Photoinitiator package containing a phosphine oxide photoinitiator, an oxazole-based sensitizer and an amine additive

Abstract

A photoinitiator package comprising one or more mono- or bisacylphosphine oxide photoinitiators, one or more oxazole-based sensitizers and one or more amines, a photopolymerizable composition comprising the photoinitiator package and a suitable polymerizable compound, a method for polymerizing the photopolymerizable composition, the use of the photoinitiator package in photopolymerization applications, and the use of a combination of one or more amines and one or more oxazole-based sensitizers to enhance the surface cure rate of photopolymerizable compositions comprising Norrish Type I photoinitiators.

Description

[Technical field]

[0001] The present invention relates to a photoinitiator package comprising one or more mono- or bisacylphosphine oxide photoinitiators, one or more oxazole-based sensitizers and one or more amines, a photopolymerizable composition comprising the photoinitiator package and a suitable polymerizable compound, a method for polymerizing the photopolymerizable composition, the use of the photoinitiator package in photopolymerization applications, and the use of a combination of one or more amines and one or more oxazole-based sensitizers to enhance the surface cure rate of photopolymerizable compositions comprising Norrish Type I photoinitiators. [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 structure and energy levels of the photoinitiator. Providing a highly active photoinitiator package is desirable, as it allows for improved photopolymerization without the need to develop new photoinitiators.

[0006] Additionally, while the concept of combining a Type I photoinitiator with a sensitizer is well established, it would be most beneficial to provide additional additives that further enhance the activity of the photoinitiator package. [Means for solving the problem]

[0007] The present disclosure is based on the observation that the effect of certain sensitizers is enhanced by the presence of an amine, resulting in further improvement in the photoinitiator performance.

[0008] Thus, in a first aspect, the present invention provides a method for producing a method for treating a cancer a) one or more mono- or bis-acylphosphine oxide photoinitiators; b) one or more oxazole sensitizers each having the structure of formula (I); [ka] (In the formula, R 1 ~R 4 Each of the is independently hydrogen, C1 to C 10 Alkyl and C6-C 14aryl; R 1 and R 2 may be linked to form a 6-membered saturated or unsaturated ring, which may be hydrogen, C1-C 10 Alkyl and C6-C 14 aryl, R 3 and R 4 may be linked to form a 6-membered saturated or unsaturated ring, which may be hydrogen, C1-C 10 Alkyl and C6-C 14 aryl, A represents a linking group represented by any one of the following formulas (II) to (VI): [ka] Each * represents the bonding position of A in each formula. c) one or more amines The present invention is directed to a photoinitiator package comprising:

[0009] 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:

[0010] 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:

[0011] In a fourth 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.

[0012] In a final aspect, the present invention is directed to the use of a combination of one or more amines and one or more oxazole-based sensitizers to enhance the surface cure rate of photopolymerizable compositions containing one or more Norrish Type I photoinitiators. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] 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.

[0014] 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.

[0015] "C1-C interrupted by one or more oxygen 40The 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 -OCH2OCH3, -OCH2CH2OCH2CH3, -O[CH2CH2O] v CH3, -O[CH2CH2O] v OH, -O[CH2CH2O] v CH2CH3, -CH2O[CH2CH2O] v CH3(v=1-19), -O[CH2CH2CH2O] p OH, -O[CH2CH2CH2O] p CH3, -O[CH2CH2CH2O] p CH2CH3, -CH2O[CH2CH2CH2O] p CH3 (p=1-12) is an example.

[0016] When 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, phenyl ... amino, dicyclohexylamino, acetylamino, piperidino, pyrrolidyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, phenoxy, hydroxyl, acetoxy, -POH, 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.

[0017] The phrase "direct bond" means that there is no linking group and that a direct bond joins the two moieties on either side.

[0018] The methylene group is sp linked to two hydrogen groups. 3 The methanetriyl group refers to a carbon atom with a sp bond connected to one hydrogen group, i.e. -CHR. 3 Refers to a hybrid orbital carbon, i.e. -CHR2.

[0019] 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.

[0020] Mono- or Bisacylphosphine Oxide Photoinitiators One of the essential features of the photoinitiator package of the present invention is one or more mono- or bis-acylphosphine oxide photoinitiators.

[0021] In the broadest sense, any mono- or bis-acylphosphine oxide photoinitiator can be used.

[0022] Suitable monoacylphosphine oxide photoinitiators include, for example, photoinitiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate, Phenyl(2,4,6-trimethylbenzoyl)phosphinic acid, glycerol ethoxylated trimester (Omnipol® TP from IGM Resins BV), or those described in U.S. Patent Application Publication No. 2017 / 0240659, and Speedcure XKM (from Lambson).

[0023] However, it is preferred that one or more bisacylphosphine oxide photoinitiators are used.

[0024] In the broadest sense, any mono- or bis-acylphosphine oxide photoinitiator can be used, however, it is preferred that at least one, and preferably all, of the one or more bis-acylphosphine oxide photoinitiators have a structure according to any one of formulas (VII)-(X). Formula (VII): [ka] (In the formula, R 1a , R 2a , R 3a , R 1b , R 2b and R 3b each instance of is independently selected from the group consisting of C1-C4 alkyl, C1-C4 alkoxy, and halogen; X is a direct single bond, O, S, NR 5a , -CH2CO2-, and -CH2CH2CO2-; R 4a is hydrogen, (CO)R 6a , (CO)OR 6a , (CO)NR 5a R 6a , (SO2)R6a , [Si(R 7a )(R 8a )] m -Si(R 7a )(R 8a )(R 9a ), [Si(R 7a )(R 8a )O] m -Si(R 7a )(R 8a )(R 9a or R 4a is C1~C 28 Alkyl, or one or more O, NR 5a , C2-C interrupted by S, (CO), (CO)O or SO2 28 Alkyl, the above C1-C 28 Alkyl or interrupted C2-C 28 Alkyl is unsubstituted or substituted with one or more substituents, where one or more of the substituents are OH, C-C 14 Aryl, [Si(R 7a )(R 8a )] m -Si(R 7a )(R 8a )(R 9a ), [Si(R 7a )(R 8a )-O] m -Si(R 7a )(R 8a )(R 9a ), N(R 5a ) 2,2-oxiranyl, unsubstituted or C1-C4 alkyl, C1-C4 alkoxy or OH-substituted C3-C 12 Cycloalkyl, one or more O, NR 5a Or C3~C interrupted by S 12 Cycloalkyl (interrupted C3-C 12 Cycloalkyl is unsubstituted or substituted with C1-C4 alkyl, C1-C4 alkoxy or OH; C6-C8 alkyl is unsubstituted or substituted with C1-C4 alkyl, C1-C4 alkoxy or OH; 14 aryl; or R 4a is unsubstituted or has one or more C1-C 12 Alkyl, C2-C interrupted by one or more O 20 Alkyl, C1-C 12 C6-C substituted with alkoxy or OH 14 is aryl, or X is NR 5a If R 4a is R 5a and together with the N atom form a 5- or 6-membered saturated ring, which ring is uninterrupted or is O or NR 5a and the uninterrupted or interrupted ring is unsubstituted or substituted with one or more C1-C4 alkyl, C1-C4 alkoxy or OH; or R 4a is selected from the group consisting of structures (A)-(G): [ka] R 4a All the options are OH and R 17a may be further substituted with one or more groups selected from R 17a teeth, [ka] and A is PF6, SbF6, AsF6 or B(C6F5)4; R 5a is hydrogen, (CO)R 6a , Phenyl, C1-C 12 Alkyl, C2-C interrupted by one or more O 12 Alkyl, C3-C 12 Cycloalkyl, the above C1 to C 12 Alkyl or interrupted C2-C 12 Alkyl is unsubstituted or substituted with one or more C3-C7 cycloalkyl, OH or NCO, and the above C3-C 12Cycloalkyl is unsubstituted or substituted with one or more C1-C4 alkyl, C1-C4 alkoxy, OH or NCO; R 6a is C1~C 12 Alkyl or C2-C interrupted by one or more O 12 Alkyl, the above C1-C 12 Alkyl or interrupted C2-C 12 Alkyl is unsubstituted or substituted with one or more C3-C7 cycloalkyl, OH, NCO or NCO-substituted phenyl, or R 6a is C3~C 12 Cycloalkyl or C2-C 10 alkenyl, and the above C2-C 10 Alkenyl is unsubstituted or substituted with one or more C1-C4 alkyl, OH or C1-C4 alkoxy; R 6a is unsubstituted or C1-C 12 Alkyl, C1-C 12 Alkoxy, NCO or NCO substituted C1-C 12 Alkyl-substituted C6-C 14 is aryl, or Group N(R 5a )2, R 5a An example of this is (CO)R 6a R may be 5a Other examples of and R 6a forms a 5- or 6-membered ring together with the N and CO moieties, which ring is uninterrupted or is O or NR 5a and the uninterrupted or interrupted ring is unsubstituted or substituted with one or more C1-C4 alkyl, C1-C4 alkoxy or OH; R 7a , R 8a and R 9a are each independently C1-C4 alkyl, C6-C 14 selected from the group consisting of aryl and C1-C4 alkoxy; m is an integer in the range of 0 to 10, Y 1a is a direct single bond, O, S, NR 5a , O(CO)—* and O(CO)CHO—*, where the asterisk indicates the attachment of group (A), (B), (D) or (E) to the phenyl ring; Y 2a is a direct single bond, O, S and NR 5a is selected from the group consisting of R 11a and R 12a are independent of each other, C1 to C 10 Alkyl, C2-C 10 alkenyl or phenyl, C1-C4 alkyl unsubstituted or substituted with C1-C4 alkyl, or R 11a and R 12a form a cyclohexane or cyclopentane ring together with the C atom to which they are attached, Z a is OH or NR 13a R 14a and Z 1a is C1~C 12 Alkoxy or C2-C interrupted by one or more O 12 Alkoxy, the above C1-C 12 Alkoxy or interrupted C2-C 12 Alkoxy is unsubstituted or substituted with OH; R 13a and R 14a are independent of each other, C1 to C 12 Alkyl, C1-C substituted with one or more OH or halogen 12 is alkyl, or R 13a and R 14a form together with the N atom to which they are attached a 5- or 6-membered unsaturated or saturated ring, which ring is uninterrupted or is O or NR 15a It is interrupted by R 15a is C1-C4 alkyl, R 16a is hydrogen or C1-C4 alkyl, provided that: (i) R as C1-C4 alkyl 1a , R 2a and R 3a When is methyl and X is O, C1-C 28 R as alkyl 4 is not methyl, ethyl, n-propyl, 2-propyl, n-butyl, sec-butyl, tert-butyl, or n-hexyl, (ii) R as halogen 1a and R 3a is Cl, and R 2a is hydrogen and X is O, then the substitution C3-C 10 R as alkylaryl 4a is not 4-butyl-phenyl, (iii) R as C1-C4 alkoxy 1a and R 3a is methoxy and R 2a is hydrogen and X is NR 5a and R 4a R 5a and together with the N atom form a 5- or 6-membered saturated ring, said ring is not a piperidine ring. Formula (VIII): [ka] (In the formula, Ar 1 and Ar 2 are each independently [ka] or naphthyl, said naphthyl being unsubstituted or 1c , R 2c , R 3c , R 4c Or R 5c is substituted one or more times with R 1c and R 5c are each independently selected from the group consisting of C1-C4 alkyl, C1-C4 alkoxy, and halogen; R 3cis hydrogen, C1-C4 alkyl, halogen, C1-C4 alkoxy, and C2-C interrupted by one or more O. 20 alkoxy; Q is a C1-C4 alkylene; R 2c and R 4c are each independently hydrogen or PG c -Y c -Z c -X c - and PG c is a polymerizable group, methyl or ethyl, Y c is a direct single bond, O or S, X c is a direct single bond, O or S, Z c is a direct single bond, C1-C 20 Alkylene or C2-C interrupted by one or more O 20 is alkylene, R 6c is unsubstituted or is OH and [ka] C3 to C substituted with one or more groups selected from 30 is alkyl, or R 6c is a C3-C alkyl group interrupted by one or more O or C3-C8 cycloalkylene. 28 Alkyl, interrupted C3-C 28 Alkyl is unsubstituted or can be selected from the group consisting of OH and [ka] is substituted with one or more groups selected from Formula (IX): [ka] (In the formula, R 1d is C1-C4 alkyl, C1-C4 alkoxy or halogen; R 2dis hydrogen, C1-C4 alkyl, C1-C4 alkoxy or halogen, R 3d is C1~C 20 alkyl, cyclopentyl, cyclohexyl, phenyl-C1-C4 alkyl, naphthyl, biphenylyl, or an O-, S- or N-containing 5- or 6-membered heterocycle, the naphthyl, biphenylyl, and O-, S- or N-containing 5- or 6-membered heterocycle radicals being unsubstituted or substituted with C1-C4 alkyl, C1-C4 alkoxy, halogen, C1-C4 alkylthio, or R 3d teeth, [ka] and In the formula, R 4d , R 5d , R 6d , R 7d and R 8d are each independently hydrogen, halogen, or C1-C 20 Alkyl, cyclopentyl, cyclohexyl, C2-C 12 Alkenyl, C2-C interrupted by one or more non-consecutive O atoms 20 Alkyl, Phenyl-C1-C4 Alkyl, C1-C 20 alkoxy, or phenyl, wherein the phenyl is unsubstituted or substituted with one or two C1-C4 alkyl and / or C1-C4 alkoxy substituents. Formula (V): [ka] (wherein each A is independently O, S, NR 3e represents G is a multifunctional compound (core) G-(AH) p+q where each AH represents an alcohol, amino or thiol group; p and q are both integers, p+q is an integer in the range of 3 to 10, and p is an integer in the range of 3 to 8; R1e and R 2e are each independently C1 to C 18 Alkyl, C6-C 14 Aryl and C5-C 12 cycloalkyl, C1-C 18 Alkyl, C6-C 14 Aryl and C5-C 12 Each cycloalkyl is uninterrupted or interrupted by one or more oxygen atoms and / or sulfur atoms and / or one or more substituted or unsubstituted amino groups, or R 1e and R 2e is a 5-6 membered heterocyclyl containing oxygen and / or nitrogen and / or sulfur atoms, each of which may be substituted with aryl, alkyl, aryloxy, alkoxy, heteroatoms and / or heterocyclic radicals; R 2e HA(CO)R 1e may be R 3e is hydrogen or C1-C4 alkyl.

[0025] In one embodiment, at least one of the one or more bisacylphosphine oxide photoinitiators each has the structure of formula (XI): [ka] (In the formula, R 1f each instance of is independently selected from the group consisting of C1-C4 alkyl; X f is a direct single bond, O, S, NR 4f , -CH2CO2-, and -CH2CH2CO2-; R 2f is C1~C 40 Alkyl and interrupted C2-C interrupted by one or more O or C3-C8 cycloalkylene 40 alkyl, and the C1 to C 40 Alkyl or interrupted C2-C 40 Alkyl is unsubstituted or is selected from the group consisting of OH and R 3fand optionally substituted with one or more groups selected from R 3f teeth, [ka] and R 4f is hydrogen, (CO)R 5f , Phenyl, C1-C 12 Alkyl and C2-C interrupted by one or more O 12 Alkyl, C3-C 12 cycloalkyl, and the C1 to C 12 Alkyl or interrupted C2-C 12 Alkyl is unsubstituted or substituted with one or more C3-C7 cycloalkyl, OH or NCO, and the above C3-C 12 Cycloalkyl is unsubstituted or substituted with one or more C1-C4 alkyl, C1-C4 alkoxy, OH or NCO; R 5f is C1~C 12 Alkyl and C2-C interrupted by one or more O 12 alkyl, and the C1 to C 12 Alkyl or interrupted C2-C 12 The alkyl is unsubstituted or substituted with one or more C3-C7 cycloalkyl, OH, NCO, or phenyl, the phenyl being selected from NCO, C3-C 12 Cycloalkyl, C2-C 10 Alkenyl, C6-C 14 Substituted with aryl, C2-C 10 Alkenyl is unsubstituted or substituted with one or more C1-C4 alkyl, OH or C1-C4 alkoxy, and is selected from the group consisting of C6-C 14 Aryl is unsubstituted or C1-C 12 Alkyl, C1-C 12 Alkoxy, NCO or NCO substituted C1-C 12 substituted with alkyl.

[0026] R 1fEach instance of R may be independently selected from the group consisting of C1-C4 alkyl, i.e., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, and t-butyl. 1f It is particularly preferred that each instance of R is selected from methyl and ethyl. Most preferably, 1f Each instance of is methyl.

[0027] X f is a direct single bond, O, S, NR 3f More preferably, X is selected from the group consisting of -CHCO-, -CHCHCO-, and -CHCHCO-. f is selected from the group consisting of a direct single bond, O, -CH2CO2- and -CH2CH2CO2-. Even more preferably, X f is selected from the group consisting of a direct single bond, -CH2CO2- and -CH2CH2CO2-. Most preferably, X f is a direct single bond.

[0028] R 1f is C1~C 40 Alkyl and interrupted C2-C interrupted by one or more O or C3-C8 cycloalkylene 40 alkyl, and the C1 to C 40 Alkyl or interrupted C2-C 40 Alkyl is unsubstituted or is selected from the group consisting of OH and R 3f and optionally substituted with one or more groups selected from R 3f teeth, [ka] It is.

[0029] In some embodiments, R 3f is not present, which means that the structure of formula (XI) has a single bisacylphosphine oxide moiety.

[0030] In such an embodiment, R 2f is C1~C 20Alkyl, -(CH2CH2O-) n CH3 and -(CH2CH2O-) n H (n is an integer in the range of 1 to 20). 2f C1~C 20 Alkyl is particularly preferred.

[0031] Particularly preferred is X f is a direct single bond, and R 2f C1~C 20 In certain embodiments, R 1f It is especially preferred that each instance of is methyl.

[0032] Similarly, X f is O and R 2f -(CH2CH2O-) n CH3 or -(CH2CH2O-) n Also particularly preferred are embodiments in which R is H. In such embodiments, R 1f It is especially preferred that each instance of is methyl.

[0033] In other embodiments, R 3f There is at least one instance of: which means that the structure of formula (XI) has two or more bisacylphosphine oxide moieties.

[0034] Such an embodiment preferably comprises R 1f is described by formula (XI) having the structure of formula (XII). [ka] wherein each instance of M is independently selected from (CH2CH2O) and (CH2CH(CH3)O); Each instance of Y is independently selected from hydrogen and C1-C4 alkyl; Each example of Z has the structure CH2(M 1 ) c R 2f having M 1each instance of is independently selected from (OCHCH) and (OCH(CH)CH); 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; X f Each instance of is independently selected from the group consisting of -CH2CO2- and -CH2CH2CO2-.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] When using the glycerol core, R 2f is referred to as "optionally ethoxylated / propoxylated glycerol."

[0040] When using trimethylolpropane core, R 2f is referred to as "optionally ethoxylated / propoxylated trimethylolpropane."

[0041] When using a pentaerythritol core, R 2f is referred to as "optionally ethoxylated / propoxylated pentaerythritol."

[0042] When using the neopentyl glycol core, R 2f is referred to as "optionally ethoxylated / propoxylated neopentyl glycol."

[0043] When using an ethylene glycol core, R 2f is referred to as "optionally ethoxylated / propoxylated ethylene glycol."

[0044] When using the 1,6-hexanediol core, R 2f is referred to as "optionally ethoxylated / propoxylated 1,6-hexanediol."

[0045] 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.

[0046] 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.

[0047] R 2f is C1~C 20 Alkyl, -(CH2CH2O-) n CH3, -(CH2CH2O-) n H (n is an integer in the range of 1 to 20), ethoxylated / propoxylated glycerol, ethoxylated / propoxylated trimethylolpropane, and ethoxylated / propoxylated pentaerythritol are particularly preferred.

[0048] R 2f C1~C 20 If it is alkyl, R 2f is C1~C 15 Alkyl, more preferably C1-C 12 Alkyl is particularly preferred.

[0049] It is particularly preferred that the one or more bisacylphosphine oxide photoinitiators each have the structure of formula (XI):

[0050] In an alternative embodiment, at least one of the one or more bisacylphosphine oxide photoinitiators each has the formula: R 1f Each instance of X is independently selected from the group consisting of C1-C4 alkyl; f is a direct single bond, and R 2f C6~C 14 Aryl, C1-C 20 Alkyl, -(CH2CH2O-) n CH3 and -(CH2CH2O-) n H (n is an integer ranging from 1 to 20),

[0051] R 2f More preferably, C6 to C 14 It is selected from aryl, most preferably phenyl.

[0052] In one particularly preferred embodiment, R 1f Each instance of X is methyl. fis a direct single bond, and R 2f is phenyl.

[0053] Oxazole sensitizers Another essential feature of the photoinitiator package of the present invention is the presence of one or more oxazole-based sensitizers, each having the structure of formula (I). [ka] (In the formula, R 1 ~R 4 Each of the is independently hydrogen, C1 to C 10 Alkyl and C6-C 14 aryl; R 1 and R 2 may be linked to form a 6-membered saturated or unsaturated ring, which may be hydrogen, C1-C 10 Alkyl and C6-C 14 aryl, R 3 and R 4 may be linked to form a 6-membered saturated or unsaturated ring, which may be hydrogen, C1-C 10 Alkyl and C6-C 14 aryl, A represents a linking group represented by any one of the following formulas (II) to (VI): [ka] Each * represents the bonding position of A in each formula.

[0054] R 1 ~R 4 Each of the is independently hydrogen, C1 to C 10 Alkyl and C6-C 14 aryl; R 1 and R 2 may be linked to form a 6-membered saturated or unsaturated ring, which may be hydrogen, C1-C 10 Alkyl and C6-C 14aryl, R 3 and R 4 may be linked to form a 6-membered saturated or unsaturated ring, which may be hydrogen, C1-C 10 Alkyl and C6-C 14 It may be substituted with one or more substituents selected from the group consisting of aryl.

[0055] In one embodiment, R 1 ~R 4 each independently represents hydrogen, C1-C6 alkyl, and C6-C 10 aryl.

[0056] In a particularly preferred embodiment, R 1 and R 3 Both are R 2 and R 4 to form a 6-membered saturated or unsaturated ring, which is composed of hydrogen, C1-C 10 Alkyl and C6-C 14 It may be substituted with one or more substituents selected from the group consisting of aryl.

[0057] In one embodiment of the particularly preferred embodiment above, each six-membered ring formed is aromatic, meaning that the oxazole sensitizer is a benzoxazole sensitizer having the structure of formula (Ia): [ka] (In the formula, R 1g ~R 8g Each of the is independently hydrogen, C1 to C 10 Alkyl and C6-C 14 aryl.

[0058] Preferably, R 1g ~R 8g each independently represents hydrogen, C1-C6 alkyl, and C6-C 10 aryl.

[0059] In one embodiment, each of the one or more oxazole sensitizers has the structure of Formula (Ia).

[0060] In other embodiments, at least one of the one or more oxazole sensitizers has a structure of formula (Ia), while any remaining oxazole sensitizers in the photoinitiator package have other structures of formula (I).

[0061] Particularly preferred compounds of formula (I) 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].

[0062] Amine Another essential feature of the photoinitiator package according to the present invention is the presence of one or more amines.

[0063] It is a discovery of the present invention that the presence of an amine in a Norrish Type I photoinitiator system package, in combination with an oxazole-based sensitizer, can dramatically improve the rate of cure, particularly the surface cure.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] Preferably, the one or more amines are not type I or type II photoinitiators, such as the well-known aminoketone type I initiators.More preferably, 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, apparently, the only role of the amine in the photopolymerization package is to act as a synergist and improve the effect of one or more mono- or bisacylphosphine oxide photoinitiators and / or one or more oxazole-based sensitizers.

[0068] 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 Attachment to a carbon in a hybrid orbital is particularly preferred. Thus, amines preferably have a nitrogen atom with a direct single bond to either a methyl group (i.e., CH), a methylene group (i.e., CH of CHR), or a methanetriyl group (i.e., CH of CHR).

[0069] 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.

[0070] 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.

[0071] 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 Bis 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.

[0072] 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).

[0073] Photoinitiator Package Photoinitiator packages according to the present invention include one or more mono- or bisacylphosphine oxide photoinitiators as described above, one or more oxazole-based sensitizers as described above, and one or more amines as described above.

[0074] The photoinitiator package preferably comprises: a) one or more mono- or bisacylphosphine oxide photoinitiators in an amount in the range of 40 to 98.9 wt.%, more preferably in the range of 60 to 96.0 wt.%, and most preferably in the range of 65 to 92.0 wt.%, based on the total weight of the photoinitiator package; b) one or more oxazole sensitizers in an amount ranging from 0.1 to 50 weight percent, more preferably ranging from 1.0 to 37 weight percent, and most preferably 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 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.

[0075] In a further embodiment, the photoinitiator package comprises: a) one or more mono- or bis-acylphosphine oxide photoinitiators in an amount ranging from 40 to 98.9 weight percent, based on the total weight of the photoinitiator package; b) one or more oxazole sensitizers in an amount ranging from 0.1 to 50 weight percent, 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 based on the total weight of the photoinitiator package; and more preferably, consists of these.

[0076] In another embodiment, the photoinitiator package comprises: a) one or more mono- or bisacylphosphine oxide photoinitiators in an amount ranging from 60 to 96.0 weight percent, based on the total weight of the photoinitiator package; b) one or more oxazole 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.

[0077] In yet a further embodiment, the photoinitiator package comprises: a) one or more mono- or bis-acylphosphine oxide photoinitiators in an amount ranging from 65 to 92.0 weight percent, based on the total weight of the photoinitiator package; b) one or more oxazole 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.

[0078] When further components other than the one or more mono- or bisacylphosphine oxide photoinitiators, the one or more oxazole-based sensitizers and the one or more amines are present, they are preferably further Type I photoinitiators.

[0079] It is particularly preferred that the only photoinitiator present in the photoinitiator package is a Norrish Type I photoinitiator or a cationic photoinitiator.

[0080] It is further preferred that the only photoinitiator present in the photoinitiator package is a Norrish Type I photoinitiator.

[0081] Additionally or alternatively, a further optical brightener sensitizer may be present.

[0082] As will be appreciated by those skilled in the art, the term "additional optical brightener sensitizers" means that these additional sensitizers have a structure other than one or more oxazole-based sensitizers.

[0083] 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.

[0084] Furthermore, 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.

[0085] Thus, the photoinitiator package preferably comprises, and more preferably consists of, one or more bisacylphosphine oxide photoinitiators, one or more oxazole-based sensitizers, one or more amines, optionally one or more further Type I photoinitiators, and optionally one or more further optical brightener sensitizers.

[0086] Thus, the photoinitiator package preferably comprises: a) one or more mono- or bisacylphosphine oxide photoinitiators in an amount in the range of 40 to 98.9 wt.%, more preferably in the range of 60 to 96.0 wt.%, and most preferably in the range of 65 to 92.0 wt.%, based on the total weight of the photoinitiator package; b) one or more oxazole sensitizers in an amount ranging from 0.1 to 50 weight percent, more preferably ranging from 1.0 to 37 weight percent, and most preferably 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 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) a further type I initiator in an amount ranging from 0.0 to 58.9% by weight, more preferably in the range of 0 to 36.0% by weight, and most preferably in the range of 0.0 to 27.0% by weight, e) a further optical brightener sensitizer in an amount ranging from 0.0 to 58.9% by weight, more preferably in the range of 0 to 36.0% by weight, and most preferably in the range of 0.0 to 27.0% by weight; It consists of:

[0087] Photopolymerizable composition In a second aspect, the present invention is also directed to a photopolymerizable composition.

[0088] 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:

[0089] 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:

[0090] 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.

[0091] Suitable further components include photosensitizers, further photoinitiators, pigments, binders and conventional additives.

[0092] 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.

[0093] Additionally, the photopolymerizable composition may be formulated into a composition that further comprises a solvent, such as water and / or an organic solvent.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] Specific examples of such unsaturated polyamides are methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide, bis(methacrylamidopropoxy)ethane and N-[(β-hydroxyethoxy)ethyl]-acrylamide.

[0107] 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.

[0108] Polybutadiene and polyisoprene, as well as copolymers thereof, may also be used.

[0109] 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.

[0110] Examples of photosensitizers are those commonly used in the art: terphenyls, styryl ketones, and 3-(aroylmethylene)-thiazolines, as well as eosin, rhodamine and erythrosine dyes.

[0111] 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.

[0112] Examples of other suitable photoinitiators are acetophenone, acetophenone derivatives, dialkoxyacetophenones, α-hydroxyketones, α-aminoketones, benzoin alkyl ethers and benzil ketals (e.g., benzil dimethyl ketal), acylphosphine photoinitiators (which can be selected from monoacylphosphine oxides, bisacylphosphine oxides, trisacylphosphine oxides, and polyfunctional monoacylphosphine oxides or bisacylphosphine oxides), halomethyltriazines, hexaarylbisimidazole / coinitiator 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.

[0113] 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).

[0114] 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).

[0115] 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.

[0116] 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).

[0117] Any pigment known to one of ordinary skill in the art can be used in the photopolymerizable composition.

[0118] 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.

[0119] 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).

[0120] 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.

[0121] 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).

[0122] 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.

[0123] 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).

[0124] 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.

[0125] 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:

[0126] Preferably, the light source operates in the near UV or visible range of the EM spectrum.

[0127] 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.

[0128] use In a fourth 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.

[0129] 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.

[0130] In a final aspect, the present invention is directed to the use of a combination of one or more amines and one or more oxazole-based sensitizers to enhance the surface cure rate of photopolymerizable compositions containing one or more Norrish Type I photoinitiators.

[0131] It is particularly preferred that the one or more Norrish Type I photoinitiators are selected from mono- or bisacylphosphine oxide photoinitiators.

[0132] All alternatives and preferred embodiments of the one or more mono- or bisacylphosphine oxide photoinitiators, oxazole-based sensitizers and / or amines described in the first aspect are applicable for use according to this aspect, mutatis mutandis.

[0133] Further, it is preferred that the photopolymerizable composition is a photopolymerizable composition according to the second aspect. All alternatives and preferred embodiments of the photopolymerizable composition of the second aspect are applicable mutatis mutandis for use according to this aspect.

[0134] A combination of one or more amines and one or more oxazole sensitizers is particularly preferred to significantly increase the surface cure rate.

[0135] In one embodiment, the effect of "increasing the surface cure rate" is achieved when the surface cure rate (expressed as tack-free m / min) in the presence of the combination of one or more amines and one or more oxazole sensitizers is at least 1.5 times higher, more preferably at least 2.0 times higher, more preferably at least 3.0 times higher, and most preferably at least 5.0 times higher, than in the absence of the combination of one or more amines and one or more oxazole sensitizers. EXAMPLES

[0136] 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.

[0137] B. Experiment 1.Materials used The following commercially available compounds were used in preparing the inventive and comparative formulations:

[0138] PI-1: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, CAS number: 162881-26-7, commercially available as Omnirad 819 from IGM Group BV (The Netherlands).

[0139] PI-2: Bis(2,4,6-trimethylbenzoyl)octylphosphine oxide, prepared as described in US Pat. No. 5,534,559A.

[0140] S: 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).

[0141] 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).

[0142] A2: Triethanolamine, CAS number: 102-71-6, commercially available from Merck KGaA (Germany).

[0143] A3: Poly(ethylene glycol) bis(p-dimethylaminobenzoate), CAS number: 71512-90-8, commercially available as Omnipol ASA from IGM Group BV, The Netherlands.

[0144] Mi: a photopolymerizable monomer blend of M1, M2 and M3 (40:30:30).

[0145] M-ii: A photopolymerizable monomer blend of M1, M4, M5 and M6 (50:15:15:20).

[0146] M-iii: A photopolymerizable monomer blend of M1, M4 and M6 (50:25:25).

[0147] M1: Bisphenol Y epoxy diacrylate, CAS number: 55818-57-0, commercially available as Photomer 3016 from IGM Group BV, The Netherlands.

[0148] M2: Glyceryl [4 PO] triacrylate, CAS number: 52408-84-1, commercially available as Photomer 4094 from IGM Group BV, The Netherlands.

[0149] M3: Trimethylolpropane triacrylate, CAS number: 15625-89-5, commercially available as Photomer 4006 from IGM Group BV, The Netherlands.

[0150] 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).

[0151] M5: Dipentaerythritol penta / hexaacrylate, CAS number: 1384855-91-7, commercially available as Photomer 4600 from IGM Group BV, The Netherlands.

[0152] M6: Pentaerythritol [5 EO] tetraacrylate, CAS number: 51728-26-8, commercially available as Photomer 4172 from IGM Group BV (The Netherlands).

[0153] 2. Compound (photopolymerizable composition) The following inventive and comparative formulations were used for surface cure evaluation, with the amounts of each component listed in weight percent (wt%). The formulations were prepared by adding photoinitiator, sensitizer, and amine to photopolymerizable monomer blend M 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 to a thickness of 12 microns (12 μm) on varnished cardboard using a bar coater. The formulations were then photopolymerized using a light source (Table 2).

[0154] [Table 1]

[0155] [Table 2]

[0156] 3. Evaluation of surface photocuring The inventive and comparative formulations were evaluated for their surface light curing capabilities according to the test method provided in the Determination Methods using different light sources (values ​​in Table 2 correspond to the maximum tack-free speed (m / min)).

[0157] [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.

[0158] [Table 4] 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 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.

[0159] As can be seen from the data in Table 2, the use of benzoxazole sensitizer S in combination with photoinitiators PI-1 and PI-2 improves the cure speed for each lamp used (CE3 / CE4 vs. CE1 and CE6 vs. CE5). However, it is the synergistic use of sensitizer and amine that provides the greatest improvement. As can be seen by comparing CE2 to CE1, the amine alone affects the cure speed of the Type I photoinitiator, but the effect when both an amine and sensitizer are used is generally greater than would be predicted from a simple additive effect (i.e., the amine and sensitizer act synergistically).

[0160] Little insight can be gained from the results using Lamp 1 as activity was generally above the limits of the test, however Lamps 2-5 demonstrate that the addition of A1 provides significant improvements, with values ​​typically about 20 m / min higher than the examples without the amine (IE1 vs. CE3).

[0161] A similar improvement is seen when using PI-2 (i.e., IE5 vs. CE6), with good surface cure across all five lamps.

[0162] Furthermore, the use of the amine allows the amount of sensitizer to be dramatically reduced, with only 1.5 wt% sensitizer used in CE4 and IE2-IE4. A1 shows a dramatic improvement (IE2 vs. CE4), with the sensitizer / amine combinations (1.5 wt% and 5 wt%) being significantly more active than 10 wt% sensitizer alone (IE2 vs. CE3). IE3 and IE4 have slightly lower activity than IE2, but are still very valuable sensitizer / amine combinations, especially given the lower cost of A2 compared to the more complex amines.

[0163] Comparing IE6 with CE7–CE9 further supports the conclusions drawn from Table 2a, while IE7 reveals that while amines improve surface cure compared to CE10, amides such as acryloylmorpholine have a detrimental effect (CE11), not only performing worse than amines but also worse than CE10 without the amine / amide.

Claims

1. a) one or more mono- or bis-acylphosphine oxide photoinitiators; b) one or more oxazole sensitizers each having the structure of formula (I); 【Chemistry 1】 (In the formula, R １ ~R ４ Each of the groups is independently hydrogen, C １ ~C １０ Alkyl and C ６ ~C １４ aryl; R １ and R ２ 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 ３ and R ４ 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, A represents a linking group represented by any one of the following formulas (II) to (VI): 【Chemistry 2】 Each * represents the bonding position of A in each formula. c) one or more amines; a photoinitiator package comprising:

2. 10. The photoinitiator package of claim 1, wherein each of the one or more amines has a nitrogen atom with a direct single bond to either a methyl group, a methylene group, or a methanetriyl group.

3. 3. The photoinitiator package of claim 1 or 2, wherein at least one of the one or more bisacylphosphine oxide photoinitiators has a structure according to any one of formulas (VII)-(X): 【Chemistry 3】 (In the formula, R １ａ , R ２ａ , R ３ａ , R １ｂ , R ２ｂ and R ３ｂ Each instance of is independently １ ~C ４ Alkyl, C １ ~C ４ alkoxy, and halogen; X is a direct single bond, O, S, NR ５ａ , -CH ２ CO ２ - and -CH ２ CH ２ CO ２ - selected from the group consisting of R ４ａ is hydrogen, (CO)R ６ａ , (CO)OR ６ａ , (CO)NR ５ａ R ６ａ , (SO ２ ) R ６ａ [Si(R ７ａ ) (R ８ａ ) ] ｍ -Si(R ７ａ ) (R ８ａ ) (R ９ａ ), [Si(R ７ａ ) (R ８ａ ) O] ｍ -Si(R ７ａ ) (R ８ａ ) (R ９ａ or R ４ａ is C １ ~C ２８ Alkyl, or one or more of O, NR ５ａ , S, (CO), (CO)O or SO ２ C interrupted by ２ ~C ２８ alkyl, １ ~C ２８ Alkyl or interrupted C ２ ~C ２８ Alkyl is unsubstituted or substituted with one or more substituents, said one or more substituents being OH, C ６ ~C １４ Aryl, [Si(R ７ａ ) (R ８ａ ) ] ｍ -Si(R ７ａ ) (R ８ａ ) (R ９ａ ), [Si(R ７ａ ) (R ８ａ ) -O] ｍ -Si(R ７ａ ) (R ８ａ ) (R ９ａ ), N(R ５ａ ) ２ , 2-oxiranyl, unsubstituted or C １ ~C ４ Alkyl, C １ ~C ４ Alkoxy or OH substituted C ３ ~C １２ Cycloalkyl, one or more O, NR ５ａ Or C interrupted by S ３ ~C １２ Cycloalkyl (interrupted C ３ ~C １２ Cycloalkyl is unsubstituted or C １ ~C ４ Alkyl, C １ ~C ４ substituted with alkoxy or OH), unsubstituted or １ ~C ４ Alkyl, C １ ~C ４ Alkoxy or OH substituted C ６ ~C １４ aryl; or R ４ａ is unsubstituted or contains one or more C １ ~C １２ Alkyl, C interrupted by one or more O ２ ~C ２０ Alkyl, C １ ~C １２ Alkoxy or OH substituted C ６ ~C １０ is aryl, or X is NR ５ａ If R ４ａ is R ５ａ and together with the N atom form a 5- or 6-membered saturated ring, which ring is uninterrupted or is O or NR ５ａ and the uninterrupted or interrupted ring is unsubstituted or has one or more C １ ~C ４ Alkyl, C １ ~C ４ substituted with alkoxy or OH; R ４ａ is selected from the group consisting of structures (A)-(G): 【Chemistry 4】 R ４ａ All options are OH and R １７ａ may be further substituted with one or more groups selected from R １７ａ teeth, 【Chemistry 5】 and A is PF ６ , SbF ６ , AsF ６ Or B(C ６ F ５ ) ４ and R ５ａ is hydrogen, (CO)R ６ａ , phenyl, C １ ~C １２ Alkyl, 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 ６ａ is C １ ~C １２ Alkyl or 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 substituted with cycloalkyl, OH, NCO or NCO-substituted phenyl; R ６ａ is C ３ ~C １２ Cycloalkyl or C ２ ~C １０ alkenyl, 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, or R ６ａ is unsubstituted or C １ ~C １２ Alkyl, C １ ~C １２ Alkoxy, NCO or NCO substituted C １ ~C １２ Alkyl-substituted C ６ ~C １４ is aryl, or Group N(R ５ａ ) ２ If R ５ａ An example of the formula is (CO)R ６ａ R may be ５ａ Other examples of and R ６ａ together with the N and CO moieties form a 5- or 6-membered ring, which ring is uninterrupted or is joined by O or NR ５ａ and the uninterrupted or interrupted ring is unsubstituted or has one or more C １ ~C ４ Alkyl, C １ ~C ４ alkoxy or OH substituted; R ７ａ , R ８ａ and R ９ａ are each independently １ ~C ４ Alkyl, C ６ ~C １４ Aryl and C １ ~C ４ alkoxy; m is an integer ranging from 0 to 10; Y １ａ is a direct single bond, O, S, NR ５ａ , O(CO)-* and O(CO)CH ２ O-*, where the asterisk indicates the attachment of group (A), (B), (D) or (E) to the phenyl ring; Y ２ａ is a direct single bond, O, S and NR ５ａ is selected from the group consisting of R １１ａ and R １２ａ are, independently of each other, C １ ~C １０ Alkyl, C ２ ~C １０ alkenyl or phenyl, unsubstituted or C １ ~C ４ Alkyl-substituted C １ ~C ４ alkyl or R １１ａ and R １２ａ form a cyclohexane or cyclopentane ring together with the C atom to which they are attached, Z ａ is OH or NR １３ａ R １４ａ and Z １ａ is C １ ~C １２ Alkoxy or C interrupted by one or more O ２ ~C １２ Alkoxy, １ ~C １２ Alkoxy or interrupted C ２ ~C １２ Alkoxy is unsubstituted or substituted with OH; R １３ａ and R １４ａ are, independently of each other, C １ ~C １２ Alkyl, C substituted with one or more OH or halogen １ ~C １２ is alkyl, or R １３ａ and R １４ａ form together with the N atom to which they are attached a 5- or 6-membered unsaturated or saturated ring, which ring is uninterrupted or is joined by O or NR １５ａ It is interrupted by R １５ａ is C １ ~C ４ is alkyl, R １６ａ is hydrogen or C １ ~C ４ Alkyl, provided that: (i) C １ ~C ４ R as alkyl １ａ , R ２ａ and R ３ａ When is methyl and X is O, C １ ~C ２８ R as alkyl ４ is not methyl, ethyl, n-propyl, 2-propyl, n-butyl, sec-butyl, tert-butyl, or n-hexyl, (ii) R as halogen １ａ and R ３ａ is Cl, R ２ａ is hydrogen and X is O, the substitution C ３ ~C １０ R as Aryl ４ａ is not 4-butyl-phenyl, (iii) C １ ~C ４ R as alkoxy １ａ and R ３ａ is methoxy, R ２ａ is hydrogen and X is NR ５ａ and R ４ａ R ５ａ and together with the N atom form a 5- or 6-membered saturated ring, said ring is not a piperidine ring. 【Chemistry 6】 (In the formula, Ar １ and Ar ２ are each independently 【Chemistry 7】 or naphthyl, said naphthyl being unsubstituted or １ｃ , R ２ｃ , R ３ｃ , R ４ｃ Or R ５ｃ is substituted one or more times with R １ｃ and R ５ｃ are each independently １ ~C ４ Alkyl, C １ ~C ４ selected from the group consisting of alkoxy and halogen; R ３ｃ is hydrogen, C １ ~C ４ Alkyl, halogen, C １ ~C ４ Alkoxy and C interrupted by one or more O ２ ~C ２０ alkoxy; Q is C １ ~C ４ is alkylene, R ２ｃ and R ４ｃ are each independently hydrogen or PG ｃ -Y ｃ -Z ｃ -X ｃ - and P.G. ｃ is a polymerizable group, methyl or ethyl, Y ｃ is a direct single bond, O or S, X ｃ is a direct single bond, O or S, Z ｃ is a direct single bond, C １ ~C ２０ Alkylene or C interrupted by one or more O ２ ~C ２０ is alkylene, R ６ｃ is unsubstituted or is selected from the group consisting of OH and 【Chemistry 8】 C substituted with one or more groups selected from ３ ~C ３０ is alkyl, or R ６ｃ is one or more O or C ３ ~C ８ Cycloalkylene-interrupted C ３ ~C ２８ Alkyl, interrupted C ３ ~C ２８ Alkyl is unsubstituted or is selected from the group consisting of OH and 【Chemistry 9】 is substituted with one or more groups selected from 【Chemistry 10】 (In the formula, R １ｄ is C １ ~C ４ Alkyl, C １ ~C ４ alkoxy or halogen; R ２ｄ is hydrogen, C １ ~C ４ Alkyl, C １ ~C ４ alkoxy or halogen; R ３ｄ is C １ ~C ２０ Alkyl, cyclopentyl, cyclohexyl, phenyl-C １ ~C ４ alkyl, naphthyl, biphenylyl, or an O-, S- or N-containing 5- or 6-membered heterocycle, the naphthyl, biphenylyl, and O-, S- or N-containing 5- or 6-membered heterocycle radicals being unsubstituted or １ ~C ４ Alkyl, C １ ~C ４ Alkoxy, halogen, C １ ~C ４ is substituted with alkylthio, or R ３ｄ teeth, 【Chemistry 11】 and R ４ｄ , R ５ｄ , R ６ｄ , R ７ｄ and R ８ｄ are each independently hydrogen, halogen, or C １ ~C ２０ Alkyl, cyclopentyl, cyclohexyl, C ２ ~C １２ Alkenyl, C interrupted by one or more non-consecutive O atoms ２ ~C ２０ Alkyl, phenyl-C １ ~C ４ Alkyl, C １ ~C ２０ alkoxy, or phenyl, wherein the phenyl is unsubstituted or has one or two C １ ~C ４ Alkyl and / or C １ ~C ４ substituted with an alkoxy substituent. 【Chemistry 12】 wherein each A is independently O, S, NR ３ｅ represents G is a polyfunctional compound (core) G-(A-H) ｐ＋ｑ where each A-H represents an alcohol group, an amino group, or a thiol group; p and q are both integers, p+q is an integer in the range of 3 to 10, and p is an integer in the range of 3 to 8; R １ｅ and R ２ｅ are each independently １ ~C １８ Alkyl, C ６ ~C １２ Aryl and C ５ ~C １２ cycloalkyl; １ ~C １８ Alkyl, C ６ ~C １２ Aryl and C ５ ~C １２ Each cycloalkyl is uninterrupted or interrupted by one or more oxygen atoms and / or sulfur atoms and / or one or more substituted or unsubstituted amino groups, or R １ｅ and R ２ｅ is a 5-6 membered heterocyclyl containing oxygen and / or nitrogen and / or sulfur atoms, each of which is optionally substituted with aryl, alkyl, aryloxy, alkoxy, heteroatom and / or heterocyclic radicals; R ２ｅ HA(CO)R １ｅ may be R ３ｅ is hydrogen or C １ ~C ４ It is an alkyl group.

4. 4. The photoinitiator package of any one of claims 1 to 3, wherein at least one of the one or more bisacylphosphine oxide photoinitiators has the structure of formula (XI): 【Chemistry 13】 (In the formula, R １ｆ Each instance of is independently １ ~C ４ is selected from the group consisting of alkyl, X ｆ is a direct single bond, O, S, NR ４ｆ , -CH ２ CO ２ - and -CH ２ CH ２ CO ２ - selected from the group consisting of R ２ｆ 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 ３ｆ and optionally substituted with one or more groups selected from R ３ｆ teeth, 【Chemistry 14】 and R ４ｆ is hydrogen, (CO)R ５ｆ , 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 ５ｆ 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.

5. The photoinitiator package of any one of claims 1 to 4, wherein at least one of the one or more oxazole sensitizers has the structure of formula (Ia): 【Chemistry 15】 (In the formula, R １ｇ ~R ８ｇ Each of the groups is independently hydrogen, C １ ~C １０ Alkyl and C ６ ~C １４ aryl.

6. 6. The photoinitiator package of any one of claims 1 to 5, wherein the one or more oxazole sensitizers, each having the structure of formula (II), are selected from the group consisting of 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].

7. a) one or more of said mono- or bisacylphosphine oxide photoinitiators in an amount in the range of 40 to 98.9 wt.%, more preferably in the range of 60 to 96.0 wt.%, and most preferably in the range of 65 to 92.0 wt.%, based on the total weight of said photoinitiator package; b) one or more of said oxazole sensitizers, each having the structure of formula (I), in an amount in the range of 0.1 to 50 wt %, more preferably in the range of 1.0 to 37 wt %, and most preferably in the range of 3.0 to 30 wt %, based on the total weight of said photoinitiator package; c) one or more of said 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 said photoinitiator package; The photoinitiator package of any one of claims 1 to 6, comprising:

8. 8. The photoinitiator package of any one of claims 1 to 7, wherein the only photoinitiator present in the photoinitiator package is a Norrish Type I photoinitiator or a cationic photoinitiator.

9. a) one or more ethylenically unsaturated free radically polymerizable compounds; b) a photoinitiator package according to any one of claims 1 to 8; 1. A photopolymerizable composition comprising:

10. 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 8 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 9 comprising:

11. 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 9 or 10, further comprising one or more of:

12. 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 9 to 11 onto a substrate; b) photopolymerizing the composition coated or printed on the substrate with a light source; in a given order.

13. 9. Use of the photoinitiator package according to any one of claims 1 to 8 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.

14. Use of a combination of one or more amines and one or more oxazole-based sensitizers to enhance the surface cure rate of photopolymerizable compositions containing one or more Norrish Type I photoinitiators.

Images