Photoinitiator package containing phosphine oxide photoinitiator, coumarin-based sensitizer, and amine additive.

Abstract

A photoinitiator package comprising one or more mono- or bisacylphosphine oxide photoinitiators, one or more coumarin-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 coumarin-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 coumarin-based sensitizers, and one or more amines; a photopolymerizable composition comprising this photoinitiator package and a suitable polymerizable compound; a method for polymerizing this photopolymerizable composition; the use of the above photoinitiator package in photopolymerization applications; and the use of a combination of one or more amines and one or more coumarin-based sensitizers to increase the surface curing rate of a photopolymerizable composition comprising a Norish type I photoinitiator. [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 a further molecule to form a free radical from that further molecule that acts to initiate radical polymerization. Type II photoinitiators require the presence of specific additives / co-initiators, which are not typically required for type I photoinitiators.

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

[0004] Phosphine oxides are a well-known family of type I photoinitiators that provide excellent activity due to the highly reactive phosphinoyl radicals formed during fragmentation. While phosphine oxides are excellent photoinitiators in deep curing systems, they are notoriously less effective for achieving surface curing. Therefore, blends of phosphine oxide photoinitiators with other photoinitiators known to be effective for surface curing are often used to ensure complete curing. [Overview of the project] [Problems that the invention aims to solve]

[0005] The extent to which various type I photoinitiators interact with sensitizers is difficult to predict and often depends on the structure and energy level of the photoinitiator. Providing highly active photoinitiator packages is desirable because it would improve photopolymerization without the need to develop new photoinitiators.

[0006] Furthermore, while the concept of combining type I photoinitiators and sensitizers 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] This disclosure is based on the observation that the effect of certain sensitizers is enhanced by the presence of amines, resulting in a further improvement in the capabilities of photoinitiators.

[0008] Therefore, in the first aspect, the present invention a) One or more mono- or bisacylphosphine oxide photoinitiators, b) One or more coumarin-based sensitizers, each having the structure of formula (I), [ka] (In the formula, R 3 is hydrogen, C1~C 10 Alkyl, C6~C 14 Selected from the group consisting of aryls and heteroaryls, R 4 is selected from the group consisting of hydrogen, C1-C alkyl optionally substituted with one or more fluorine atoms, and OR 10 alkyl, and OR 1 and is selected from the group consisting of each of R 5 ~R 8 is independently selected from the group consisting of hydrogen, halogen, C1-C alkyl, OR 10 alkyl, and NR 1 2 2 and is selected from the group consisting of each example of R 1 is independently selected from hydrogen, C1-C alkyl, and C6-C 10 alkyl, and each example of R 14 is independently selected from hydrogen, C1-C alkyl, and C6-C 2 alkyl, and each example of R 10 is independently selected from hydrogen, C1-C alkyl, and C6-C 14 alkyl, and each example of R 1 ~R 8 each example of 1 ~R 8 may optionally combine with one or more further examples of R c) a photoinitiator package containing one or more amines is targeted.

[0009] In a second aspect, the present invention relates to a) one or more ethylenically unsaturated free-radical polymerizable compounds, and b) a photoinitiator package according to the first aspect and relates to a photopolymerizable composition containing

[0010] In a third aspect, the present invention is a method for photocuring a photopolymerizable composition, a coating, an adhesive, and an ink, comprising a) coating or printing a photopolymerizable composition according to the second aspect on a substrate, and b) photopolymerizing the coated or printed composition on the substrate with a light source and relates to a method including in a given order.

[0011] In a fourth aspect, the present invention relates to the use of the photoinitiator package according to the first aspect in the manufacture of printing inks, screen printing inks, gravure printing inks, solder masks, etching offset printing inks, flexographic printing inks, gravure printing inks, inkjet inks, resist materials, insulators, encapsulating materials, image recording materials, solder masks, passivation layers, protective coatings, 3D printed objects and molds, holographic applications, optical fiber coatings, waveguides and lenses, overprint varnishes, wood, vinyl, metal and plastic coatings.

[0012] In its final embodiment, the present invention relates to the use of a combination of one or more amines and one or more coumarin-based sensitizers to increase the surface curing rate of a photopolymerizable composition comprising one or more Norish type I photoinitiators. [Modes for carrying out the invention]

[0013] definition In this specification, the expression "alkyl" or "alkyl group" means a linear or branched saturated alkyl chain containing a given number of carbon atoms, unless otherwise specified, and includes all possible numbers of carbon atoms for each alkyl group, namely, n-propyl and i-propyl when there are three carbon atoms, n-butyl, i-butyl, s-butyl and t-butyl when there are four carbon atoms, and so on for other numbers of carbon atoms.

[0014] The terms "aryl" or "aryl group" include substituted or unsubstituted aryl groups (i.e., aromatic carbocyclic groups) such as substituted or unsubstituted phenyl groups, substituted or unsubstituted naphthyl groups, anthracenyl groups, indenyl groups, and fluorenyl groups.

[0015] The terms "heteroaryl" or "heteroaryl group" include, for example, substituted or unsubstituted heteroatom-containing aromatic ring systems such as pyridine, pyrrole, furan, triazine, indole, quinolone, and thiophene.

[0016] "C1-C interrupted by one or more oxygen units" 40 The term "alkyl" means that, when two or more oxygen atoms are present, these oxygen atoms are separated from each other by at least one methylene group, i.e., the oxygen atoms are discontinuous. Examples include -OCH2OCH3, -OCH2CH2OCH2CH3, and -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 one example.

[0017] When a group is substituted, the term "substituted" means that the group has one or more substituents, the substituents are preferably selected from halogen atoms, alkyl, cycloalkyl, alkoxy, alkylamino, dialkylamino, alkylthio or arylthio groups, heterocyclic groups, and more preferably methyl, ethyl, isopropyl, tert-butyl, phenyl, trifluoromethyl, cyano, acetyl, ethoxycarbonyl, carboxyl, carboxylate, amino, methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, diisopropylamino, cyclohexylamino Selected from mino, dicyclohexylamino, acetylamino, piperidino, pyrrolidyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, phenoxy, hydroxyl, acetoxy, -PO3H, methylthio, ethylthio, i-propylthio, n-propylthio, phenylthio, mercapto, acetylthio, thiocyano, methylsulfinyl, methylsulfonyl, dimethylsulfonyl, sulfonate group, fluorine atom, chlorine atom, bromine atom, iodine atom, trimethylsilyl, pentamethyldisilyl, triethylsilyl, trimethylstannyl, furyl, thienyl, pyridyl, and morpholino.

[0018] The term "direct bond" means that there is no linking group, and the direct bond connects the two parts on either side.

[0019] The methylene group is sp-linked to two hydrogen groups. 3 This refers to the hybridized carbon, i.e., -CH2R, while the methanetriyl group is sp, which is linked to one hydrogen group. 3 This refers to carbon in hybrid orbitals, i.e., -CHR2.

[0020] As is well understood by those skilled in the art, photoinitiators may be classified as either Nourish type I, in which an electronically excited photoinitiator decomposes to form free radicals that act to initiate radical polymerization, or Nourish 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.

[0021] Mono or bisacylphosphine oxide photoinitiators One of the essential features of the photoinitiator package according to the present invention is one or more mono- or bisacylphosphine oxide photoinitiators.

[0022] In its broadest sense, any mono- or bisacylphosphine oxide photoinitiator can be used.

[0023] Suitable monoacylphosphine oxide photoinitiators include, for example, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and ethyl(2,4,6-trimethylbenzoyl)phenylphosphine, phenyl(2,4,6-trimethylbenzoyl)phosphinic acid, glycerol ethoxylated trimester (Omnipol® TP, manufactured by IGM Resins BV), or those described in U.S. Patent Application Publication No. 2017 / 0240659, and photoinitiators such as Speedcure XKM (manufactured by Lambson).

[0024] However, it is preferable to use one or more bisacylphosphine oxide photoinitiators.

[0025] In the broadest sense, any mono or bisacylphosphine oxide photoinitiator can be used, but it is preferable that at least one, preferably all, of the one or more bisacylphosphine oxide photoinitiators have one of the structures of formulas (II) to (V). Formula (II): [ka] (In the formula, R 1a , R 2a , R 3a , R 1b , R 2b and R 3b Each example is independently selected from the group consisting of C1-C4 alkyl, C1-C4 alkoxy, and halogens. X is a direct single bond, O, S, NR 5a Selected from the group consisting of -CH2CO2- and -CH2CH2CO2-, R 4a (CO)R 6a , (CO)OR 6a (CO)NR 5a R 6a (SO2)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 ) selected from the group consisting of, R 4a C1~C 28 Alkyl, or one or more O, NR 5a C2-C interrupted by S, (CO), (CO)O, or SO2 28 It is alkyl, and the above C1~C 28 Alkyl or interrupted C2-C 28The alkyl is unsubstituted or substituted with one or more substituents, and one or more of the above substituents are OH, C6-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 C3-C 12 cycloalkyl substituted with OH, one or more O, NR 5a or S interrupted C3-C 12 cycloalkyl (the interrupted C3-C 12 cycloalkyl is unsubstituted or substituted with C1-C4 alkyl, C1-C4 alkoxy or OH), unsubstituted or C1-C4 alkyl, C1-C4 alkoxy or C6-C 14 aryl selected from the group consisting of, or R 4a is unsubstituted or one or more C1-C 12 alkyl, C2-C 20 alkyl interrupted by one or more O, C1-C 12 alkoxy or C6-C 10 aryl substituted with OH, or When X is NR 5a , R 4a forms a 5- or 6-membered saturated ring together with R 5a and the N atom, and this ring is uninterrupted or interrupted by 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 4ais selected from the group consisting of structures (A) to (G), [Chemical formula] R 4a All options of may be further substituted with one or more groups selected from OH and R 17a and R 17a is [Chemical formula] and A is PF6, SbF6, AsF6 or B(C6F5)4, R 5a is hydrogen, (CO)R 6a , phenyl, C1-C 12 alkyl, C2-C 12 alkyl interrupted by one or more O, C3-C 12 cycloalkyl, wherein the above C1-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 6a is C1-C 12 alkyl or C2-C 12 alkyl interrupted by one or more O, wherein 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, wherein the above C2-C 10 alkenyl is unsubstituted or substituted with one or more C1-C4 alkyl, OH or C1-C4 alkoxy, or R 6a is either non-substitutable or C1~C 12 Alkyl, C1-C 12 Alkyl, NCO, or NCO-substituted C1-C 12 C6-C substituted with alkyl 14 Is it an aryl, or Group N(R 5a If )2 exists, R 5a One example is (CO)R 6a It may be R 5a Other examples and R 6a It forms a 5 or 6-membered ring with the N and CO moieties, and this ring is uninterrupted or O or NR 5a The ring is interrupted, and the uninterrupted or interrupted ring is either unsubstituted or substituted with one or more C1-C4 alkyl, C1-C4 alkoxy or OH groups. R 7a , R 8a and R 9a These are, independently, C1-C4 alkyl and C6-C 14 Selected from the group consisting of aryls and C1-C4 alkoxys, m is an integer in the range of 0 to 10. Y 1a This is a direct single bond, O, S, NR 5a Selected from the group consisting of O(CO)-* and O(CO)CH2O-*, the asterisk indicates the bond of group (A), (B), (D), or (E) to the phenyl ring. Y 2a These are direct single bonds, O, S and NR 5a Selected from the group consisting of, R 11a and R 12a These are independent of each other, C1~C 10 Alkyl, C2~C 10 Alkenyl or phenyl, unsubstituted or C1-C4 alkyl, or R 11a and R 12a These, together with the C atom to which they are bonded, form a cyclohexane or cyclopentane ring. Za is OH or NR 13a R 14a And, Z 1a C1~C 12 Alkoxy, or C2-C suspended by one or more oxygen atoms 12 It is an alkoxy, and the above C1~C 12 Alkoxy or interrupted C2-C 12 alkoxy groups are either unsubstituted or substituted with an OH group. R 13a and R 14a These are independent of each other, C1~C 12 C1-C substituted with alkyl, one or more OH groups, or halogens. 12 Alkyl or R 13a and R 14a These atoms, together with the N atoms to which they are bonded, form a 5- or 6-membered unsaturated or saturated ring, which is uninterrupted or O or NR. 15a It is interrupted at R 15a These are C1-C4 alkyl groups, R 16a is hydrogen or a C1-C4 alkyl group, however, (i) R as a C1-C4 alkyl 1a , R 2a and R 3a If is methyl and X is O, then C1~C 28 R as an alkyl group 4 It is not methyl, ethyl, n-propyl, 2-propyl, n-butyl, sec-butyl, tert-butyl, or n-hexyl, (ii) R as a halogen 1a and R 3a Cl is and R 2a If is hydrogen and X is O, substitution C3~C 10 R as an aryl 4a It is not 4-butylphenyl, (iii) R as C1-C4 alkoxy 1a and R 3a is methoxy, and R 2a is hydrogen, and X is NR 5aAnd R 4a R 5a (And when it forms a 5- or 6-membered saturated ring with an N atom, the above ring is not a piperidine ring.) Formula (III): [ka] (In the formula, Ar 1 and Ar 2 Each of them operates independently. [ka] or naphthyl, wherein the naphthyl is unsubstituted or R 1c , R 2c , R 3c , R 4c Or R 5c It has been replaced at least once, R 1c and R 5c Each of these is independently selected from the group consisting of C1-C4 alkyl, C1-C4 alkoxy, and halogen. R 3c These include hydrogen, C1-C4 alkyl, halogen, C1-C4 alkoxy, and C2-C suspended by one or more oxygen atoms. 20 Selected from the group consisting of alkoxys, Q is a C1-C4 alkylene, R 2c and R 4c These are, independently of each other, hydrogen or PG. c -Y c -Z c -X c -and, PG c The polymerizable group is methyl or ethyl. Y c It is a direct single bond, O or S, X c It is a direct single bond, O or S, Z c This is a direct single bond, C1~C 20 Alkylene, or C2-C2 interrupted by one or more oxygen atoms. 20 It is alkylene, R 6cis either unsubstituted or OH and [ka] C3~C substituted with one or more groups selected from 30 Alkyl or R 6c C3-C8 cycloalkylene is interrupted by one or more O or C3-C8 cycloalkylenes. 28 It is alkyl and interrupted C3-C 28 Alkyl is either unsubstituted or has OH and [ka] (It is replaced by one or more elements selected from the following.) Formula (IV): [ka] (In the formula, R 1d These are C1-C4 alkyl, C1-C4 alkoxy, or halogen. R 2d These are hydrogen, C1-C4 alkyl, C1-C4 alkoxy, or halogen. R 3d C1~C 20 Alkyl, cyclopentyl, cyclohexyl, phenyl-C1-C4 alkyl, naphthyl, biphenylyl, or O-containing, S-containing, or N-containing 5 or 6-membered heterocyclic radicals, wherein the naphthyl, biphenylyl, and O-containing, S-containing, or N-containing 5 or 6-membered heterocyclic radicals are either 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 These are, independently, hydrogen, halogen, and C1-C.20 Alkyl, cyclopentyl, cyclohexyl, C2-C 12 Alkenyls are C2-C atoms interrupted by one or more discontinuous oxygen atoms. 20 Alkyl, phenyl-C1~C4 alkyl, C1~C 20 Selected from the group consisting of alkoxy or phenyl, the phenyl is either unsubstituted or substituted with one or two C1-C4 alkyl and / or C1-C4 alkoxy substituents. Formula (V): [ka] (In the formula, each A is independent of O, S, NR) 3e This represents, G is a polyfunctional compound (core) G-(AH) p+q These are residues, where each AH represents an alcohol group, an amino group, or a thiol group. p and q are both integers, p+q is an integer between 3 and 10, and p is an integer between 3 and 8. R 1e and R 2e These are, independently, C1~C 18 Alkyl, C6~C 12 Aryl and C5~C 12 Selected from the group consisting of cycloalkyl groups, C1~C 18 Alkyl, C6~C 12 Aryl and C5~C 12 Each cycloalkyl group is either 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 heterocycline containing an oxygen atom and / or a nitrogen atom and / or a sulfur atom, and each of the above groups may be substituted with an aryl, alkyl, aryloxy, alkoxy, heteroatom and / or heterocyclic radical, R 2e (CO)R 1e Even if that is the case, R 3e(This is hydrogen or a C1-C4 alkyl group.)

[0026] In one embodiment, at least one of the one or more bisacylphosphine oxide photoinitiators each has the structure of formula (VI). [ka] (In the formula, R 1f Each example was independently selected from the group consisting of C1-C4 alkyl groups. X f This is a direct single bond, O, S, NR 4f Selected from the group consisting of -CH2CO2- and -CH2CH2CO2-, R 2f C1~C 40 Alkyl and interrupted C2-C3-C8 cycloalkylenes. 40 Selected from the group consisting of alkyl groups, C1~C 40 Alkyl or interrupted C2-C 40 Alkyl groups are either unsubstituted or consist of OH and R groups. 3f It may be replaced by one or more elements selected from, R 3f teeth, [ka] And, R 4f (CO)R 5f phenyl, C1~C 12 Alkyl and C2-C suspended by one or more oxygen atoms 12 Alkyl, C3~C 12 Selected from the group consisting of cycloalkyls, C1~C 12 Alkyl or interrupted C2-C 12 The alkyl group is either unsubstituted or substituted with one or more C3-C7 cycloalkyl groups, OH groups, or NCO groups. 12 Cycloalkyls are either unsubstituted or substituted with one or more C1-C4 alkyl, C1-C4 alkoxy, OH, or NCO groups. R5f C1~C 12 Alkyl and C2-C suspended by one or more oxygen atoms 12 Selected from the group consisting of alkyl groups, C1~C 12 Alkyl or interrupted C2-C 12 The alkyl group is either unsubstituted or substituted with one or more C3-C7 cycloalkyl groups, OH groups, NCO groups, or phenyl groups, where the phenyl group is NCO group, C3-C7 cycloalkyl group. 12 Cycloalkyl, C2~C 10 Alkenil, C6~C 14 It is replaced with aryl, as shown above in C2~C 10 The alkenyl is either unsubstituted or substituted with one or more C1-C4 alkyl, OH, or C1-C4 alkoxy groups, and the above C6-C 14 The aryl group is either unsubstituted or C1-C 12 Alkyl, C1-C 12 Alkyl, NCO, or NCO-substituted C1-C 12 (It is substituted with alkyl.)

[0027] R 1f Each example may be independently selected from the group consisting of C1-C4 alkyl groups, i.e., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, and t-butyl. 1f Each example is particularly preferably selected from methyl and ethyl. Most preferably, R 1f Each example is methyl.

[0028] X f This is a direct single bond, O, S, NR 3f Selected from the group consisting of -CH2CO2- and -CH2CH2CO2-. More preferably, X f The group is selected from the group consisting of a direct single bond, O, -CH2CO2- and -CH2CH2CO2-. More preferably, X f The is selected from the group consisting of a direct single bond, -CH2CO2-, and -CH2CH2CO2-. Most preferably, X f This is a direct single bond.

[0029] R 1f C1~C 40 Alkyl and interrupted C2-C3-C8 cycloalkylenes. 40 Selected from the group consisting of alkyl groups, C1~C 40 Alkyl or interrupted C2-C 40 Alkyl groups are either unsubstituted or consist of OH and R groups. 3f It may be replaced by one or more elements selected from, R 3f teeth, [ka] That is the case.

[0030] In some embodiments, R 3f It does not exist, which means that the structure of formula (VI) has a single bisacylphosphine oxide moiety.

[0031] In such embodiments, R 2f C1~C 20 Alkyl, -(CH2CH2O-) n CH3 and -(CH2CH2O-) n It is preferable to select from the group H (where n is an integer in the range of 1 to 20). 2f C1~C 20 Being alkyl is particularly preferred.

[0032] X is particularly preferable. f It is a direct single bond, R 2f C1~C 20 This is an embodiment in which R is alkyl. In such an embodiment, R 1f It is particularly preferable that each example is methyl.

[0033] Similarly, X f O is R 2f ga-(CH2CH2O-) n CH3 or -(CH2CH2O-) n Embodiments in which H is present are also particularly preferred.1f It is particularly preferable that each example is methyl.

[0034] In other embodiments, R 3f There is at least one example of this, which means that the structure of formula (VI) has two or more bisacylphosphine oxide moieties.

[0035] Such embodiments are preferably R 1f This is described by equation (VI), which has the structure of equation (VII). [ka] (In the formula, each example of M is independently selected from (CH2CH2O) and (CH2CH(CH3)O), Each example of Y is independently selected from hydrogen and C1-C4alkyl groups. Each example of Z is structure CH2(M 1 ) c R 2f It has, M 1 Each example is independently selected from (OCH2CH2) and (OCH(CH3)CH2), a is an integer in the range of 0 to 15. b is an integer in the range of 0 to 6. Each example of c is an integer in the range of 0 to 15, independently. m is an integer in the range of 0 to 2. X f Each example is independently selected from the group consisting of -CH2CO2- and -CH2CH2CO2-.

[0036] Such structures are typically formed by combining a central polyol core with multiple BAPO-based carboxylic acid residues and an ethylene glycol / propylene glycol spacer (i.e., units M and M). 1 ) is optionally used to separate the central polyol core from the BAPO-based carboxylic acid residues.

[0037] Suitable polyol cores include glycerol with b=0, m=1 and Y=H; trimethylolpropane with b=1, m=1 and Y=ethyl; pentaerythritol with b=1 and m=0; neopentyl glycol with b=1, m=2 and two examples of Y=methyl; ethylene glycol with b=0, m=2 and two examples of Y=H; and 1,6-hexanediol with b=4, m=2 and two examples of Y=H.

[0038] Other suitable polyols include propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-hexanediol, 1,5-hexanediol, and 2,5-hexanediol. Those skilled in the art will know which values ​​of b and m and the choice of Y correspond to these polyols.

[0039] Particularly preferred polyol cores are glycerol with b=0, m=1 and Y=H, trimethylolpropane with b=1, m=1 and Y=ethyl, and pentaerythritol with b=1 and m=0.

[0040] When using a glycerol core, R 2f This is called "optionally ethoxylated / propoxylated glycerol."

[0041] When using trimethylolpropane core, R 2f This is called "optionally ethoxylated / propoxylated trimethylolpropane."

[0042] When using pentaerythritol core, R 2f This is called "optionally ethoxylated / propoxylated pentaerythritol."

[0043] When using a neopentyl glycol core, R 2f This is called "arbitrarily ethoxylated / propoxylated neopentyl glycol."

[0044] When using an ethylene glycol core, R 2f This is called "optionally ethoxylated / propoxylated ethylene glycol."

[0045] When using a 1,6-hexanediol core, R 2f This is called "arbitrarily ethoxylated / propoxylated 1,6-hexanediol".

[0046] 'a' is an integer in the range of 1 to 15, and each example of 'c' is preferably an integer in the range of 1 to 15, with the sum of 'a' and each example of 'c' being in the range of 3 to 20, more preferably 3 to 15, and most preferably 3 to 10.

[0047] 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.

[0048] R 2f C1~C 20 Alkyl, -(CH2CH2O-) n CH3, -(CH2CH2O-) n It is particularly preferable to select from the group consisting of H (where n is an integer in the range of 1 to 20), ethoxylated / propoxylated glycerol, ethoxylated / propoxylated trimethylolpropane, and ethoxylated / propoxylated pentaerythritol.

[0049] R 2f C1~C 20 If it is alkyl, R 2f C1~C 15 Alkyl, more preferably C1-C 12 Being alkyl is particularly preferred.

[0050] It is particularly preferable that one or more bisacylphosphine oxide photoinitiators each have the structure of formula (VI).

[0051] In an alternative embodiment, at least one of one or more bisacylphosphine oxide photoinitiators is R 1f Each example is independently selected from the group consisting of C1-C4 alkyl groups, X f It is a direct single bond, R 2f C6~C 14 Aryl, C1~C 20 Alkyl, -(CH2CH2O-) n CH3 and -(CH2CH2O-) n The expression has the structure of (VI), which is selected from the group H (where n is an integer in the range of 1 to 20).

[0052] R 2f is more C6~C 14 Selected from aryls, most preferably phenyl.

[0053] In one particularly preferred embodiment, R 1f Each example is methyl, X f It is a direct single bond, R 2f It is phenyl.

[0054] Coumarin-based sensitizers Another essential feature of the photoinitiator package according to the present invention is the presence of one or more coumarin-based sensitizers, each having the structure of formula (I). [ka] (In the formula, R 3 is hydrogen, C1~C 10 Alkyl, C6~C 14 Selected from the group consisting of aryls and heteroaryls, R 4 is hydrogen, C1~C 10 Alkyl and OR 1 Selected from the group consisting of, R 5 ~R 8Each of these independently consists of hydrogen, halogen, alkyl, OR 1 , and NR 2 Selected from a group consisting of 2, R 1 Each example is hydrogen, C1~C 10 Alkyl, and C6-C 14 Selected from the aryl, R 2 Each example is hydrogen, C1~C 10 Alkyl, and C6-C 14 Selected from the aryl, R 1 ~R 8 Each example can be arbitrarily written in R 1 ~R 8 (It may be combined with one or more further examples to form one or more five-membered or six-membered rings.)

[0055] In one preferred embodiment, R 3 is hydrogen and C1~C 10 Selected from the group consisting of alkyl groups, or R 4 is hydrogen and C1~C 10 Selected from the group consisting of alkyl groups.

[0056] In another preferred embodiment, R 3 is hydrogen and C1~C 10 Selected from the group consisting of alkyl, R 4 is hydrogen and C1~C 10 Selected from the group consisting of alkyl groups.

[0057] In another preferred embodiment, R 7 is OR 1 and NR 2 Selected from the group consisting of 2, most preferably NR 2 The answer is 2.

[0058] In a particularly preferred embodiment, R 3 is hydrogen and C1~C 10 Selected from the group consisting of alkyl groups, or R 4 is hydrogen and C1~C 10 Selected from the group consisting of alkyl groups, on the other hand, R 7 is OR 1 and NR2 Selected from the group consisting of 2, most preferably NR 2 The answer is 2.

[0059] In a particularly preferred embodiment, R 3 is hydrogen and C1~C 10 Selected from the group consisting of alkyl, R 4 is hydrogen and C1~C 10 Selected from the group consisting of alkyl, R 7 is OR 1 and NR 2 Selected from the group consisting of 2, most preferably NR 2 The answer is 2.

[0060] At least one, preferably all, of the coumarin sensitizers are 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-benzoxazollyl)-7-(diethylamino)coumarin, 7-methylcoumarin, 7-methoxycoumarin, 4-hydroxycoumarin, 5,7-dimethoxycoumarin, 3-(3-biphenyl-4-yl-1, Selected from the group consisting of 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]quinoridine-11-one, 7-(diethylamino)-4-(trifluoromethyl)coumarin, and 7-(ethylamino)-4-(trifluoromethyl)coumarin.

[0061] More preferably, at least one, 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-benzoxazollyl)-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]quinoridine-11-one, 7-(diethylamino)-4-(trifluoromethyl)coumarin, and 7-(ethylamino)-4-(trifluoromethyl)coumarin.

[0062] Most preferably, at least one, 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.

[0063] Amine Another essential feature of the photoinitiator package according to the present invention is the presence of one or more amines.

[0064] The finding of this invention is that the presence of an amine in a Norish type I photoinitiator package, when combined with a coumarin-based sensitizer, can dramatically improve the curing rate, particularly surface curing.

[0065] In its broadest sense, one or more amines according to the present invention may be any amine, including aliphatic, alicyclic, 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, dimethylaminobenzoic acid esters, and corresponding derivatives. Furthermore, amine-modified acrylates can be used. Examples of such amine-modified acrylates include acrylates modified by reaction with primary or secondary amines, as described in U.S. Patent No. 3,844,916, European Patent Publication No. 280222, U.S. Patent No. 5,482,649, or U.S. Patent No. 5,734,002.

[0066] Suitable polyfunctional amines and polymer amine derivatives include Omnipol ASA from IGM Resins BV, Genopol AB-2 from Rahn AG, Speedcure 7040 from Lambson Limited, or those described in U.S. Patent Application Publication No. 2013 / 0012611.

[0067] 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 bonded to an alkyl group. Similarly, ammonium salts are not amines.

[0068] It is preferable that one or more amines are not type I or type II photoinitiators, such as well-known aminoketone type I initiators. It is even more preferable that 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. Clearly, the sole role of the amines in the photopolymerization package is to act as synergists, improving the effects of one or more mono or bisacylphosphine oxide photoinitiators and / or one or more coumarin sensitizers.

[0069] Preferably, one or more amines have so-called α-hydrogens, i.e., hydrogens bonded to carbons directly bonded to the nitrogen of the amine. These hydrogens are sp 3 It is particularly preferable that the nitrogen atom is bonded to a hybridized carbon orbital. Therefore, it is preferable that the amine has a nitrogen atom that has a direct single bond to any of the following: a methyl group (i.e., CH3), a methylene group (i.e., CH2 of CH2R), or a methanetriyl group (i.e., CH of CHR2).

[0070] While not intended to be constrained by theory, it is thought that α-hydrogens can be readily abstracted by radicals, potentially forming stabilized α-amino radicals, which may play a role in improving the curing rate, particularly by removing molecular oxygen that could potentially slow down the polymerization reaction.

[0071] It is particularly preferable that the nitrogen atom is bonded to at least one alkyl group. It is even more preferable that the nitrogen atom is bonded to at least two alkyl groups.

[0072] In one particularly preferred embodiment, one or more amines are independently of formula NR A R B R C Selected from the group consisting of amines having R A and R B R is independently selected from optionally substituted alkyl groups.C This is selected from the group consisting of optionally substituted alkyl groups and optionally substituted aryl groups.

[0073] In the embodiments described above, 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 as acyl groups (i.e., =O substitution on the first carbon atom of the alkyl chain) that would cause the group to no longer be considered an alkyl group.

[0074] Photoinitiator Package The photoinitiator package according to the present invention comprises one or more mono- or bisacylphosphine oxide photoinitiators, one or more coumarin-based sensitizers, and one or more amines.

[0075] The photoinitiator package is preferably, a) One or more mono- or bisacylphosphine oxide photoinitiators in an amount ranging from 40 to 98.9% by weight, more preferably 60 to 96.0% by weight, and most preferably 65 to 92.0% by weight, relative to the total weight of the photoinitiator package, b) One or more coumarin-based sensitizers in an amount ranging from 0.1 to 50% by weight, more preferably 1.0 to 37% by weight, and most preferably 3.0 to 30% by weight, relative to 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 3.0 to 35% by weight, and most preferably 5.0 to 30% by weight, relative to the total weight of the photoinitiator package. This includes, and more preferably consists of, these.

[0076] In further embodiments, the photoinitiator package is a) One or more mono- or bisacylphosphine oxide photoinitiators in an amount ranging from 40% to 98.9% by weight relative to the total weight of the photoinitiator package, b) One or more coumarin-based sensitizers in an amount ranging from 0.1% to 50% by weight relative to the total weight of the photoinitiator package, c) One or more amines in an amount ranging from 1.0 to 45% by weight relative to the total weight of the photoinitiator package This includes, and more preferably consists of, these.

[0077] In another embodiment, the photoinitiator package is a) One or more mono- or bisacylphosphine oxide photoinitiators in an amount ranging from 60% to 95% by weight relative to the total weight of the photoinitiator package, b) One or more coumarin-based sensitizers in an amount ranging from 1.0% to 37% by weight relative to the total weight of the photoinitiator package, c) One or more amines in an amount ranging from 3.0% to 35% by weight relative to the total weight of the photoinitiator package This includes, and more preferably consists of, these.

[0078] In further embodiments, the photoinitiator package is a) One or more mono- or bisacylphosphine oxide photoinitiators in an amount ranging from 65% to 92.0% by weight relative to the total weight of the photoinitiator package, b) One or more coumarin-based sensitizers in an amount ranging from 3.0% to 30% by weight relative to the total weight of the photoinitiator package, c) One or more amines in an amount ranging from 5.0% to 30% by weight relative to the total weight of the photoinitiator package This includes, and more preferably consists of, these.

[0079] If there are one or more mono- or bisacylphosphine oxide photoinitiators, one or more coumarin-based sensitizers, and one or more amines, these are preferably further type I photoinitiators.

[0080] It is particularly preferable that the only photoinitiator present in the photoinitiator package is a Norish type I photoinitiator or a cationic photoinitiator.

[0081] It is even more preferable that the only photoinitiator present in the photoinitiator package is a Norrish type I photoinitiator.

[0082] Additional or alternative fluorescent whitening agents or sensitizers may be present.

[0083] As those skilled in the art will understand, the term “further fluorescent whitening agent sensitizers” means that these further sensitizers have structures other than one or more coumarin-based sensitizers.

[0084] As will be understood by those skilled in the art, the term "sensitizer" in "one or more fluorescent whitening sensitizers" describes the purpose of the fluorescent whitening agent in the photoinitiator package and does not limit the selection of fluorescent whitening agents that may be used.

[0085] Furthermore, those skilled in the art will be well aware that fluorescent whitening agents 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.

[0086] Therefore, the photoinitiator package preferably comprises, and more preferably comprises, one or more bisacylphosphine oxide photoinitiators, one or more coumarin-based sensitizers, one or more amines, optionally one or more further type I photoinitiators, and optionally one or more further fluorescent whitening sensitizers.

[0087] Therefore, the photoinitiator package is preferably, a) One or more mono- or bisacylphosphine oxide photoinitiators in an amount ranging from 40 to 98.9% by weight, more preferably 60 to 96.0% by weight, and most preferably 65 to 92.0% by weight, relative to the total weight of the photoinitiator package, b) One or more coumarin-based sensitizers in an amount ranging from 0.1 to 50% by weight, more preferably 1.0 to 37% by weight, and most preferably 3.0 to 30% by weight, relative to 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 3.0 to 35% by weight, and most preferably 5.0 to 30% by weight, relative to the total weight of the photoinitiator package. d) A further amount of type I initiator in the range of 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) an amount of further fluorescent whitening agent sensitizer in the range of 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.

[0088] Photopolymerizable composition In a second embodiment, the present invention also covers photopolymerizable compositions.

[0089] In the broadest sense, photopolymerizable compositions are a) One or more ethylenically unsaturated free radical polymerizable compounds, b) Photoinitiator package according to the first embodiment and It includes or consists of these.

[0090] The photopolymerizable composition is preferably, a) One or more ethylenically unsaturated free radical polymerizable compounds in an amount ranging from 30 to 99.0% by weight, more preferably 50 to 95.0% by weight, and most preferably 70 to 90% by weight, relative to the total weight of the photopolymerizable composition, b) A photoinitiator package according to the first embodiment in an amount ranging from 0.5 to 50% by weight, more preferably from 0.8 to 40% by weight, and most preferably from 1.0 to 30% by weight, relative to the total weight of the photopolymerizable composition. It includes or consists of these.

[0091] In addition to one or more ethylenically unsaturated free radical polymerizable compounds and the photoinitiator package according to the first embodiment, the photopolymerizable composition may also contain further components, as will be well understood by those skilled in the art.

[0092] Suitable additional components include photosensitizers, further photoinitiators, pigments, binders, and conventional additives.

[0093] Therefore, photopolymerizable compositions, a) One or more ethylenically unsaturated free radical polymerizable compounds in an amount ranging from 30 to 99.0% by weight, more preferably 50 to 95.0% by weight, and most preferably 70 to 90% by weight, relative to the total weight of the photopolymerizable composition, b) A photoinitiator package according to the first embodiment in an amount ranging from 0.5 to 50% by weight, more preferably from 0.8 to 40% by weight, and most preferably from 1.0 to 30% by weight, relative to the total weight of the photopolymerizable composition, c) Optionally, one or more additional photoinitiators, one or more photosensitizers and / or one or more coinitiators in an amount ranging from 0.5 to 30% by weight, more preferably from 0.8 to 20% by weight, and most preferably from 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 1.0 to 25% by weight, and most preferably 10 to 20% by weight, relative to the total weight of the photopolymerizable composition. e) Optionally, one or more binders in an amount ranging from 5.0 to 60% by weight, more preferably 8.0 to 50% by weight, and most preferably 10 to 40% by weight, relative to the total weight of the photopolymerizable composition. f) Optionally, one or more additives in an amount ranging from 0.01 to 10% by weight, more preferably 0.01 to 8.0% by weight, and most preferably 0.01 to 5.0% by weight, relative to the total weight of the photopolymerizable composition. This includes, and more preferably consists of, these.

[0094] Furthermore, the photopolymerizable composition may be incorporated into a composition further containing a solvent such as water and / or an organic solvent.

[0095] It is preferable that there are no further photoinitiators, photosensitizers, or co-initiators other than those that form part of the photoinitiator package. In other words, it is preferable that all components that contribute to the photopolymerization properties of the photoinitiator are included in the photoinitiator package as defined above and below.

[0096] 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 (monomers) or high molecular weight (oligomers) compounds.

[0097] Examples of suitable low molecular weight polymerizable compounds (monomer compounds) having one double bond include alkyl acrylates or hydroxyalkyl acrylates or alkyl methacrylates 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 include silicon or fluorine-modified resins, such as silicone acrylates. Further examples of these polymerizable compounds include acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamide, styrene, alkylstyrene and halogenostyrene, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, N-vinylpyrrolidone, vinyl chloride, or vinylidene chloride.

[0098] Examples of polymerizable compounds having two or more double bonds include 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.

[0099] Examples of high molecular weight (oligomeric) polyunsaturated compounds include acrylated epoxy resins, acrylated or vinyl ether-containing or epoxy group-containing polyesters, acrylated polyurethanes or acrylated polyethers.

[0100] 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.

[0101] Examples of polymerizable compounds particularly suitable for the implementation of 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 having (meth)acrylic groups in the side chain), and mixtures thereof.

[0102] Examples of unsaturated carboxylic acids or anhydrides useful for the preparation of the above esters are acrylic acid, methacrylic acid, maleic anhydride, crotonic acid, itaconic acid, cinnamic acid and unsaturated fatty acids (e.g., linolenic acid and oleic acid). Acrylic acid and methacrylic acid are preferred.

[0103] Examples of polyols that can also be esterified include aromatic, aliphatic, and alicyclic polyols, preferably aliphatic and alicyclic polyols. Aromatic polyols include, for example, hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di(4-hydroxyphenyl)propane, and novolac and resol.

[0104] Polyepoxides that can be esterified include those based on reaction products between the above-mentioned polyols, particularly aromatic polyols, and epichlorohydrins. Suitable polyols include polymers and copolymers containing hydroxyl groups in the polymer chain or side groups (e.g., polyvinyl alcohol and its copolymers, or polyhydroxyalkyl methacrylates or their copolymers). Even more suitable polyols are oligoesters having hydroxyl terminal groups.

[0105] Examples of aliphatic and alicyclic polyols include alkylenediols 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 glycol having a molecular weight of 200 Da to 1,500 Da, preferably 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.

[0106] Further suitable ethylenically unsaturated compounds are unsaturated polyamides obtained from unsaturated carboxylic acids and aromatic, aliphatic, and alicyclic polyamines having preferably 2 to 6, more 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, octilenediamine, 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 their side chains, and oligoamides containing amino-terminated groups.

[0107] Specific examples of such unsaturated polyamides include methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide, bis(methacrylamidepropoxy)ethane, and N-[(β-hydroxyethoxy)ethyl]acrylamide.

[0108] Unsaturated polyurethanes, such as those derived from saturated or unsaturated diisocyanates and unsaturated or saturated diols, are also suitable as polymerizable compounds for carrying out the present invention.

[0109] Polybutadiene and polyisoprene, as well as copolymers thereof, may be used.

[0110] Suitable polymerizable compounds include, for example, olefins (e.g., ethylene, propene, butene, and hexene), (meth)acrylates, acrylonitrile, styrene, and vinyl chloride. Polymers having unsaturated (meth)acrylate groups in their side chains may also be used as one or more ethylenically unsaturated free radical polymerizable compounds. These are typically reaction products of novolac epoxy resins and (meth)acrylic acid, homo- or copolymers of vinyl alcohols esterified with (meth)acrylic acid or their hydroxyalkyl derivatives, and homo- and copolymers of (meth)acrylates esterified with hydroxyalkyl (meth)acrylates.

[0111] Examples of photosensitizers commonly used in the art include terphenyl, styryl ketone, and 3-(aloylmethylene)-thiazoline, as well as eosin, rhodamine, and erythrosine dyes.

[0112] The above-mentioned photosensitizers were observed to enhance 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, with appropriate selection of the photosensitizer, the spectral sensitivity of the photoinitiator package can be shifted to any desired wavelength range. Those skilled in the art can select an appropriate photosensitizer to make the photoinitiator package function in any desired wavelength range.

[0113] Other suitable photoinitiators include acetophenone, acetophenone derivatives, dialkoxyacetophenone, α-hydroxyketone, α-aminoketone, benzoin alkyl ethers and benzyl ketals (e.g., benzyldimethyl ketal), acylphosphine photoinitiators (selectable from monoacylphosphine oxide, bisacylphosphine oxide, trisacylphosphine oxide, and polyfunctional monoacylphosphine oxide or bisacylphosphine oxide), halomethyltriazine, hexaarylbisimidazole / coinitiator systems (e.g., combination of orthochlorohexaphenylbisimidazole and 2-mercaptobenzothiazole), ferrocenium compounds or titanocene (e.g., dicyclopentadienyl-bis(2,6-difluoro-3-pyrrolophenyl)titanium), and O-acyloxime ester photoinitiators.

[0114] Examples of α-hydroxyketones and α-aminoketones include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-ethyl-propan-1-one), and 2-hydroxy-1-{ These are 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).

[0115] 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)phenylphosphine, and phenyl(2,4,6-trimethylbenzoyl)phosphinate ethoxylated glycerol triester (Omnipol® TP manufactured by IGM Resins BV).

[0116] Examples of halomethyltriazine photoinitiators include 2-[2-(4-methoxyphenyl)-vinyl]-4,6-bis-trichloromethyl[1,3,5]triazine, 2-(4-methoxyphenyl)-4,6-bis-trichloromethyl[1,3,5]triazine, 2-(3,4-dimethoxyphenyl)-4,6-bis-trichloromethyl[1,3,5]triazine, and 2-methyl-4,6-bis-trichloromethyl[1,3,5]triazine.

[0117] Cationic photoinitiators may also be used as further photoinitiators when the photopolymerizable composition according to the present invention is used in a hybrid system (in this context, a hybrid system means a mixture of a free radical curing system and a cationic curing system). Examples of suitable cationic photoinitiators include aromatic sulfonium salts, aromatic phosphonium salts or aromatic iodonium salts, for example, those described in U.S. Patent No. 4,950,581, or cyclopentadienylarene-iron(II) complex salts, for example, (η 6 -Isopropylbenzene)(η 5These are cyclopentadienyl)iron(II) hexafluorophosphate or oxime-based photolatent acids (for example, as described in British Patent Application Publication No. 2348644, U.S. Patent No. 4,450,598, U.S. Patent No. 4,136,055, and International Publication Brochures No. 00 / 10972 and 00 / 26219).

[0118] Any pigment known to those skilled in the art can be used in the photopolymerizable composition.

[0119] Depending on the intended use, both inorganic and organic pigments can be used. Such additives are well known to those skilled in the art, and some examples include carbon black, iron oxides (e.g., yellow iron oxide, red iron oxide), chromium yellow, chromium green, nickel titanium yellow, ultramarine, cobalt blue, bismuth vanadate, cadmium yellow, and cadmium red. Examples of organic pigments include 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. Pigments may be used individually or in combination in formulations.

[0120] 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 according to the application and required properties, such as developability in aqueous and organic solvent systems, adhesion to the substrate, and sensitivity to oxygen. Suitable binders are 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. Exemplary examples include homopolymers and copolymers of acrylates and methacrylates, e.g., copolymers of methyl methacrylate / ethyl acrylate / methacrylic acid, poly(alkyl methacrylate), poly(alkyl acrylate); cellulose esters and ethers, e.g., cellulose acetate, cellulose butyrate acetate, methylcellulose, ethylcellulose; polyvinyl butyral, polyvinyl formal, cyclocompound rubber, polyethers, e.g., polyethylene oxide, polypropylene oxide, polytetrahydrofuran, polystyrene, polycarbonate, polyurethane; polyolefins with chloride, e.g., polyvinyl chloride, vinyl chloride / vinylidene chloride copolymer, copolymer of vinylidene chloride and acrylonitrile, copolymer of methyl methacrylate and vinyl acetate, polyvinyl acetate, co-poly(ethylene / vinyl acetate), polymers, e.g., polycaprolactam and poly(hexamethylene adipamide); polyesters, e.g., poly(ethylene glycol terephthalate) and poly(hexamethylene glycol succinate).

[0121] The selection of additives is determined by the application and the desired properties for that application. Typical additives include thermal initiators, stabilizers, light stabilizers, fillers, colorants, antistatic agents, wetting agents, flow improvers, and adhesion enhancers.

[0122] For example, especially in the case of a coloring composition, the composition may also contain, as additional additives, thermal initiators, compounds that form free radicals when heated, such as azo compounds, such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), triazenes, diazosulfides, pentaazadienes, or peroxy compounds, such as hydroperoxides or peroxyesters, such as tert-butyl hydroperoxide (for example, as described in European Patent Application Publication No. 245639).

[0123] 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 stability during storage in the dark, 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 a similar wax-like substance (insoluble in the polymer) can be added for the purpose of removing oxygen in the atmosphere, and this substance migrates to the surface at the start of polymerization and forms a transparent surface layer that prevents the intrusion of air.

[0124] It is also possible to add light stabilizers, such as UV absorbers, such as hydroxyphenylbenzotriazoles, hydroxyphenylbenzophenones, oxalic acid amides, or hydroxyphenyl-s-triazine types. Such components can be used alone or in the form of mixtures, with or without using sterically hindered amines (HALS).

[0125] All alternative and preferred embodiments of the photoinitiator packages described above or below are applicable to the photopolymerizable compositions according to this embodiment, with necessary modifications.

[0126] method In a third aspect, the present invention relates to a method for photocuring a photopolymerizable composition, coating, adhesive, and ink, a) A step of coating or printing a photopolymerizable composition according to the second embodiment onto a substrate, b) A step of photopolymerizing the coating or printed composition on the substrate using a light source. This study focuses on methods that include the elements in a given order.

[0127] Preferably, the light source operates in the near-UV or visible range of the EM spectrum.

[0128] All alternative and preferred embodiments of the above or below photoinitiator packages and photopolymerizable compositions are applicable, with necessary modifications, to methods for photocuring photopolymerizable compositions, coatings, adhesives, and inks according to this embodiment.

[0129] use In a fourth aspect, the present invention relates to the use of the photoinitiator package according to the first aspect in the manufacture of printing inks, screen printing inks, gravure printing inks, solder masks, etching offset printing inks, flexographic printing inks, gravure printing inks, inkjet inks, resist materials, insulators, encapsulating materials, image recording materials, solder masks, passivation layers, protective coatings, 3D printed objects and molds, holographic applications, optical fiber coatings, waveguides and lenses, overprint varnishes, wood, vinyl, metal and plastic coatings.

[0130] All alternative and preferred embodiments of the photoinitiator packages described above or below are applicable to the use according to this embodiment with necessary modifications.

[0131] In its final embodiment, the present invention relates to the use of a combination of one or more amines and one or more oxazole-based sensitizers to increase the surface curing rate of a photopolymerizable composition comprising one or more Norish type I photoinitiators.

[0132] It is particularly preferable that one or more Norish type I photoinitiators be selected from mono or bisacylphosphine oxide photoinitiators.

[0133] All alternative forms and preferred embodiments of one or more mono- or bisacylphosphine oxide photoinitiators, coumarin sensitizers and / or amines described in the first embodiment are applicable to the use according to this embodiment with necessary modifications.

[0134] Furthermore, the photopolymerizable composition is preferably the photopolymerizable composition according to the second embodiment. All alternative forms and preferred embodiments of the photopolymerizable composition according to the second embodiment are applicable to the use according to this embodiment with necessary modifications.

[0135] A combination of one or more amines and one or more coumarin-based sensitizers is particularly preferable as it significantly increases the surface hardening rate.

[0136] In one embodiment, the effect of "increasing the surface hardening rate" is achieved when the surface hardening rate (expressed as tack-free m / min) in the presence of a combination of one or more amines and one or more coumarin-based sensitizers is at least 1.5 times, more preferably at least 2.0 times, more preferably at least 3.0 times, 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-based sensitizers. [Examples]

[0137] A.Measurement method Tack-Free Measurement: Tack-free refers to the state of a coating where it has completely hardened on the surface. Evaluation Method: Using a bar coater, the mixture is applied to a varnished cardboard to a thickness of 12 microns (12 μm) and photopolymerized under a light source. Next, the operator's thumb is placed in contact with the coating with slight pressure. If no fingerprint / mark remains on the surface, the coating is completely hardened. The maximum speed (m / min) at which no fingerprint / mark remains on the surface is indicated as the tack-free value. The higher the maximum speed, the higher the reactivity.

[0138] B. Experiment 1.Materials used The following commercially available compounds were used to prepare the formulations of the present invention and comparative formulations.

[0139] PI-1 is bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, with CAS number 162881-26-7, and is commercially available as Omnirad 819 from IGM Group BV (Netherlands).

[0140] PI-2 is bis(2,4,6-trimethylbenzoyl)octylphosphine oxide, which is prepared as described in U.S. Patent No. 5534559A.

[0141] S1 is 7-diethylamino-4-methylcoumarin, with CAS number 91-44-1, and is commercially available as Coumarin 1 from Merck KGaA (Germany).

[0142] It is S2:7-methoxycoumarin, with CAS number 531-59-9, and is commercially available from abcr GmbH (Germany).

[0143] S3 is 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinoridine-11-one, with CAS number 41267-76-9, and is commercially available as Coumarin 102 from abcr GmbH (Germany).

[0144] S4 is coumarin, with CAS number 91-64-5, and is commercially available from abcr GmbH (Germany).

[0145] S5 is 7-diethylamino-3-phenylcoumarin, with CAS number 84865-19-0, and is commercially available from abcr GmbH (Germany).

[0146] A1 is 1H-azepine-1-propanoic acid, hexahydro-2,2-bis[[(1-oxo-2-propen-1-yl)oxy]methyl]butyl ester, which is commercially available as Photomer 4250 from IGM Group BV (Netherlands).

[0147] A2 is triethanolamine, with CAS number 102-71-6, and is commercially available from Merck KGaA (Germany).

[0148] A3 is poly(ethylene glycol)bis(p-dimethylaminobenzoate), with CAS number 71512-90-8, and is commercially available as Omnipol ASA from IGM Group BV (Netherlands).

[0149] Mi:M1, M2, and M3 (40:30:30) are photopolymerizable monomer blends.

[0150] M-ii: A photopolymerizable monomer blend of M1, M4, M5, and M6 (50:15:15:20).

[0151] M-iii is a photopolymerizable monomer blend of M1, M4, and M6 (50:25:25).

[0152] M1 is bisphenol Y epoxy diacrylate, with CAS number 55818-57-0, and is commercially available as Photomer 3016 from IGM Group BV (Netherlands).

[0153] M2 is glyceryl[4PO] triacrylate, with CAS number 52408-84-1, and is commercially available as Photomer 4094 from IGM Group BV (Netherlands).

[0154] M3 is trimethylolpropane triacrylate, with CAS number 15625-89-5, and is commercially available as Photomer 4006 from IGM Group BV (Netherlands).

[0155] M4 is a blend of pentaerythritol tri and tetraacrylate, CAS numbers 3524-68-3 and 4986-89-4, and is commercially available as Photomer 4335 from IGM Group BV (Netherlands).

[0156] M5 is dipentaerythritol penta / hexaacrylate, with CAS number 1384855-91-7, and is commercially available as Photomer 4600 from IGM Group BV (Netherlands).

[0157] M6 is pentaerythritol[5EO]tetraacrylate, with CAS number 51728-26-8, and is commercially available as Photomer 4172 from IGM Group BV (Netherlands).

[0158] 2. Compound (photopolymerizable composition) For the evaluation of surface hardening, the following reference formulations, the formulation of the present invention, and comparative formulations were used, with the amount of each component indicated in weight percent (W%). The formulations were prepared by adding a photoinitiator, a sensitizer, and an amine to a photopolymerizable monomer blend M (i.e., Mi, M-ii, or M-iii) at the concentrations shown in Table 1 at room temperature. The formulations were stirred at 60°C for 2 hours, cooled to room temperature, and then coated to a thickness of 12 microns (12 μm) onto varnished cardboard using a bar coater. Subsequently, these formulations were photopolymerized using a light source (Table 2).

[0159] [Table 1]

[0160] [Table 2]

[0161] [Table 3]

[0162] [Table 4]

[0163] 3. Evaluation of surface photocuring The formulations of the present invention and comparative formulations were evaluated for their surface photocuring ability using different light sources and according to the test methods provided in the measurement method (the values ​​in Table 2 correspond to the maximum tack-free speed (m / min)).

[0164] [Table 5] *n / m=not measured Lamp 1: This is a UV Hg lamp with an intensity of 120 W / cm and a distance of 8 cm. Lamp 2: This is a UV Hg lamp with an intensity of 85 W / cm and a distance of 8 cm. Lamp 3: Wavelength 395nm, intensity 4W / cm 2 It is a UV LED lamp with a distance of 0.5 cm. Lamp 4: Wavelength 365nm, intensity 4W / cm 2 It is a UV LED lamp with a distance of 0.5 cm. Lamp 5: Wavelength 278nm, intensity 4W / cm 2 It is a UV LED lamp with a distance of 0.5 cm.

[0165] [Table 6] Lamp 1: This is a UV Hg lamp with an intensity of 120 W / cm and a distance of 8 cm. Lamp 6: Wavelength 395nm, intensity 16W / cm 2 It is a UV LED lamp with a distance of 0.5 cm. Lamp 7: Wavelength 365nm, intensity 16W / cm 2 It is a UV LED lamp with a distance of 0.5 cm.

[0166] [Table 7] *n / m=not measured Lamp 1: This is a UV Hg lamp with an intensity of 120 W / cm and a distance of 8 cm. Lamp 2: This is a UV Hg lamp with an intensity of 85 W / cm and a distance of 8 cm. Lamp 3: Wavelength 395nm, intensity 4W / cm 2 It is a UV LED lamp with a distance of 0.5 cm. Lamp 4: Wavelength 365nm, intensity 4W / cm 2 It is a UV LED lamp with a distance of 0.5 cm. Lamp 6: Wavelength 395nm, intensity 16W / cm 2 It is a UV LED lamp with a distance of 0.5 cm. Lamp 7: Wavelength 365nm, intensity 16W / cm 2 It is a UV LED lamp with a distance of 0.5 cm.

[0167] As can be seen from the data in Table 2a, when coumarin-based sensitizers S1 to S5 are used in combination with photoinitiators PI-1 and PI-2, the curing rate (CE3 / CE4 / CE5 vs CE1 (PI-1 / S1), CE6 vs CE1 (PI-1 / S2), CE7 vs CE1 (PI-1 / S3), CE8 vs CE1 (PI-1 / S4), CE9 vs CE1 (PI-1 / S5), and CE11 vs CE10 (PI-2 / S1)) is generally improved, or in some cases the curing rate is hardly affected (for example, when S2, S4, and S5 are used with lamp 2, lamp 3, or lamp 4).

[0168] Regardless of whether the use of coumarin-based sensitizers improves the curing rate, the use of amines A1-A3 has been shown to (further) improve the curing rate by synergistically interacting with the sensitizers to enhance the effect of type I photoinitiators. As can be seen by comparing CE2 with CE1, amines alone affect the curing rate of type I photoinitiators, but the effect when both amines and sensitizers are used is generally greater than that predicted from a simple additive effect (i.e., amines and sensitizers act synergistically).

[0169] In IE1, which uses only 0.5% by weight of the coumarin-based sensitizer S1, the effect of amine (A1) is particularly pronounced, with the amine more than doubling the effect of the sensitizer (e.g., in lamp 3, the addition of amine resulted in an improvement of 14 m / min (CE3 vs. IE1), and the addition of the sensitizer resulted in an improvement of 6 m / min (CE1 vs. CE3)).

[0170] Similar effects are observed when using 1.5 wt% S1, with amines A1-A3 all contributing to improvement. A2 is particularly effective in synergistically interacting with the sensitizer when lamp 5 is used (IE3 vs CE4).

[0171] In the above case, the activity of the composition of the present invention exceeded the limits of the test, making it difficult to confirm the effect when using lamp 1. However, when 10% by weight of S1 is used, the true effect of the amine is observed, and surface hardening is significantly improved in IE4-IE6 compared to CE5 (and CE1).

[0172] IE7-IE10 show the effects of combining amine A1 with various coumarin-based sensitizers S2-S5 (compared to CE6-CE9, respectively).

[0173] Finally, similar improvements were observed when using PI-2 (i.e., IE11 vs CE11), with particularly good surface hardening observed on ramps 1-4.

[0174] The data in Table 2b further supports the conclusions drawn from Table 2a, demonstrating that a smaller amount of photopolymerized package can lead to better surface curing.

[0175] The results of several control experiments are shown in Table 2c. RE1 and RE2 indicate that coumarin-based sensitizers do not act as type I (RE1) or type II (RE2) photoinitiators. Furthermore, IE16 / CE18 indicates that a 50:50 combination of sensitizer and amine is more effective than the sensitizer alone.

Claims

1. a) One or more mono or bisacylphosphine oxide photoinitiators, b) One or more coumarin-based sensitizers, each having the structure of formula (I), 【Chemistry 1】 (In the formula, R ３ is hydrogen, C １ ~C １０ Alkyl, C ６ ~C １４ Selected from the group consisting of aryls and heteroaryls, R ４ is selected from the group consisting of hydrogen, C １ to C １０ alkyl optionally substituted with one or more fluorine atoms, and OR １ and is selected from the group consisting of: R ５ ~R ８ Each of these independently consists of hydrogen, halogen, and C. １ ~C １０ Alkyl, OR １ , and NR ２ ２ Selected from the group consisting of, R １ Each example independently involves hydrogen, C １ ~C １０ Alkyl and C ６ ~C １４ Selected from the aryl, R ２ Each example independently involves hydrogen, C １ ~C １０ Alkyl and C ６ ~C １４ Selected from the aryl, R １ ~R ８ Each example is arbitrarily R １ ~R ８ (It may be combined with one or more further examples to form one or more five-membered or six-membered rings.) c) One or more amines and A photoinitiator package comprising a photoinitiator, wherein the only photoinitiator present in the photoinitiator package is a Norish type I photoinitiator or a cationic photoinitiator.

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

3. The photoinitiator package according to claim 1, wherein at least one of the one or more bisacylphosphine oxide photoinitiators has a structure of any one of formulas (II) to (V). 【Chemistry 2】 (In the formula, R １ａ , R ２ａ , R ３ａ , R １ｂ , R ２ｂ and R ３ｂ Each example is independent of C １ ~C ４ Alkyl, C １ ~C ４ Selected from the group consisting of alkoxys and halogens, X is a direct single bond, O, S, NR ５ａ ien-CH ２ CO ２ -, and -CH ２ CH ２ CO ２ - Selected from the group consisting of, R ４ａ (CO)R is hydrogen. ６ａ , (CO) OR ６ａ (CO)NR ５ａ R ６ａ , (SO ２ ) R ６ａ [Si(R ７ａ ) (Caution ８ａ )] ｍ -Si(R ７ａ ) (Caution ８ａ ) (Caution ９ａ ), [Si(R ７ａ ) (Caution ８ａ )O] ｍ -Si(R ７ａ ) (Caution ８ａ ) (Caution ９ａ Selected from the group consisting of ) or R ４ａ is C １ -C ２８ alkyl, or C interrupted by one or more O, NR ５ａ , S, (CO), (CO)O or SO ２ -C ２ -C ２８ alkyl, and the C １ -C ２８ alkyl or interrupted C ２ -C ２８ alkyl is unsubstituted or substituted with one or more substituents, and one or more of the substituents are 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 C substituted with OH ３ -C １２ cycloalkyl, C interrupted by one or more O, NR ５ａ or S ３ -C １２ cycloalkyl (interrupted C ３ -C １２ cycloalkyl is unsubstituted or C １ -C ４ alkyl, C １ -C ４ alkoxy or substituted with OH), unsubstituted or C １ -C ４ alkyl, C １ -C ４ alkoxy or C substituted with OH ６ -C １４ Selected from the group consisting of aryls, or R ４ａ is either unsubstituted or one or more C １ ~C １２ Alkyl, C suspended by one or more oxygen atoms ２ ~C ２０ Alkyl, C １ ~C １２ C substituted with alkoxy or OH groups ６ ~C １０ Is it an aryl, or X is NR ５ａ If R ４ａ R ５ａ and together with N atoms, they form a 5- or 6-membered saturated ring, which is uninterrupted or O or NR ５ａ The interrupted ring is either unsubstituted or has one or more C １ ~C ４ Alkyl, C １ ~C ４ Substituted with alkoxy or OH, or R ４ａ It is selected from the group consisting of structures (A) to (G), 【Transformation 3】 R ４ａ All options are OH and R １７ａ It may be further substituted with one or more elements selected from, R １７ａ teeth, 【Chemistry 4】 And, A is PF ６ SbF ６ AsF ６ or B (C ６ F ５ ) ４ And, R ５ａ (CO)R is hydrogen. ６ａ phenyl, C １ ~C １２ Alkyl, C suspended by one or more oxygen atoms ２ ~C １２ Alkyl, C ３ ~C １２ It is a cycloalkyl, and the C １ ~C １２ Alkyl or interrupted C ２ ~C １２ Alkyl is either unsubstituted or has one or more C ３ ~C ７ It is substituted with cycloalkyl, OH, or NCO, and the C ３ ~C １２ Cycloalkyls are either unsubstituted or have one or more C １ ~C ４ Alkyl, C １ ~C ４ Substituted with alkoxy, OH, or NCO, R ６ａ C １ ~C １２ C interrupted by alkyl or one or more oxygen atoms ２ ~C １２ Alkyl, and the C １ ~C １２ Alkyl or interrupted C ２ ~C １２ Alkyl is either unsubstituted or has one or more C ３ ~C ７ It is substituted with a cycloalkyl, OH, NCO, or NCO-substituted phenyl, or R ６ａ C ３ ~C １２ Cycloalkyl or C ２ ~C １０ It is an alkenyl, and the C ２ ~C １０ Alkenyls are either unsubstituted or have one or more C １ ~C ４ Alkyl, OH, or C １ ~C ４ Substituted with alkoxy, or R ６ａ is either non-substitutive or C １ ~C １２ Alkyl, C １ ~C １２ Alkoxy, NCO, or NCO-substituted C １ ~C １２ C substituted with alkyl ６ ~C １４ Is it an aryl, or Group N(R ５ａ ) ２ If R exists, ５ａ One example is (CO)R ６ａ It may be R ５ａ Other examples and R ６ａ Together with the N and CO portions, they form a 5- or 6-membered ring, which is uninterrupted or O or NR ５ａ The interrupted ring is either unsubstituted or has one or more C １ ~C ４ Alkyl, C １ ~C ４ Substituted with alkoxy or OH groups, R ７ａ , R ８ａ and R ９ａ Each of them is independent of C １ ~C ４ Alkyl, C ６ ~C １４ Aryl and C １ ~C ４ Selected from the group consisting of alkoxys, m is an integer in the range of 0 to 10. Y １ａ This is a direct single bond, O, S, NR ５ａ , O(CO)-* and O(CO)CH ２ Selected from the group consisting of O-*, the asterisk indicates the bond of group (A), (B), (D), or (E) to the phenyl ring. Y ２ａ This is a direct single bond, O, S and NR ５ａ Selected from the group consisting of, R １１ａ and R １２ａ They are independent of each other, C １ ~C １０ Alkyl, C ２ ~C １０ Alkenyl or phenyl, unsubstituted or C １ ~C ４ C substituted with alkyl １ ~C ４ Alkyl or R １１ａ and R １２ａ These, together with the C atom to which they are bonded, form a cyclohexane or cyclopentane ring. Z ａ is OH or NR １３ａ R １４ａ And, Z １ａ C １ ~C １２ Alkoxy, or carbon suspended by one or more oxygen atoms. ２ ~C １２ It is an alkoxy, and the C １ ~C １２ Alkoxy or interrupted C ２ ~C １２ Alkoxy is either unsubstituted or substituted with an OH group. R １３ａ and R １４ａ They are independent of each other, C １ ~C １２ Alkyl, one or more OH groups, or halogen-substituted C １ ~C １２ Alkyl or R １３ａ and R １４ａ These, together with the N atom to which they are bonded, form a 5- or 6-membered unsaturated or saturated ring, and this ring is uninterrupted or O or NR １５ａ It is interrupted at R １５ａ C １ ~C ４ It is alkyl, R １６ａ is hydrogen or C １ ~C ４ It is alkyl, however, (i) C １ ~C ４ R as an alkyl group １ａ , R ２ａ and R ３ａ If is methyl and X is O, then C １ ~C ２８ R as an alkyl group ４ It is not methyl, ethyl, n-propyl, 2-propyl, n-butyl, sec-butyl, tert-butyl, or n-hexyl, (ii) R as a halogen １ａ and R ３ａ Cl is and R ２ａ If is hydrogen and X is O, substitution C ３ ~C １０ R as an aryl ４ａ It is not 4-butylphenyl, (iii) C １ ~C ４ R as an alkoxy １ａ and R ３ａ is methoxy, and R ２ａ is hydrogen, and X is NR ５ａ And R ４ａ R ５ａ (And when it forms a 5- or 6-membered saturated ring with an N atom, the ring is not a piperidine ring.) 【Transformation 5】 (In the formula, Ar １ and Ar ２ Each of them operates independently. 【Transformation 6】 or naphthyl, wherein the naphthyl is unsubstituted or R １ｃ , R ２ｃ , R ３ｃ , R ４ｃ Or R ５ｃ It has been replaced at least once, R １ｃ and R ５ｃ Each of them is independent of C １ ~C ４ Alkyl, C １ ~C ４ Selected from the group consisting of alkoxys and halogens, R ３ｃ is hydrogen, C １ ~C ４ Alkyl, halogen, C １ ~C ４ Alkoxy and C suspended by one or more oxygen atoms ２ ~C ２０ Selected from the group consisting of alkoxys, Q is C １ ~C ４ It is alkylene, R ２ｃ and R ４ｃ These are, independently of each other, hydrogen or PG ｃ -Y ｃ -Z ｃ -X ｃ - and PG ｃ The polymerizable group is methyl or ethyl. Y ｃ It is a direct single bond, O or S, X ｃ It is a direct single bond, O or S, Z ｃ C is a direct single bond. １ ~C ２０ Alkylene, or carbon suspended by one or more oxygen atoms. ２ ~C ２０ It is alkylene, R ６ｃ is either unsubstituted or OH and 【Transformation 7】 C substituted with one or more groups selected from ３ ~C ３０ Alkyl or R ６ｃ is one or more O or C ３ ~C ８ C interrupted by cycloalkylene ３ ~C ２８ It is alkyl and interrupted C ３ ~C ２８ Alkyl is either unsubstituted or has OH and 【Transformation 8】 (It is replaced by one or more elements selected from the following.) 【Chemistry 9】 (In the formula, R １ｄ C １ ~C ４ Alkyl, C １ ~C ４ It is an alkoxy or halogen, R ２ｄ is hydrogen, C １ ~C ４ Alkyl, C １ ~C ４ It is an alkoxy or halogen, R ３ｄ C １ ~C ２０ Alkyl, cyclopentyl, cyclohexyl, phenyl-C １ ~C ４ Alkyl, naphthyl, biphenylyl, or an O-containing, S-containing, or N-containing 5 or 6-membered heterocyclic radical, wherein the naphthyl, biphenylyl, and the O-containing, S-containing, or N-containing 5 or 6-membered heterocyclic radical are unsubstituted or C １ ~C ４ Alkyl, C １ ~C ４ Alkoxy, halogen, C １ ~C ４ Substituted with alkylthio, or R ３ｄ teeth, 【Chemistry 10】 And, R ４ｄ , R ５ｄ , R ６ｄ , R ７ｄ and R ８ｄ These are, independently, hydrogen, halogen, and C. １ ~C ２０ Alkyl, cyclopentyl, cyclohexyl, C ２ ~C １２ Alkenyl, a carbon atom interrupted by one or more discontinuous oxygen atoms. ２ ~C ２０ Alkyl, phenyl-C １ ~C ４ Alkyl, C １ ~C ２０ Selected from the group consisting of alkoxy or phenyl, wherein the phenyl is unsubstituted or has one or two C atoms. １ ~C ４ Alkyl and / or C １ ~C ４ (It is substituted with an alkoxy substituent.) 【Chemistry 11】 (In the formula, each A is independent of O, S, NR) ３ｅ This represents, G is a polyfunctional compound (core) G-(A-H) ｐ＋ｑ These are residues, 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 between 3 and 10, and p is an integer between 3 and 8. R １ｅ and R ２ｅ Each of them is independent of C １ ~C １８ Alkyl, C ６ ~C １２ Aryl and C ５ ~C １２ Selected from the group consisting of cycloalkyl groups, C １ ~C １８ Alkyl, C ６ ~C １２ Aryl and C ５ ~C １２ Each cycloalkyl group is either 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 heterocycline containing an oxygen atom and / or a nitrogen atom and / or a sulfur atom, and each of the groups may be substituted with an aryl, alkyl, aryloxy, alkoxy, heteroatom and / or heterocyclic radical, R ２ｅ (CO)R １ｅ Even if that is the case, R ３ｅ is hydrogen or C １ ~C ４ It is alkyl.

4. The photoinitiator package according to claim 1, wherein at least one of the one or more bisacylphosphine oxide photoinitiators has the structure of formula (VI). 【Chemistry 12】 (In the formula, R １ｆ Each example is independent of C １ ~C ４ Selected from the group consisting of alkyl groups, X ｆ This is a direct single bond, O, S, NR ４ｆ ien-CH ２ CO ２ -, and -CH ２ CH ２ CO ２ - Selected from the group consisting of, R ２ｆ C １ ~C ４０ Alkyl, and one or more O or C ３ ~C ８ Interruption C interrupted by cycloalkylene ２ ~C ４０ Selected from the group consisting of alkyl groups, the C １ ~C ４０ Alkyl or interrupted C ２ ~C ４０ Alkyl groups are either unsubstituted or consist of OH and R groups. ３ｆ It may be substituted with one or more elements selected from, R ３ｆ teeth, 【Chemistry 13】 And, R ４ｆ (CO)R is hydrogen. ５ｆ phenyl, C １ ~C １２ Alkyl and C suspended by one or more oxygen atoms ２ ~C １２ Alkyl, C ３ ~C １２ Selected from the group consisting of cycloalkyl, the C １ ~C １２ Alkyl or interrupted C ２ ~C １２ Alkyl is either unsubstituted or has one or more C ３ ~C ７ It is substituted with cycloalkyl, OH, or NCO, and the C ３ ~C １２ Cycloalkyls are either unsubstituted or have one or more C １ ~C ４ Alkyl, C １ ~C ４ Substituted with alkoxy, OH, or NCO, R ５ｆ C １ ~C １２ Alkyl and C suspended by one or more oxygen atoms ２ ~C １２ Selected from the group consisting of alkyl groups, the C １ ~C １２ Alkyl or interrupted C ２ ~C １２ Alkyl is either unsubstituted or has one or more C ３ ~C ７ It is substituted with cycloalkyl, OH, NCO, or phenyl, and the phenyl is NCO, C ３ ~C １２ Cycloalkyl, C ２ ~C １０ Alkenil, C ６ ~C １４ It is replaced with aryl, and the C ２ ~C １０ Alkenyls are either unsubstituted or have one or more C １ ~C ４ Alkyl, OH, or C １ ~C ４ Substituted with alkoxy, the C ６ ~C １４ The aryl is either unsubstituted or C １ ~C １２ Alkyl, C １ ~C １２ Alkoxy, NCO, or NCO-substituted C １ ~C １２ (It is substituted with alkyl.)

5. R ３ is hydrogen and C １ ~C １０ Selected from the group consisting of alkyl groups, and / or R ４ is hydrogen and C １ ~C １０ A photoinitiator package according to claim 1, selected from the group consisting of alkyl groups.

6. R ７ OR １ and NR ２ ２ A photoinitiator package according to claim 1, selected from the group consisting of the following.

7. Each of the coumarin-based sensitizers having the structure of formula (I) is independently 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-benzoxazollyl)-7-(diethylamino)coumarin, 7-methylcoumarin, 7-methoxycoumarin, 4-hydroxycoumarin, 5,7-dimethoxycoumarin, 3-(3-biphenyl-4 A photoinitiator package according to claim 1, selected from the group consisting of -yl-1,2,3,4-tetrahydro-1-naphthyl)-4-hydroxycoumarin, 6-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]quinoridine-11-one, 7-(diethylamino)-4-(trifluoromethyl)coumarin, and 7-(ethylamino)-4-(trifluoromethyl)coumarin.

8. a) One or more of the mono or bisacylphosphine oxide photoinitiators in an amount within the range of 40 to 98.9% by weight relative to the total weight of the photoinitiator package, b) One or more coumarin-based sensitizers, each having the structure of formula (I), in an amount ranging from 0.1 to 50% by weight relative to the total weight of the photoinitiator package, c) One or more of the amines in an amount ranging from 1.0 to 45% by weight relative to the total weight of the photoinitiator package The photoinitiator package according to claim 1, comprising:

9. a) One or more ethylenically unsaturated free radical polymerizable compounds, b) The photoinitiator package according to claim 1 and A photopolymerizable composition containing a photoinitiator package, in which no further photoinitiators, photosensitizers, or coinitiators are present.

10. a) One or more of the ethylenically unsaturated free radical polymerizable compounds in an amount ranging from 30 to 99.0% by weight relative to the total weight of the photopolymerizable composition, b) The photoinitiator package according to claim 1 in an amount ranging from 0.5 to 50% by weight relative to the total weight of the photopolymerizable composition. A photopolymerizable composition according to claim 9, comprising:

11. c) One or more pigments in an amount ranging from 0.1 to 30% by weight relative to the total weight of the photopolymerizable composition, d) One or more binders in an amount ranging from 5.0 to 60% by weight relative to the total weight of the photopolymerizable composition, e) One or more additives in an amount ranging from 0.01 to 10% by weight relative to the total weight of the photopolymerizable composition The photopolymerizable composition according to claim 9, further comprising one or more of the above.

12. A method for photocuring photopolymerizable compositions, coatings, adhesives, and inks, a) A step of coating or printing the photopolymerizable composition described in claim 10 onto a substrate, b) A step of photopolymerizing the coating or printed composition on the substrate with a light source. A method that includes in a given order.

13. Use of the photoinitiator package according to claim 1 in the manufacture of printing inks, screen printing inks, gravure printing inks, solder masks, etching offset printing inks, flexographic printing inks, gravure printing inks, inkjet inks, resist materials, insulators, encapsulating materials, image recording materials, solder masks, passivation layers, protective coatings, 3D printed objects and molds, holographic applications, optical fiber coatings, waveguides and lenses, overprint varnishes, wood, vinyl, metal and plastic coatings.

14. Use of a combination of one or more amines and one or more coumarin sensitizers for increasing the surface curing rate of a photopolymerizable composition comprising one or more mono or bisacylphosphine oxide photoinitiators, wherein the coumarin sensitizer has the structure shown in formula (I) 【Chemistry 14】 (R3 is selected from the group consisting of hydrogen, C1-C10 alkyl, C6-C14 aryl, and heteroaryl, R4 is selected from the group consisting of hydrogen, C1 to C10 alkyl which may be substituted with one or more fluorine atoms, and OR1. Each of R5 to R8 is independently selected from the group consisting of hydrogen, halogen, C1 to C10 alkyl, OR1, and NR22. Each example of R1 is independently selected from hydrogen, C1-C10 alkyl, and C6-C14 aryl; each example of R2 is independently selected from hydrogen, C1-C10 alkyl, and C6-C14 aryl; and each example of R1-R8 may optionally be combined with one or more further examples of R1-R8 to form one or more five-membered or six-membered rings. Uses that have

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