 40 Alkyl and one or more O or C 3 ~C 8 Cycloalkylene Interrupted C 2 ~C 40 alkyl, 1 ~C 40 Alkyl or interrupted C 2 ~C 40 Alkyl is unsubstituted or is selected from the group consisting of OH and R 2 and optionally substituted with one or more groups selected from R 2 teeth, [ka] and R 3 is hydrogen, (CO)R 4 , Phenyl, C 1 ~C 12 Alkyl and C interrupted by one or more O 2 ~C 12 Alkyl, C 3 ~C 12 cycloalkyl; 1 ~C 12 Alkyl or interrupted C 2 ~C 12 Alkyl is unsubstituted or has one or more C 3 ~C 7 cycloalkyl, OH or NCO substituted,3 ~C 12 Cycloalkyl is unsubstituted or has one or more C 1 ~C 4 Alkyl, C 1 ~C 4 alkoxy, OH or NCO substituted; R 4 is C 1 ~C 12 Alkyl and C interrupted by one or more O 2 ~C 12 alkyl, 1 ~C 12 Alkyl or interrupted C 2 ~C 12 Alkyl is unsubstituted or has one or more C 3 ~C 7 cycloalkyl, OH, NCO or phenyl, wherein the phenyl is substituted with NCO, C 3 ~C 12 Cycloalkyl, C 2 ~C 10 Alkenyl, C 6 ~C 14 aryl-substituted, 2 ~C 10 Alkenyl is unsubstituted or has one or more C 1 ~C 4 Alkyl, OH or C 1 ~C 4 alkoxy, and the above C 6 ~C 14 Aryl is unsubstituted or C 1 ~C 12 Alkyl, C 1 ~C 12 Alkoxy, NCO or NCO substituted C 1 ~C 12 substituted with alkyl.

[0023] Each instance of R is independently 1 ~C 4It may be selected from the group consisting of alkyl, i.e., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl and t-butyl. It is particularly preferred that each instance of R is selected from methyl and ethyl. Most preferably, each instance of R is methyl.

[0024] X is a direct single bond, O, S, NR 3 , -CH 2 CO 2 - and -CH 2 CH 2 CO 2 More preferably, X is selected from the group consisting of a direct bond, O, -CH 2 CO 2 - and -CH 2 CH 2 CO 2 Even more preferably, X is selected from the group consisting of a direct single bond, -CH 2 CO 2 - and -CH 2 CH 2 CO 2 -. Most preferably, X is a direct single bond.

[0025] X is a direct single bond, -CH 2 CO 2 - and -CH 2 CH 2 CO 2 -, this results in the phosphorus atom of the bisacylphosphine oxide moiety being bonded to carbon rather than oxygen, sulfur, or nitrogen. Bisacylphosphine oxides with carbon-bonded phosphorus, i.e., X is a direct single bond, -CH 2 CO 2 - and -CH 2 CH 2 CO 2 are particularly preferred as they have improved stability and / or improved photoinitiation properties.

[0026] R 1 is C 1 ~C 40Alkyl and one or more O or C 3 ~C 8 Cycloalkylene Interrupted C 2 ~C 40 alkyl, 1 ~C 40 Alkyl or interrupted C 2 ~C 40 Alkyl is unsubstituted or is selected from the group consisting of OH and R 2 and optionally substituted with one or more groups selected from R 2 teeth, [ka] It is.

[0027] In some embodiments, R 2 is not present, which means that the structure of formula (I) has a single bisacylphosphine oxide moiety.

[0028] In such an embodiment, R 1 is C 1 ~C 20 Alkyl, -(CH 2 CH 2 O-) n CH 3 and -(CH 2 CH 2 O-) n H (n is an integer in the range of 1 to 20). 1 C 1 ~C 20 Alkyl is particularly preferred.

[0029] Particularly preferred is where X is a direct single bond and R 1 C 1 ~C 20 It is particularly preferred that each instance of R is methyl.

[0030] Similarly, X is O and R 1 Ga-(CH 2 CH2 O-) n CH 3 or -(CH 2 CH 2 O-) n Also particularly preferred are embodiments in which R is H. Within such embodiments, it is especially preferred that each instance of R is methyl.

[0031] In other embodiments, R 2 There is at least one instance of: which means that the structure of formula (I) has two or more bisacylphosphine oxide moieties.

[0032] Such an embodiment preferably comprises R 1 is described by formula (I) having the structure of formula (II). [ka] wherein each instance of M is independently selected from the group consisting of (CH 2 CH 2 O) and (CH 2 CH(CH 3 )O) Each instance of Y is independently hydrogen and C 1 ~C 4 alkyl, Each example of Z has the structure CH 2 (M 1 ) c R 2 having M 1 Each example of (OCH 2 CH 2 ) and (OCH(CH 3 )CH 2 ), a is an integer ranging from 0 to 15; b is an integer ranging from 0 to 6; each instance of c is independently an integer in the range of 0 to 15; m is an integer ranging from 0 to 2; Each instance of X is independently -CH 2 CO 2 - and -CH 2 CH2 CO 2 - is selected from the group consisting of

[0033] Such structures are typically formed by combining a central polyol core with multiple BAPO-based carboxylic acid residues, and are separated by ethylene glycol / propylene glycol spacers (i.e., units M and M 1 ) is optionally used to separate the central polyol core from the BAPO-based carboxylic acid residues.

[0034] Suitable polyol cores include glycerol, where b=0, m=1, and Y=H; trimethylolpropane, where b=1, m=1, and Y=ethyl; pentaerythritol, where b=1, m=0; neopentyl glycol, where b=1, m=2, and two instances of Y=methyl; ethylene glycol, where b=0, m=2, and two instances of Y=H; and 1,6-hexanediol, where b=4, m=2, and two instances of Y=H.

[0035] Other suitable polyols include propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-hexanediol, 1,5-hexanediol, 2,5-hexanediol. Those skilled in the art will know which values ​​of b and m and the selection of Y correspond to these polyols.

[0036] Particularly preferred polyol cores are glycerol, where b=0, m=1 and Y=H; trimethylolpropane, where b=1, m=1 and Y=ethyl; and pentaerythritol, where b=1, m=0.

[0037] When using the glycerol core, R 1 is referred to as "optionally ethoxylated / propoxylated glycerol."

[0038] When using trimethylolpropane core, R 1is referred to as "optionally ethoxylated / propoxylated trimethylolpropane."

[0039] When using a pentaerythritol core, R 1 is referred to as "optionally ethoxylated / propoxylated pentaerythritol."

[0040] When using the neopentyl glycol core, R 1 is referred to as "optionally ethoxylated / propoxylated neopentyl glycol."

[0041] When using an ethylene glycol core, R 1 is referred to as "optionally ethoxylated / propoxylated ethylene glycol."

[0042] When using the 1,6-hexanediol core, R 1 is referred to as "optionally ethoxylated / propoxylated 1,6-hexanediol."

[0043] It is particularly preferable that a is an integer in the range of 1 to 15, each instance of c is an integer in the range of 1 to 15, and the sum of each instance of a and c is in the range of 3 to 20, more preferably in the range of 3 to 15, and most preferably in the range of 3 to 10.

[0044] Such embodiments are referred to as "ethoxylated / propoxylated polyols," and the polyol may be glycerol, trimethylolpropane, pentaerythritol, neopentyl glycol, ethylene glycol, or 1,6-hexanediol.

[0045] R 1 is C 1 ~C 20 Alkyl, -(CH 2 CH 2 O-) n CH 3 , -(CH 2 CH 2 O-) nH (n is an integer in the range of 1 to 20), ethoxylated / propoxylated glycerol, ethoxylated / propoxylated trimethylolpropane, and ethoxylated / propoxylated pentaerythritol are particularly preferred.

[0046] R 1 C 1 ~C 20 If it is alkyl, R 1 is C 1 ~C 15 Alkyl, more preferably C 1 ~C 12 Alkyl is particularly preferred.

[0047] Examples of particularly preferred bisacylphosphine oxide photoinitiators having the structure of formula (I) include: [ka] [ka] [ka] wherein each instance of a and each instance of c are independently as defined for formula (II).

[0048] It is particularly preferred that each of the one or more bisacylphosphine oxide photoinitiators having the structure of Formula (I) is a liquid at 25° C. and standard pressure.

[0049] Optical brightener sensitizer Another essential feature of the photoinitiator package according to the present invention is the presence of one or more optical brightener sensitizers.

[0050] As will be appreciated by those skilled in the art, the term "sensitizer" in "one or more optical brightener sensitizers" describes the purpose of the optical brightener in the photoinitiator package and does not limit the choice of optical brightener that may be used.

[0051] Moreover, those skilled in the art will be well aware that optical brighteners are compounds that absorb light in the ultraviolet and violet regions of the EM spectrum and re-emit light in the blue region via fluorescence. Optical brighteners have been used in laundry detergents, in paper manufacturing, in cosmetics, and in some photopolymerizable compositions for textile whitening, as well as to improve the optical properties of the cured compositions.

[0052] In the broadest sense, any compound known for use as an optical brightener may be used in the photoinitiator package of the present invention.

[0053] Examples of such well-known optical brighteners include compounds having base units such as stilbene, triazine, thiazole, benzoxazole, coumarin, xanthene, triazole, oxazole, thiophene, and pyrazoline.

[0054] Fluorescent whitening agents having a coumarin core or a (benzo)oxazole core are particularly preferred.

[0055] In a first particularly preferred embodiment, at least one of the one or more optical brightener sensitizers has the structure of formula (III): [ka] (In the formula, R 3a is hydrogen, C 1 ~C 10 Alkyl, C 6 ~C 14 Aryl and C 6 ~C 14 Heteroaryl; R 4a is hydrogen, C 1 ~C 10 Alkyl and OR 1a is selected from the group consisting of R 5a ~R 8a each independently represents hydrogen, halogen, alkyl, OR 1a , and N.R.2a 2 is selected from the group consisting of R 1a Examples of each are hydrogen, C 1 ~C 10 Alkyl, and C 6 ~C 14 aryl; R 2a Examples of each are hydrogen, C 1 ~C 10 Alkyl, and C 6 ~C 14 aryl; R 1a ~R 8a Each instance of is optionally 1a ~R 8a may be combined with one or more further examples of to form one or more 5- or 6-membered rings.

[0056] In a preferred embodiment, R 3a is hydrogen and C 1 ~C 10 alkyl, or R 4a is hydrogen and C 1 ~C 10 alkyl.

[0057] In another preferred embodiment, R 3a is hydrogen and C 1 ~C 10 alkyl; R 4a is hydrogen and C 1 ~C 10 alkyl.

[0058] In another preferred embodiment, R 7a OR 1a and N.R. 2a 2 and most preferably selected from the group consisting of NR 2a 2 It is.

[0059] In a particularly preferred embodiment, R 3a is hydrogen and C 1 ~C 10alkyl, or R 4a is hydrogen and C 1 ~C 10 alkyl, while R 7a OR 1a and N.R. 2a 2 and most preferably selected from the group consisting of NR 2a 2 It is.

[0060] In a particularly preferred embodiment, R 3a is hydrogen and C 1 ~C 10 alkyl; R 4a is hydrogen and C 1 ~C 10 alkyl; R 7a OR 1a and N.R. 2a 2 and most preferably selected from the group consisting of NR 2a 2 It is.

[0061] At least one, and preferably all, of the coumarin-based sensitizers are selected from the group consisting of coumarin, 7-amino-4-(trifluoromethyl)coumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 7-hydroxy-4-(trifluoromethyl)coumarin, 7-(ethylamino)-4,6-dimethylcoumarin, 7-methoxy-4-(trifluoromethyl)coumarin, 7-ethoxy-4-(trifluoromethyl)coumarin, 7-amino-4-methylcoumarin, 7-(diethylamino)-4-methylcoumarin, 3-(2-benzoxazolyl)-7-(diethylamino)coumarin, 7-methylcoumarin, 7-methoxycoumarin, 4-hydroxycoumarin, 5,7-dimethoxycoumarin, 3-(3-biphenyl-4-yl-1, 2,3,4-tetrahydro-1-naphthyl)-4-hydroxycoumarin, 6-methylcoumarin, 3-chloro-7-hydroxy-4-methylcoumarin, 7-hydroxycoumarin, 7-hydroxy-6-methoxycoumarin, 7-methoxy-6-hydroxycoumarin, 6-hydroxycoumarin, 7,8-dihydroxy-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 7-(dimethylamino)-4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizin-11-one, 7-(diethylamino)-4-(trifluoromethyl)-coumarin, and 7-(ethylamino)-4-(trifluoromethyl)coumarin.

[0062] More preferably, at least one, and preferably all, of the coumarin based sensitizers are selected from the group consisting of coumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 7-methoxy-4-(trifluoromethyl)coumarin, 7-ethoxy-4-(trifluoromethyl)coumarin, 7-(diethylamino)-4-methylcoumarin, 3-(2-benzoxazolyl)-7-(diethylamino)coumarin, 7-methylcoumarin, 7-methoxycoumarin, 5,7-dimethoxycoumarin, 6-methylcoumarin, 7-(dimethylamino)-4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizin-11-one, 7-(diethylamino)-4-(trifluoromethyl)-coumarin, and 7-(ethylamino)-4-(trifluoromethyl)coumarin.

[0063] Most preferably, at least one, and preferably all, of the coumarin-based sensitizers are selected from the group consisting of coumarin, 7-(diethylamino)-4-methylcoumarin, 7-methylcoumarin, 7-methoxycoumarin, 5,7-dimethoxycoumarin, and 7-(diethylamino)-4-(trifluoromethyl)-coumarin.

[0064] In a second particularly preferred embodiment, at least one of the one or more optical brightener sensitizers has the structure of formula (IV). [ka] (In the formula, R 1b ~R 4b each independently represents hydrogen, C 1 ~C 10 Alkyl and C 6 ~C 14 aryl; R 1b and R 2b may be joined to form a 6-membered saturated or unsaturated ring, which may be joined by hydrogen, C 1 ~C 10 Alkyl and C 6 ~C 14aryl, R 3b and R 4b may be linked to form a 6-membered saturated or unsaturated ring, which may be hydrogen, C 1 ~C 10 Alkyl and C 6 ~C 14 aryl, A represents a linking group represented by any one of the following formulas (V) to (IX): [ka] Each * represents the bonding position of A in each formula.

[0065] R 1b ~R 4b each independently represents hydrogen, C 1 ~C 10 Alkyl and C 6 ~C 14 aryl; R 1b and R 2b may be linked to form a 6-membered saturated or unsaturated ring, which may be hydrogen, C 1 ~C 10 Alkyl and C 6 ~C 14 aryl, R 3b and R 4b may be linked to form a 6-membered saturated or unsaturated ring, which may be hydrogen, C 1 ~C 10 Alkyl and C 6 ~C 14 It may be substituted with one or more substituents selected from the group consisting of aryl.

[0066] In one embodiment, R 1b ~R 4b each independently represents hydrogen, C 1 ~C 6 Alkyl and C 6 ~C 10 aryl.

[0067] In a particularly preferred embodiment, R 1b and R 3b Both are R 2b and R 4b to form a 6-membered saturated or unsaturated ring, which may be joined to any one of hydrogen, C 1 ~C 10 Alkyl and C 6 ~C 14 It may be substituted with one or more substituents selected from the group consisting of aryl.

[0068] In one embodiment of the particularly preferred embodiment, each six-membered ring formed is aromatic, meaning that at least one of the one or more oxazole sensitizers is a benzoxazole sensitizer having the structure of formula (X). [ka] (In the formula, R 1c ~R 8c each independently represents hydrogen, C 1 ~C 10 Alkyl and C 6 ~C 14 aryl.

[0069] Preferably, R 1c ~R 8c each independently represents hydrogen, C 1 ~C 6 Alkyl and C 6 ~C 10 aryl.

[0070] In one embodiment, each of the one or more oxazole sensitizers has the structure of formula (X).

[0071] In other embodiments, at least one of the one or more oxazole sensitizers has a structure of formula (X), while any remaining oxazole sensitizers in the photoinitiator package have other structures of formula (IV).

[0072] Particularly preferred compounds of formula (IV) include 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole), 2,2'-(vinylenedi-p-phenylene)bisbenzoxazole, 2,2'-(naphthalene-1,4-diyl)bis(benzoxazole), 2-[4-[2-[4-(benzoxazol-2-yl)phenyl]vinyl]phenyl]-5-methylbenzoxazole, and 2,2'-(1,4-phenylene)bis[5-phenyl-oxazole].

[0073] Photoinitiator Package Photoinitiator packages according to the present invention include one or more bisacylphosphine oxide photoinitiators as described above and one or more optical brightener sensitizers as described above.

[0074] The photoinitiator package comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of formula (I) in an amount ranging from 15 to 99.9 wt.%, more preferably ranging from 30 to 99.0 wt.%, and most preferably ranging from 50 to 97.0 wt.%, based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 0.1 to 50% by weight, more preferably in the range of 1.0 to 40% by weight, and most preferably in the range of 3.0 to 35% by weight, based on the total weight of the photoinitiator package; It is preferred that the compound contains

[0075] In one embodiment, the photoinitiator package comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of Formula (I) in an amount ranging from 15 to 99.9 wt. %, based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 0.1 to 50% by weight, based on the total weight of the photoinitiator package; Includes.

[0076] In a further embodiment, the photoinitiator package comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of formula (I) in an amount ranging from 30 to 99.0 weight percent based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 1.0 to 40% by weight, based on the total weight of the photoinitiator package; Includes.

[0077] In yet a further embodiment, the photoinitiator package comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of Formula (I) in an amount ranging from 50 to 97.0 wt. %, based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 3.0 to 35% by weight, based on the total weight of the photoinitiator package; Includes.

[0078] The photoinitiator package comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of formula (I) in an amount ranging from 40 to 99.9 wt.%, more preferably ranging from 60 to 99.0 wt.%, and most preferably ranging from 65 to 97.0 wt.%, based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 0.1 to 50% by weight, more preferably in the range of 1.0 to 40% by weight, and most preferably in the range of 3.0 to 35% by weight, based on the total weight of the photoinitiator package; It is further preferred that the composition comprises:

[0079] In one embodiment, the photoinitiator package comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of Formula (I) in an amount ranging from 40 to 99.9 weight percent based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 0.1 to 50% by weight, based on the total weight of the photoinitiator package; Includes.

[0080] In a further embodiment, the photoinitiator package comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of formula (I) in an amount ranging from 60 to 99.0 weight percent based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 1.0 to 40% by weight, based on the total weight of the photoinitiator package; Includes.

[0081] In yet a further embodiment, the photoinitiator package comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of formula (I) in an amount ranging from 65 to 97.0 wt. %, based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 3.0 to 35% by weight, based on the total weight of the photoinitiator package; Includes.

[0082] In addition to one or more bisacylphosphine oxide photoinitiators and one or more optical brightener sensitizers, the photoinitiator package may also include one or more amines.

[0083] In the broadest sense, the one or more amines according to the present invention may be any amine, including aliphatic, cycloaliphatic, aromatic, arylaliphatic, heterocyclic, oligomeric or polymeric amines. They may be primary, secondary or tertiary amines, such as butylamine, dibutylamine, tributylamine, cyclohexylamine, benzyldimethylamine, dicyclohexylamine, N-phenylglycine, triethylamine, phenyl-diethanolamine, triethanolamine, piperidine, piperazine, morpholine, quinolone, esters of dimethylaminobenzoic acid and corresponding derivatives. In addition, amine-modified acrylates may be used. Examples of such amine-modified acrylates include acrylates modified by reaction with primary or secondary amines, as described in US Pat. No. 3,844,916, EP 280222, US Pat. No. 5,482,649 or US Pat. No. 5,734,002.

[0084] Also suitable for use as polyfunctional amines and polymeric amine derivatives are Omnipol ASA from IGM Resins BV, Genopol AB-2 from Rahn AG, Speedcure 7040 from Lambson Limited, or those described in US Patent Application Publication No. 2013 / 0012611.

[0085] Those skilled in the art will understand that the term "amine" does not include amides or imides, regardless of whether the nitrogen of the amide / imide is attached to an alkyl group. Similarly, ammonium salts are not amines.

[0086] It is preferred that the one or more amines are not type I or type II photoinitiators, such as the well-known aminoketone type I initiators.It is even more preferred that the one or more amines are not optical brighteners, i.e. compounds that absorb light in the ultraviolet and violet regions of the EM spectrum and re-emit light in the blue region via fluorescence.Therefore, it is clear that the only role of the amine in the photopolymerization package is to act as a synergist and improve the effect of one or more bisacylphosphine oxide photoinitiators having the structure of formula (I) and / or one or more optical brightener sensitizers.

[0087] Preferably, one or more of the amines have a so-called alpha hydrogen, i.e., a hydrogen attached to the carbon that is directly attached to the nitrogen of the amine. This hydrogen is sp 3 It is particularly preferred that the amine be bonded to a carbon atom in a hybrid orbital. Thus, the amine may be bonded to a methyl group (i.e., CH 3 ), methylene groups (i.e., CH 2 R CH 2 ) or methanetriyl group (i.e., CHR 2 It is preferred that the nitrogen atom has a direct single bond to either one of the groups (CH).

[0088] Without intending to be bound by theory, it is believed that the alpha hydrogen can be readily abstracted by radicals to form stabilized alpha amino radicals, which can serve to improve cure rates, among other things, by scavenging molecular oxygen that can slow the polymerization reaction.

[0089] It is particularly preferred that the nitrogen atom is bonded to at least one alkyl group, and it is even more preferred that the nitrogen atom is bonded to at least two alkyl groups.

[0090] In one particularly preferred embodiment, the one or more amines are independently of the formula NR A R B R C and R A and R B is independently selected from optionally substituted alkyl groups; R C is selected from the group consisting of optionally substituted alkyl groups and optionally substituted aryl groups.

[0091] In the above embodiments, the term "optionally substituted aryl group" does not include aryl groups having two or more substituents linked to form a fused ring system, such as quinoline, indole, or coumarin. Similarly, the term "optionally substituted alkyl group" does not include substitutions such that the group is no longer considered an alkyl group, such as acyl groups (i.e., =O substitution on the first (leading) carbon atom of the alkyl chain).

[0092] When present, the one or more amines are preferably present in an amount in the range of 1.0 to 45 wt.%, more preferably in the range of 3.0 to 35 wt.%, and most preferably in the range of 5.0 to 30 wt.%, based on the total weight of the photoinitiator package.

[0093] Thus, in one embodiment, the photoinitiator package comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of formula (I) in an amount ranging from 15 to 98.9 wt.%, more preferably ranging from 30 to 96.0 wt.%, and most preferably ranging from 50 to 92.0 wt.%, based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 0.1 to 50% by weight, more preferably in the range of 1.0 to 37% by weight, and most preferably in the range of 3.0 to 30% by weight, based on the total weight of the photoinitiator package; c) one or more amines in an amount ranging from 1.0 to 45% by weight, more preferably ranging from 3.0 to 35% by weight, and most preferably ranging from 5.0 to 30% by weight, based on the total weight of the photoinitiator package; and more preferably consists of these.

[0094] In a further embodiment, the photoinitiator package comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of Formula (I) in an amount ranging from 15 to 98.9 weight percent based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 0.1 to 50% by weight, based on the total weight of the photoinitiator package; c) one or more amines in an amount ranging from 1.0 to 45 weight percent based on the total weight of the photoinitiator package; and more preferably consists of these.

[0095] In another embodiment, the photoinitiator package comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of formula (I) in an amount ranging from 30 to 96.0 weight percent based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 1.0 to 37 weight percent, based on the total weight of the photoinitiator package; c) one or more amines in an amount ranging from 3.0 to 35 weight percent based on the total weight of the photoinitiator package; and more preferably consists of these.

[0096] In yet a further embodiment, the photoinitiator package comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of Formula (I) in an amount ranging from 50 to 92.0 wt. %, based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 3.0 to 30 weight percent, based on the total weight of the photoinitiator package; c) one or more amines in an amount ranging from 5.0 to 30% by weight based on the total weight of the photoinitiator package; and more preferably consists of these.

[0097] In the absence of an amine, the photoinitiator package preferably comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of formula (I) in an amount ranging from 50 to 99.9 wt.%, more preferably ranging from 70 to 99.0 wt.%, and most preferably ranging from 80 to 97.0 wt.%, based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 0.1 to 50% by weight, more preferably in the range of 1.0 to 30% by weight, and most preferably in the range of 3.0 to 20% by weight, based on the total weight of the photoinitiator package; and more preferably consists of these.

[0098] In another embodiment, the photoinitiator package comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of formula (I) in an amount ranging from 50 to 99.9 weight percent based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 0.1 to 50% by weight, based on the total weight of the photoinitiator package; and more preferably consists of these.

[0099] In a further embodiment, the photoinitiator package comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of Formula (I) in an amount ranging from 70 to 99.0 wt. %, based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 1.0 to 30% by weight, based on the total weight of the photoinitiator package; and more preferably consists of these.

[0100] In a final embodiment, the photoinitiator package comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of formula (I) in an amount ranging from 80 to 97.0 wt. %, based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 3.0 to 20% by weight, based on the total weight of the photoinitiator package; and more preferably consists of these.

[0101] When further components are present other than the one or more bisacylphosphine oxide photoinitiators having the structure of formula (I), the one or more optical brightener sensitizers and the one or more amines, they are preferably further Type I or Type II photoinitiators.

[0102] Thus, the photoinitiator package preferably comprises, and more preferably consists of, one or more bisacylphosphine oxide photoinitiators having the structure of Formula (I), one or more optical brightener sensitizers, optionally one or more amines, and optionally one or more additional Type I or Type II photoinitiators.

[0103] As will be appreciated by those skilled in the art, the term "additional Type I or Type II photoinitiators" means that these additional photoinitiators have a structure other than one or more of the bisacylphosphine oxide photoinitiators having the structure of Formula (I).

[0104] Thus, the photoinitiator package preferably comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of formula (I) in an amount ranging from 15 to 98.9 wt.%, more preferably ranging from 30 to 96.0 wt.%, and most preferably ranging from 50 to 92.0 wt.%, based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 0.1 to 50% by weight, more preferably in the range of 1.0 to 37% by weight, and most preferably in the range of 3.0 to 30% by weight, based on the total weight of the photoinitiator package; c) optionally one or more amines in an amount in the range of 1.0 to 45 wt.%, more preferably in the range of 3.0 to 35 wt.%, and most preferably in the range of 5.0 to 30 wt.%, based on the total weight of the photoinitiator package; d) optionally, a further type I or type II photoinitiator in an amount ranging from 0.0 to 84.9% by weight, more preferably in the range from 0.0 to 69.0% by weight, most preferably in the range from 0.0 to 47.0% by weight. It consists of:

[0105] When one or more amines are present, the photoinitiator package preferably comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of formula (I) in an amount ranging from 15 to 98.9 wt.%, more preferably ranging from 30 to 96.0 wt.%, and most preferably ranging from 50 to 92.0 wt.%, based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 0.1 to 50% by weight, more preferably in the range of 1.0 to 37% by weight, and most preferably in the range of 3.0 to 30% by weight, based on the total weight of the photoinitiator package; c) one or more amines in an amount ranging from 1.0 to 45% by weight, more preferably ranging from 3.0 to 35% by weight, and most preferably ranging from 5.0 to 30% by weight, based on the total weight of the photoinitiator package; d) optionally, a further type I or type II photoinitiator in an amount ranging from 0.0 to 83.9% by weight, more preferably in the range from 0.0 to 66.0% by weight, most preferably in the range from 0.0 to 42.0% by weight; It consists of:

[0106] In the absence of an amine, the photoinitiator package preferably comprises: a) one or more bisacylphosphine oxide photoinitiators having the structure of formula (I) in an amount ranging from 15 to 99.9 wt.%, more preferably ranging from 30 to 99.0 wt.%, and most preferably ranging from 50 to 97.0 wt.%, based on the total weight of the photoinitiator package; b) one or more optical brightener sensitizers in an amount ranging from 0.1 to 50% by weight, more preferably in the range of 1.0 to 30% by weight, and most preferably in the range of 3.0 to 20% by weight, based on the total weight of the photoinitiator package; c) optionally a further type I or type II photoinitiator in an amount ranging from 0.0 to 84.9% by weight, more preferably in the range from 0.0 to 69.0% by weight, most preferably in the range from 0.0 to 47.0% by weight; It consists of:

[0107] Additionally, it is preferred that the photoinitiator package be in the form of a blend that is liquid at 25° C. and standard pressure.

[0108] This means that the one or more bisacylphosphine oxides, the one or more optical brightener sensitizers and optionally the one or more amines must be miscible and form a stable liquid blend at the indicated temperatures and pressures, and not, for example, present as a mixture of dry powders or as a suspension or emulsion.

[0109] Photopolymerizable composition In a second aspect, the present invention is also directed to a photopolymerizable composition.

[0110] In the broadest sense, a photopolymerizable composition is a) one or more ethylenically unsaturated free radically polymerizable compounds; b) a photoinitiator package according to the first aspect; It comprises or consists of:

[0111] The photopolymerizable composition preferably comprises a) one or more ethylenically unsaturated free radically polymerizable compounds in an amount in the range of 30 to 99.0 wt %, more preferably in the range of 50 to 95.0 wt %, and most preferably in the range of 70 to 90 wt %, based on the total weight of the photopolymerizable composition; b) a photoinitiator package according to the first aspect in an amount ranging from 0.5 to 50% by weight, more preferably ranging from 0.8 to 40% by weight, and most preferably ranging from 1.0 to 30% by weight, based on the total weight of the photopolymerizable composition; It comprises or consists of:

[0112] In addition to one or more ethylenically unsaturated free radically polymerizable compounds and a photoinitiator package according to the first aspect, the photopolymerizable composition may include further ingredients, as will be well understood by those skilled in the art.

[0113] Suitable further components include photosensitizers, further photoinitiators, pigments, binders and conventional additives.

[0114] Thus, the photopolymerizable composition is a) one or more ethylenically unsaturated free radically polymerizable compounds in an amount in the range of 30 to 99.0 wt %, more preferably in the range of 50 to 95.0 wt %, and most preferably in the range of 70 to 90 wt %, based on the total weight of the photopolymerizable composition; b) a photoinitiator package according to the first aspect in an amount ranging from 0.5 to 50% by weight, more preferably ranging from 0.8 to 40% by weight, and most preferably ranging from 1.0 to 30% by weight, based on the total weight of the photopolymerizable composition; c) optionally one or more further photoinitiators, one or more photosensitizers and / or one or more coinitiators in an amount in the range of 0.5 to 30% by weight, more preferably in the range of 0.8 to 20% by weight, most preferably in the range of 1.0 to 15% by weight, d) optionally one or more pigments in an amount ranging from 0.1 to 30% by weight, more preferably in the range of 1.0 to 25% by weight, and most preferably in the range of 10 to 20% by weight, based on the total weight of the photopolymerizable composition; e) optionally one or more binders in an amount in the range of 5.0 to 60 wt. %, more preferably in the range of 8.0 to 50 wt. %, and most preferably in the range of 10 to 40 wt. %, based on the total weight of the photopolymerizable composition; f) optionally, one or more additives in an amount in the range of 0.01 to 10 wt %, more preferably in the range of 0.01 to 8.0 wt %, and most preferably in the range of 0.01 to 5.0 wt %, based on the total weight of the photopolymerizable composition; and more preferably, consists of these.

[0115] Additionally, the photopolymerizable composition may be formulated into a composition that further comprises a solvent, such as water and / or an organic solvent.

[0116] It is preferred that there are no further photoinitiators, photosensitizers or coinitiators present other than those which form part of the photoinitiator package, in other words all components which contribute to the photopolymerisation properties of the photoinitiator are preferably contained within the photoinitiator package as defined above and below.

[0117] The selection of one or more ethylenically unsaturated free radical polymerizable compounds is not particularly limited. The polymerizable compounds may contain one or more olefin double bonds. They may be low molecular weight (monomer) or high molecular weight (oligomer) compounds.

[0118] Examples of suitable low molecular weight polymerizable compounds (monomer compounds) having one double bond are alkyl or hydroxyalkyl acrylates or alkyl or hydroxyalkyl methacrylates (e.g. methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate or isobornyl acrylate), and methyl methacrylate or ethyl methacrylate. Further examples are silicon or fluorine modified resins, such as silicone acrylates. Further examples of these polymerizable compounds are acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamides, styrene, alkylstyrenes and halogenostyrenes, vinyl esters such as vinyl acetate, vinyl ethers such as iso-butyl vinyl ether, N-vinylpyrrolidone, vinyl chloride or vinylidene chloride.

[0119] Examples of polymerizable compounds having two or more double bonds are ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate, bisphenol A diacrylate, 4,4'-bis-(2-acryloyloxyethoxy)-diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris-(2-acryloylethyl)isocyanurate.

[0120] Examples of higher molecular weight (oligomeric) polyunsaturated compounds are acrylated epoxy resins, acrylated or vinyl ether-containing or epoxy group-containing polyesters, acrylated polyurethanes or acrylated polyethers.

[0121] Further examples of unsaturated oligomers are unsaturated polyester resins, usually prepared from maleic acid, phthalic acid and one or more diols, and having a molecular weight of about 500 Da to 3,000 Da. Such unsaturated oligomers are also called prepolymers.

[0122] Examples of polymerizable compounds that are particularly suitable for carrying out the present invention are esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers containing ethylenically unsaturated groups in the chain or in side groups (e.g. unsaturated polyesters, polyamides, polyurethanes and their copolymers, alkyl resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers with (meth)acrylic groups in the side chain), and mixtures thereof.

[0123] Illustrative of unsaturated carboxylic acids or anhydrides useful in preparing such esters are acrylic acid, methacrylic acid, maleic anhydride, crotonic acid, itaconic acid, cinnamic acid and unsaturated fatty acids such as linoleic acid and oleic acid. Acrylic acid and methacrylic acid are preferred.

[0124] Examples of polyols which may also be esterified are aromatic, aliphatic and cycloaliphatic polyols, preferably aliphatic and cycloaliphatic polyols. Aromatic polyols are, for example, hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di(4-hydroxyphenyl)propane, as well as novolaks and resols.

[0125] Polyepoxides that can be esterified include those based on the abovementioned polyols, especially those based on the reaction product between aromatic polyols and epichlorohydrin. Also suitable as polyols are polymers and copolymers that contain hydroxyl groups in the polymer chain or in side groups, such as polyvinyl alcohol and its copolymers, or polymethacrylic acid hydroxyalkyl esters or their copolymers. Further suitable polyols are oligoesters with hydroxyl end groups.

[0126] Examples of aliphatic and cycloaliphatic polyols include alkylene diols preferably containing 2 to 12 carbon atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols preferably having a molecular weight of 200 Da to 1,500 Da, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris(β-hydroxyethyl)amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol.

[0127] Further suitable ethylenically unsaturated compounds are unsaturated polyamides obtained from unsaturated carboxylic acids and aromatic, aliphatic and cycloaliphatic polyamines, preferably having 2 to 6, preferably 2 to 4 amino groups. Examples of such polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di-(β-aminoethyl)ether, diethylenetriamine, triethylenetetramine, and di(β-aminoethoxy)- and di(β-aminopropoxy)ethane. Other suitable polyamines are polymers and copolymers which may contain additional amino groups in the side chain, as well as oligoamides containing amino end groups.

[0128] Specific examples of such unsaturated polyamides are methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide, bis(methacrylamidopropoxy)ethane and N-[(β-hydroxyethoxy)ethyl]-acrylamide.

[0129] Unsaturated polyurethanes, such as those derived from saturated or unsaturated diisocyanates and unsaturated or saturated diols, are also suitable as polymerizable compounds in the practice of the present invention.

[0130] Polybutadiene and polyisoprene, as well as copolymers thereof, may also be used.

[0131] Suitable polymerizable compounds include, for example, olefins (e.g., ethylene, propene, butene, and hexene), (meth)acrylates, acrylonitrile, styrene, and vinyl chloride. Polymers with unsaturated (meth)acrylate groups in the side chain may also be used as one or more ethylenically unsaturated free radical polymerizable compounds. They may typically be reaction products of novolac-based epoxy resins and (meth)acrylic acid, homo- or copolymers of vinyl alcohol or its hydroxyalkyl derivatives esterified with (meth)acrylic acid, and homo- and copolymers of (meth)acrylates esterified with hydroxyalkyl (meth)acrylates.

[0132] Examples of photosensitizers are those commonly used in the art: aromatic carbonyl compounds such as benzophenones, thioxanthones, anthraquinones, and 3-acylcumarine derivatives, terphenyls, styryl ketones, and 3-(aroylmethylene)-thiazolines, camphorquinones, and eosin, rhodamine and erythrosine dyes.

[0133] Examples of thioxanthone include thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methylthioxanthone, 1-cyano-3-chlorothioxanthone, thioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl-3-phenylsulfurylthioxanthone, 3,4-di[2-(2-methoxyethoxy)ethoxycarbonyl]thioxanthone, 1-ethoxycarbonyl-3-(1-methyl-1-morpholinoethyl)thioxanthone, 2-methyl-6-dimethoxymethyl ... (1,1-dimethoxybenzyl)thioxanthone, 2-morpholinomethylthioxanthone, 2-methyl-6-morpholinomethylthioxanthone, N-allylthioxanthone-3,4-dicarboximide, N-octylthioxanthone-3,4-dicarboximide, N-(1,1,3,3-tetramethylbutyl)-thioxanthone-3,4-dicarboximide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-1-2-methoxythioxanthone, 6-ethoxycarbonyl-2 -methylthioxanthone, thioxanthone-2-polyethylene glycol ester, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, or those described in patent application PCT / EP2011 / 069514, such as n-dodecyl-7-methyl-thioxanthone-3-carboxylate and N,N-diisobutyl-7-methyl-thioxanthone-3-carboxamide.Polymeric thioxanthone derivatives (eg Omnipol® TX from IGM Resins BV, Genopol® TX-1 from Rahn AG, Speedcure® 7010 from Lambson Limited) are also suitable.

[0134] Examples of benzophenones are benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-(4-methylthiophenyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, methyl 2-Benzoylbenzoate, 4-(2-hydroxyethylthio)benzophenone, 4-(4-tolylthio)benzophenone, 4-benzoyl-N,N,N-trimethylbenzenemethanaminium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propanaminium chloride monohydrate, 4-(13-acryloyl-1,4,7,10,13-pentaoxatridecyl)benzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyl)oxylethyl-benzenemethanaminium chloride, or those described in U.S. Pat. No. 9,938,231 (e.g. Omnirad® 991 from IGM Resins BV).

[0135] Polymeric benzophenone derivatives (eg Omnipol® BP, Omnipol® 2702 and Omnipol® 682, all from IGM Resins BV, Genopol® BP-2 from Rahn AG and Speedcure® 7005 from Lambson Limited) are also suitable.

[0136] Examples of 3-acylcoumarin derivatives are 3-benzoylcoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-di(propoxy)coumarin, 3-benzoyl-6,8-dichlorocoumarin, 3-benzoyl-6-chlorocoumarin, 3,3'-carbonyl-bis[5,7-di(propoxy)coumarin], 3,3'-carbonyl-bis(7-methoxycoumarin), 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-isobutyroylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-diethoxycoumarin, 3-benzoyl-5,7-dibutoxycoumarin, 3-benzoyl-5,7-di (methoxyethoxy)coumarin, 3-benzoyl-5,7-di(allyloxy)coumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-isobutyroyl-1,7-dimethylaminocoumarin, 5,7-dimethoxy-3-(1-naphthoyl)coumarin, 5,7-dimethoxy-3(1-naphthoyl)-coumarin, 3-benzoylbenzo[f]coumarin, 7-diethylamino-3-thienoylcoumarin, 3-(4-cyanobenzoyl)-5,7-dimethoxycoumarin, or those described in EP 2 909 243 and WO 2017216699.

[0137] Examples of 3-(aroylmethylene)thiazolines are 3-methyl-1,2-benzoylmethylene-β-naphthothiazoline, 3-methyl-2-benzoylmethylene-benzothiazoline, 3-ethyl-2-propionylmethylene-β-naphthothiazoline.

[0138] Examples of other aromatic carbonyl compounds are acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzils such as those described in WO 2013 / 164394, 2-acetylnaphthalene, 2-naphthaldehyde, 9,10-anthraquinone, 9-fluorenone, dibenzosuberone, xanthone, 2,5-bis(4-diethylaminobenzylidene)cyclopentanone, α-(para-dimethylaminobenzylidene)ketones such as 2-(4-dimethylamino-benzylidene)-indan-1-one or 3-(4-dimethylaminophenyl)-1-indan-5-yl-propenone, 3-phenylthiophthalimide, N-methyl-3,5-di(ethylthio)phthalimide.

[0139] Thioxanthone and 3-acylcumarine are particularly preferred.

[0140] It has been observed that the photosensitizer enhances the activity of one or more bisacylphosphine oxide photoinitiators without shortening the shelf life of the composition.Furthermore, such compositions have the special advantage that the spectral sensitivity of the photoinitiator package can be shifted to any desired wavelength region by appropriate selection of the photosensitizer.Those skilled in the art can select the appropriate photosensitizer to make the photoinitiator package function in any desired wavelength region.

[0141] Examples of other suitable photoinitiators are camphorquinone, benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, dialkoxyacetophenones, α-hydroxyketones, α-aminoketones, 4-aroyl-1,3-dioxolanes, benzoin alkyl ethers and benzil ketals (e.g., benzil dimethyl ketal), ketosulfones (e.g., 1-[4-[(4-benzoyl-phenyl)-thio]-phenyl]-2-methyl-2-[(4-methyl-phenyl)-sulfonyl]-propan-1-one (Esacure® from IGM Resins BV). 1001), 3-ketocoumarins, such as those described in EP 2909243 and WO 2017216699, phenylglyoxylate and its derivatives, dimeric phenylglyoxylate, peresters, such as benzophenonetetracarboxylic acid peresters, such as those described in EP 126541), acylphosphine photoinitiators (monoacylphosphine oxides, bisacylphosphine oxides, trisacylphosphine oxides, and polyfunctional monoacylphosphine oxides or bisacylphosphine oxides), halomethyltriazines, hexaarylbisimidazole / co-initiator systems (e.g., a combination of orthochlorohexaphenylbisimidazole and 2-mercaptobenzothiazole), ferrocenium compounds or titanocenes (e.g., dicyclopentadienyl-bis(2,6-difluoro-3-pyrrolo-phenyl)titanium), O-acyloxime ester photoinitiators.

[0142] Examples of α-hydroxyketones and α-aminoketones are 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-ethyl-propan-1-one), 2-hydroxy-1-{ 4-[4-(2-hydroxy-2-methyl-propionyl)-phenoxy]-phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone).

[0143] Examples of O-acyloxime ester photoinitiators are 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] 1-(O-acetyloxime) or those described in GB 2 339 571 A1.

[0144] Examples of acylphosphine photoinitiators include, but are not limited to, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-(2,4-dipentyloxyphenyl), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, phenyl(2,4,6-trimethylbenzoyl)phosphinic acid ethoxylated glycerol triester (Omnipol® TP, available from IGM Resins BV).

[0145] Examples of halomethyltriazine photoinitiators are 2-[2-(4-methoxy-phenyl)-vinyl]-4,6-bis-trichloromethyl[1,3,5]triazine, 2-(4-methoxy-phenyl)-4,6-bis-trichloromethyl[1,3,5]triazine, 2-(3,4-dimethoxyphenyl)-4,6-bis-trichloromethyl[1,3,5]triazine, 2-methyl-4,6-bis-trichloromethyl[1,3,5]triazine.

[0146] Cationic photoinitiators may also be used as further photoinitiators when the photopolymerizable composition according to the invention is used in a hybrid system (hybrid system in this context means a mixture of a free radical curing system and a cationic curing system). Examples of suitable cationic photoinitiators are aromatic sulfonium salts, aromatic phosphonium salts or aromatic iodonium salts, such as those described, for example, in US Pat. No. 4,950,581, or cyclopentadienyl arene-iron(II) complex salts, such as (η 6 -isopropylbenzene)(η 5 -cyclopentadienyl)iron(II) hexafluorophosphate or oxime-based photolatent acids (described, for example, in GB 2348644, U.S. Pat. No. 4,450,598, U.S. Pat. No. 4,136,055, WO 00 / 10972 and WO 00 / 26219).

[0147] Any pigment known to one of ordinary skill in the art can be used in the photopolymerizable composition.

[0148] Depending on the intended application, both inorganic and organic pigments can be used. Such additives are well known to those skilled in the art, some examples are carbon black, iron oxides (e.g., yellow iron oxide, red iron oxide), chrome yellow, chrome green, nickel titanium yellow, ultramarine blue, cobalt blue, bismuth vanadate, cadmium yellow, and cadmium red. Examples of organic pigments are mono- or bis-azo pigments and their metal complexes, phthalocyanine pigments, polycyclic pigments such as perylene, anthraquinone, thioindigo, quinacridone or triphenylmethane pigments, and diketo-pyrrolo-pyrrole, isoindolinone, such as tetrachloroisoindolinone, isoindoline, dioxazine, benzimidazolone, and quinophthalone pigments. The pigments may be used individually or mixed in the formulation.

[0149] The addition of a binder is particularly advantageous when the ethylenically unsaturated free radical polymerizable compound is a liquid or viscous substance. The binder is selected depending on the field of use and the required properties, such as developability in aqueous and organic solvent systems, adhesion to substrates, and sensitivity to oxygen. Suitable binders are, for example, polymers having a weight average molecular weight (Mw) of about 5,000 Da to 2,000,000 Da, preferably 10,000 Da to 1,000,000 Da. Illustrative examples are homopolymers and copolymers of acrylates and methacrylates, such as copolymers of methyl methacrylate / ethyl acrylate / methacrylic acid, poly(methacrylic acid alkyl esters), poly(acrylic acid alkyl esters); cellulose esters and ethers, such as cellulose acetate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose; polyvinyl butyral, polyvinyl formal, cyclized rubbers, polyethers, such as polyethylene oxide, polypropylene oxide, polytetrahydrofuran, polystyrene, polycarbonate, polyurethanes, chlorinated polyolefins, such as polyvinyl chloride, vinyl chloride / vinylidene chloride copolymers, copolymers of vinylidene chloride with acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, co-poly(ethylene / vinyl acetate), polymers such as polycaprolactam and poly(hexamethylene adipamide), polyesters, such as poly(ethylene glycol terephthalate) and poly(hexamethylene glycol succinate).

[0150] Suitable examples of coinitiators (also known as accelerators) are alcohols, thiols, thioethers, amines or ethers, disulfides and phosphines having an available hydrogen attached to the carbon adjacent to a heteroatom, as described, for example, in EP 438123 and GB 2180358. Suitable examples of amine accelerators / coinitiators include, but are not limited to, aliphatic, cycloaliphatic, aromatic, aryl-aliphatic, heterocyclic, oligomeric or polymeric amines. They can be primary, secondary or tertiary amines, such as butylamine, dibutylamine, tributylamine, cyclohexylamine, benzyldimethylamine, di-cyclohexylamine, N-phenylglycine, triethylamine, phenyl-diethanolamine, triethanolamine, piperidine, piperazine, morpholine, pyridine, quinoline, esters of dimethylaminobenzoic acid, Michler's ketone (4,4'-bis-dimethylaminobenzophenone) and its derivatives. As amine accelerators / co-initiators, amine-modified acrylate compounds can be used. Examples of such amine-modified acrylates include acrylates modified by reaction with primary or secondary amines, as described in US Pat. No. 3,844,916, EP-A-280222, US Pat. No. 5,482,649 or US Pat. No. 5,734,002. Multifunctional amines and polymeric amine derivatives are also suitable as coinitiators, some examples are Omnipol® ASA from IGM Resins BV, Genopol® AB-2 from Rahn AG, Speedcure® 7040 from Lambson Limited or those described in US Patent Application Publication No. 2013 / 0012611.

[0151] The choice of additives is determined by the field of use and the properties desired for that field. Typical additives include thermal initiators, stabilizers, light stabilizers, fillers, colorants, antistatic agents, wetting agents, flow improvers, and adhesion promoters.

[0152] For example, especially in the case of colouring compositions, the composition may also comprise as further additives thermal initiators, compounds which form free radicals when heated, such as azo compounds, for example 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), triazenes, diazosulfides, pentaazadienes, or peroxy compounds, for example hydroperoxides or peroxycarbonates, for example tert-butyl hydroperoxide (as described, for example, in EP-A-245639).

[0153] Suitable stabilizers are, for example, thermal inhibitors such as hydroquinone, hydroquinone derivatives, p-methoxyphenol, β-naphthol, or sterically hindered phenols such as 2,6-di(tert-butyl)-p-cresol, which prevent premature polymerization termination. To increase the dark storage stability, for example, copper compounds such as copper naphthenate, copper stearate, or copper octanoate, phosphorus compounds such as triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl phosphite, or tribenzyl phosphite, quaternary ammonium compounds such as tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives such as N,N-diethylhydroxylamine can be used. During polymerization, paraffin or similar wax-like substances (insoluble in the polymer) can be added to remove oxygen from the atmosphere, which migrates to the surface at the beginning of the polymerization and forms a transparent surface layer that prevents air from entering.

[0154] It is also possible to add light stabilizers, such as UV absorbers, for example of the hydroxyphenylbenzotriazole, hydroxyphenylbenzophenone, oxalic acid amide or hydroxyphenyl-s-triazine type. Such components can be used alone or in mixtures, with or without sterically hindered amines (HALS).

[0155] All alternatives and preferred embodiments of the photoinitiator package described above or below are applicable mutatis mutandis to the photopolymerizable composition according to this aspect.

[0156] method In a third aspect, the present invention provides a method of photocuring photopolymerizable compositions, coatings, adhesives and inks, comprising: a) coating or printing the photopolymerizable composition according to the second aspect onto a substrate; b) photopolymerizing the composition coated or printed on the substrate with a light source; In one embodiment, the method includes, in a given order:

[0157] Preferably, the light source operates in the near UV or visible range of the EM spectrum.

[0158] All alternatives and preferred embodiments of the photoinitiator packages and photopolymerizable compositions described above or below are applicable mutatis mutandis to the methods of photocuring photopolymerizable compositions, coatings, adhesives and inks according to the present aspect.

[0159] use In a final aspect the present invention is directed to the use of a photoinitiator package according to the first aspect in the manufacture of printing inks, screen printing inks, gravure printing inks, solder masks, etch offset printing inks, flexographic printing inks, gravure printing inks, inkjet inks, resist materials, insulators, encapsulants, image recording materials, solder masks, passivation layers, protective coatings, 3D printed objects and moulds, holographic applications, optical fibre coatings, wave guides and lenses, overprint varnishes, wood, vinyl, metal and plastic coatings.

[0160] All alternatives and preferred embodiments of the photoinitiator package described above or below are applicable mutatis mutandis for use in accordance with the present aspect. EXAMPLES

[0161] A.Determination method Tack-free measurement: Tack-free refers to the state of a coating where the coating is completely cured on the surface. Evaluation method: Using a bar coater, the formulation is spread on a varnished cardboard at a thickness of 12 microns (12 μm) and photopolymerized under a light source. Then, the worker's thumb is placed on the coating with slight pressure. If no fingerprints / marks are left on the surface, the coating is completely cured. The maximum speed (m / min) at which no fingerprints / marks are left on the surface is indicated as the tack-free value. The higher the maximum speed, the higher the reactivity.

[0162] B. Experiment 1.Materials used The following commercially available compounds were used in the preparation of the reference, inventive and comparative formulations:

[0163] PI-I: Bis(2,4,6-trimethylbenzoyl)octylphosphine oxide, prepared as described in US Pat. No. 5,534,559A.

[0164] PI-C1: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, CAS number: 75980-60-8, commercially available as Omnirad TPO from IGM Group BV, The Netherlands.

[0165] PI-C2: Bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, CAS number: 145052-34-2, commercially available as Omnirad 403 from IGM Group BV, The Netherlands.

[0166] PI-C3: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, CAS number: 162881-26-7, commercially available as Omnirad 819 from IGM Group BV, The Netherlands.

[0167] S1: 7-diethylamino-4-methylcoumarin, CAS number: 91-44-1, commercially available as Coumarin 1 from Merck KGaA, Germany.

[0168] S2: 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole), CAS number: 7128-64-5, commercially available as Omnistab OB from IGM Group BV, The Netherlands.

[0169] S3: 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizin-11-one, CAS number: 41267-76-9, commercially available as Coumarin 102 from abcr GmbH, Germany.

[0170] A1: 1H-Azepine-1-propanoic acid, hexahydro-2,2-bis[[(1-oxo-2-propen-1-yl)oxy]methyl]butyl ester, commercially available as Photomer 4250 from IGM Group BV (The Netherlands).

[0171] A2: Poly(ethylene glycol) bis(p-dimethylaminobenzoate), CAS number: 71512-90-8, commercially available as Omnipol ASA from IGM Group BV, The Netherlands.

[0172] Mi: a photopolymerizable monomer blend of M1, M2 and M3 (40:30:30).

[0173] M-ii: A photopolymerizable monomer blend of M1, M4, M5 and M6 (50:15:15:20).

[0174] M-iii: A photopolymerizable monomer blend of M1, M4 and M6 (50:25:25).

[0175] M1: Bisphenol Y epoxy diacrylate, CAS number: 55818-57-0, commercially available as Photomer 3016 from IGM Group BV, The Netherlands.

[0176] M2: Glyceryl [4 PO] triacrylate, CAS number: 52408-84-1, commercially available as Photomer 4094 from IGM Group BV, The Netherlands.

[0177] M3: Trimethylolpropane triacrylate, CAS number: 15625-89-5, commercially available as Photomer 4006 from IGM Group BV, The Netherlands.

[0178] M4: A blend of pentaerythritol tri- and tetraacrylates, CAS numbers 3524-68-3 and 4986-89-4, commercially available as Photomer 4335 from IGM Group BV (The Netherlands).

[0179] M5: Dipentaerythritol penta / hexaacrylate, CAS number: 1384855-91-7, commercially available as Photomer 4600 from IGM Group BV, The Netherlands.

[0180] M6: Pentaerythritol [5 EO] tetraacrylate, CAS number: 51728-26-8, commercially available as Photomer 4172 from IGM Group BV (The Netherlands).

[0181] 2. Compound (photopolymerizable composition) The following reference, inventive and comparative formulations were used for the surface cure evaluation, with the amount of each component given in weight percent (wt%). The formulations were prepared by adding the photoinitiator, sensitizer and amine (if present) to the photopolymerizable monomer blend M (i.e. Mi, M-ii or M-iii) at room temperature in the concentrations shown in Table 1. The formulations were stirred at 60°C for 2 hours, cooled at room temperature and then spread on varnished cardboard at a thickness of 12 microns (12 μm) using a bar coater. The formulations were then photopolymerized using a light source (Table 2).

[0182] [Table 1]

[0183] [Table 2]

[0184] 3. Evaluation of surface photocuring The reference formulation, the formulation of the invention and the comparative formulation were evaluated for their surface light curing capabilities according to the test method provided in the Determination Methods using different light sources (the values ​​in Table 2 correspond to the maximum tack-free speed (m / min)).

[0185] [Table 3] *n / m=not measured Lamp 1: UV Hg lamp with an intensity of 120 W / cm and a distance of 8 cm. Lamp 2: UV Hg lamp with an intensity of 85 W / cm and a distance of 8 cm. Lamp 3: Wavelength 395 nm, Intensity 4 W / cm 2 , UV LED lamp with a distance of 0.5 cm. Lamp 4: Wavelength 365 nm, Intensity 4 W / cm 2 , UV LED lamp with a distance of 0.5 cm. Lamp 5: Wavelength 278 nm, Intensity 4 W / cm 2, UV LED lamp with a distance of 0.5 cm.

[0186] [Table 4] Lamp 1: UV Hg lamp with an intensity of 120 W / cm and a distance of 8 cm. Lamp 6: Wavelength 395 nm, Intensity 16 W / cm 2 , UV LED lamp with a distance of 0.5 cm. Lamp 7: Wavelength 365 nm, Intensity 16 W / cm 2 , UV LED lamp with a distance of 0.5 cm.

[0187] As can be seen from the data in Table 2a, sensitizers S1 and S2 enhanced the surface cure speed for almost all combinations. However, the inventive photoinitiator (PI-I) was generally comparable or inferior to the comparative photoinitiators in the absence of sensitizer (i.e., RE4 vs. RE1-RE3), while combinations of the inventive photoinitiators with sensitizers S1 and S2 resulted in inventive formulations (IE1 and IE2) that were much more active (as seen by improved cure speed) than the same formulations with the comparative photoinitiators.

[0188] When using Lamp 1, the compositions of the invention (IE1 and IE2) had more than twice the cure speed of the reference (RE4), whereas the comparative compositions generally had only modest improvements, generally ranging from 10 to 44% (CE1 to CE5) over the original cure speed (RE1 to RE3). In general, the improvement could be much higher, since the activity of the compositions of the invention exceeded the limits of the test.

[0189] Indeed, the effect of the inventive combination was even more evident in the case of Lamps 2-5, where the initial activity was generally much lower for RE1-RE4, with dramatic improvements of 5-8 fold improvement in reactivity. In contrast, comparative combinations showed much lesser improvements, e.g., <10 vs. 71 for RE4 vs. IE2 (Lamp 3), compared to <10 vs. 31 for RE1 vs. CE2, <10 vs. 35 for RE2 vs. CE4, and 12 vs. 56 for RE3 vs. CE6.

[0190] It should be noted that benzoxazole sensitizer S2 was particularly effective with Lamp 5 which showed poor reactivity with all other combinations.

[0191] IE3 and IE4 reveal that the inventive combination of PI-I with S1 or S2 can be further improved by the addition of an amine additive, with much better surface cure being observed in all cases with the amine (IE3 / IE4 vs. IE1 / IE2, respectively).

[0192] The data in Table 2b further support the conclusions drawn from Table 2a, with IE5-IE9 all demonstrating improved surface cure (vs. RE5) despite lower amounts of photoinitiator, with the 4:1 blend ratio (IE6) being particularly effective, as was the use of benzoxazole sensitizer S2 (IE9). A similar effect can also be seen by comparing IE10-IE14 with RE6 and RE7. Again, the use of amines is shown to be particularly beneficial (IE8 vs. IE7, IE14 vs. IE10, IE15 vs. IE10, IE16 vs. IE11, and IE17 vs. IE13).

[0193] 4. Photoinitiator package in the form of a liquid blend The photopolymerization package of the present invention can also be prepared in the form of a liquid blend. The photoinitiator is placed in a three-neck round bottom flask under stirring and the temperature is slowly raised to 60°C. The sensitizer and amine (if present - see Table 3) are then added and the solution is stirred at 80°C for another hour. The clear solution is then slowly cooled to room temperature to obtain a liquid blend. This liquid blend may be directly used to prepare a polymerizable composition.

[0194] [Table 5] * - No reprecipitation As can be seen from Table 3, the photoinitiator packages of the present invention exist in liquid form, while those using the comparative photoinitiators cannot be prepared as such. This liquid blend is preferred because it avoids any problems associated with dissolving the package during preparation of the photopolymerizable composition and reduces the time required to prepare the composition.

[0195] Additionally, samples of IE21 were stored for 3 months at 4° C., 20° C., 40° C. and 60° C. No drop in reactivity was observed for samples stored at 4° C., 20° C. or 40° C., while the 60° C. sample underwent a slight drop in reactivity over the 3 months (maximum tack-free speed dropped from 49 m / min to 42 m / min). All samples maintained a constant viscosity over the test period (i.e., 3 months).

[0196] Photopolymerizable compositions (i.e., formulations comparable to those in Table 2) were prepared by adding Photopolymerizable Monomer Blend M to a photoinitiator package in the form of a liquid blend at room temperature. The formulation was stirred at 40° C. for 1 hour, cooled at room temperature, and then spread onto varnished cardboard at a thickness of 12 microns (12 μm) using a bar coater, and then photopolymerized using a light source in a manner similar to that in Table 3 above.

[0197] When formulations corresponding to IE1, IE3, IE5 and IE6 were prepared in this manner (i.e., by mixing IE18, IE19, IE20 or IE21 with Mi or M-ii in the appropriate ratios), the results of the surface cure evaluation were the same as those reported in Table 3. This reveals that the method of preparing the photopolymerizable composition is not critical in this example, and liquid blends are preferred solely for procedural economy.

Claims

1. a) one or more bisacylphosphine oxide photoinitiators, each having the structure of formula (I): 【Chemistry 1】 wherein each instance of R is independently selected from C １ ~C ４ is selected from the group consisting of alkyl, X is a direct single bond, O, S, NR ３ , -CH ２ CO ２ - and -CH ２ CH ２ CO ２ - selected from the group consisting of R １ is C １ ~C ４０ Alkyl and one or more O or C ３ ~C ８ Cycloalkylene-interrupted C ２ ~C ４０ alkyl, １ ~C ４０ Alkyl or interrupted C ２ ~C ４０ Alkyl is unsubstituted or is selected from the group consisting of OH and R ２ and optionally substituted with one or more groups selected from R ２ teeth, 【Chemistry 2】 and R ３ is hydrogen, (CO)R ４ , phenyl, C １ ~C １２ Alkyl and C interrupted by one or more O ２ ~C １２ Alkyl, C ３ ~C １２ cycloalkyl, １ ~C １２ Alkyl or interrupted C ２ ~C １２ Alkyl is unsubstituted or has one or more C ３ ~C ７ cycloalkyl, OH or NCO; ３ ~C １２ Cycloalkyl is unsubstituted or has one or more C １ ~C ４ Alkyl, C １ ~C ４ alkoxy, OH or NCO substituted; R ４ is C １ ~C １２ Alkyl and C interrupted by one or more O ２ ~C １２ alkyl, １ ~C １２ Alkyl or interrupted C ２ ~C １２ Alkyl is unsubstituted or has one or more C ３ ~C ７ cycloalkyl, OH, NCO or phenyl, wherein the phenyl is NCO, C ３ ~C １２ Cycloalkyl, C ２ ~C １０ Alkenyl, C ６ ~C １４ substituted with aryl; ２ ~C １０ Alkenyl is unsubstituted or has one or more C １ ~C ４ Alkyl, OH or C １ ~C ４ substituted with alkoxy; ６ ~C １４ Aryl is unsubstituted or C １ ~C １２ Alkyl, C １ ~C １２ Alkoxy, NCO or NCO substituted C １ ~C １２ is substituted with alkyl. b) one or more optical brightener sensitizers; a photoinitiator package comprising:

2. 2. The photoinitiator package of claim 1 , wherein each instance of R is Me.

3. X is a direct single bond, O, -CH ２ CO ２ - and -CH ２ CH ２ CO ２ -, more preferably a direct single bond, -CH ２ CO ２ - and -CH ２ CH ２ CO ２ -, most preferably a direct single bond.

4. R １ is C １ ~C ２０ Alkyl, -(CH ２ CH ２ O-) ｎ CH ３ , and -(CH ２ CH ２ O-) ｎ H (n is an integer ranging from 1 to 20), more preferably R １ is C １ ~C ２０ The photoinitiator package of any one of claims 1 to 3, wherein the photoinitiator package is an alkyl.

5. R １ The photoinitiator package of any one of claims 1 to 4, wherein: 【Chemistry 3】 wherein each instance of M is independently (CH ２ CH ２ O) and (CH ２ CH (CH ３ ) O) Each instance of Y is independently selected from hydrogen and C １ ~C ４ alkyl, Each example of Z is the structure CH ２ (M １ ) ｃ R ２ having M １ Each instance of is independently ２ CH ２ ) and (OCH(CH ３ ) CH ２ ) are selected from a is an integer ranging from 0 to 15; b is an integer ranging from 0 to 6; each instance of c is independently an integer in the range of 0 to 15; m is an integer ranging from 0 to 2; Each instance of X is independently -CH ２ CO ２ - and -CH ２ CH ２ CO ２ - is selected from the group consisting of

6. The photoinitiator package of any one of claims 1 to 5, wherein at least one of the one or more optical brightener sensitizers has the structure of formula (III): 【Chemistry 4】 (In the formula, R ３ａ is hydrogen, C １ ~C １０ Alkyl, C ６ ~C １４ Aryl, and C ６ ~C １４ Heteroaryl; R ４ａ is hydrogen, C １ ~C １０ Alkyl and OR １ａ wherein C is selected from the group consisting of １ ~C １０ The alkyl may be substituted with one or more fluorine atoms. R ５ａ ~R ８ａ Each of is independently hydrogen, halogen, C １ ~C １０ Alkyl, OR １ａ , and N.R. ２ａ ２ is selected from the group consisting of R １ａ Each instance of is independently hydrogen, C １ ~C １０ Alkyl, and C ６ ~C １４ aryl; R ２ａ Each instance of is independently hydrogen, C １ ~C １０ Alkyl, and C ６ ~C １４ aryl; R １ａ ~R ８ａ Each instance of is optionally １ａ ~R ８ａ may be combined with one or more further examples of to form one or more 5- or 6-membered rings.

7. The photoinitiator package of any one of claims 1 to 6, wherein at least one of the one or more optical brightener sensitizers has the structure of formula (IV): 【Chemistry 5】 (In the formula, R １ｂ ~R ４ｂ Each of the groups is independently hydrogen, C １ ~C １０ Alkyl and C ６ ~C １４ aryl; R １ｂ and R ２ｂ may be linked to form a 6-membered saturated or unsaturated ring, which may be selected from the group consisting of hydrogen, C １ ~C １０ Alkyl and C ６ ~C １４ aryl, R ３ｂ and R ４ｂ may be linked to form a six-membered ring, which may be joined to form a ring selected from the group consisting of hydrogen, C １ ~C １０ Alkyl and C ６ ~C １４ aryl, A represents a linking group represented by any one of the following formulas (V) to (IX): 【Chemistry 6】 Each * represents the bonding position of A in each formula.

8. 8. The photoinitiator package of claim 7, wherein at least one of the one or more optical brightener sensitizers has the structure of formula (X): 【Chemistry 7】 (In the formula, R １ｃ ~R ８ｃ Each of the groups is independently hydrogen, C １ ~C １０ Alkyl and C ６ ~C １４ aryl.

9. a) one or more bisacylphosphine oxide photoinitiators having the structure of formula (I) in an amount ranging from 40 to 99.9 wt.%, more preferably ranging from 60 to 99.0 wt.%, and most preferably ranging from 65 to 97.0 wt.%, based on the total weight of the photoinitiator package; b) one or more of said optical brightener sensitizers in an amount in the range of 0.1 to 50% by weight, more preferably in the range of 1.0 to 40% by weight, and most preferably in the range of 3.0 to 35% by weight, based on the total weight of said photoinitiator package; c) optionally one or more amines in an amount ranging from 1.0 to 45% by weight, more preferably in the range of 3.0 to 35% by weight, and most preferably in the range of 5.0 to 30% by weight, based on the total weight of the photoinitiator package; The photoinitiator package of any one of claims 1 to 8, comprising:

10. 10. The photoinitiator package of any one of claims 1 to 9, which is in the form of a blend that is liquid at 25°C and standard pressure.

11. a) one or more ethylenically unsaturated free radically polymerizable compounds; b) a photoinitiator package according to any one of claims 1 to 10; 1. A photopolymerizable composition comprising:

12. a) one or more of said ethylenically unsaturated free radically polymerizable compounds in an amount ranging from 30 to 99.0 wt %, more preferably ranging from 50 to 95.0 wt %, and most preferably ranging from 70 to 90 wt %, based on the total weight of said photopolymerizable composition; b) a photoinitiator package according to any one of claims 1 to 10 in an amount ranging from 0.5 to 50% by weight, more preferably in the range of 0.8 to 40% by weight, and most preferably in the range of 1.0 to 30% by weight, based on the total weight of the photopolymerizable composition; The photopolymerizable composition of claim 11 comprising:

13. c) one or more further photoinitiators, one or more photosensitizers and / or one or more coinitiators in an amount in the range of 0.5 to 30% by weight, more preferably in the range of 0.8 to 20% by weight, most preferably in the range of 1.0 to 15% by weight, d) one or more pigments in an amount ranging from 0.1 to 30% by weight, more preferably from 1.0 to 25% by weight, and most preferably from 10 to 20% by weight, based on the total weight of said photopolymerizable composition; e) one or more binders in an amount ranging from 5.0 to 60% by weight, more preferably ranging from 8.0 to 50% by weight, and most preferably ranging from 10 to 40% by weight, based on the total weight of the photopolymerizable composition; f) one or more additives in an amount ranging from 0.01 to 10% by weight, more preferably from 0.01 to 8.0% by weight, and most preferably from 0.01 to 5.0% by weight, based on the total weight of said photopolymerizable composition; The photopolymerizable composition of claim 11 or 12, further comprising one or more of:

14. 1. A method for photocuring photopolymerizable compositions, coatings, adhesives and inks comprising: a) coating or printing the photopolymerizable composition according to any one of claims 11 to 13 onto a substrate; b) photopolymerizing the composition coated or printed on the substrate with a light source; in a given order.

15. 11. Use of the photoinitiator package according to any one of claims 1 to 10 in the manufacture of printing inks, screen printing inks, gravure printing inks, solder masks, etch offset printing inks, flexographic printing inks, gravure printing inks, inkjet inks, resist materials, insulators, encapsulants, image recording materials, solder masks, passivation layers, protective coatings, 3D printing objects and moulds, holographic applications, optical fibre coatings, wave guides and lenses, overprint varnishes, wood, vinyl, metal and plastic coatings.

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