WO2012159213A1 - Compounds with oxime ester and/or acyl groups - Google Patents

Compounds with oxime ester and/or acyl groups Download PDF

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Publication number
WO2012159213A1
WO2012159213A1 PCT/CA2012/050340 CA2012050340W WO2012159213A1 WO 2012159213 A1 WO2012159213 A1 WO 2012159213A1 CA 2012050340 W CA2012050340 W CA 2012050340W WO 2012159213 A1 WO2012159213 A1 WO 2012159213A1
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WIPO (PCT)
Prior art keywords
optionally substituted
alkyl
compound
phenyl
formula
Prior art date
Application number
PCT/CA2012/050340
Other languages
French (fr)
Inventor
My T. Nguyen
Jean-Philipe TREMBLAY-MORIN
Philippe GAUDREAULT
Original Assignee
American Dye Source, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority to CN201280036919.5A priority Critical patent/CN103842338B/en
Priority to JP2014511694A priority patent/JP5923597B2/en
Priority to MX2013013793A priority patent/MX351447B/en
Priority to BR112013030253A priority patent/BR112013030253A2/en
Priority to AU2012260397A priority patent/AU2012260397B2/en
Priority to UAA201315210A priority patent/UA114403C2/en
Priority to RU2013157532A priority patent/RU2628076C2/en
Priority to US14/122,126 priority patent/US9127017B2/en
Application filed by American Dye Source, Inc. filed Critical American Dye Source, Inc.
Priority to EP12789315.4A priority patent/EP2714659B1/en
Priority to KR1020137034409A priority patent/KR101599120B1/en
Priority to CA2836817A priority patent/CA2836817C/en
Publication of WO2012159213A1 publication Critical patent/WO2012159213A1/en
Priority to HK14110788.9A priority patent/HK1197243A1/en
Priority to US14/801,223 priority patent/US9382259B2/en

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    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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    • C08F2/00—Processes of polymerisation
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    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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    • G—PHYSICS
    • G02—OPTICS
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    • G02B5/00—Optical elements other than lenses
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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    • C07C2603/00—Systems containing at least three condensed rings
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    • C07D495/04—Ortho-condensed systems
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    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • the present invention is concerned with compounds comprising at least one oxime ester and/or acyl group. More specifically, present invention is concerned with compounds based on indene fused with fluorene or 9,10-dihydroanthracene and derivatives thereof.
  • Photosensitive or photopolymerizable compositions typically include, for example, an ethylenic unsaturated bond-containing polymerizable compound and a photopolymerization initiator. Such photosensitive or photopolymerizable compositions polymerize and cure when irradiated with light, and are therefore used, for example, in photosetting or photocuring inks, photosensitive printing plates, color filter resists, black matrix resins, and a variety of photoresists, including dry film resists.
  • Photopolymerization initiators are also called free radical photoinitiators. Upon exposure to light of a wavelength to which they are sensitive, they generate free radicals and thus initiate free radical polymerization of surrounding polymerizable compounds.
  • photoinitiators exhibit good sensitivity to light, especially in the UV region of the spectrum, low discoloration upon use, and good thermal stability (for storage and processing).
  • Some organic compounds comprising acyl and/or oxime ester groups are known as free radical photoinitiators. They have found use in color filter resists due to their absorption in the ultra-violet radiation region (between 300 and 450 nm). Irgacure OXE-01TM and OXE-02TM (available from BASF, Germany) are known photoinitiators for some applications, including color filter resists. Some triazine-based compounds are also known as useful photoinitiators.
  • a compound comprising optionally substituted (FORMULA I) fused with one or
  • ⁇ phenyl optionally substituted with one or more:
  • L is hydrogen or C1-C6 alkyl and wherein each of Re, Rg and R10 is independently hydrogen, C1-C12 alkyl; C4-C10 cycloalkyi; C1-C12 alkenyl; C4-C10 cycloalkenyl; C2-C12 alkynyl; C4-C10 cycloalkynyl; C1-C12 haloalkyl; or optionally substituted aryl.
  • R7 represents alkyl, cycloalkyi, alkenyl, or cycloalkenyl, each of which being optionally substituted with aryl or halogen, or R7 is aryl optionally substituted with alkyl or halogen.
  • R7 represents C1-C12 alkyl optionally substituted with phenyl; C4-C10 cycloalkyi; or phenyl optionally substituted with C1-C6 alkyl.
  • R7 is C1-C12 alkyl; C4-C10 cycloalkyi; or phenyl.
  • R30 is optionally substituted alkyl, cycloalkyi, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, or aryl, each of which optionally comprising one or more oxygen atom, sulfur atom, nitrogen atom, carbonyl group, carbamate group, carbamide group, and/or ester group.
  • o phenyl optionally substituted with one or more: Ci alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
  • aryl such as phenyl, thiophenyl, biphenyl and naphthyl, each of which being optionally substituted with one or more:
  • R30 is linear alkyl, phenyl or thiophenyl, all of which being optionally substituted with a linear alkyl or with -O-L.
  • R30 is methyl, 2-methylphenyl, phenyl, thiophenyl, or 4-methoxyphenyl.
  • -LK- is optionally substituted alkylene, cycloalkylene, alkenylene, cycloalkenylene, alkynylene, cycloalkynylene, arylene, -S-arylene, -NH-arylene, or -N(aryl)-arylene, each of which optionally comprising one or more oxygen atom, sulfur atom, nitrogen atom, carbonyl group, carbamate group, carbamide group, and/or ester group.
  • o phenyl optionally substituted with one or more: Ci alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
  • aryl such as phenyl, biphenyl and naphthyl, or aryloyl, such as benzoyl, each of which being optionally substituted with one or more:
  • o phenyl optionally substituted with one or more Ci alkyl, halogen atom, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl; and/or
  • phenyl, biphenyl and/or naphthyl each of which being optionally substituted with one or more: o Ci-C 6 alkyl, o halogen atom,
  • L, f3 ⁇ 4, Rg and R10 are as defined in item 3.
  • R4, R5, R4' and R5' are optional and independently represent, in the case of R4 and R5, one to four and, in the case of R4' and R5', one or two:
  • phenyl optionally substituted with one or more: Ci alkyi, halogen atom, nitrile, alkyloxy, COOR10, and/or C2 to C1 ⁇ 2 alkylcarboxyl;
  • C4-C10 cycloalkyl C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, C4-C10 cycloalkynyl, each of which being optionally substituted by alkyi and/or -O-L, and/or o phenyl, biphenyl and naphthyl, each of which being optionally substituted with one or more: Ci-C 6 alkyl,
  • Qi and Q2 are optional and independently represent one to four acyl groups and/or oxime ester
  • phenyl optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR10, and/or C2-C12 alkylcarboxyl;
  • o Q 4 represents an oxime ester of formula:
  • o Ar is a linker -LK- as defined in any one of items 15 to 17,
  • L, f3 ⁇ 4, f3 ⁇ 4 and R10 are as defined in item 3, and wherein R6 and R7 are as defined in any one of items 2 to 10 .
  • o phenyl optionally substituted with one or more: Ci alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
  • Ri2 are optional and independently represent one or more:
  • C1-C12 alkyl optionally substituted with one or more:
  • o phenyl optionally substituted with one or more: Ci alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
  • C4-C10 cycloalkyl C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, and/or C4-C10 cycloalkynyl, each of which being optionally substituted by alkyl and/or -O-L; and/or phenyl, biphenyl and naphthyl, each of which being optionally substituted with one or more: o Ci-C 6 alkyl,
  • L, f3 ⁇ 4, Rg and R10 are as defined in item 3.
  • ⁇ R4 and R5 are optional and independently represent one C1-C12 alkyl or C1-C12 alkyloxy,
  • ⁇ optional and independently represent one oxime ester group of formula
  • ⁇ Ri, R2, and Ra each independently represent a hydrogen atom or C1-C12 alkyl
  • Q3 represents a hydrogen atom or an oxime ester group of formula:
  • ⁇ f3 ⁇ 4 and R7 independently represents alkyl.
  • the compound item 26 being truxene, truxenone, triazatruxene or a derivative thereof, said truxene, truxenone, triazatruxene or derivative thereof having attached thereto, directly or indirectly, at least one acyl and/or oxime ester group.
  • the compound of item 36 being:
  • LK is as defined in any one of items 15 to 17, f3 ⁇ 4 and R7 are as defined in any one of items 2 to 10 and R30 is as defined in any one of items 11 to 14.
  • each Q independently represents 1 to 4:
  • ⁇ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
  • phenyl or -N(Rig)-phenyl each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl;
  • thiophene carbonyl or pyrrolidinyl each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl, and
  • each R21 independently represents:
  • ⁇ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
  • phenyl optionally substituted with one or more C1-C6 alkyl, nitrile, alkyloxy, -COOR16, and/or C2-C12 alkylcarboxyl,
  • L represents a hydrogen atom or C1-C6 alkyl
  • R16 and Ri7 independently represent:
  • ⁇ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
  • phenyl or benzoyl each of which optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl group, and
  • Rig and R20 independently represent hydrogen, C1-C12 alkyl; C1-C12 haloalkyl; C4-C8 cycloalkenyl; or C2-C12 alkynyl,
  • the compound of item 38 being of formula:
  • each of Qn, Q12 and Q13 independently represent:
  • ⁇ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
  • phenyl or -N(Rig)-phenyl each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl;
  • thiophene carbonyl or pyrrolidinyl each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl,
  • each R22 independently represents:
  • ⁇ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
  • R16, R17, R19, R20, R21, and L are as defined in item 38,
  • R18 is hydrogen or C1-C12 alkyl optionally substituted with one or more -O-L and/or -S-L, and wherein L, R16 and R17 are as defined in item 38.
  • ⁇ all R21 when present, represent hydrogen or C1-C12 alkyl.
  • ⁇ all R21 when present, represents hydrogen or C1-C12 alkyl
  • f1 ⁇ 2 is hydrogen or benzoyl substituted with C1-C6 alkyl
  • R17 represents hydrogen
  • R18 represents C1-C12 alkyl
  • each of Qn, Q12, and Q13, when present, represents hydrogen
  • ⁇ all R21 when present, represent C1-C12 alkyl
  • ⁇ -LK- represents 2-phenylene or 4-phenylene.
  • the compound of item 46 or 47, wherein the photopolymenzable composition is a black matrix resin composition.
  • the compound of item 46 or 47, wherein the photopolymenzable composition is a photosetting or photocuring ink.
  • a photopolymenzable composition comprising a compound according to any one of items 1 to 45.
  • the photopolymenzable composition of item 53 being a lithographic printing plate composition.
  • the photopolymenzable composition of item 53 being a color filter resist composition.
  • the photopolymenzable composition of item 53 being a black matrix resin composition.
  • the photopolymenzable composition of item 53 being a photosetting or photocuring ink.
  • the photopolymenzable composition of item 53 being an oxygen scavenging film composition.
  • FORMULA I includes:
  • FORMULA II includes: (1 H-indene),
  • FORMULA I is fused with one or two FORMULA II.
  • FORMULA I being fused with FORMULA II means that one ring of FORMULA I will share a bond with one ring of FORMULA II so as to form a phenyl / 5-membered ring / phenyl structure as, for example, in the following compound:
  • FORMULA I fused with FORMULA II includes:
  • a second FORMULA II When a second FORMULA II is present, it may be the same or different from the first FORMULA II. Also, it may be fused with either phenyl group of FORMULA I or with the phenyl group of the first FORMULA II. For example, for the last FORMULA l-FORMULA II structure shown in the previous paragraph, the second
  • FORMULA II can be fused at the following location: (i.e. again all the bonds between carbon atoms that bear at least one hydrogen atom each).
  • the second FORMULA II is fused so as to form a phenyl / 5-membered ring / phenyl structure. Therefore, for each of the FORMULA l-FORMULA II structures shown in the previous paragraph, there are 14 different ways of fusing a second FORMULA II. These 14 ways are shown below for the last FORMULA I- FORMULA II structure of the previous paragraph only; the skilled person will understand from this example how to fuse a second FORMULA II on any of the above FORMULA l-FORMULA II structure. These 14 ways are:
  • truexene refers to a compound of formula: or with all the hydrogen atoms shown:
  • Truxene, truxenone, and triazatruxene bear CAS numbers 548-35-6, 4430-15-3 and 109005-10-9, respectively.
  • FORMULA I and FORMULA II are “optionally substituted”. This means that one or more hydrogen atoms of FORMULA I and/or FORMULA II (including the hydrogen atoms in the A, B and E groups) can be replaced by substituents. The nature of these substituents is not crucial to the invention as long as they do not prevent the compound of the invention to act as a photoinitiator.
  • FORMULA I and FORMULA II are optionally substituted by one or more:
  • phenyl optionally substituted with one or more C1-C6 alkyl, halogen atom, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl; and/or
  • L is a hydrogen atom or C1-C6 alkyl
  • each of Re, Rg and R10 is independently an hydrogen atom, C1-C12 alkyl; C4-C10 cycloalkyl; C1-C12 alkenyl; C4-C10 cycloalkenyl; C2-C12 alkynyl; C4-C10 cycloalkynyl; C1-C12 haloalkyl; or optionally substituted aryl, such as unsubstituted or substituted phenyl and naphthyl.
  • the optionally substituted aryl is substituted with alkyl or alkyloxy.
  • one or more of these substituents are located on the phenyl rings of FORMULA I and FORMULA II that are not involved in a fusion between FORMULA I and FORMULA II.
  • FORMULA I and FORMULA II For enyl rings circled in the following formula: There may be from zero to four substituents on such a phenyl ring.
  • one or more of these substituents are located on the carbon and nitrogen atoms of the A, B and E groups. Therefore, one or both of the hydrogen atoms of -CH2- in A, B and E can independently be replaced by such a substituent. Similarly, the hydrogen atom of -NH- in A, B and E can be replaced by such a substituent.
  • one or more of the above substituents are located on the phenyl rings that are involved in a fusion between FORMULA I and FORMULA II (this would be the phenyl ring that is not circled in the above example). There may be from zero to two substituents on such a phenyl ring.
  • the compounds of the invention have attached thereto, directly or indirectly, at least one oxime ester and/or acyl group.
  • "having attached thereto” means that one or two hydrogen atoms on a carbon or nitrogen atom of the compound (including the hydrogen atoms in the A, B and E groups) are replaced by an oxime ester or acyl group.
  • the oxime ester groups and the acyl groups can be directly or indirectly attached.
  • directly or indirectly attached means that there can be a linker (-LK-) between the group and FORMULA I or FORMULA II. When such a linker is present, the group is said to be indirectly attached, otherwise it is directly attached.
  • -LK- is optionally substituted alkylene, cycloalkylene, alkenylene, cycloalkenylene, alkynylene, cycloalkynylene, arylene, -S-arylene, -NH-arylene, or -N(aryl)-arylene, each of which optionally comprising one or more oxygen atom, sulfur atom, nitrogen atom, carbonyl group, carbamate group, carbamide group, and/or ester group.
  • the nature of the substituents of these radicals is not crucial to the invention as long as they do not prevent the compound of the invention to act as a photoinitiator.
  • These substituents may replace any hydrogen atoms of these groups, including the hydrogen atom attached to the nitrogen atom in -NH-arylene. In embodiments, these substituents are one or more:
  • o phenyl optionally substituted with one or more: Ci alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
  • aryl such as phenyl, biphenyl and naphthyl, or aryloyl, such as benzoyl, each of which being optionally substituted with one or more:
  • linker -LK- serves to attach an acyl group
  • -LK- is arylene, such as phenylene.
  • R6 represents:
  • C4-C10 cycloalkyl C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, or C4-C10 cycloalkenyl, each of which being optionally substituted by alkyl and/or -O-L; or ⁇ phenyl optionally substituted with one or more:
  • L, f3 ⁇ 4, Rg and R10 are as defined above.
  • R6 is alkyl optionally substituted with - ⁇ -Ci-Ce alkyl. In more specific embodiments R6 is methyl or butyl. In embodiments, R6 is methyl.
  • the R7 group is related to the production of free radicals. Therefore, it should not comprise oxygen, nitrogen or sulfur atoms as such atoms could quench the free radicals. Also, smaller R7 groups, although not essential, are preferred as they have higher rates of diffusion and therefore lead to faster polymerization.
  • R7 is alkyl, cycloalkyl, alkenyl, or cycloalkenyl, each of which being optionally substituted with aryl or halogen, or R7 is aryl optionally substituted with alkyl or halogen.
  • R7 represents C1-C12 alkyl optionally substituted with phenyl; C4-C10 cycloalkyl; or phenyl optionally substituted with C1-C6 alkyl.
  • R7 is C1-C12 alkyl; C4-C10 cycloalkyl; or phenyl.
  • R7 is methyl.
  • the oxime ester group can be attached to FORMULA I or FORMULA II.
  • the oxime ester group can be attached directly to the atom that was bearing the hydrogen atom, or it may be attached to a linker (-LK-) that is itself attached to the that atom (i.e. it can be indirectly attached).
  • the atom of this linker that is bonding with the first carbon atom of the oxime ester group as defined above should optimally be a carbon atom. Otherwise, the nature of the linker is not crucial to the invention.
  • R30 is a substituent.
  • the nature of R30 is not crucial to the invention as long as it does not prevent the compound of the invention to act as a photoinitiator.
  • f3 ⁇ 4o is optionally substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, or aryl, each of which optionally comprising one or more oxygen atom, sulfur atom, nitrogen atom, carbonyl group, carbamate group, carbamide group, and/or ester group.
  • these substituents are one or more:
  • o phenyl optionally substituted with one or more: Ci alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
  • aryl such as phenyl, thiophenyl, biphenyl and naphthyl, each of which being optionally substituted with one or more:
  • L, f3 ⁇ 4, Rg and R10 are as defined above.
  • R30 is linear alkyl, phenyl or thiophenyl, all of which being optionally substituted with a linear alkyl or with -O-L.
  • R30 is methyl, 2-methylphenyl, phenyl, thiophenyl, or 4-methoxyphenyl.
  • At least one oxime ester and/or acyl group means that several hydrogen atoms in FORMULA I and/or FORMULA II can be replaced by several oxime ester groups, several acyl groups, or a combination of oxime ester and acyl groups (each being either directly or indirectly attached).
  • the FORMULA I and/or FORMULA II have attached thereto more than one oxime ester and/or acyl group, some of these groups can be directly attached, while others are indirectly attached.
  • various indirectly attached groups do not need to be attached using identical linkers (-LK-).
  • a compound of the invention has attached thereto, directly or indirectly, one, two, or three oxime ester groups or one, two, or three acyl groups. In embodiments, a compound of the invention has attached thereto, directly or indirectly, two or more oxime ester groups or two or more acyl groups. In embodiments, a compound of the invention has attached thereto, directly or indirectly, three oxime ester groups or three acyl groups.
  • the oxime ester and acyl groups are located on the phenyl rings of FORMULA I and FORMULA II that are not involved in a fusion between FORMULA I and FORMULA II.
  • FORMULA I and FORMULA II For enyl rings circled in the following formula:
  • one or more oxime ester or acyl groups are located on the phenyl rings that are involved in a fusion between FORMULA I and FORMULA II (this would be the phenyl ring that is not circled in the above example).
  • oxime ester and/or acyl groups may be located on the carbon and nitrogen atoms of the A, B and E groups. Therefore, one or both of the hydrogen atoms of -CH2- in A, B and E can independently be replaced by such a group. Also, the hydrogen atom of -NH- in A, B and E can be replaced by an oxime ester or acyl group.
  • FORMULA 1 is optionally substituted
  • FORMULA 1 is optionally substituted and FORMULA II is optionally substituted
  • FORMULA 1 is optionally substituted and FORMULA II is optionally substituted
  • FORMULA 1 is optionally substituted and FORMULA II is optionally substituted [0059] In embodiments FORMULA 1 is optionally substituted and FORMULA II is optionally substituted
  • the compound comprises optionally substituted as
  • the compound com rises optionally substituted as
  • FORMULA I optionally substituted first FORMULA II and optionally substituted as a second FO RM U LA I
  • the compound is :
  • phenyl optionally substituted with one or more: Ci alkyi, halogen atom, nitrile, alkyloxy, COOR10, and/or C2 to C1 ⁇ 2 alkylcarboxyl;
  • each of X, represent Ri , or wherein:
  • Ri, R2, and Ra each independently represent:
  • phenyl optionally substituted with one or more Ci alkyl, halogen, nitrile, alkyloxy, -COOR10, and/or C2-C12 alkylcarboxyl;
  • o Q4 represents an oxime ester of formula: .wherein R7 is as defined above, and
  • o -Ar- is a linker -LK- as define above and in more specific embodiments, an optionally substituted arylene as defined above with respect to -LK-,
  • -Ar- i.e. a linker -LK-
  • arylene as defined above with respect to -LK-.
  • each -Ar-Ch independently represents
  • ⁇ C1-C12 alkyl optional and independently represent one or more:
  • o phenyl optionally substituted with one or more: Ci alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
  • L, f3 ⁇ 4, Rg and R10 are as defined above.
  • the Q3 group(s) may be attached at positions of the Ar group different from that shown above.
  • the compound is:
  • R4 and R5 are optional and independently represent one C1-C12 alkyl or C1-C12 alkyloxy,
  • Ri, R2, and Ra each independently represent a hydrogen atom or Ci-Ci2 alkyl
  • Q3 represents a hydrogen atom, an acyl group, or an oxime ester group of formula:
  • Q represents acyl or an oxime ester of formula:
  • ⁇ R6 and R7 independently represents alkyl
  • the compound comprise at least one acyl or oxime ester group.
  • the compound comprises at least oxime ester group, but no acyl group.
  • the compound is:
  • the various rings in the compound of the invention will be referred as follows: the central phenyl ring (i.e. the phenyl ring comprising carbon atoms no. 1-2, 6-7, and 1 1 -12), the three intermediate five-membered rings (i.e. the five-membered rings made of carbon atoms no. 2-6, carbon atoms no. 7-1 1 , and carbon atoms no. 1 , and 12-15, respectively), and the three outer phenyl rings (i.e. the phenyl rings made of carbon atoms no. 3-4 and 16-19, of carbon atoms no. 8-9 and 20-23, and of carbon atoms no. 13-14 and 24-27, respectively).
  • the central phenyl ring i.e. the phenyl ring comprising carbon atoms no. 1-2, 6-7, and 1 1 -12
  • the three intermediate five-membered rings i.e. the five-membered rings made of carbon atoms no. 2-6,
  • the truxene, triazatruxene, truxenone or derivative thereof has attached thereto, directly or indirectly, one, two, three, four, five or six oxime ester groups or one, two, three, four, five or six acyl groups.
  • they comprise one, two, three, four, five oxime ester groups or more and/or six, five, four, three, two oxime ester groups or less.
  • they comprise one, two, three, four, five acyl groups or more and/or six, five, four, three, two acyl groups or less.
  • some or all of the oxime ester or acyl groups are directly or indirectly attached to the outer phenyl rings of the truxene, truxenone, triazatruxene or derivative thereof.
  • some or all of the oxime ester or acyl groups are directly or indirectly attached to carbon atoms no. 16-19, 20-23, and 24-27.
  • some or all of the oxime ester or acyl groups are directly or indirectly attached to the intermediate five-membered rings of the truxene, triazatruxene or derivative thereof.
  • some or all of the oxime ester or acyl groups are directly or indirectly attached to carbon or nitrogen atoms no. 5, 10, and 15.
  • the compound is of formula:
  • each Q independently represents 1 to 4:
  • ⁇ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
  • phenyl or -N(Rig)-phenyl each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl;
  • thiophene carbonyl or pyrrolidinyl each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl, and
  • each R21 independently represents: ⁇ hydrogen
  • ⁇ C1-C12 alkyl optionally substituted with one or more phenyl, -NR19R20, -O-L and/or -S-L;
  • phenyl optionally substituted with one or more C1-C6 alkyl, nitrile, alkyloxy, -COOR16, and/or C2-C12 alkylcarboxyl,
  • ⁇ R16 and Ri7 independently represent:
  • o C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
  • phenyl or benzoyl each of which optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl group,
  • ⁇ Rig and R20 independently represent hydrogen, C1-C12 alkyl; C1-C12 haloalkyl; C4-C8 cycloalkenyl; or C2-C12 alkynyl,
  • each Q independently represent 1 to 4 [list of substituents] means that each Q may represent 1 , 2, 3 or 4 substituents, each independently selected from the list. Also, it means that the substituents for each Q are selected independently from those selected for the other Q groups.
  • each Q represents one substituent
  • these substituents are attached to carbon atoms no. 17 or 18, carbon atoms no. 21 or 22, and carbon atoms no. 25 or 26, respectively.
  • the compound is of formula:
  • ⁇ -LK-(Ei) 2 ⁇ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
  • phenyl or -N(Rig)-phenyl each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl;
  • thiophene carbonyl or pyrrolidinyl each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl,
  • each R22 independently represents:
  • ⁇ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
  • phenyl or -N(Rig)-phenyl each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl; or
  • -LK-E1 represents:
  • f1 ⁇ 2 and f1 ⁇ 2 are as defined above and wherein f1 ⁇ 2 is hydrogen or C1-C12 alkyl optionally substituted with one or more -O-L and/or -S-L, L being as defined above.
  • the Ei group(s) may be attached at other positions of the linkers shown above.
  • the compound comprises one or more oxime ester group, but no acyl groups.
  • the compound comprises one or more, acyl groups, but not oxime ester group.
  • ⁇ all R21 when present, represent hydrogen or C1-C12 alkyl.
  • ⁇ all R when present, represents hydrogen or C1-C12 alkyl
  • R16 is hydrogen or benzoyl substituted with C1-C6 alkyl
  • R17 represents hydrogen
  • R18 represents C1-C12 alkyl
  • each of Qn, Q12, and Q13 when present, represents hydrogen
  • ⁇ all R21 when present, represent C1-C12 alkyl
  • ⁇ LK represents 2-phenylene or 4-phenylene.
  • the com ound is of formula: - ,CH 3
  • the compounds of the invention are useful as photoinitiators. They absorb UV light and then emit free radicals. As such, they are useful in photosensitive or photopolymerizable compositions. Such compositions typically comprise, in addition to the compound of the invention, a free radical polymerizable compound. Such free radical polymerizable compound will typically be an ethylenic unsaturated bond-containing polymerizable compound. These compositions also often comprise other components, which are known to the skilled person who will select them depending on the intended use of the polymerizable composition.
  • Photosensitive or photopolymerizable compositions and polymerizable compounds for use therein are well known to the skilled person.
  • Non-limiting examples of such compositions include photosetting or photocuring inks (including inks for inkjet printing (for example UV curable inkjet ink), gravure, and flexo printing), photosensitive printing plates, color filter resists, black matrix resin, lithographic printing plates, and a variety of photoresists, including dry film resists.
  • the compounds of the invention are also useful as photoinitiators in compositions for oxygen scavenging films.
  • the compounds of the invention can replace photoinitiators used in photosensitive or photopolymerizable compositions of the prior art.
  • the compounds of the invention can be used in color filter resists such as those described in Kura et al., "New Oxime Ester Photoinitiators for Color Filter Resists", Radtech Report, May/June 2004, p30-35.
  • photopolymerizable compositions in addition to the compound of the invention and a polymerizable compound, can include further known photoinitiators and other additives such as thermal inhibitors, copper compounds, wax-like substances, an oxygen-impermeable layer, light stabilizers, amines to accelerate photopolymerization, chain transfer agents, photosensitizers, cross-linking agents, co-initiators, photoreducable dyes, flow improvers, adhesion promoters, surfactants, optical brighteners, pigments, dyes, wetting agent, leveling assistants, dispersants, aggregation preventers, antioxidants, fillers, microspheres, glass fibers, binders, etc.
  • photoinitiators and other additives such as thermal inhibitors, copper compounds, wax-like substances, an oxygen-impermeable layer, light stabilizers, amines to accelerate photopolymerization, chain transfer agents, photosensitizers, cross-linking agents, co-initiators, photoreducable dye
  • the photopolymerizable compositions can be used for various purposes, for example as printing ink, e.g. screen printing inks, inkjet printing inks, inks for offset- or flexo printing, as a clear finish, as a white or colored finish, for example for wood or metal, as powder coating, as a coating material, inter alias for paper, wood, metal or plastic, as a daylight-curable coating for the marking of buildings and roadmarking, for photographic reproduction techniques, for holographic recording materials, for image recording techniques or to produce printing plates which can be developed with organic solvents or with aqueous alkalis, for producing masks for screen printing, as dental filling compositions, as adhesives, as pressure-sensitive adhesives, as laminating resins, as etch resists, solder resists, electroplating resists, or permanent resists, both liquid and dry films, as photostructurable dielectric, for printed circuit boards and electronic circuits, as resists to manufacture color filters for a variety of display applications or to generate structures
  • compositions according to the invention are further suitable for the production of medical equipment, auxiliaries or implants. Further, the compositions according to the invention are suitable for the preparation of gels with thermotropic properties, as for example described in DE 19700064 and EP 678,534.
  • the photoinitiators may additionally be employed as initiators for emulsion polymerizations, pearl polymerizations or suspension polymerizations, as polymerization initiators for fixing ordered states of liquid-crystalline monomers and oligomers, or as initiators for fixing dyes on organic materials. They can also be used for the polymerization of radiation-curable powder coatings. They further find application in negative resist compositions, suitable for the production of printing forms for relief printing, planographic printing, photogravure or of screen printing forms, for the production of relief copies, for example for the production of texts in Braille, for the production of stamps, for use in chemical milling or as a microresist in the production of integrated circuits.
  • compositions further may be used as photopatternable dielectric layer or coating, encapsulating material and isolating coating in the production of computer chips, printed boards and other electric or electronic components.
  • the possible layer supports, and the processing conditions of the coating substrates, are just as varied.
  • compositions can also be photosensitive thermosetting resin compositions that can be used to form a solder resist pattern. These can be useful as materials for the production of printed circuit boards, the precision fabrication of metallic articles, the etching of glass and stone articles, the relief of plastic articles, and the preparation of printing plates.
  • the solder resist is a substance which is used during the soldering of a given part to a printed circuit board for the purpose of preventing molten solder from adhering to irrelevant portions and protecting circuits.
  • Color filters are suitable for the production of color filters or color mosaic systems, such as described, for example, in EP 320,264.
  • Color filters usually are employed in the manufacturing of LCD's, projection systems and image sensors.
  • the color filters can be used, for example, for display and image scanner in television receivers, video monitors or computers, in flat panel display technology etc.
  • the photosensitive compositions can further be used for manufacturing spacers, which control a cell gap of the liquid crystal part in liquid crystal display panels.
  • the photosensitive compositions are also suitable for manufacturing microlens arrays used in liquid crystal display panels, image sensors and the like. These are also suitable for photo-lithographic steps used in the production process of plasma display panels (PDP), particularly for the imaging forming process of barrier rib, phosphor layer and electrodes.
  • PDP plasma display panels
  • the compositions also find application for the production of one- or more-layered materials for the image recording or image reproduction (copies, reprography), which may be mono- or polychromatic. Furthermore the materials are suitable for color proofing systems.
  • the compounds of the invention are also suitable as photoinitiators in the holographic data storage application.
  • the photoinitiators are suitable for the preparation of optical articles (for example optical waveguides) or holographic recording media e.g. comprising a polymer and an organic photoinitiator. As already mentioned above, the photoinitiators are suitable also for producing printing plates. Also of interest is the use of the novel photoinitiators for curing shaped articles made from composite compositions.
  • the compounds according to the invention can be used for the production of holographies, waveguides, optical switches wherein advantage is taken of the development of a difference in the index of refraction between irradiated and unirradiated areas.
  • the compounds of the invention can also be used in the photosensitive resin compositions described in US 2010/0210749 and in the curable compositions, photopolymerizable compositions, color filters and the like described in US 2009/0023085, for example at paras [0130]-[0342] and at paras [0407]-[0607].
  • the compounds of the invention can also be used in the photosensitive compositions described in US 7,556,910 and the photopolymerizable compositions of US 6,051 ,367.
  • an aspect of the present invention is related to the use of the compounds as photoinitiators in color filter resist compositions.
  • the color filter resist compositions may, in embodiments, comprise:
  • coating compositions for production of lithographic offset printing plates, which can be digitally imaged with laser light having emission wavelength between 350 and 410 nm.
  • coating compositions may, in embodiments, comprise:
  • This coating composition can be coated on an anodized aluminum substrate having a coating weight between 0.8 and 3.0 gram per square meter.
  • the compounds of the invention are relatively easy to make. For example, some of them are easily purified by crystallization, avoiding thus the need for flash chromatography. Also, many of them are soluble in one or more alcohols, which are relatively environmentally friendly solvents. In addition, many of them are colorless, which makes them useful in a wide range of application. Others are lightly colored and are more useful, for example, in black matrix resins and other applications where color is not an issue. Also, many compounds of the invention do not discolor upon use.
  • alkyl refers to a univalent saturated linear or branched C1-12 hydrocarbyl radical of formula -Cnh n+i .
  • alkenyl and alkynyl refer to linear or branched C1-12 unsaturated (with double and triple bond(s), respectively) univalent hydrocarbyl radicals.
  • alkylene refers to a bivalent saturated linear or branched C1-12 hydrocarbyl radical of formula -C n H2n-
  • alkenylene and alkynylene refer to linear or branched C1-12 unsaturated (with double and triple bond(s), respectively) bivalent hydrocarbyl radicals.
  • aryl and arylene refers respectively to univalent and bivalent aromatic radicals comprising between 1 and four aromatic rings.
  • the rings can be fused or attached together through a covalent bond.
  • Figure 1 shows the reaction scheme for the production of 3-acetyloxime-0-acetate-6, 12-diethyl-12- methyl-6, 12-dihydro-6-aza-indeno[1 ,2-b]fluorene;
  • Figure 2 shows the reaction scheme for the production of 7-acetyloxime-O-acetate-10-ethyl-12, 12- dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -bjfluorene;
  • Figure 3 shows the reaction scheme for the production of 9-acetyloxime-0-acetate-2-methoxy-12, 12- diethyl-6, 12-dihydro-6-thia-indeno[1 ,2-b]fluorene;
  • Figure 4 shows the reaction scheme for the production of 7-acetyloxime-0-acetate-12, 12-dimethyl- 10, 12-dihydro-10-oxo-indeno[2, 1 -bjfluorene;
  • Figure 5 shows the reaction scheme for the production of 8-acetyloxime-0-acetate-1 1 ,13,13-triethyl-6,6- dimethyl-1 1 , 13-dihydro-6H-1 1-aza-indeno[2, 1 -b]anthracene;
  • Figure 6 shows the reaction scheme for the production of 10-(4-acetyloxime-O-acetate phenyl)-7- acetyloxime-0-acetate-2-methoxy-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -bjfluorene;
  • Figure 7 shows the reaction scheme for the production of 10-(4-acetyloxime-O-acetate phenyl)-2,7- diacetyloxime-O-acetate-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -bjfluorene;
  • Figure 8 shows the reaction scheme for the production of 3,9-diacetyloxime-0-acetate-6-hexyl-6H-12- thia-6-aza-indeno[1 ,2-b]fluorene;
  • Figure 9 the reaction scheme for the production of 10-hexyl-10H-10-aza-indeno[2, 1 -b]fluoren-12-O- acetyloxime
  • Figure 10 the reaction scheme for the production of 7,7'-acetyloxime-0-acetate-1 , 1 '-dimethyl- bisindeno[3,2-b:2',3'-h]-9-sec-butyl carbazole;
  • Figure 11 shows the reaction scheme for the production of 4,9,13-triethoxyacetyloxime-O- triacetatetruxenone
  • Figure 12 shows the UV-Vis spectrum of 3,8, 13-triacetyl-5, 10, 15-trihexyl-10, 15-dihydro-5H-5, 10, 15- triazadiindeno[1 ,2-a; 1 ',2'-c]fluorene trioxime tri-O-acetate;
  • Figure 13 shows the UV-Vis spectra of Carba-05, Truxe-08, Truxe-07 and Truxe-12;
  • Figure 14 shows the relative UV-Vis absorbance of Truxe-04 (INDENO 332), Truxe-13 (INDENO 336), Truxe-14 (INDENO 332B), Truxe-15 (INDENO 338) and Truxe-16 (INDENO 333);
  • Figure 15 shows the oxygen consumption of an oxygen scavenging film comprising INDENO 332 as a function of time
  • Figure 16 shows the oxygen consumption of an oxygen scavenging film comprising INDENO 336 of as a function of time.
  • BG4 Basic green 4
  • BYK 307 Polyethylene glycol modified polysiloxane surfactant, available from BYK Chemie, USA
  • TRUXE-6H 5,5 ' , 10, 10 ' , 15, 15 ' -Hexahexyltruxene (98 %), available from American Dye Source, Inc., Canada.
  • TRUXA-3H 5, 10, 15-Trihexyl-10, 15-dihydro-5H-5, 10, 15-triazadiindeno[1 ,2-a; 1 ',2'-c]fluorene (98 %), available from American Dye Source, Inc., Canada.
  • TRUXE-3Br 2, 7, 12-Tribromo-5, 5, 10, 10, 15, 15-hexahexyltruxene, available from American Dye Source, Inc., Canada.
  • TRUXE-3F 4,9,14-Trifluoro truxenone (98 %), available from American Dye Source, Inc., Canada
  • TRUX-2Br 2,2-Dibromo-5-fluoroindan-1 -one (97 %), available from American Dye Source, Inc., Canada
  • Silane -Methacryloxypropyl triethoxysilane, available from Sigma Aldrich, Canada
  • UR07-015 Reactive oligomer, available from American Dye Source, Inc., Canada and having the following formula:
  • Irgacure OXE-02 Photoinitiator available from BASF, Germany and having the following formula:
  • UR07-009 Reactive oligomer (60 % in 1 ,3-dioxolane solution), available from American Dye Source, I
  • COBALT Cobalt (II) oleate salt, available from Sigma Aldrich, Ontario, Canada.
  • ADD-9995 Propoxylated neopentyl glycol diacrylate, available from Sartomer, USA.
  • ADD-2614 3-Methacryloxypropyltrimethoxysilane, available from Polysciences, USA.
  • POL-0138 Aliphatic Polyester Urethane Acrylate, available from Mylan Group, Travinh, Vietnam.
  • POL-1001 Aromatic monoacrylate oligomer, available from Mylan Group, Travinh, Vietnam.
  • POL-0137 Stabilizer for radically curable inks, available from Mylan Group, Travinh, Vietnam.
  • 600-B307 Silicone surface additive, available from Mylan Group, Travinh, Vietnam.
  • ADD-9993 Trimethylcyclohexane acrylate, available from Sigma Aldrich, Ontario, Canada.
  • Yellow-150 Pigment yellow dispersion comprising 7.5 g of CI Pigment Yellow 150 (available from Hangzhou Multicolor Chemical Company, China), 2.5 g of AC07-001 and 40 g of cyclohexanone. The mixture was dispersed for 24 hours using a ball mill. It was filtered with a 5 ⁇ pore filter and cyclohexanone was added to give 15% solid weight.
  • Red-254 Pigment red dispersion comprising 7.5 g of CI Pigment Red 254 (Hostapern Red D2G 70 LV 2647, available from Clarian, Germany), 2.5 g of AC07-001 and 40 g of cyclohexanone. The mixture was dispersed for 24 hours by using a ball mill. It was filtered with a 5 ⁇ pore filter and cyclohexanone was added to give 15% solid weight.
  • Green-36 Pigment green dispersion comprising 7.5 g of CI Pigment Green 36 (Heliogen Green K9360, available from BASF, Germany), 2.5 g of AC07-001 and 40 g cyclohexanone. The mixture was dispersed for 24 hours by using a ball mill. It was filtered with a 5 ⁇ pore filter and cyclohexanone was added to give 15% solid weight.
  • Blue-15 Pigment blue dispersion comprising 7.5 g of CI Pigment Blue 15:6 (Hangzhou Multicolor Chemical Company, China), 2.5 g of AC07-001 , and 40 g of cyclohexanone. The mixture was dispersed for 24 hours by using a ball mill. It was filtered with a 5 ⁇ pore filter and cyclohexanone was added to give 15% solid weight.
  • Black-250 Carbon black dispersion comprising 7.5 g of carbon black (Special Black 250, available from Degussa, USA), 7.5 g of AC07-001 and 40 g of cyclohexanone. The mixture was dispersed for 24 hours by using a ball mill. It was filtered with a 5 ⁇ pore filter and cyclohexanone was added to give 15% solid weight.
  • Resist vehicle A resist vehicle was prepared by dissolving 6.0 g of BR07-001, 6.0 g of UR07-015, 1.0 g of Silane in 102 g of cyclohexanone.
  • Triethylamine (1.7 mL, 12.2 mmol) was slowly added into 100 mL of a tetrahydrofuran solution containing 7-acetyloxime-10-ethyl-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -b]fluorene (3.54 g, 10.0 mmol) and acetyl chloride (915 L, 12.8 mmol) at 0°C under nitrogen atmosphere. After 3 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate.
  • Triethylamine (1.7 mL, 12.2 mmol ) was slowly added into 100 mL of a tetrahydrofuran solution containing 9-acetyloxime-2-methoxy-12, 12-diethyl-6,12-dihydro-6-thia-indeno[1 ,2-b]fluorene (3.87 g, 10.0 mmol) and acetyl chloride (915 ⁇ _, 12.8 mmol) at 0°C under nitrogen atmosphere. After 3 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate.
  • Triethylamine (1.7 mL, 12.2 mmol) was slowly added into a tetrahydrofuran solution (100 mL) containing 7-butyryloxime-12, 12-dimethyl-10, 12-dihydro-10-oxo-indeno[1 ,2-b]fluorene (3.41 g, 10.0 mmol) and acetyl chloride (915 ⁇ , 12.8 mmol) at 0°C under nitrogen atmosphere. After 3 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate.
  • Example 1.5 8-Acetyloxime-O-acetate-H, 13, 13-triethyl-6, 6-dimethyl-H, 13-dihydro-6H-11-aza-indeno[2, 1- bjanthracene
  • Triethylamine (1.7 mL, 12.2 mmol ) was slowly added into 100 mL of a tetrahydrofuran solution containing 8-acetyloxime-11 , 13, 13-triethyl -6, 6-d i methyl- 1 1 , 13-dihydro-6H-1 1 -aza-indeno[1 ,2-b]anthracene (3.97 g, 10.0 mmol) and acetyl chloride (915 ⁇ , 12.8 mmol) at 0°C under nitrogen atmosphere. After 3 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate.
  • Example 1.6 10-(4-acetyloxime-O-acetate phenyl)-7-acetyloxime-0-acetate-2-methoxy-12,12-dihexyl- 10, 12-dihydro-10-aza-indeno[2, 1-b]fluorene
  • the synthesis of 10-(4-acetyloxime-O-acetate phenyl)-7-acetyloxime-0-acetate-2-methoxy-12, 12- dihexyl-10, 12-dihydro-10-aza-indeno[2,1 -b]fluorene was performed according to the scheme shown in Figure 6.
  • Triethylamine (4.18 mL, 30.0 mmol) was slowly added into 100 mL of tetrahydrofuran solution containing 10-(4-acetyloxime phenyl)-7-acetyloxime-2-methoxy-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -bjfluorene (4.88 g, 10.0 mmol) and acetyl chloride (2.13 mL, 30.0 mmol) at 0°C under nitrogen atmosphere. After 5 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate.
  • Triethylamine (8.36 mL, 60.0 mmol ) was slowly added into 100 mL of a tetrahydrofuran solution containing 10-(4-acetyloxime phenyl)-2,7-diacetyloxime-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 - bjfluorene (5.31 g, 10.0 mmol) and acetyl chloride (4.27 mL, 60.0 mmol) at 0°C under nitrogen atmosphere. After 3 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate.
  • Triethylamine (5.78 mL, 40.0 mmol) was slowly added into 100 mL of a tetrahydrofuran solution containing 3,9-diacetyloxime-6-hexyl-6H-12-thia-6-aza-indeno[1 ,2-b]fluorene (4.01 g, 10.0 mmol) and acetyl chloride (3.45 mL, 40.0 mmol) at 0°C under nitrogen atmosphere. After 3 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate.
  • Triethylamine (3.40 mL, 24.4 mmol) was slowly added into 80 mL of a tetrahydrofuran solution containing 10-hexyl-10H-10-aza-indeno[2, 1-b]fluoren-12-oxime (2.98 g, 10.0 mmol) and acetyl chloride (1.83 mL, 25.6 mmol) at 0°C under nitrogen atmosphere. After 3 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate.
  • Triethylamine (4.18 mL, 30.0 mmol) was slowly added into 100 mL of a tetrahydrofuran solution containing 7,7'-acetyloxime-1 , 1'-dimethyl-bisindeno[3,2-b:2',3'-h]-9-sec-butyl carbazole (5.70 g, 10.0 mmol) and acetyl chloride (2.13 mL, 30.0 mmol) at 0°C under nitrogen atmosphere. After 5 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate.
  • Examples 1.11 and fallowings [00171] The syntheses of the photoinitiators of Examples 1.11 and following were performed in a flame dried glass wares, which were equipped with mechanical stirrer, water condenser, heating mental, nitrogen gas inlet and temperature controller. The obtained products and intermediates were characterized by FTIR spectrophotometer (Perkin Elmer, Model Spectrum 100), NMR (Nicolet 500 MHz), UV-Vis Spectrophotometer (Perkin Elmer, Model Lambda 25), DSC (TA Instruments, Model Q2000), TGA (TA Instrument, Model Q500), and HPLC (Waters, Model Breeze 2).
  • FTIR spectrophotometer Perkin Elmer, Model Spectrum 100
  • NMR Nicolaset 500 MHz
  • UV-Vis Spectrophotometer Perkin Elmer, Model Lambda 25
  • DSC TA Instruments, Model Q2000
  • TGA TA Instrument, Model Q500
  • HPLC Waters, Model Breeze 2
  • reaction was monitored by TLC using ethyl acetate (20 %) and hexane (80 %) as eluent. After the reaction was completed, the product was precipitated in cold water (200 mL). A beige solid product was obtained by vacuum filtration, copiously washed with water and dried under vacuum at 30°C until constant weight (790 mg, 93% yield).
  • Acetyl chloride (167 ⁇ , 2.34 mmol) was slowly added into a tetrahydrofuran solution (500 mL) containing 3,8, 13-triacetyl-5, 10, 15-trihexyl-10, 15-dihydro-5H-5, 10, 15-triazadiindeno[1 ,2-a; 1 ',2'-c]fluorene trioxime (500 mg, 0.65 mmol) and triethylamine (312 ⁇ , 2.24 mmol). The reaction mixture was stirred overnight. Then solvent was evaporated under reduced pressure to give a dark brown oil.
  • Example 1.14 3,8, 13-trihexanoyl-5, 10, 15-trihexyl-10, 15-dihydro-5H-5, 10, 15-triazadiindeno[1,2-a;1',2'-c] fluorene tiioxime tri-O-acetate
  • UV-Vis spectrum of 3,8, 13-Triacetyl-5, 10, 15-trihexyl-10, 15-dihydro-5H-5, 10, 15- triazadiindeno[1 ,2-a; 1 ',2'-c]fluorene trioxime tri-O-acetate is shown in Figure 12.
  • This spectrum shows strong absorption bands between 300 and 400 nm. More particularly, the spectrum shows a strong absorption at 365 nm followed by a sharp decline. This enhances sensitivity, while avoiding color interference.
  • the reaction was stirred 2h at 0°C and monitored on TLC using 5% ethyl acetate in toluene as eluent.
  • the reaction mixture was extracted in ethyl acetate and water, dried over magnesium sulphate and the solvent evaporated under reduced pressure.
  • methanol 500mL was added to the crude product and the solution was heated and filtered.
  • the crude product was dissolved in 2-propanol, the solution was heated, and left at -20°C for 1 h then filtered to afford 2g (60%) of a white powder.
  • UV-Vis (THF) 338 nm.
  • DSC 124°C.
  • FIG. 13 shows the UV spectra of Carba-05 (which is Irgacure OXE-02 from BASF), aHd-Truxe-08 T and Truxe-07 (from above), [My T: Which Examples above are Truxe -08 and -07?1 and Truxe-12 (from Example 1.15).
  • the spectra have been normalized so that the maximum absorption of Carba-05 is 1.
  • Carba-05 is the curve with a maximum absorption at 277 nm and a relative absorption at 365 nm or 0.161.
  • Truxe-08 has two absorption peaks at 304 and 333 nm with a relative absorption at 365 nm of 0.754.
  • Truxe-07 has one absorption peak at 325 nm and a relative absorption at 365 nm of 0.043. Finally, Truxe-12 has an absorption peak at 338 nm and a relative absorption at 365 nm of 0.666. It should be noted that Truxe-12 has a higher absorption than OXE-02.
  • the maximum absorption peak and absorption coefficient of 2,7,12-triacetyl-5,5', 10, 10', 15, 15'- hexahexyltruxene in tetrahydrofuran solution are 332 nm and 8.66 x 104 L / mol .cm, respectively.
  • the melting point was measured to be 217 °C by DSC.
  • TRUXE-03 [MY T: What is Truxo 03? Do you moan TRUXE 3H, TRUXE 3Br or TRUXE 3F?] (8.5g), 4-acetylphenylboronic acid (4.2g) and toluene (500mL) were introduced in a 500mL flask, flushed with nitrogen. Potassium carbonate (28g) dissolved in water (l OOmL) was added to this mixture. The reaction mixture was bubbled with nitrogen for 30min. Then, palladium acetate (52mg) and triphenylphosphine (62mg) were added to the solution.
  • the reaction mixture was heated at reflux for 2 days before adding 4-acetylphenylboronic acid (4.2g). The reaction was once again refluxed for 2 days before the final addition of 4-acetylphenylboronic acid (4.2g). The reaction was then refluxed for 4 days. The reaction was monitored using 100% toluene as eluent. The reaction mixture was washed three times with water, dried over magnesium sulphate and concentrated under reduced pressure. The mixture was quickly passed over a silica gel pad using 100% toluene as eluent to afford 7g (75%) of the desired product.
  • the maximum absorption peak and absorption coefficient of 2C in tetrahydrofuran solution are 340 nm and 12.64 x 10 4 L moMcrrr 1 , respectively.
  • the melting point is 85°C.
  • aluminium chloride 130 mg, 0.76 eq
  • o-toluloyl chloride 160 mg, 0.80 eq
  • aluminium chloride 130 mg, 0.76 eq
  • o-toluloyl chloride 160 mg, 0.80 eq
  • the reaction was stirred at room temperature overnight.
  • the reaction was quenched by the careful and slow addition of water.
  • An extraction was performed using CH2CI2 and water.
  • the mixture was then dried over MgS04.
  • the crude product was purified on a silica gel column using 50% hexanes in toluene to 100% toluene.
  • the resulting thick oil was triturated in methanol and filtered to afford a light yellow powder (720 mg, 46%).
  • the maximum absorption peak and absorption coefficient of 2, 7, 12-tri-(o-toluloyl)-5,5', 10, 10', 15, 15'- hexahexyltruxene in tetrahydrofuran solution are 336 nm and 7.90 x 10 4 L mo crrr 1 , respectively.
  • the melting point is 125°C.
  • aluminium chloride 825 mg, 0.76 eq
  • benzoyl chloride 650 mg, 0.80 eq
  • An extraction was performed using CH2CI2 and water.
  • the organic layer was washed with a 1 M solution of NaHC03 and then dried over MgS04.
  • the solution was concentrated under reduced pressure.
  • the resulting tarry solid was triturated in methanol for 1 h and filtered. After filtration, the crude product was recrystalized from 2-propanol to afford 3.3g (48%, 100% : 6.84g). Further purification, when desired, was achieved on a silica gel column using 50% hexanes in toluene to 100% toluene (started with 500 mg, recovered 60 mg, 12%).
  • the maximum absorption peak and absorption coefficient of 2, 7, 12-tri-(phenoyl)- 5,5', 10, 10', 15, 15 -hexahexyltruxene in tetrahydrofuran solution are 332 nm and 8.55 x 10 4 L mo crrr 1 , respectively.
  • the melting point is 155°C.
  • aluminium chloride 825 mg, 0.76 eq
  • 2-thiophenecarbonyl chloride 700 mg, 0.80 eq
  • An extraction was performed using CH2CI2 and water.
  • the organic layer was washed with a 1 M solution of NaHC03 and then dried over MgSC .
  • the solution was concentrated under reduced pressure.
  • the resulting tarry solid was triturated in methanol for 1 h and filtered.
  • the maximum absorption peak and absorption coefficient of 2,7, 12-tri-(2-thienyloyl)- 5,5', 10, 10', 15, 15'-hexahexyltruxene in tetrahydrofuran solution are 338 nm and 8.53 x 10 4 L mo crrr 1 , respectively.
  • the melting point is 125°C.
  • aluminium chloride 825 mg, 0.76 eq
  • 3-methoxybenzyol chloride 800 mg, 0.80 eq
  • An extraction was performed using CH2CI2 and water.
  • the organic layer was washed with a 1 M solution of NaHC03 then dried over MgSC .
  • the solution was concentrated under reduced pressure.
  • the resulting tarry solid was triturated in methanol for 1 h and filtered. After filtration, the crude product was recrystalized from 2-propanol to afford 700 mg (9%, 100% : 7.37 g). Further purification, when desired, was achieved on a silica gel column using 100% toluene to 10% ethyl acetate in toluene (recovered 30 mg).
  • reaction mixture was washed with water three times, dried over magnesium sulphate and concentrated under reduced pressure.
  • the mixture was quickly passed over a silica gel using 100% toluene, then 1 to 3% acetone in toluene as eluent to afford 500mg (27%) of the desired product.
  • the maximum absorption peak and absorption coefficient of 2, 7, 12-tri-(2-acetylphenyl)- 5,5', 70, 70', 75, 75'-hexahexyltruxene in tetrahydrofuran solution are 323 nm and 9.20 x 10 4 L moMcrrr 1 , respectively.
  • the melting point is 136°C.
  • Figure 13 shows the relative UV-Vis absorbance of the photoinitiators of Examples 1.16 and 1.18 to 1.23.
  • Red, green, and blue color filter resists and black matrix with different photoinitiators were prepared by mixing 1.0 part of photoinitiators, 13 parts of resist vehicles, 6.0 parts of the corresponding pigment dispersions, i.e., Red-254, Green-36, Blue-15 and Black-250, respectively, using a high shear mixer for 2 hours. The resulting mixtures were filtered through a 1 ⁇ pore filter. The pigmented solutions were coated on glass using a spin coater, dried at 100°C for 2 minutes to produce uniform films having a thickness around 3 ⁇ .
  • the color resist films were exposed using a 250 W super high pressure mercury lamp under air with a dose of 1 ,000 mJ/cm 2 through a 21 -gray-scale step target mask (Stouffer Graphic Arts T21 15).
  • the exposed films were developed using aqueous potassium hydroxide solution (pH 12), washed copiously with de-ionized water, and then dried at 100°C for 30 minutes. The results are summarized in the table below.
  • the value reported for the sensitivity is the minimum dose required to fully cure the color resist films. It was calculated from the transmittance of the highest step number remaining after development. It is desirable that the minimum dose (mJ/cm 2 ) required be as small as possible, which indicates a highly sensitive compound. Generally, the more sensitive the photoinitiator, the less time it takes to cure the composition.
  • Red, green, blue and black color resists were prepared by mixing the pigment dispersion, resist vehicle and the photoinitiators of Examples 1.1 1 and 1.12 using a high shear mixer for 2 hours. The resulting mixture was filtered through a 1 ⁇ pore filter. The pigmented solutions were coated on glass using spin coater, dried at 100°C for 2 minutes to produce a uniform film having a thickness around 3 ⁇ . For comparison, commercially available photoinitiator, Irgacure OXE-02 was also used.
  • the color resist films were exposed using a 250 W super high pressure mercury lamp under air with a dose of 1 ,000 mJ/cm 2 through a 21 -gray-scale step target mask (Stouffer Graphic Arts T21 15).
  • the exposed films were developed using aqueous potassium hydroxide solution (pH 12), copiously washed with de-ionized water, and then dried at 100°C for 30 minutes. The results are summarized in the table below.
  • the value reported for photosensitivity is the minimum dose required to fully cure the color resist films. It was calculated from the transmittance of the highest step number remaining after development. It is desirable that the minimum dose (mJ/cm 2 ) required be as small as possible, which indicates a highly sensitive compound. Generally, the more sensitive the photoinitiator, the less time it takes to cure the composition.
  • a coating composition was prepared by mixing 250 g of BR10-010, 67 g of UR07-009, 1.0 g of basic green 4, 33 g of Blue-15, and 5.0 g of photoinitiator from Example 1.7, and 900 g of cyclohexanone solution using a high shear mixer for 5 hours. The resulted solution was filtered through a 5 ⁇ pore filter. It was coated on an anodized aluminum substrate, which was postreated with phosphate fluoride (PF) using a wire-wound rod, then dried in a hot air oven at 100 °C for 5 minutes.
  • PF phosphate fluoride
  • the plate was exposed using a 250 W super high pressure mercury lamp under air with an energy density of 100 mJ/cm 2 through a 21-gray-scale step target mask (Stouffer Graphic Arts T2115).
  • the exposed plate was developed with aqueous solution containing 1 % soap solution using a Tung Sung 800 processor at 25°C and 20 seconds dwell time to give a high resolution image.
  • the developed plate was placed on a Heidelberg 46 press using black ink (Toyo Black) and fountain solution (UF300, available from Mylan Group, Vietnam) and produced 20,000 copies with good quality.
  • a printing plate was prepared in a manner similar to that described in Example 3.1 excepted that the photoinitiator from Example 1.10 was used to replace the photoinitiator from Example 1.7.
  • the plate was exposed using a 250 W super high pressure mercury lamp under air with an energy density of 100 mJ/cm 2 through a 21-gray-scale step target mask (Stouffer Graphic Arts T2115).
  • the exposed plate was developed with aqueous solution containing 1 % soap solution using a Tung Sung 800 processor at 25°C and 20 seconds dwell time to give high resolution image.
  • the developed plate was placed on a Heidelberg 46 press using black ink (Toyo Black) and fountain solution (UF300, available from Mylan Group, Vietnam) and produced 20,000 copies with good quality
  • a coating composition was prepared by mixing 250 g of BR10-010, 67 g of UR07-009, 1.0 g of basic green 4, 33 g of Blue-15, and 5.0 g of photoinitiators 1 E (Example 1.1 1) and 900 g of 2-methoxypropanol solution using a high shear mixer for 5 hours. The resulted solution was filtered through a 5 ⁇ pore filter. It was coated on an anodized aluminum substrate, which was postreated with phosphate fluoride (PF) using a wire-wound rod, then dried in a hot air oven at 100 °C for 5 minutes.
  • PF phosphate fluoride
  • the plate was exposed using a 250 W super high pressure mercury lamp under air with an energy density of 100 mJ/cm 2 through a 21-gray-scale step target mask (Stouffer Graphic Arts T2115).
  • the exposed plate was developed with aqueous solution containing 1 % Mr. Clean soap solution using a Tung Sung 800 processor at 25°C and 20 seconds dwell time to give high resolution image.
  • the developed plate was placed on a Heidelberg 46 press using black ink (Toyo Black) and fountain solution (UF300, available from Mylan Group, Vietnam) to produce 20,000 copies with good quality.
  • black ink Toyo Black
  • fountain solution U300, available from Mylan Group, Vietnam
  • the printing plate was prepared similar to Example 3.3 except that the photoinitiator from Example 1.12 was used instead of that of Example 1.1 1.
  • the plate was exposed using a 250 W super high pressure mercury lamp under air with an energy density of 100 mJ/cm 2 through a 21-gray-scale step target mask (Stouffer Graphic Arts T2115).
  • the exposed plate was developed with aqueous solution containing 1 % Mr. Clean soap solution using a Tung Sung 800 processor at 25°C and 20 seconds dwell time to give high resolution image.
  • the developed plate was placed on a Heidelberg 46 press using black ink (Toyo Black) and fountain solution (UF300, available from Mylan Group, Vietnam) to produce 20,000 copies with good quality.
  • black ink Toyo Black
  • fountain solution U300, available from Mylan Group, Vietnam
  • Ultra-violet radiation curable inkjet printing inks having the compositions shown in the table below were prepared by using a high shear mixer to form uniform solutions. These solutions were filtered throught a 1.0 ⁇ propylene filter. The filtered inks were printed on polyester films with different testing patterns and 300 DPI resolution using the Richol G4 print heads, which were jetted at 50 °C. The printed patterns were cured with a UV-LED curing unit (Model: 8 Watt/cm 2 Fireline, available from Phoseon Technology, Oregon, USA) at a speed of ten meter per minute. The UV-LED curing unit was placed 5 cm about the printed films. Fully cured printing patterns from inkjet inks comprising the invented photoinitiators were obtained with high resolution and good adhesion to the polyester substrate.
  • Photoinitiator of Example 1.16 5.00 0.00 0.00 0.00
  • the oxygen scavenging activity of the polymeric films comprising photoinitiators of the invention was demonstrated by monitoring the reduction in oxygen concentration as a result of consumption of oxygen by the prepared film sample.
  • 1.0 gram of film sample made from acetal copolymer comprising cyclohexane pendant groups (PACH-001), cobalt (II) oleate salt and a photoinitiator was placed in a glass bottle.
  • the glass bottle was sealed with a homemade cap containing an oxygen fluorescent probe.
  • the glass bottle was then flushed with nitrogen gas containing around 21 % of oxygen.
  • the bottle was then sealed and activated by exposure to a UV light at 254 nm at room temperature with a dosage of 100 mJ/cm 2 .
  • the reduction in oxygen concentration over time was monitored using an Oxysense's GEN III 5000 non-invasive oxygen monitoring and permeation system.

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Abstract

There are provided compounds comprising optionally substituted (FORMULA I) fused with one or two optionally substituted (FORMULA II), wherein A and E each independently represent -CH 2 -, -NH-, -O-, -S-, or -C(=O)- and B represents a bond, -CH 2 -, -NH-, -O-, -S-, or - C(=O)-, said compound having directly or indirectly attached thereto at least one acyl and/or oxime ester group. Such compounds are useful inter alias as photoinitiators.

Description

TITLE OF THE INVENTION
COMPOUNDS WITH OXIME ESTER AND/OR ACYL GROUPS
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims benefit, under 35 U.S.C. § 119(e), of U.S. provisional applications Serial No. 61/489,910 and 61/489,892, both filed on May 25, 201 1.
FIELD OF THE INVENTION
[0001] The present invention is concerned with compounds comprising at least one oxime ester and/or acyl group. More specifically, present invention is concerned with compounds based on indene fused with fluorene or 9,10-dihydroanthracene and derivatives thereof.
BACKGROUND OF THE INVENTION
[0002] Photosensitive or photopolymerizable compositions typically include, for example, an ethylenic unsaturated bond-containing polymerizable compound and a photopolymerization initiator. Such photosensitive or photopolymerizable compositions polymerize and cure when irradiated with light, and are therefore used, for example, in photosetting or photocuring inks, photosensitive printing plates, color filter resists, black matrix resins, and a variety of photoresists, including dry film resists.
[0003] In recent years, demand has arisen for photosensitive or photopolymerizable compositions sensitive to shorter wavelength (365 nm or 405 nm) light sources, and consequently the demand for photopolymerization initiators sensitive to such light sources has also increased.
[0004] Photopolymerization initiators are also called free radical photoinitiators. Upon exposure to light of a wavelength to which they are sensitive, they generate free radicals and thus initiate free radical polymerization of surrounding polymerizable compounds.
[0005] It is typically desired that such photoinitiators exhibit good sensitivity to light, especially in the UV region of the spectrum, low discoloration upon use, and good thermal stability (for storage and processing).
[0006] Some organic compounds comprising acyl and/or oxime ester groups are known as free radical photoinitiators. They have found use in color filter resists due to their absorption in the ultra-violet radiation region (between 300 and 450 nm). Irgacure OXE-01™ and OXE-02™ (available from BASF, Germany) are known photoinitiators for some applications, including color filter resists. Some triazine-based compounds are also known as useful photoinitiators.
[0007] The present description refers to a number of documents, the content of which is herein incorporated by reference in their entirety.
SUMMARY OF THE INVENTION
[0008] In accordance with the present invention, there is provided: A compound comprising optionally substituted
Figure imgf000003_0001
(FORMULA I) fused with one or
two optionally substituted
Figure imgf000003_0002
(FORMULA II), wherein A and E each independently represent
-CH2- -NH-, -0-, -S-, or -C(=0)- and B represents a bond, -CH2-, -NH-, -0-, -S-, or -C(=0)-, said compound having directly or indirectly attached thereto at least one oxime ester and/or acyl group.
The compound of item 1 , wherein the oxime ester group is -CR6=N-0-(C=0)-R7 or =N-0-(C=0)-R7, wherein R6 and R7 are the same or different substituents.
The compound of item 2, wherein R6 represents:
■ hydrogen;
■ C1-C12 alkyl optionally substituted with one or more:
o phenyl,
o halogen,
Figure imgf000003_0003
o -0-L, and/or
o -S-L;
■ C4-C10 cycloalkyi, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, or C4-C10 cycloalkenyl, each of which being optionally substituted by alkyl and/or -0-L; or
■ phenyl optionally substituted with one or more:
o Ci-C6 alkyl,
o halogen,
o nitrile,
o alkyloxy,
Figure imgf000003_0004
o C2-C12 alkylcarboxyl,
wherein L is hydrogen or C1-C6 alkyl and wherein each of Re, Rg and R10 is independently hydrogen, C1-C12 alkyl; C4-C10 cycloalkyi; C1-C12 alkenyl; C4-C10 cycloalkenyl; C2-C12 alkynyl; C4-C10 cycloalkynyl; C1-C12 haloalkyl; or optionally substituted aryl.
The compound of item 3, wherein R6 is alkyl optionally substituted with -O-C1-6 alkyl.
The compound of item 4, wherein R6 is methyl or butyl.
The compound of item 5, wherein R6 is methyl.
The compound of any one of items 2 to 6, wherein R7 represents alkyl, cycloalkyi, alkenyl, or cycloalkenyl, each of which being optionally substituted with aryl or halogen, or R7 is aryl optionally substituted with alkyl or halogen.
The compound of item 7, wherein R7 represents C1-C12 alkyl optionally substituted with phenyl; C4-C10 cycloalkyi; or phenyl optionally substituted with C1-C6 alkyl.
The compound of item 8, wherein R7 is C1-C12 alkyl; C4-C10 cycloalkyi; or phenyl.
The compound of item 9, wherein R7 is methyl.
The compound of any one of items 1 to 10, wherein the acyl group is -C(=0)-R3o, wherein R30 is optionally substituted alkyl, cycloalkyi, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, or aryl, each of which optionally comprising one or more oxygen atom, sulfur atom, nitrogen atom, carbonyl group, carbamate group, carbamide group, and/or ester group.
The compound of item 11 , wherein said alkyl, cycloalkyi, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, and aryl in R30 is substituted with one or more
■ polyethylene glycol chain,
■ C1-C12 alkyl optionally substituted with one or more:
Figure imgf000004_0001
o -O-L,
o -S-L, and/or
o phenyl optionally substituted with one or more: Ci alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
■ C4-C10 cycloalkyi, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, C4-C10 cycloalkynyl, each of which being optionally substituted by alkyl and/or -O-L, and/or
■ aryl, such as phenyl, thiophenyl, biphenyl and naphthyl, each of which being optionally substituted with one or more:
o Ci-C6 alkyl,
o halogen,
o nitrile,
o alkyloxy,
Figure imgf000004_0002
o C2-C12 alkylcarboxyl.
wherein L, Re, Rg and R10 are as defined in item 3.
The compound of item 12, wherein R30 is linear alkyl, phenyl or thiophenyl, all of which being optionally substituted with a linear alkyl or with -O-L.
The compound of item 13, wherein R30 is methyl, 2-methylphenyl, phenyl, thiophenyl, or 4-methoxyphenyl. The compound of any one of items 1 to 14, wherein at least one of the oxime ester group and/or acyl groups is attached to the compound through a linker -LK-.
The compound of item 15, wherein -LK- is optionally substituted alkylene, cycloalkylene, alkenylene, cycloalkenylene, alkynylene, cycloalkynylene, arylene, -S-arylene, -NH-arylene, or -N(aryl)-arylene, each of which optionally comprising one or more oxygen atom, sulfur atom, nitrogen atom, carbonyl group, carbamate group, carbamide group, and/or ester group.
The compound of item 16, wherein the alkylene, cycloalkylene, alkenylene, cycloalkenylene, alkynylene, cycloalkynylene, arylene, -S-arylene, -NH-arylene, and -N(aryl)-arylene are substituted with one or more:
■ polyethylene glycol chain,
■ C1-C12 alkyl optionally substituted with one or more:
Figure imgf000005_0001
o -O-L,
o -S-L, and/or
o phenyl optionally substituted with one or more: Ci alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
■ C4-C10 cycloalkyl, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, C4-C10 cycloalkynyl, each of which being optionally substituted by alkyl and/or -O-L, and/or
■ aryl, such as phenyl, biphenyl and naphthyl, or aryloyl, such as benzoyl, each of which being optionally substituted with one or more:
o Ci-C6 alkyl,
o halogen,
o nitrile,
o alkyloxy,
Figure imgf000005_0002
o C2-C12 alkylcarboxyl.
wherein L, Re, Rg and R10 are as defined in item 3.
The compound of any one of items 1 to 17, wherein FORMULA I and/or either or both FORMULA II are independently substituted by one or more of the following substituents:
■ C1-C12 alkyl, C1-C12 alkyloxy, C4-C10 cycloalkyl, C1-C12 alkenyl, C4-C10 cycloalkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, and/or C4-C10 cycloalkynyl, each of which being optionally substituted with one or more:
Figure imgf000005_0003
o -O-L,
o -S-L, and/or
o phenyl optionally substituted with one or more Ci alkyl, halogen atom, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl; and/or
■ phenyl, biphenyl and/or naphthyl, each of which being optionally substituted with one or more: o Ci-C6 alkyl, o halogen atom,
o nitrile,
o alkyloxy,
Figure imgf000006_0001
o C2-C12 alkylcarboxyl,
wherein L, f¾, Rg and R10 are as defined in item 3.
The compound of any one of items 1 to 18 comprising one optionally substituted FORMULA I
The compound of item 19 comprising optionally substituted
Figure imgf000006_0002
Figure imgf000006_0003
fused with optionally substituted
The c
Figure imgf000006_0004
ompound of item 20 comprising optionally substituted fused with optionally
substituted
The compou
Figure imgf000006_0005
nd of item 20 comprising optionally substituted fused with optionally
substituted
Figure imgf000006_0006
, or The compound of item 20 comprising optionally substituted
Figure imgf000007_0001
fused with optionally
substituted
The compou
Figure imgf000007_0002
nd of item 20 comprising optionally substituted fused with optionally
substituted
The compou
Figure imgf000007_0003
nd of item 20 comprising optionally substituted fused with optionally
substituted
Figure imgf000007_0004
The compound of any one of items 1 to 18 comprising two optionally substituted FORMULA I
The compo fused with optionally
substituted
Figure imgf000007_0005
and with optionally substituted
The compou fused with optionally
substituted
Figure imgf000007_0006
and with optionally substituted
The compound of any one of items 1 to 18 being
Figure imgf000008_0001
wherein:
■ R4, R5, R4' and R5' are optional and independently represent, in the case of R4 and R5, one to four and, in the case of R4' and R5', one or two:
o C 1 -C 12 alkyi or alkyloxy, said alkyi and alkyloxy being optionally substituted with one or more :
■ -NRsRg,
■ -O-L or -S-L, and/or
■ phenyl optionally substituted with one or more: Ci alkyi, halogen atom, nitrile, alkyloxy, COOR10, and/or C2 to C½ alkylcarboxyl;
o C4-C10 cycloalkyl, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, C4-C10 cycloalkynyl, each of which being optionally substituted by alkyi and/or -O-L, and/or o phenyl, biphenyl and naphthyl, each of which being optionally substituted with one or more: Ci-C6 alkyl,
halogen,
nitrile,
alkyloxy,
Figure imgf000009_0001
C2-C12 alkylcarboxyl,
Qi and Q2 are optional and independently represent one to four acyl groups and/or oxime ester
groups of formula
each of X, Y and
Figure imgf000009_0002
Z independentl represent
*0' O or
Figure imgf000009_0003
, wherein:
, f¾, and Ra each independently represent:
■ a hydrogen atom;
■ C1-C12 alkyl optionally substituted with one or more:
• -NRsRg,
• -O-L,
• -S-L, and/or
• phenyl optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR10, and/or C2-C12 alkylcarboxyl;
■ C4-C10 cycloalkyl, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, C4-C10 cycloalkynyl, each of which being optionally substituted by alkyl and/or -O-L, and/or
■ phenyl, biphenyl or naphthyl, each of which being optionally substituted with one or more:
• Ci-C6 alkyl,
• halogen,
• nitrile,
• alkyloxy,
Figure imgf000009_0004
• C2-C12 alkylcarboxyl, o a hydrogen atom, an acyl group, or an oxime ester group of formula:
o Q
Figure imgf000010_0001
4 represents an oxime ester of formula: , and
o Ar is a linker -LK- as defined in any one of items 15 to 17,
wherein L, f¾, f¾ and R10 are as defined in item 3, and wherein R6 and R7 are as defined in any one of items 2 to 10 .
The com ound of item 29 being:
Figure imgf000010_0002
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000013_0001
R2 R3 Ar R2 R3
Q3
wherein Qi, Q2, Q3, Q4, Ri, R2, R3, R4, R5, and Ar are as defined in item 29.
The compound of item 29 or 30, wherein -Ar- is optionally substituted arylene, said arylene optionally comprising one or more oxygen atom, sulfur atom, nitrogen atom, carbonyl group, carbamate group, carbamide group, and/or ester group.
The compound of item 31 , wherein the substituents of the arylene are one or more:
■ C1-C12 alkyl optionally substituted with one or more:
Figure imgf000013_0002
o -O-L,
o -S-L,
o phenyl optionally substituted with one or more: Ci alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
■ C4-C10 cycloalkyl, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, C4-C10 cycloalkynyl, each of which being optionally substituted by alkyl and/or -O-L, and/or
■ phenyl, biphenyl and naphthyl, each of which being optionally substituted with one or more:
o Ci-C6 alkyl,
o halogen,
o nitrile,
o alkyloxy,
Figure imgf000013_0003
o C2-C12 alkylcarboxyl. wherein L, Re, Rg and R10 are as defined in item 3.
The com ound of any one of items 29 to 32, wherein each -Ar-Ch independently represents
Figure imgf000014_0001
1 and Ri2 are optional and independently represent one or more:
C1-C12 alkyl optionally substituted with one or more:
Figure imgf000014_0002
o -O-L,
o -S-L, and/or
o phenyl optionally substituted with one or more: Ci alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
C4-C10 cycloalkyl, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, and/or C4-C10 cycloalkynyl, each of which being optionally substituted by alkyl and/or -O-L; and/or phenyl, biphenyl and naphthyl, each of which being optionally substituted with one or more: o Ci-C6 alkyl,
o halogen,
o nitrile, o alkyloxy,
Figure imgf000015_0001
o C2-C12 alkylcarboxyl.
wherein L, f¾, Rg and R10 are as defined in item 3.
com ound of any one of items 29 to 33 being:
Figure imgf000015_0002
wherein:
■ R4 and R5 are optional and independently represent one C1-C12 alkyl or C1-C12 alkyloxy,
■ optional and independently represent one oxime ester group of formula
Figure imgf000015_0003
■ Ri, R2, and Ra each independently represent a hydrogen atom or C1-C12 alkyl, Q3 represents a hydrogen atom or an oxime ester group of formula:
Figure imgf000016_0001
Q represents an oxime ester of formula:
Figure imgf000016_0002
Figure imgf000016_0003
■ f¾ and R7 independently represents alkyl.
. The compound of item 34 being:
Figure imgf000016_0004
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
The compound item 26, being truxene, truxenone, triazatruxene or a derivative thereof, said truxene, truxenone, triazatruxene or derivative thereof having attached thereto, directly or indirectly, at least one acyl and/or oxime ester group.
The compound of item 36 being:
Figure imgf000019_0002
triazatruxene:
or a derivative thereof, the truxene, truxenone, triazatruxene, or derivative thereof having attached thereto at least one of -Ei, -LK-Ei, -LK-(Ei)2 or =E2,
-Ei representing an acyl group of formula-C(=0)-R3o or an oxime ester group of formula -CR6=N-0-(C=0)-R7, and =E2 representing an oxime ester group of formula =N-0-(C=0)-R7,
wherein LK is as defined in any one of items 15 to 17, f¾ and R7 are as defined in any one of items 2 to 10 and R30 is as defined in any one of items 11 to 14.
The com ound of items 36 or 37 being of formula:
or
Figure imgf000020_0001
Formula 3,
wherein:
each Q independently represents 1 to 4:
■ hydrogen; ■ -Ει;
Figure imgf000021_0001
■ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
■ C1-C12 haloalkyl;
■ C4-C8 cycloalkenyl;
■ C2-C12 alkynyl;
■ phenyl or -N(Rig)-phenyl, each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl;
■ benzoyl, naphthoyl, phenyloxycarbonyl, or naphtyloxycarbonyl, each of which being optionally substituted by one or more C1-C20 alkyl, C1-C4 haloalkyl, -SR19 , -OR19 , -NR19R20, halogen, phenyl, -COOR19, -CONR19R20, -CN, -NO2 and/or C3-C10 cycloalkyl, wherein the C3-C10 cycloalkyl may be interrupted by -0-, -(C=0)- or -N(Ri9)-;
Figure imgf000021_0002
■ thiophene carbonyl or pyrrolidinyl, each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl, and
each R21 independently represents:
■ hydrogen;
Figure imgf000021_0003
■ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
■ C4-C8 cycloalkenyl;
■ C2-C12 alkynyl; or
■ phenyl optionally substituted with one or more C1-C6 alkyl, nitrile, alkyloxy, -COOR16, and/or C2-C12 alkylcarboxyl,
and/or two R21 attached to the same carbon atom represent =0 or =E2,
wherein:
L represents a hydrogen atom or C1-C6 alkyl,
R16 and Ri7 independently represent:
■ hydrogen,
■ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
■ C4-C10 cycloalkyl;
■ C4-C10 cycloalkenyl; ■ C2-C12 alkynyl;
■ C1-C12 haloalkyl; or
■ phenyl or benzoyl, each of which optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl group, and
Rig and R20 independently represent hydrogen, C1-C12 alkyl; C1-C12 haloalkyl; C4-C8 cycloalkenyl; or C2-C12 alkynyl,
provided that the compound comprises at least one oxime ester or acyl group, and provided that when R21 is attached to a nitrogen atom and R21 is -Ei, -Ei is not -CR6=N-0-(C=0)-R7.
The compound of item 38 being of formula:
Figure imgf000022_0001
Formula 2', or
Figure imgf000023_0001
Formula 3',
wherein:
each of Qn, Q12 and Q13 independently represent:
■ hydrogen;
Figure imgf000023_0002
■ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
■ C1-C12 haloalkyl;
■ C4-C8 cycloalkenyl;
■ C2-C12 alkynyl;
■ phenyl or -N(Rig)-phenyl, each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl;
■ benzoyl, naphthoyi, phenyloxycarbonyl, or naphtyloxycarbonyl, each of which being optionally substituted by one or more C1-C20 alkyl, C1-C4 haloalkyl, -SR19 , -OR19 , -NR19R20, halogen, phenyl, -COOR19, -CONR19R20, -CN, -NO2 and/or C3-C10 cycloalkyl, wherein the C3-C10 cycloalkyl may be interrupted by -0-, -(C=0)- or -N(Ri9)-;
■ thiophene carbonyl or pyrrolidinyl, each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl,
each R22 independently represents:
■ hydrogen;
■ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
■ C1-C12 haloalkyl;
■ C4-C8 cycloalkenyl;
■ C2-C12 alkynyl; ■ phenyl or -N(Rig)-phenyl, each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl; or
■ benzoyl, naphthoyl, phenyloxycarbonyl, or naphtyloxycarbonyl, each of which being optionally substituted by one or more C1-C20 alkyl, C1-C4 haloalkyl, -SR19 , -OR19 , -NR19R20, halogen, phenyl, -COOR9, -CONR19R20, -CN, -NO2 and/or C3-C10 cycloalkyl, wherein the C3-C10 cycloalkyl is interrupted by -0-, -(C=0)- or -N(Ri9)-,
wherein R16, R17, R19, R20, R21, and L are as defined in item 38,
provided that the compound comprises at least one oxime ester or acyl group, and provided that when R21 is attached to a nitrogen atom and R21 is -Ei, -Ei is not -CR6=N-0-(C=0)-R7.
The com ound according to item 38 or 39, wherein -LK-E1 represents:
Figure imgf000024_0001
wherein R18 is hydrogen or C1-C12 alkyl optionally substituted with one or more -O-L and/or -S-L, and wherein L, R16 and R17 are as defined in item 38.
The compound of any one of items 38 to 40, wherein
■ each Q, Qi, Q2, and Q3, when present, represents one -Ei of formula -CR6=N-0-(C=0)-R7, wherein R6 represents C1-C12 alkyl optionally substituted with -O-L, wherein L is C1-C6 alkyl, and R7 represents Ci- C12 alkyl;
■ all R22, when present, represent hydrogen; and
■ all R21, when present, represent hydrogen or C1-C12 alkyl.
The compound of any one of items 38 to 40, wherein:
■ each Q, Qn, Q12, and Q13, when present, represents one -LK-E1, wherein Ei is of formula -CR6=N-0-(C=0)-R7, wherein R6 represents C1-C12 alkyl optionally substituted with -O-L, wherein L is C1-C6 alkyl, and R7 represents C1-C12 alkyl;
■ all R22, when present, represent hydrogen;
■ all R21, when present, represents hydrogen or C1-C12 alkyl; and
Figure imgf000025_0001
Figure imgf000025_0002
wherein f½ is hydrogen or benzoyl substituted with C1-C6 alkyl, R17 represents hydrogen and R18 represents C1-C12 alkyl.
The compound of any one of items 38 to 40, wherein each of Qn, Q12, and Q13, when present, represents hydrogen, each of Q and R22, when present, represents one -N(Rig)-phenyl wherein R19 represents C1-C12 alkyl, and every pair of R21 attached to a common carbon atom represent =E2 wherein R7 represents C1-C12 alkyl.
The compound of any one of items 38 to 40, wherein
■ each Q, Qi, Q2, and Q3, when present, represents one -LK- Ei or -Ei, wherein Ei is of formula -C(=0)- R30, wherein R30 represents C1-C12 linear alkyl, phenyl, phenyl substituted with alkyl or alkyloxy, or thiophenyl;
■ all R22, when present, represent hydrogen;
■ all R21, when present, represent C1-C12 alkyl, and
■ -LK- represents 2-phenylene or 4-phenylene.
The compound of any one of items 36 to 40, being of formula:
Figure imgf000025_0003
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000027_0002
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
46. The compound of any one of items 1 to 45 for use as a photoinitiator in a photopolymenzable composition.
47. The compound of any one of items 1 to 45 being comprised in a photopolymenzable composition.
48. The compound of item 46 or 47, wherein the photopolymenzable composition is a lithographic printing plate composition.
49. The compound of item 46 or 47, wherein the photopolymenzable composition is a color filter resist composition.
50. The compound of item 46 or 47, wherein the photopolymenzable composition is a black matrix resin composition.
51. The compound of item 46 or 47, wherein the photopolymenzable composition is a photosetting or photocuring ink.
52. The compound of item 46 or 47, wherein the photopolymenzable composition is an oxygen scavenging film composition.
53. A photopolymenzable composition comprising a compound according to any one of items 1 to 45.
54. The photopolymenzable composition of item 53 being a lithographic printing plate composition.
55. The photopolymenzable composition of item 53 being a color filter resist composition.
56. The photopolymenzable composition of item 53 being a black matrix resin composition.
57. The photopolymenzable composition of item 53 being a photosetting or photocuring ink.
58. The photopolymenzable composition of item 53 being an oxygen scavenging film composition.
DETAILLED DESCRIPTION OF THE INVENTION
The Compounds of the Invention
[0009] Turni in more details, there is provided a compound comprising optionally
substituted
Figure imgf000031_0002
(FORMULA I) fused with one or two optionally substituted
Figure imgf000032_0001
(FORMULA II), wherein A and E each independently represent -CH2-, -NH-, -0-, -S-, or -C(=0)- and B represents a bond, -CH2-, -NH-, -0-, -S-, or -C(=0)-, said compound having directly or indirectly attached thereto at least one oxime ester and/or acyl group.
[0010] In FORMULA I, B can represent a bond, so this formula also represents compounds of
formula
Figure imgf000032_0002
. In this formula and in FORMULA I, A and B (when it is not a bond) independently represent -CH2-, -NH-, -0-, -S-, or -C(=0)-. Therefore, FORMULA I includes:
Figure imgf000032_0003
(9H-carbazole), (dibenzo[b,d]furan)
Figure imgf000032_0004
(dibenzo[b,d]thiophene), (9H-fluoren-9-one)
(9H-thioxanthene),
(9H-xanthene),
Figure imgf000032_0005
(anthracen-9(10H)-one); (9H-thioxanthen-9-one);
Figure imgf000033_0001
(9H-xanthen-9-one), (acridin-9(10H)-one)
Figure imgf000033_0002
(10H-phenoxazine) (phenoxathiin)
Figure imgf000033_0003
(10H-phenothiazine), (oxanthrene)
Figure imgf000033_0004
(5, 10-dihydrophenazine), (thianthrene),
Figure imgf000033_0005
and (anthracene-9,10-dione).
[0011] Similarly, FORMULA II includes:
Figure imgf000033_0006
(1 H-indene),
benzofuran),
Figure imgf000033_0007
(1 -benzothiophene), and (1 H-inden-1 -one).
[0012] In the compound of the invention, FORMULA I is fused with one or two FORMULA II. Herein, FORMULA I being fused with FORMULA II means that one ring of FORMULA I will share a bond with one ring of FORMULA II so as to form a phenyl / 5-membered ring / phenyl structure as, for example, in the following compound:
Figure imgf000034_0001
phenyl / 5-memb. / phenyl
ring
[0013] The bonds that participate in the fusion of a FORMULA I with a first FORMULA II are those marked with
stars in the following formulas: (i.e. all the bonds between carbon atoms that
bear at least one hydrogen atom e
Figure imgf000034_0002
ach) and Therefore, FORMULA I fused with FORMULA II includes:
Figure imgf000034_0003
Figure imgf000035_0001
[0014] When a second FORMULA II is present, it may be the same or different from the first FORMULA II. Also, it may be fused with either phenyl group of FORMULA I or with the phenyl group of the first FORMULA II. For example, for the last FORMULA l-FORMULA II structure shown in the previous paragraph, the second
Figure imgf000035_0002
FORMULA II can be fused at the following location: (i.e. again all the bonds between carbon atoms that bear at least one hydrogen atom each).
[0015] Again, the second FORMULA II is fused so as to form a phenyl / 5-membered ring / phenyl structure. Therefore, for each of the FORMULA l-FORMULA II structures shown in the previous paragraph, there are 14 different ways of fusing a second FORMULA II. These 14 ways are shown below for the last FORMULA I- FORMULA II structure of the previous paragraph only; the skilled person will understand from this example how to fuse a second FORMULA II on any of the above FORMULA l-FORMULA II structure. These 14 ways are:
Figure imgf000036_0001
Figure imgf000037_0001
[0016] It should be noted that when B is a bond, the last structure of the previous paragraph corresponds to truxene-like compounds. In embodiments of the invention, the compound is truxene (i.e. when B is a bond and A and E are -CH2-), truxenone (i.e. when B is a bond and A and E are -C(=0)- ), triazatruxene (i.e. when B is a bond and A and E are -NH-), or a derivative thereof.
[0017] For more certainty, herein, "truxene" refers to a compound of formula:
Figure imgf000038_0001
Figure imgf000039_0001
or with all the hydrogen atoms shown:
Figure imgf000039_0002
[0020] Truxene, truxenone, and triazatruxene bear CAS numbers 548-35-6, 4430-15-3 and 109005-10-9, respectively.
[0021] Embodiments in which the fusion of FORMULA I with two FORMULA II produces truxene, truxenone, triazatruxene and derivatives thereof will be discussed further below after the following more general discussion of the compounds of the invention.
[0022] In the compounds of the invention, FORMULA I and FORMULA II are "optionally substituted". This means that one or more hydrogen atoms of FORMULA I and/or FORMULA II (including the hydrogen atoms in the A, B and E groups) can be replaced by substituents. The nature of these substituents is not crucial to the invention as long as they do not prevent the compound of the invention to act as a photoinitiator.
[0023] In embodiments, FORMULA I and FORMULA II are optionally substituted by one or more:
■ C1-C12 alkyl, C1-C12 alkyloxy, C4-C10 cycloalkyl, C1-C12 alkenyl, C4-C10 cycloalkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, and/or , C4-C10 cycloalkynyl, each of which being optionally substituted with one or more: o -O-L,
o -S-L, and/or
o phenyl optionally substituted with one or more C1-C6 alkyl, halogen atom, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl; and/or
■ phenyl, biphenyl and/or naphthyl, each of which being optionally substituted with one or more: o Ci-C6 alkyl,
o halogen atom,
o nitrile,
o alkyloxy,
Figure imgf000040_0001
o C2-C12 alkylcarboxyl,
wherein L is a hydrogen atom or C1-C6 alkyl, and wherein each of Re, Rg and R10 is independently an hydrogen atom, C1-C12 alkyl; C4-C10 cycloalkyl; C1-C12 alkenyl; C4-C10 cycloalkenyl; C2-C12 alkynyl; C4-C10 cycloalkynyl; C1-C12 haloalkyl; or optionally substituted aryl, such as unsubstituted or substituted phenyl and naphthyl. In embodiments, the optionally substituted aryl is substituted with alkyl or alkyloxy.
[0024] In more specific embodiments, one or more of these substituents are located on the phenyl rings of FORMULA I and FORMULA II that are not involved in a fusion between FORMULA I and FORMULA II. For enyl rings circled in the following formula:
Figure imgf000040_0002
There may be from zero to four substituents on such a phenyl ring.
[0025] In the same or other embodiments, one or more of these substituents are located on the carbon and nitrogen atoms of the A, B and E groups. Therefore, one or both of the hydrogen atoms of -CH2- in A, B and E can independently be replaced by such a substituent. Similarly, the hydrogen atom of -NH- in A, B and E can be replaced by such a substituent.
[0026] In the same or other embodiments, one or more of the above substituents are located on the phenyl rings that are involved in a fusion between FORMULA I and FORMULA II (this would be the phenyl ring that is not circled in the above example). There may be from zero to two substituents on such a phenyl ring.
[0027] The compounds of the invention have attached thereto, directly or indirectly, at least one oxime ester and/or acyl group. Herein, "having attached thereto" means that one or two hydrogen atoms on a carbon or nitrogen atom of the compound (including the hydrogen atoms in the A, B and E groups) are replaced by an oxime ester or acyl group.
[0028] The oxime ester groups and the acyl groups can be directly or indirectly attached. Herein, "directly or indirectly attached" means that there can be a linker (-LK-) between the group and FORMULA I or FORMULA II. When such a linker is present, the group is said to be indirectly attached, otherwise it is directly attached.
[0029] In embodiments, -LK- is optionally substituted alkylene, cycloalkylene, alkenylene, cycloalkenylene, alkynylene, cycloalkynylene, arylene, -S-arylene, -NH-arylene, or -N(aryl)-arylene, each of which optionally comprising one or more oxygen atom, sulfur atom, nitrogen atom, carbonyl group, carbamate group, carbamide group, and/or ester group. The nature of the substituents of these radicals is not crucial to the invention as long as they do not prevent the compound of the invention to act as a photoinitiator. These substituents may replace any hydrogen atoms of these groups, including the hydrogen atom attached to the nitrogen atom in -NH-arylene. In embodiments, these substituents are one or more:
■ polyethylene glycol chain,
■ C1-C12 alkyl optionally substituted with one or more:
Figure imgf000041_0001
o -O-L,
o -S-L, and/or
o phenyl optionally substituted with one or more: Ci alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
■ C4-C10 cycloalkyl, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, C4-C10 cycloalkynyl, each of which being optionally substituted by alkyl and/or -O-L, and/or
■ aryl, such as phenyl, biphenyl and naphthyl, or aryloyl, such as benzoyl, each of which being optionally substituted with one or more:
o Ci-C6 alkyl,
o halogen,
o nitrile,
o alkyloxy,
Figure imgf000041_0002
o C2-C12 alkylcarboxyl.
wherein L, Rs, Rg and R10 are as defined above.
[0030] In embodiments where the linker -LK- serves to attach an acyl group, -LK- is arylene, such as phenylene.
[0031] Herein, an oxime ester group is -CR6=N-0-(C=0)-R7 or =N-0-(C=0)-R7, wherein R6 and R7 are the same or different substituents.
[0032] The nature of the R6 group is not crucial to the invention as long as it does not prevent the compound of the invention to act as a photoinitiator. In embodiments, R6 represents:
■ hydrogen;
■ C1-C12 alkyl optionally substituted with one or more:
o phenyl,
o halogen,
Figure imgf000041_0003
o -O-L, and/or
o -S-L;
■ C4-C10 cycloalkyl, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, or C4-C10 cycloalkenyl, each of which being optionally substituted by alkyl and/or -O-L; or ■ phenyl optionally substituted with one or more:
o Ci-C6 alkyl,
o halogen,
o nitrile,
o alkyloxy,
Figure imgf000042_0001
o C2-C12 alkylcarboxyl,
wherein L, f¾, Rg and R10 are as defined above.
[0033] In embodiments, R6 is alkyl optionally substituted with -Ο-Ci-Ce alkyl. In more specific embodiments R6 is methyl or butyl. In embodiments, R6 is methyl.
[0034] In oxime ester groups, the R7 group is related to the production of free radicals. Therefore, it should not comprise oxygen, nitrogen or sulfur atoms as such atoms could quench the free radicals. Also, smaller R7 groups, although not essential, are preferred as they have higher rates of diffusion and therefore lead to faster polymerization.
[0035] In embodiments, R7 is alkyl, cycloalkyl, alkenyl, or cycloalkenyl, each of which being optionally substituted with aryl or halogen, or R7 is aryl optionally substituted with alkyl or halogen. In specific embodiments, R7 represents C1-C12 alkyl optionally substituted with phenyl; C4-C10 cycloalkyl; or phenyl optionally substituted with C1-C6 alkyl. In embodiments, R7 is C1-C12 alkyl; C4-C10 cycloalkyl; or phenyl. In embodiments, R7 is methyl.
[0036] There are two ways in which the oxime ester group can be attached to FORMULA I or FORMULA II. First, if the oxime ester group replaces two hydrogen atoms attached to the same carbon atom in FORMULA I or FORMULA II, the oxime ester group may be =N-0-(C=0)-R7, in which the nitrogen atom (=N) is directly attached though a double bond to the carbon atom (of FORMULA I or FORMULA II) that was bearing the two hydrogen atoms. Secondly, if the oxime ester group replaces only one hydrogen atom on a nitrogen or carbon atom in FORMULA I or FORMULA II, the oxime ester group will be -CR6=N-0-(C=0)-R7. In this case, the oxime ester group can be attached directly to the atom that was bearing the hydrogen atom, or it may be attached to a linker (-LK-) that is itself attached to the that atom (i.e. it can be indirectly attached).
[0037] It is to be noted that the first carbon atom of the oxime ester group (i.e. the carbon atom bearing the R6 group and that which is underlined in the following -CR6=N-0-(C=0)-R7 ) should preferably be attached to a carbon atom of FORMULA I or FORMULA II, rather than an oxygen, nitrogen or sulfur atom, in order to increase the thermal stability of the compound. Therefore, when the oxime ester group replaces a hydrogen atom on a nitrogen atom, a linker should optimally be used. Also, in all cases where a linker is used, the atom of this linker that is bonding with the first carbon atom of the oxime ester group as defined above should optimally be a carbon atom. Otherwise, the nature of the linker is not crucial to the invention.
[0038] Herein, an acyl group is a group of formula -C(=0)- R30, wherein R30 is a substituent. The nature of R30 is not crucial to the invention as long as it does not prevent the compound of the invention to act as a photoinitiator. [0039] In embodiments, f¾o is optionally substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, or aryl, each of which optionally comprising one or more oxygen atom, sulfur atom, nitrogen atom, carbonyl group, carbamate group, carbamide group, and/or ester group. The nature of the substituents of these radicals is not crucial to the invention as long as they do not prevent the compound of the invention to act as a photoinitiator. In embodiments, these substituents are one or more:
■ polyethylene glycol chain,
■ C1-C12 alkyl optionally substituted with one or more:
Figure imgf000043_0001
o -O-L,
o -S-L, and/or
o phenyl optionally substituted with one or more: Ci alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
■ C4-C10 cycloalkyl, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, C4-C10 cycloalkynyl, each of which being optionally substituted by alkyl and/or -O-L, and/or
■ aryl, such as phenyl, thiophenyl, biphenyl and naphthyl, each of which being optionally substituted with one or more:
o Ci-C6 alkyl,
o halogen,
o nitrile,
o alkyloxy,
Figure imgf000043_0002
o C2-C12 alkylcarboxyl.
wherein L, f¾, Rg and R10 are as defined above.
[0040] In embodiment, R30 is linear alkyl, phenyl or thiophenyl, all of which being optionally substituted with a linear alkyl or with -O-L.
[0041] In embodiment, R30 is methyl, 2-methylphenyl, phenyl, thiophenyl, or 4-methoxyphenyl.
[0042] Herein, "at least one oxime ester and/or acyl group" means that several hydrogen atoms in FORMULA I and/or FORMULA II can be replaced by several oxime ester groups, several acyl groups, or a combination of oxime ester and acyl groups (each being either directly or indirectly attached). When the FORMULA I and/or FORMULA II have attached thereto more than one oxime ester and/or acyl group, some of these groups can be directly attached, while others are indirectly attached. In addition, various indirectly attached groups do not need to be attached using identical linkers (-LK-).
[0043] In embodiments, a compound of the invention has attached thereto, directly or indirectly, one, two, or three oxime ester groups or one, two, or three acyl groups. In embodiments, a compound of the invention has attached thereto, directly or indirectly, two or more oxime ester groups or two or more acyl groups. In embodiments, a compound of the invention has attached thereto, directly or indirectly, three oxime ester groups or three acyl groups.
[0044] In more specific embodiments, the oxime ester and acyl groups are located on the phenyl rings of FORMULA I and FORMULA II that are not involved in a fusion between FORMULA I and FORMULA II. For enyl rings circled in the following formula:
Figure imgf000044_0001
In embodiments, there may be from zero to two oxime ester and/or acyl groups on such a phenyl ring.
[0045] In the same or other embodiments, one or more oxime ester or acyl groups are located on the phenyl rings that are involved in a fusion between FORMULA I and FORMULA II (this would be the phenyl ring that is not circled in the above example).
[0046] In these and other embodiments, oxime ester and/or acyl groups may be located on the carbon and nitrogen atoms of the A, B and E groups. Therefore, one or both of the hydrogen atoms of -CH2- in A, B and E can independently be replaced by such a group. Also, the hydrogen atom of -NH- in A, B and E can be replaced by an oxime ester or acyl group.
[0047 In embodiments, FORMULA 1 is optionally substituted
Figure imgf000044_0002
and FORMULA II is o tionally substituted
Figure imgf000044_0003
and FORMULA II is
optionally substituted
Figure imgf000044_0004
or [0049] In embodiments, FORMULA 1 is optionally substituted
Figure imgf000045_0001
and FORMULA II is optionally substituted
[0050] In embodime
Figure imgf000045_0002
1 is optionally substituted and FORMULA II is optionally substituted
[0051] In embodime
Figure imgf000045_0003
1 is optionally substituted and FORMULA II is optionally substituted
[0052] In embodimen
Figure imgf000045_0004
ts FORMULA 1 is optionally substituted and FORMULA II is optionally substituted
[0053] In embodime
Figure imgf000045_0005
1 is optionally substituted and FORMULA II is optionally substituted
Figure imgf000045_0006
[0054] In embodime 1 is optionally substituted
Figure imgf000046_0001
and FORMULA II is optionally substituted
[0055] In embodime
Figure imgf000046_0002
1 is optionally substituted and FORMULA II is optionally substituted
[0056] In embodimen
Figure imgf000046_0003
ts, FORMULA 1 is optionally substituted and FORMULA II is optionally substituted
[0057] In embodime
Figure imgf000046_0004
1 is optionally substituted and FORMULA II is optionally substituted
[0058] In embodimen
Figure imgf000046_0005
ts, FORMULA 1 is optionally substituted and FORMULA II is optionally substituted
Figure imgf000046_0006
[0059] In embodiments FORMULA 1 is optionally substituted
Figure imgf000047_0001
and FORMULA II is optionally substituted
[0060] In embodime
Figure imgf000047_0002
nts, the compound comprises optionally substituted as
Figure imgf000047_0003
ULA I optionally substituted first FORMULA II and optionally substituted
Figure imgf000047_0004
as a second FORMULA I
Figure imgf000047_0005
[0061] In embodiments, the compound com rises optionally substituted as
FORMULA I optionally substituted
Figure imgf000047_0006
first FORMULA II and optionally substituted
Figure imgf000047_0007
as a second FO RM U LA I
[0062] In embodiments, the compound is :
Figure imgf000047_0008
Figure imgf000048_0001
case of R4' and one or two:
O C 1 -C 12 alkyi or alkyloxy, said alkyi and alkyloxy being optionally substituted with one or more :
■ -NRsRg,
■ -O-L or -S-L, and/or
■ phenyl optionally substituted with one or more: Ci alkyi, halogen atom, nitrile, alkyloxy, COOR10, and/or C2 to C½ alkylcarboxyl;
o C4-C10 cycloalkyl, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, C4-C10 cycloalkynyl, each of which being optionally substituted by alkyi and/or -O-L, and/or
o phenyl, biphenyl and naphthyl, each of which being optionally substituted with one or more:
■ Ci-C6 alkyi,
■ halogen,
■ nitrile,
■ alkyloxy,
Figure imgf000048_0002
■ C2-C12 alkylcarboxyl,
wherein L, Rs, Rg and R10 are as defined above,
Qi and and independently represent one to four acyl groups and/or oxime ester groups of
formula
Figure imgf000048_0003
wherein R6 and R7 are as defined above, N
I
Ar
I I
each of X, represent Ri
Figure imgf000049_0001
, or wherein:
Ri, R2, and Ra each independently represent:
■ a hydrogen atom;
■ C1-C12 alkyl optionally substituted with one or more:
• -NRsRg,
• -O-L,
• -S-L, and/or
• phenyl optionally substituted with one or more Ci alkyl, halogen, nitrile, alkyloxy, -COOR10, and/or C2-C12 alkylcarboxyl;
■ C4-C10 cycloalkyl, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, C4-C10 cycloalkynyl, each of which being optionally substituted by alkyl and/or -O-L, and/or
■ phenyl, biphenyl or naphthyl, each of which being optionally substituted with one or more:
Ci-C6 alkyl,
halogen,
nitrile,
alkyloxy,
Figure imgf000049_0002
C2-C12 alkylcarboxyl,
wherein L, Re, Rg and R10 are as defined above,
a hydrogen atom, an acyl group, or an oxime ester group of formula:
Figure imgf000049_0003
, wherein R6 and R7 are as defined above,
o Q4 represents an oxime ester of formula:
Figure imgf000049_0004
.wherein R7 is as defined above, and
o -Ar- is a linker -LK- as define above and in more specific embodiments, an optionally substituted arylene as defined above with respect to -LK-,
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
wherein Qi, Q2, Q3, Q4, Ri, R2, R3, R4, R5, and Ar are as defined above.
[0064] In embodiments, -Ar- (i.e. a linker -LK-) is optionally substituted arylene as defined above with respect to -LK-. It should be noted that although the formulas above and below show only one Q3 attached to -Ar- there
ma be more than one such Q3. In embodiments, each -Ar-Ch independently represents
Figure imgf000053_0002
Figure imgf000053_0003
optional and independently represent one or more: ■ C1-C12 alkyl optionally substituted with one or more:
Figure imgf000054_0001
o -O-L,
o -S-L, and/or
o phenyl optionally substituted with one or more: Ci alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
■ C4-C10 cycloalkyl, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, and /or C4-C10 cycloalkynyl, each of which being optionally substituted by alkyl and/or -O-L; and/or
■ phenyl, biphenyl and naphthyl, each of which being optionally substituted with one or more:
o Ci-C6 alkyl,
o halogen,
o nitrile,
o alkyloxy,
Figure imgf000054_0002
o C2-C12 alkylcarboxyl.
wherein L, f¾, Rg and R10 are as defined above.
[0065] With regard to the above formulas for Ar, it should also be noted that in other embodiments, the Q3 group(s) may be attached at positions of the Ar group different from that shown above.
[0066] In embodiments the compound is:
Figure imgf000054_0003
Figure imgf000055_0001
wherein:
R4 and R5 are optional and independently represent one C1-C12 alkyl or C1-C12 alkyloxy,
optional and independently represent one acyl group or one oxime ester group of formula
Figure imgf000055_0002
Ri, R2, and Ra each independently represent a hydrogen atom or Ci-Ci2 alkyl,
Q3 represents a hydrogen atom, an acyl group, or an oxime ester group of formula:
Figure imgf000055_0003
Q represents acyl or an oxime ester of formula:
Figure imgf000055_0004
Figure imgf000055_0005
■ R6 and R7 independently represents alkyl,
with the proviso that the compound comprise at least one acyl or oxime ester group.
[0067] In embodiments of the above, the compound comprises at least oxime ester group, but no acyl group.
[0068] In embodiments, the compound is:
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
[0069] Specific embodiments in which one FORMULA I is fused with two FORMULA II to form truxene, truxenone, triazatruxene, or derivatives thereof will now be discussed. For simplicity, the following numbering will be used when discussing the general structure of these compounds:
Figure imgf000059_0001
It is to be noted however that numbering according the standard rules of chemical nomenclature will be used when naming specific compounds (for example, in the "Description of Illustrative Embodiments" section below).
[0070] Also, the various rings in the compound of the invention will be referred as follows: the central phenyl ring (i.e. the phenyl ring comprising carbon atoms no. 1-2, 6-7, and 1 1 -12), the three intermediate five-membered rings (i.e. the five-membered rings made of carbon atoms no. 2-6, carbon atoms no. 7-1 1 , and carbon atoms no. 1 , and 12-15, respectively), and the three outer phenyl rings (i.e. the phenyl rings made of carbon atoms no. 3-4 and 16-19, of carbon atoms no. 8-9 and 20-23, and of carbon atoms no. 13-14 and 24-27, respectively).
[0071] In embodiments, the truxene, triazatruxene, truxenone or derivative thereof has attached thereto, directly or indirectly, one, two, three, four, five or six oxime ester groups or one, two, three, four, five or six acyl groups. In embodiments, they comprise one, two, three, four, five oxime ester groups or more and/or six, five, four, three, two oxime ester groups or less. In embodiments, they comprise one, two, three, four, five acyl groups or more and/or six, five, four, three, two acyl groups or less.
[0072] In embodiments, some or all of the oxime ester or acyl groups are directly or indirectly attached to the outer phenyl rings of the truxene, truxenone, triazatruxene or derivative thereof. In other words, some or all of the oxime ester or acyl groups are directly or indirectly attached to carbon atoms no. 16-19, 20-23, and 24-27.
[0073] In the same or different embodiments, some or all of the oxime ester or acyl groups are directly or indirectly attached to the intermediate five-membered rings of the truxene, triazatruxene or derivative thereof. In other words, some or all of the oxime ester or acyl groups are directly or indirectly attached to carbon or nitrogen atoms no. 5, 10, and 15.
[0074] In embodiments, the compound comrprises:
truxene:
Figure imgf000059_0002
truxenone:
triazatruxen
Figure imgf000060_0001
or a derivative thereof,
the truxene, truxenone, triazatruxene or derivative thereof having attached thereto at least one of -Ei, -LK-Ei, , -LK-(Ei)2 or =E2, wherein -LK- is as defined above, -Ei is -CR6=N-0-(C=0)-R7 or -C(=0)-f¼ and =E2 is =N-0-(C=0)-R7, wherein R6, R7, and R30 are as defined above.
[0075] In embodiments, the compound is of formula:
Figure imgf000060_0002
Formula 1 ,
Formula 2, or
Figure imgf000061_0001
Formula 3, wherein:
each Q independently represents 1 to 4:
■ hydrogen;
Figure imgf000061_0002
■ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
■ C1-C12 haloalkyl;
■ C4-C8 cycloalkenyl;
■ C2-C12 alkynyl;
■ phenyl or -N(Rig)-phenyl, each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl;
■ benzoyl, naphthoyl, phenyloxycarbonyl, or naphtyloxycarbonyl, each of which being optionally substituted by one or more C1-C20 alkyl, C1-C4 haloalkyl, -SR19 , -OR19 , -NR19R20, halogen, phenyl, -COOR19, -CONR19R20, -CN, -NO2 and/or C3-C10 cycloalkyl, wherein the C3-C10 cycloalkyl may be interrupted by -0-, -(C=0)- or -N(Ri9)-;
Figure imgf000061_0003
■ thiophene carbonyl or pyrrolidinyl, each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl, and
each R21 independently represents: ■ hydrogen;
Figure imgf000062_0001
■ C1-C12 alkyl optionally substituted with one or more phenyl, -NR19R20, -O-L and/or -S-L;
■ C4-C8 cycloalkenyl;
■ C2-C12 alkynyl; or
■ phenyl optionally substituted with one or more C1-C6 alkyl, nitrile, alkyloxy, -COOR16, and/or C2-C12 alkylcarboxyl,
and/or two R21 attached to the same carbon atom represent =0 or =E2,
wherein:
■ R16 and Ri7 independently represent:
o hydrogen,
o C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
o C4-C10 cycloalkyl;
o C4-C10 cycloalkenyl;
o C2-C12 alkynyl;
o C1-C12 haloalkyl; or
o phenyl or benzoyl, each of which optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl group,
■ Rig and R20 independently represent hydrogen, C1-C12 alkyl; C1-C12 haloalkyl; C4-C8 cycloalkenyl; or C2-C12 alkynyl,
■ L, -LK- ,-Ei , =E2, -R4 and -R5 are as defined above,
provided that the compound comprises at least one oxime ester or acyl group, and provided that when R21 is attached to a nitrogen atom and R21 is -Ei, -Ei is not -CR6=N-0-(C=0)-R7.
[0076] Herein, "each R21 independently represents [list of substituents] and/or two R21 attached to the same carbon atom represent =0 or =E2" means that some or all the R21 groups may represent the substituents listed while some or all the pairs of R21 attached to a common carbon atom can be =0 or =E2.
[0077] Also, "each Q independently represent 1 to 4 [list of substituents]" means that each Q may represent 1 , 2, 3 or 4 substituents, each independently selected from the list. Also, it means that the substituents for each Q are selected independently from those selected for the other Q groups.
[0078] In embodiments, when each Q represents one substituent, these substituents are attached to carbon atoms no. 17 or 18, carbon atoms no. 21 or 22, and carbon atoms no. 25 or 26, respectively. 0079] In embodiments, the compound is of formula:
Figure imgf000063_0001
Formula 3', wherein each of Qn, Q12 and Q13 independently represents:
■ hydrogen;
Figure imgf000063_0002
■ -LK-(Ei)2 ; ■ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
■ C1-C12 haloalkyl;
■ C4-C8 cycloalkenyl;
■ C2-C12 alkynyl;
■ phenyl or -N(Rig)-phenyl, each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl;
■ benzoyl, naphthoyl, phenyloxycarbonyl, or naphtyloxycarbonyl, each of which being optionally substituted by one or more C1-C20 alkyl, C1-C4 haloalkyl, -SR19 , -OR19 , -NR19R20, halogen, phenyl, -COOR19, -CONR19R20, -CN, -NO2 and/or C3-C10 cycloalkyl, wherein the C3-C10 cycloalkyl may be interrupted by -0-, -(C=0)- or -N(Ri9)-;
Figure imgf000064_0001
■ thiophene carbonyl or pyrrolidinyl, each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl,
each R22 independently represents:
■ hydrogen;
■ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
■ C1-C12 haloalkyl;
■ C4-C8 cycloalkenyl;
■ C2-C12 alkynyl;
■ phenyl or -N(Rig)-phenyl, each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl; or
■ benzoyl, naphthoyl, phenyloxycarbonyl, or naphtyloxycarbonyl, each of which being optionally substituted by one or more C1-C20 alkyl, C1-C4 haloalkyl, -SR19 , -OR19 , -NR19R20, halogen, phenyl, -COOR19, -CONR19R20, -CN, -NO2 and/or C3-C10 cycloalkyl, wherein the C3-C10 cycloalkyl is interrupted by -0-, -(C=0)- or -N(Ri9)-,
wherein R16, R17, R19, R20, R21, L, -LK- , -Ei , =E2, -R4 and -R5 are as defined above,
provided that the compound comprises at least one oxime ester or acyl group, and provided that when R21 is attached to a nitrogen atom and R21 is -Ei, -Ei is not -CR6=N-0-(C=0)-R7.
[0080] In more specific embodiments of the above compounds, -LK-E1 represents:
Figure imgf000064_0002
represents:
Figure imgf000065_0001
wherein f½ and f½ are as defined above and wherein f½ is hydrogen or C1-C12 alkyl optionally substituted with one or more -O-L and/or -S-L, L being as defined above.
[0081] It should also be noted that in other embodiments, the Ei group(s) may be attached at other positions of the linkers shown above.
[0082] For more certainty, above "two R21 attached to the same carbon atom represent =0 or
Figure imgf000065_0002
means, for exam le, than Formula 1 above would represents compounds of the formula:
Figure imgf000065_0003
is =0 or =E2. It should be noted that among formulas 1 ,
1 ', 2, 2', 3 and 3' above, only formulas 1 and 1 ' have pairs of R21 groups attached to a common carbon atom that can become Q4.
[0083] In other embodiments of the above formulas 1 , 1 ', 2, 2', 3 and 3', the compound comprises one or more oxime ester group, but no acyl groups.
[0084] In other embodiments of the above formulas 1 , 1 ', 2, 2', 3 and 3', the compound comprises one or more, acyl groups, but not oxime ester group.
[0085] In embodiments of the above formulas 1 , 1 ', 2, 2', 3 and 3':
■ each Q, Qi, Q2, and Q3, when present, represents one -Ei of formula -CR6=N-0-(C=0)-R7, wherein R6 represents C1-C12 alkyl optionally substituted with -O-L, wherein L is C1-C6 alkyl, and R7 represents Ci- C12 alkyl;
■ all R22, when present, represent hydrogen; and
■ all R21, when present, represent hydrogen or C1-C12 alkyl.
[0086] In other embodiments of the above formulas 1 , 1 ', 2, 2', 3 and 3':
■ each Q, Qn, Q12, and Q13, when present, represents one -LK-E1, wherein Ei is of formula -CR6=N-0-(C=0)-R7, wherein R6 represents C1-C12 alkyl optionally substituted with -O-L, wherein L is C1-C6 alkyl, and R7 represents C1-C12 alkyl;
■ all R22, when present, represent hydrogen;
■ all R when present, represents hydrogen or C1-C12 alkyl; and
Figure imgf000066_0001
wherein R16 is hydrogen or benzoyl substituted with C1-C6 alkyl, R17 represents hydrogen and R18 represents C1-C12 alkyl.
[0087] In other embodiments of the above formulas 1 and 1 ', each of Qn, Q12, and Q13, when present, represents hydrogen, each of Q and R22, when present, represents one -N(Rig)-phenyl wherein R19 represents C1-C12 alkyl, and every pair of R21 attached to a common carbon atom represent =E2 wherein R7 represents Ci- C12 alkyl.
[0088] In embodiments of the above formulas 1 , 1 ', 2, 2', 3 and 3':
■ each Q, Qi, Q2, and Q3, when present, represents one -LK-E1 or -Ei, wherein Ei is of formula -C(=0)- R30, wherein R30 represents C1-C12 linear alkyl, phenyl, phenyl substituted with alkyl or alkyloxy, or thiophenyl;
■ all R22, when present, represent hydrogen;
■ all R21, when present, represent C1-C12 alkyl, and
■ LK represents 2-phenylene or 4-phenylene.
[0089] In embodiments, the com ound is of formula:
Figure imgf000066_0002
- ,CH3
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000072_0002
Uses of the Compounds of the Invention
[0090] The compounds of the invention are useful as photoinitiators. They absorb UV light and then emit free radicals. As such, they are useful in photosensitive or photopolymerizable compositions. Such compositions typically comprise, in addition to the compound of the invention, a free radical polymerizable compound. Such free radical polymerizable compound will typically be an ethylenic unsaturated bond-containing polymerizable compound. These compositions also often comprise other components, which are known to the skilled person who will select them depending on the intended use of the polymerizable composition.
[0091] Photosensitive or photopolymerizable compositions and polymerizable compounds for use therein are well known to the skilled person. Non-limiting examples of such compositions include photosetting or photocuring inks (including inks for inkjet printing (for example UV curable inkjet ink), gravure, and flexo printing), photosensitive printing plates, color filter resists, black matrix resin, lithographic printing plates, and a variety of photoresists, including dry film resists. The compounds of the invention are also useful as photoinitiators in compositions for oxygen scavenging films.
[0092] The compounds of the invention can replace photoinitiators used in photosensitive or photopolymerizable compositions of the prior art. [0093] In particular, the compounds of the invention can be used in color filter resists such as those described in Kura et al., "New Oxime Ester Photoinitiators for Color Filter Resists", Radtech Report, May/June 2004, p30-35.
[0094] They can also be used in the photopolymerizable compositions described at pages 7-61 of WO 2006/018405 and at pages 22-65 of WO 02/100903. They can also be used in the composition described in US 6,949,678.
[0095] It is noted, for example, that such photopolymerizable compositions, in addition to the compound of the invention and a polymerizable compound, can include further known photoinitiators and other additives such as thermal inhibitors, copper compounds, wax-like substances, an oxygen-impermeable layer, light stabilizers, amines to accelerate photopolymerization, chain transfer agents, photosensitizers, cross-linking agents, co-initiators, photoreducable dyes, flow improvers, adhesion promoters, surfactants, optical brighteners, pigments, dyes, wetting agent, leveling assistants, dispersants, aggregation preventers, antioxidants, fillers, microspheres, glass fibers, binders, etc.
[0096] The photopolymerizable compositions can be used for various purposes, for example as printing ink, e.g. screen printing inks, inkjet printing inks, inks for offset- or flexo printing, as a clear finish, as a white or colored finish, for example for wood or metal, as powder coating, as a coating material, inter alias for paper, wood, metal or plastic, as a daylight-curable coating for the marking of buildings and roadmarking, for photographic reproduction techniques, for holographic recording materials, for image recording techniques or to produce printing plates which can be developed with organic solvents or with aqueous alkalis, for producing masks for screen printing, as dental filling compositions, as adhesives, as pressure-sensitive adhesives, as laminating resins, as etch resists, solder resists, electroplating resists, or permanent resists, both liquid and dry films, as photostructurable dielectric, for printed circuit boards and electronic circuits, as resists to manufacture color filters for a variety of display applications or to generate structures in the manufacturing process of plasma-display panels and electroluminescence displays, (as for example described in US 5,853,446; EP 863,534; JP 09-244230-A; JP 10-62980-A; JP 08-171863-A; US 5,840,465; EP 855,731 ; JP 05-271576-A; and JP 05-67405-A) for the production of holographic data storage (HDS) material, for the production of optical switches, optical lattices (interference lattice), light circuits, for producing three-dimensional articles by mass curing (UV curing in transparent moulds) or by the stereolithography technique, as is described, for example, in US 4,575,330, to produce composite materials (for example styrenic polyesters, which may, if desired, contain glass fibers and/or other fibers and other auxiliaries) and other thick-layered compositions, for coating or sealing electronic components and integrated circuits, or as coatings for optical fibers, or for producing optical lenses, e.g. contact lenses or Fresnel lenses. The compositions according to the invention are further suitable for the production of medical equipment, auxiliaries or implants. Further, the compositions according to the invention are suitable for the preparation of gels with thermotropic properties, as for example described in DE 19700064 and EP 678,534.
[0097] The photoinitiators may additionally be employed as initiators for emulsion polymerizations, pearl polymerizations or suspension polymerizations, as polymerization initiators for fixing ordered states of liquid-crystalline monomers and oligomers, or as initiators for fixing dyes on organic materials. They can also be used for the polymerization of radiation-curable powder coatings. They further find application in negative resist compositions, suitable for the production of printing forms for relief printing, planographic printing, photogravure or of screen printing forms, for the production of relief copies, for example for the production of texts in Braille, for the production of stamps, for use in chemical milling or as a microresist in the production of integrated circuits. The compositions further may be used as photopatternable dielectric layer or coating, encapsulating material and isolating coating in the production of computer chips, printed boards and other electric or electronic components. The possible layer supports, and the processing conditions of the coating substrates, are just as varied.
[0098] These compositions can also be photosensitive thermosetting resin compositions that can be used to form a solder resist pattern. These can be useful as materials for the production of printed circuit boards, the precision fabrication of metallic articles, the etching of glass and stone articles, the relief of plastic articles, and the preparation of printing plates. The solder resist is a substance which is used during the soldering of a given part to a printed circuit board for the purpose of preventing molten solder from adhering to irrelevant portions and protecting circuits.
[0099] They are suitable for the production of color filters or color mosaic systems, such as described, for example, in EP 320,264. Color filters usually are employed in the manufacturing of LCD's, projection systems and image sensors. The color filters can be used, for example, for display and image scanner in television receivers, video monitors or computers, in flat panel display technology etc.
[00100] The photosensitive compositions can further be used for manufacturing spacers, which control a cell gap of the liquid crystal part in liquid crystal display panels. The photosensitive compositions are also suitable for manufacturing microlens arrays used in liquid crystal display panels, image sensors and the like. These are also suitable for photo-lithographic steps used in the production process of plasma display panels (PDP), particularly for the imaging forming process of barrier rib, phosphor layer and electrodes. The compositions also find application for the production of one- or more-layered materials for the image recording or image reproduction (copies, reprography), which may be mono- or polychromatic. Furthermore the materials are suitable for color proofing systems. The compounds of the invention are also suitable as photoinitiators in the holographic data storage application. The photoinitiators are suitable for the preparation of optical articles (for example optical waveguides) or holographic recording media e.g. comprising a polymer and an organic photoinitiator. As already mentioned above, the photoinitiators are suitable also for producing printing plates. Also of interest is the use of the novel photoinitiators for curing shaped articles made from composite compositions. The compounds according to the invention can be used for the production of holographies, waveguides, optical switches wherein advantage is taken of the development of a difference in the index of refraction between irradiated and unirradiated areas.
[00101] The compounds of the invention can also be used in the photosensitive resin compositions described in US 2010/0210749 and in the curable compositions, photopolymerizable compositions, color filters and the like described in US 2009/0023085, for example at paras [0130]-[0342] and at paras [0407]-[0607].
[00102] The compounds of the invention can also be used in the photosensitive compositions described in US 7,556,910 and the photopolymerizable compositions of US 6,051 ,367.
[00103] Thus, an aspect of the present invention is related to the use of the compounds as photoinitiators in color filter resist compositions. More specifically, the color filter resist compositions may, in embodiments, comprise:
■ from about 1 to about 5% by weight of the compound of the invention or a mixture thereof;
■ an alkaline soluble polymer;
■ a reactive oligomer;
■ a pigment; and
■ one or more optional additives.
[00104] Thus, another aspect of the present invention is related to the use of the invented compounds in the coating composition for production of lithographic offset printing plates, which can be digitally imaged with laser light having emission wavelength between 350 and 410 nm. More specifically, such coating compositions may, in embodiments, comprise:
■ from about 1 to about 5% by weight of the compound of the invention or a mixture thereof;
■ a polymeric binder resin;
■ a reactive oligomer;
■ one or more colorants; and
■ one or more optional film forming additives
[00105] This coating composition can be coated on an anodized aluminum substrate having a coating weight between 0.8 and 3.0 gram per square meter.
[00106] In many embodiments, the compounds of the invention are relatively easy to make. For example, some of them are easily purified by crystallization, avoiding thus the need for flash chromatography. Also, many of them are soluble in one or more alcohols, which are relatively environmentally friendly solvents. In addition, many of them are colorless, which makes them useful in a wide range of application. Others are lightly colored and are more useful, for example, in black matrix resins and other applications where color is not an issue. Also, many compounds of the invention do not discolor upon use.
[00107] Herein, unless otherwise noted, "alkyl" refers to a univalent saturated linear or branched C1-12 hydrocarbyl radical of formula -Cnh n+i . Similarly, "alkenyl" and "alkynyl" refer to linear or branched C1-12 unsaturated (with double and triple bond(s), respectively) univalent hydrocarbyl radicals.
[00108] Herein, unless otherwise noted, "alkylene" refers to a bivalent saturated linear or branched C1-12 hydrocarbyl radical of formula -CnH2n- Similarly, "alkenylene" and "alkynylene" refer to linear or branched C1-12 unsaturated (with double and triple bond(s), respectively) bivalent hydrocarbyl radicals.
[00109] Herein, unless otherwise noted, "aryl" and "arylene" refers respectively to univalent and bivalent aromatic radicals comprising between 1 and four aromatic rings. The rings can be fused or attached together through a covalent bond.
[00110] Herein, "about" has it ordinary meaning. In embodiments, it can mean plus or minus 5% of the numerical value it qualifies.
[00111] Herein, "comprising" is an open-ended term meaning "including, but not being limited to".
[00112] Other objects, advantages and features of the present invention will become more apparent upon reading of the following non-restrictive description of specific embodiments thereof, given by way of example only with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[00113] In the appended drawings:
[00114] Figure 1 shows the reaction scheme for the production of 3-acetyloxime-0-acetate-6, 12-diethyl-12- methyl-6, 12-dihydro-6-aza-indeno[1 ,2-b]fluorene;
[00115] Figure 2 shows the reaction scheme for the production of 7-acetyloxime-O-acetate-10-ethyl-12, 12- dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -bjfluorene;
[00116] Figure 3 shows the reaction scheme for the production of 9-acetyloxime-0-acetate-2-methoxy-12, 12- diethyl-6, 12-dihydro-6-thia-indeno[1 ,2-b]fluorene;
[00117] Figure 4 shows the reaction scheme for the production of 7-acetyloxime-0-acetate-12, 12-dimethyl- 10, 12-dihydro-10-oxo-indeno[2, 1 -bjfluorene;
[00118] Figure 5 shows the reaction scheme for the production of 8-acetyloxime-0-acetate-1 1 ,13,13-triethyl-6,6- dimethyl-1 1 , 13-dihydro-6H-1 1-aza-indeno[2, 1 -b]anthracene;
[00119] Figure 6 shows the reaction scheme for the production of 10-(4-acetyloxime-O-acetate phenyl)-7- acetyloxime-0-acetate-2-methoxy-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -bjfluorene;
[00120] Figure 7 shows the reaction scheme for the production of 10-(4-acetyloxime-O-acetate phenyl)-2,7- diacetyloxime-O-acetate-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -bjfluorene;
[00121] Figure 8 shows the reaction scheme for the production of 3,9-diacetyloxime-0-acetate-6-hexyl-6H-12- thia-6-aza-indeno[1 ,2-b]fluorene;
[00122] Figure 9 the reaction scheme for the production of 10-hexyl-10H-10-aza-indeno[2, 1 -b]fluoren-12-O- acetyloxime;
[00123] Figure 10 the reaction scheme for the production of 7,7'-acetyloxime-0-acetate-1 , 1 '-dimethyl- bisindeno[3,2-b:2',3'-h]-9-sec-butyl carbazole;
[00124] Figure 11 shows the reaction scheme for the production of 4,9,13-triethoxyacetyloxime-O- triacetatetruxenone;
[00125] Figure 12 shows the UV-Vis spectrum of 3,8, 13-triacetyl-5, 10, 15-trihexyl-10, 15-dihydro-5H-5, 10, 15- triazadiindeno[1 ,2-a; 1 ',2'-c]fluorene trioxime tri-O-acetate; [00126] Figure 13 shows the UV-Vis spectra of Carba-05, Truxe-08, Truxe-07 and Truxe-12;
[00127] Figure 14 shows the relative UV-Vis absorbance of Truxe-04 (INDENO 332), Truxe-13 (INDENO 336), Truxe-14 (INDENO 332B), Truxe-15 (INDENO 338) and Truxe-16 (INDENO 333);
[00128] Figure 15 shows the oxygen consumption of an oxygen scavenging film comprising INDENO 332 as a function of time; and
[00129] Figure 16 shows the oxygen consumption of an oxygen scavenging film comprising INDENO 336 of as a function of time.
DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
[00130] The present invention is illustrated in further details by the following non-limiting examples.
GLOSSARY
[00131] The following have been used in the Examples below:
Figure imgf000077_0001
Figure imgf000078_0001
Basic green 4 (BG4): Colorant available from Spectra Colors, USA
BYK 307: Polyethylene glycol modified polysiloxane surfactant, available from BYK Chemie, USA
TRUXE-6H : 5,5', 10, 10', 15, 15'-Hexahexyltruxene (98 %), available from American Dye Source, Inc., Canada.
TRUXA-3H : 5, 10, 15-Trihexyl-10, 15-dihydro-5H-5, 10, 15-triazadiindeno[1 ,2-a; 1 ',2'-c]fluorene (98 %), available from American Dye Source, Inc., Canada.
TRUXE-3Br: 2, 7, 12-Tribromo-5, 5, 10, 10, 15, 15-hexahexyltruxene, available from American Dye Source, Inc., Canada.
TRUXE-3F: 4,9,14-Trifluoro truxenone (98 %), available from American Dye Source, Inc., Canada
TRUX-2Br: 2,2-Dibromo-5-fluoroindan-1 -one (97 %), available from American Dye Source, Inc., Canada
Silane: -Methacryloxypropyl triethoxysilane, available from Sigma Aldrich, Canada
BR07-001 : Alkaline soluble polymeric binder resin (MW= 37,000 g/mole) available from American Dye Source, Inc., Canada and having the following formula:
Figure imgf000079_0001
(a= 0.45, b= 0.25 and c=0.30).
UR07-015: Reactive oligomer, available from American Dye Source, Inc., Canada and having the following formula:
Figure imgf000079_0002
AC07-001 : Acetal copolymer dispersant (MW= 47,000 g/mole), available from American Dye Source, Inc., Canada and having the following formula:
Figure imgf000079_0003
(a= 0.30, b= 0.50, c= 0.15, d= 0.03 and e= 0.02).
AC12-001 : Acetal copolymer comprising cyclohexenyl pendant group (a= 0.5, b=0.48 and c=0.02), available from Mylan Group, Travinh, Vietnam. [MY T: Do you have the formula?]
Irgacure OXE-02: Photoinitiator available from BASF, Germany and having the following formula:
Figure imgf000080_0001
BR10-010: Polymeric particle, 20 % dispersed in isopropanol / water mixture (80/20) (Particle size = 150 nm; polydispersity = 0.08), available from America Dye Source, Inc., Canada and having the following formula:
Figure imgf000080_0002
(a= 0.83, b= 0.10 and c= 0.07; n= 29 and m= 6).
UR07-009: Reactive oligomer (60 % in 1 ,3-dioxolane solution), available from American Dye Source, I
Figure imgf000080_0003
(a= 7).
COBALT: Cobalt (II) oleate salt, available from Sigma Aldrich, Ontario, Canada.
ADD-2204: 2,4,6-Trimethylbenzoyl-diphenyl-phosphineoxide, available from Aceto Corporation, New
York, USA.
ADD-9984 N-vinylcaprolactam, available from Sigma Adrich, Ontario, Canada.
ADD-9991 1 ,6-hexanediol diacrylate, available from Sigma Adrich, Ontario, Canada.
ADD-9992 2-phenoxyethyl acrylate, available from TCI America, USA.
ADD-9995 Propoxylated neopentyl glycol diacrylate, available from Sartomer, USA. ADD-2614: 3-Methacryloxypropyltrimethoxysilane, available from Polysciences, USA.
POL-0138: Aliphatic Polyester Urethane Acrylate, available from Mylan Group, Travinh, Vietnam.
POL-1001 : Aromatic monoacrylate oligomer, available from Mylan Group, Travinh, Vietnam.
POL-0137: Stabilizer for radically curable inks, available from Mylan Group, Travinh, Vietnam.
600-B307: Silicone surface additive, available from Mylan Group, Travinh, Vietnam.
COL-1829: Pigment Blue 15:4 - 25 % dispersed in ADD-9995, available from Mylan Group, Travinh,
Vietnam.
ADD-9993: Trimethylcyclohexane acrylate, available from Sigma Aldrich, Ontario, Canada.
Yellow-150: Pigment yellow dispersion comprising 7.5 g of CI Pigment Yellow 150 (available from Hangzhou Multicolor Chemical Company, China), 2.5 g of AC07-001 and 40 g of cyclohexanone. The mixture was dispersed for 24 hours using a ball mill. It was filtered with a 5 μηι pore filter and cyclohexanone was added to give 15% solid weight.
Red-254: Pigment red dispersion comprising 7.5 g of CI Pigment Red 254 (Hostapern Red D2G 70 LV 2647, available from Clarian, Germany), 2.5 g of AC07-001 and 40 g of cyclohexanone. The mixture was dispersed for 24 hours by using a ball mill. It was filtered with a 5 μηι pore filter and cyclohexanone was added to give 15% solid weight.
Green-36: Pigment green dispersion comprising 7.5 g of CI Pigment Green 36 (Heliogen Green K9360, available from BASF, Germany), 2.5 g of AC07-001 and 40 g cyclohexanone. The mixture was dispersed for 24 hours by using a ball mill. It was filtered with a 5 μηι pore filter and cyclohexanone was added to give 15% solid weight.
Blue-15: Pigment blue dispersion comprising 7.5 g of CI Pigment Blue 15:6 (Hangzhou Multicolor Chemical Company, China), 2.5 g of AC07-001 , and 40 g of cyclohexanone. The mixture was dispersed for 24 hours by using a ball mill. It was filtered with a 5 μηι pore filter and cyclohexanone was added to give 15% solid weight.
Black-250: Carbon black dispersion comprising 7.5 g of carbon black (Special Black 250, available from Degussa, USA), 7.5 g of AC07-001 and 40 g of cyclohexanone. The mixture was dispersed for 24 hours by using a ball mill. It was filtered with a 5 μηι pore filter and cyclohexanone was added to give 15% solid weight.
Resist vehicle: A resist vehicle was prepared by dissolving 6.0 g of BR07-001, 6.0 g of UR07-015, 1.0 g of Silane in 102 g of cyclohexanone.
SYNTHESES AND CHARACTERIZATION OF COMPOUNDS OF THE INVENTION
Example 1.1 - 3-Acetyloxime-0-acetate-6,12-diethyl-12-methyl-6,12-dihydro-6-aza-indeno
[00132] The synthesis of 3-acetyloxime-0-acetate-6, 12-diethyl-12-methyl-6,12-dihydro-6-aza-indeno[1 ,2- bjfluorene was performed according to the reaction scheme shown in Figure 1.
(a) Synthesis of 3-acetyl-Q, 12-diethyl-12-methyl-6, 12-dihydro-6-aza-indeno[1 ,2-b]fluorene;
[00133] Aluminum chloride (3.43 g, 25.6 mmol) was slowly added into a dichloromethane solution (80 mL) in which were dissolved 6, 12-diethyl-12-methyl-6, 12-dihydro-6-aza-indeno[1 ,2-b]f luorene (5.95 g, 20.0 mmol) and acetyl chloride (1.83 mL, 25.7 mmol) at 0°C under nitrogen atmosphere. After stirring at room temperature overnight, the reaction mixture was poured into ice-water. The product was extracted twice with dichloromethane. The combined organic layer was washed with brine, and dried over MgSC . The dichloromethane was removed under high vacuum and the product thus obtained was used for the next step without further purification.
(b) Synthesis of 3-acetyloxime-Q, 12-diethyl-12-methyl-6, 12-dihydro-6-aza-indeno[1 ,2-b]fluorene;
[00134] 3-Acetyl-6, 12-diethyl-12-methyl-6, 12-dihydro-6-aza-indeno[1 ,2-b]fluorene (3.39 g, 10.0 mmol) was added into a solution mixture containing 100 mL of 1 ,3-dioxane, sodium acetate (1.06 g, 13.0 mmol), hydroxylammonium chloride (0.83 g, 12.0 mmol) and water (60 mL). The reaction mixture was refluxed overnight, cooled to room temperature, and then poured into water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried over MgSC , and concentrated to give a residue, which was further dried in a vacuum oven at 40 C. The product thus obtained was used for the next step without further purification (3.22 g, 92 % yield).
(c) Synthesis of 3-acetyloxime-0-acetate-6, 12-diethyl-12-methyl-6,12-dihydro-6-aza-indeno[1 ,2-b]fluorene;
[00135] Triethylamine (1.7 mL, 12.2 mmol ) and acetyl chloride (915 μί, 12.8 mmol) were slowly added into 100 mL of a tetrahydrofuran solution containing 3-acetyloxime-6, 12-diethyl-12-methyl-6, 12-dihydro-6-aza-indeno[1 ,2- bjfluorene (3.54 g, 10.0 mmol) at 0°C under nitrogen atmosphere. After 3 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried with MgSC , and concentrated by vacuum evaporation to give a residue, which was purified by flash chromatography on silica gel with ethyl acetate and hexane as eluents. The solvent was removed using vacuum evaporation to give a white powder product with 32% yield and 99% purity.
Example 1.2 - 7-Acetyloxime-O-acetate-10-ethyl-12, 12-dihexyl-10,12-dihydro-10-aza-indeno[2, 1-b]f luorene
[00136] The synthesis of 7-acetyloxime-0-acetate-10-ethyl-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 - bjfluorene was performed according to the reaction scheme shown in Figure 2.
(a) Synthesis of 7-acetyl-10-ethyl-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1-b]fluorene:
[00137] Aluminum chloride (3.43 g, 25.6 mmol) was slowly added into a dichloromethane solution (80 mL) in which were dissolved 10-ethyl-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -bjfluorene (5.95 g, 20.0 mmol) and acetyl chloride (1.83 mL, 25.7 mmol) at 0°C under nitrogen atmosphere. After stirring at room temperature overnight, the reaction mixture was poured into ice-water. The product was extracted twice with dichloromethane. The combined organic layer was washed with brine, and dried over MgSC . The dichloromethane was removed under high vacuum and the product thus obtained was used for the next step without further purification. (b) Synthesis of 7-acetyloxime-10-ethyl-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1-b]fluorene:
[00138] 7-Acetyl-10-ethyl-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -b]fluorene (3.39 g, 10.0 mmol) was added into a solution mixture containing 100 mL of 1 ,3-dioxane, sodium acetate (1.06 g, 13.0 mmol), hydroxylammonium chloride (0.83 g, 12.0 mmol) and water (60 mL). The reaction mixture was refluxed overnight, cooled to room temperature, and then poured into water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried over MgSC , and concentrated to give a residue, which was further dried in a vacuum oven at 40 C. The product thus obtained was used for the next step without further purification (3.22 g, 92 % yield).
(c) Synthesis of 6-acetyloxime-0-acetate-1 , 1-dihexyl indeno-[2,3-b]-9-ethyl carbazole:
[00139] Triethylamine (1.7 mL, 12.2 mmol) was slowly added into 100 mL of a tetrahydrofuran solution containing 7-acetyloxime-10-ethyl-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -b]fluorene (3.54 g, 10.0 mmol) and acetyl chloride (915 L, 12.8 mmol) at 0°C under nitrogen atmosphere. After 3 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried with MgS04, and concentrated by vacuum evaporation to give a residue, which was purified by flash chromatography on silica gel with ethyl acetate and hexane as eluent. The solvent was removed using vacuum evaporation to give a white powder product with 32% yield and 99% purity.
Example 1.3 - 9-Acetyloxime-0-acetate-2-methoxy-12, 12-diethyl-6, 12-dihydro-6-thia-indeno[1,2-b]fluorene
[00140] The synthesis of 9-acetyloxime-0-acetate-2-methoxy-12, 12-diethyl-6, 12-dihydro-6-thia-indeno[1 ,2- bjfluorene was performed according to the reaction scheme shown in Figure 3.
(a) Synthesis of 9-acetyl-2-methoxy-12, 12-diethyl-6, 12-dihydro-6-thia-indeno[1,2-b]fluorene:
[00141] Aluminum chloride (3.43 g, 25.6 mmol) was slowly added into a dichloromethane solution (100 mL) in which were dissolved 2-methoxy-12, 12-diethyl-6, 12-dihydro-6-thia-indeno[1 ,2-b]fluorene (6.60 g, 20.0 mmol) and acetyl chloride (1.83 mL, 25.7 mmol) at 0°C under nitrogen atmosphere. After stirring at room temperature overnight, the reaction mixture was poured into ice-water. The product was extracted twice with dichloromethane. The combined organic layer was washed with brine, and dried over MgSC . Dichloromethane was removed under high vacuum and the product thus obtained was used for the next step without further purification.
(b) Synthesis of 9-acetyloxime-2-methoxy-12, 12-diethyl-6, 12-dihydro-6-thia-indeno[1,2-b]fluorene:
[00142] 9-Acetyl-2-methoxy-12, 12-diethyl-6, 12-dihydro-6-thia-indeno[1 ,2-b]fluorene (3.56 g, 10.0 mmol) was added into a solution mixture containing 100 mL of 1 ,3-dioxane, sodium acetate (1.06 g, 13.0 mmol), hydroxylammonium chloride (0.83 g, 12.0 mmol) and water (60 mL). The reaction mixture was refluxed overnight, cooled to room temperature, and then poured into water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried over MgSC , and concentrated to give a residue, which was further dried in a vacuum oven at 40°C. The product thus obtained was used for the next step without further purification.
(c) Synthesis of 9-acetyloxime-0-acetate-2-methoxy-12, 12-diethyl-6, 12-dihydro-6-thia-indeno[1,2-b]fluorene:
[00143] Triethylamine (1.7 mL, 12.2 mmol ) was slowly added into 100 mL of a tetrahydrofuran solution containing 9-acetyloxime-2-methoxy-12, 12-diethyl-6,12-dihydro-6-thia-indeno[1 ,2-b]fluorene (3.87 g, 10.0 mmol) and acetyl chloride (915 μΙ_, 12.8 mmol) at 0°C under nitrogen atmosphere. After 3 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried with MgSC , and concentrated to give a residue, which was purified by flash chromatography using ethyl acetate-hexane as eluent. The solvent was removed using vacuum evaporations to give a white powder product with 32% yield and 99% purity.
Example 1.4 - 7-Acetyloxime-O-acetate-12,12-dimethyl-10,12-dihydro-10-oxo-indeno[2,1-b]fluorene
[00144] The synthesis of 7-acetyloxime-O-acetate-12, 12-dimethyl-10, 12-dihydro-10-oxo-indeno[2, 1-b]fluorene was performed according to the scheme shown in Figure 4.
(a) Synthesis of 7-butyryl-12, 12-dimethyl-10, 12-dihydro-10-oxo-indeno[2, 1-b]fluorene:
[00145] Aluminum chloride (3.43 g, 25.6 mmol) was slowly added into a dichloromethane solution (80 mL) in which were dissolved 12, 12-dimethyl-10, 12-dihydro-10-oxo-indeno[2, 1 -b]f luorene (5.68 g, 20.0 mmol) and acetyl chloride (1.83 mL, 25.7 mmol) at 0°C under nitrogen atmosphere. After stirring at room temperature overnight, the reaction mixture was poured into ice-water. The product was extracted twice with dichloromethane. The combined organic layer was washed with brine, and dried over MgS04. Dichloromethane was removed under high vacuum and the product thus obtained was used for the next step without further purification.
(b) Synthesis of 7-butyryloxime-12, 12-dimethyl-10, 12-dihydro-10-oxo-indeno[2, 1-b]fluorene:
[00146] 7-Butyryl-12, 12-dimethyl-10, 12-dihydro-10-oxo-indeno[2, 1 -b]fluorene (3.26 g, 10.0 mmol) was added into a solution mixture containing 100 mL of 1 ,3-dioxane, sodium acetate (1.06 g, 13.0 mmol), hydroxylammonium chloride (0.83 g, 12.0 mmol) and water (60 mL). The reaction mixture was refluxed overnight, cooled to room temperature, and then poured into water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried over MgSC , and concentrated to give a residue, which was further dried in a vacuum oven at 40°C. The product thus obtained was used for the next step without further purification.
(c) Synthesis of 7-butyryloxime-0-acetate-12, 12-dimethyl-10, 12-dihydro-10-oxo-indeno[2, 1-b]fluorene:
[00147] Triethylamine (1.7 mL, 12.2 mmol) was slowly added into a tetrahydrofuran solution (100 mL) containing 7-butyryloxime-12, 12-dimethyl-10, 12-dihydro-10-oxo-indeno[1 ,2-b]fluorene (3.41 g, 10.0 mmol) and acetyl chloride (915 μί, 12.8 mmol) at 0°C under nitrogen atmosphere. After 3 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried with MgSC , and concentrated by vacuum evaporation to give a residue, which was purified by flash chromatography on silica gel with ethyl acetate and hexane as eluents. The solvent was removed using vacuum evaporation to give a white powder product with 37% yield and 99% purity.
Example 1.5 - 8-Acetyloxime-O-acetate-H, 13, 13-triethyl-6, 6-dimethyl-H, 13-dihydro-6H-11-aza-indeno[2, 1- bjanthracene
[00148] The synthesis of 8-acetyloxime-0-acetate-11 , 13, 13-triethyl-6,6-dimethyl-1 1 , 13-dihydro-6H-1 1 -aza- indeno[2,1 -b]anthracene was performed according to the scheme shown in Figure 5.
(a) Synthesis of 8-acetyl-11, 13, 13-triethyl-6, 6-dimethyl-11, 13-dihydro-6H-11-aza-indeno[2, 1-b]anthracene
[00149] Aluminum chloride (3.43 g, 25.6 mmol) was slowly added into a dichloromethane solution (80 mL) in which were dissolved 11 , 13, 13-triethyl-6,6-dimethyl-11 , 13-dihydro-6H-11 -aza-indeno[2, 1 -bjanthracene (6.80 g, 20.0 mmol) and acetyl chloride (1.83 mL, 25.7 mmol) at 0°C under nitrogen atmosphere. After stirring at room temperature overnight, the reaction mixture was poured into ice-water. The product was extracted twice with dichloromethane. The combined organic layer was washed with brine, and dried over MgSC . Dichloromethane was removed under high vacuum and the product thus obtained was used for the next step without further purification.
(b) Synthesis of 8-acetyloxime-11 , 13, 13-tnethyl-6,6-dimethyl-11, 13-dihydro-6H-11-aza-indeno[2, 1 -bjanthracene
[00150] 8-Acetyl-1 1 , 13, 13-triethyl-6,6-dimethyl-11 , 13-dihydro-6H-11 -aza-indeno[2, 1 -bjanthracene (3.82 g, 10.0 mmol) was added into a solution mixture containing 100 mL of 1 ,3-dioxane, sodium acetate (1.06 g, 13.0 mmol), hydroxylammonium chloride (0.83 g, 12.0 mmol) and water (60 mL). The reaction mixture was refluxed overnight, cooled to room temperature, and then poured into water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried over MgSC , and concentrated to give a residue, which was further dried in a vacuum oven at 40°C. The product thus obtained was used for the next step without further purification.
(c) Synthesis of 8-acetyloxime-0-acetate-11, 13, 13-triethyl-6,6-dimethyl-11, 13-dihydro-6H-11-aza-indeno[2, 1- bjanthracene
[00151] Triethylamine (1.7 mL, 12.2 mmol ) was slowly added into 100 mL of a tetrahydrofuran solution containing 8-acetyloxime-11 , 13, 13-triethyl -6, 6-d i methyl- 1 1 , 13-dihydro-6H-1 1 -aza-indeno[1 ,2-b]anthracene (3.97 g, 10.0 mmol) and acetyl chloride (915 μί, 12.8 mmol) at 0°C under nitrogen atmosphere. After 3 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried with MgS04, and concentrated by vacuum evaporation to give a residue, which was purified by flash chromatography on silica gel with ethyl acetate and hexane as eluents. The solvent was removed using vacuum evaporation to give a white powder product with 46% yield and 99% purity.
Example 1.6 - 10-(4-acetyloxime-O-acetate phenyl)-7-acetyloxime-0-acetate-2-methoxy-12,12-dihexyl- 10, 12-dihydro-10-aza-indeno[2, 1-b]fluorene [00152] The synthesis of 10-(4-acetyloxime-O-acetate phenyl)-7-acetyloxime-0-acetate-2-methoxy-12, 12- dihexyl-10, 12-dihydro-10-aza-indeno[2,1 -b]fluorene was performed according to the scheme shown in Figure 6.
(a) Synthesis of 10-(4-acetyl phenyl)-7-acetyl-2-methoxy-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1- bjfluorene:
[00153] Aluminum chloride (8.00 g, 60.0 mmol) was slowly added into a dichloromethane solution (120 mL) in which were dissolved 2-methoxy-10-phenyl-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -b]fluorene (7.47 g, 20.0 mmol) and acetyl chloride (3.56 mL, 50.0 mmol) at 0°C under nitrogen atmosphere. After stirring at room temperature overnight, the reaction mixture was cooled to room temperature and poured into ice-water. The product was extracted twice with dichloromethane. The combined organic layer was washed with brine, and dried over MgS04. Dichloromethane was removed under high vacuum and the product thus obtained was used for the next step without further purification.
(b) Synthesis of 10-(4-acetyloxime phenyl)-7-acetyloxime-2-methoxy-12, 12-dihexyl-10, 12-dihydro-10-aza- indeno[2, 1-b]fluorene:
[00154] 10-(4-acetylphenyl)-7-acetyl-2-methoxy-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -b]fluorene (4.58 g, 10.0 mmol) was added into a solution mixture containing 120 mL of 1 ,3-dioxane, sodium acetate (2.46 g, 30.0 mmol), hydroxylammonium chloride (2.08 g, 30.0 mmol) and water (80 mL). The reaction mixture was refluxed overnight, cooled to room temperature, and then poured into water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried over MgSC , and concentrated to give a residue, which was further dried in a vacuum oven at 40°C. The product thus obtained was used for the next step without further purification.
(c) Synthesis of 10-(4-acetyloxime-O-acetate phenyl)-7-acetyloxime-O-acetate-2-methoxy-12, 12-dihexyl-10, 12- dihydro-10-aza-indeno[2, 1-b]fluorene:
[00155] Triethylamine (4.18 mL, 30.0 mmol) was slowly added into 100 mL of tetrahydrofuran solution containing 10-(4-acetyloxime phenyl)-7-acetyloxime-2-methoxy-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -bjfluorene (4.88 g, 10.0 mmol) and acetyl chloride (2.13 mL, 30.0 mmol) at 0°C under nitrogen atmosphere. After 5 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried with MgS04, and concentrated by vacuum evaporation to give a residue, which was purified by flash chromatography on silica gel with ethyl acetate and hexane as eluents. The solvent was removed using vacuum evaporation to give a white powder product with 56% yield and 99% purity.
Example 1.7 - 10-(4-acetyloxime-O-acetate phenyl)-2,7-diacetyloxime-O-acetate-12,12-dihexyl-10,12- dihydro-10-aza-indeno[2,1 -bjfluorene:
[00156] The synthesis of 10-(4-acetyloxime-O-acetate phenyl)-2,7-diacetyloxime-0-acetate-12, 12-dihexyl-10, 12- dihydro-10-aza-indeno[2, 1 -bjfluorene was performed according to the scheme shown in Figure 7. (a) Synthesis of 10-(4-acetyl phenyl)-2, 7-diacetyl^ 2, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -bjfluorene;
[00157] Aluminum chloride (12.0 g, 90.0 mmol) was slowly added into a dichloromethane solution (120 mL) in which were dissolved 10-ethyl-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -bjfluorine (7.20 g, 20.0 mmol) and acetyl chloride (6.40 mL, 90.0 mmol) at 0°C under nitrogen atmosphere. After refluxing overnight, the reaction mixture was cooled to room temperature and poured into ice-water. The product was extracted twice with dichloromethane. The combined organic layer was washed with brine, and dried over MgSC . Dichloromethane was removed under high vacuum and the product thus obtained was used for the next step without further purification.
(b) Synthesis of 10-(4-acetyloxime phenyl)-2, 7-diacetyloxime^ 2,12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1- bjfluorene;
[00158] 10-(4-acetylphenyl)-2J-diacetyl-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 -b]fluorene (4.86 g, 10.0 mmol) was added into a solution mixture containing 150 mL of 1 ,3-dioxane, sodium acetate (4.92 g, 60.0 mmol), hydroxylammonium chloride (4.17 g, 60.0 mmol) and water (100 mL). The reaction mixture was refluxed overnight, cooled to room temperature, and then poured into water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried over MgSC , and concentrated to give a residue, which was further dried in a vacuum oven at 40 C. The product thus obtained was used for the next step without further purification.
(c) Synthesis of 10-(4-acetyioxime-O-acetate phenyij^J-diacetyioxime-O-acetate-l 2, 12-dihexyl-10, 12-dihydro- 10-aza-indeno[2, 1 -bjfluorene;
[00159] Triethylamine (8.36 mL, 60.0 mmol ) was slowly added into 100 mL of a tetrahydrofuran solution containing 10-(4-acetyloxime phenyl)-2,7-diacetyloxime-12, 12-dihexyl-10, 12-dihydro-10-aza-indeno[2, 1 - bjfluorene (5.31 g, 10.0 mmol) and acetyl chloride (4.27 mL, 60.0 mmol) at 0°C under nitrogen atmosphere. After 3 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried with MgS04, and concentrated by vacuum evaporation to give a residue, which was purified by flash chromatography on silica gel with ethyl acetate and hexane as eluents. The solvent was removed using vacuum evaporation to give a white powder product with 45% yield and 99% purity.
Example 1.8 - 3,9-Diacetyloxime-0-acetate-6-hexyl-6H-12-thia-6-aza-indeno[1,2-b]fluorene
[00160] The synthesis of 3,9-diacetyloxime-0-acetate-6-hexyl-6H-12-thia-6-aza-indeno[1 ,2-b]fluorene was performed according to the scheme shown in Figure 8.
(a) Synthesis of 3,9-Diacetyi-6-hexyi-6H-12-thia-6-aza-indeno[1,2-b]fiuorene:
[00161] Aluminum chloride (8.00 g, 60.0 mmol) was slowly added into a dichloromethane solution (120 mL) in which were dissolved 6-hexyl-6H-12-thia-6-aza-indeno[1 ,2-b]fluorene (5.75 g, 20.0 mmol) and acetyl chloride (3.56 mL, 50.0 mmol) at 0°C under nitrogen atmosphere. After stirring at room temperature overnight, the reaction mixture was cooled to room temperature and poured into ice-water. The product was extracted twice with dichloromethane. The combined organic layer was washed with brine, and dried over MgSC . Dichloromethane was removed under high vacuum and the product thus obtained was used for the next step without further purification.
(b) Synthesis of 3,9-Diacetyloxime-6-hexyl-6H-12-thia-6-aza-indeno[1,2-b]fluorene:
[00162] 3,9-Diacetyl-6-hexyl-6H-12-thia-6-aza-indeno[1 ,2-b]fluorene (3.71 g, 10.0 mmol) was added into a solution mixture containing 120 mL of 1 ,3-dioxane, sodium acetate (3.28 g, 40.0 mmol), hydroxylammonium chloride (2.78 g, 40.0 mmol) and water (80 mL). The reaction mixture was refluxed overnight, cooled to room temperature, and then poured into water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried over MgS04, and concentrated to give a residue, which was further dried in a vacuum oven at 40°C. The product thus obtained was used for the next step without further purification.
(c) Synthesis of 3,9 iacetyloxime-0-acetate-6-hexyl-6H-12-thia-6-aza-indeno[1,2-b]fluorene:
[00163] Triethylamine (5.78 mL, 40.0 mmol) was slowly added into 100 mL of a tetrahydrofuran solution containing 3,9-diacetyloxime-6-hexyl-6H-12-thia-6-aza-indeno[1 ,2-b]fluorene (4.01 g, 10.0 mmol) and acetyl chloride (3.45 mL, 40.0 mmol) at 0°C under nitrogen atmosphere. After 3 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried with MgSC , and concentrated by vacuum evaporation to give a residue, which was purified by flash chromatography on silica gel with ethyl acetate and hexane as eluents. The solvent was removed using vacuum evaporation to give a white powder product with 68% yield and 99% purity.
Example 1.9 - 10-Hexyl-10H-10-aza-indeno[2,1-b]fluoren-12-O-acetyloxime
[00164] The synthesis of 10-hexyl-10H-10-aza-indeno[2, 1 -b]fluoren-12-O-acetyloxime was performed according to the scheme shown in Figure 9.
(a) Synthesis of 10-hexyl-10H-10-aza-indeno[2, 1-b]fluoren-12-oxime:
[00165] 10-Hexyl-10H-10-aza-indeno[2, 1 -b]fluoren-12-one (2.83 g, 10.0 mmol) and hydroxylammonium chloride (3.35 g, 40.0 mmol) were dissolved in 120 mL of 1 ,3-dioxane. Pyridine (3.96, 50 mmol) was added into the solution via a syringe. The reaction mixture was stirred overnight. The solvent was removed by vacuum evaporation and then poured into water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water and brine, dried over MgSC , and concentrated to give a residue, which was further dried in a vacuum oven at 40°C. The product thus obtained was used for the next step without further purification.
(b) Synthesis of 10-hexyl-10H-10-aza-indeno[2, 1-b]fluoren-12-0-acetyloxime:
[00166] Triethylamine (3.40 mL, 24.4 mmol) was slowly added into 80 mL of a tetrahydrofuran solution containing 10-hexyl-10H-10-aza-indeno[2, 1-b]fluoren-12-oxime (2.98 g, 10.0 mmol) and acetyl chloride (1.83 mL, 25.6 mmol) at 0°C under nitrogen atmosphere. After 3 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried with MgSC , and concentrated by vacuum evaporation to give a residue, which was purified by flash chromatography on silica gel with ethyl acetate and hexane as eluents. The solvent was removed using vacuum evaporation to give a white powder product with 86% yield and 99% purity.
Example 1.10 - 7J'-Acetyloxime-0-acetate-1,1'-Dimethyl-bisindeno[3,2-b:2 3'-h]-9-sec-butyl carbazole
[00167] The synthesis of 7J'-acetyloxime-0-acetate-1 , 1 '-Dimethyl-bisindeno[3,2-b:2',3'-h]-9-sec-butyl carbazole was performed according to the scheme shown in Figure 10.
(a) Synthesis of 7, 7'-acetyl-1, 1'-Dimethyl-bisindeno[3,2-b:2',3'-h]-9-sec-butyl carbazole:
[00168] Aluminum chloride (8.00 g, 60.0 mmol) was slowly added into a dichloromethane solution (150 mL) in which were dissolved 1 , 1 '-dimethyl-bisindeno[3,2-b:2',3'-h]-9-sec-butyl carbazole (9.12 g, 20.0 mmol) and acetyl chloride (3.56 mL, 50.0 mmol) at 0°C under nitrogen atmosphere. After stirring at room temperature overnight, the reaction mixture was cooled to room temperature and poured into ice-water. The product was extracted twice with dichloromethane. The combined organic layer was washed with brine, and dried over MgS04. Dichloromethane was removed under high vacuum and the product thus obtained was used for the next step without further purification.
(b) Synthesis of 7, 7'-Acetyloxime-1, 1'-dimethyl-bisindeno[3,2-b:2',3'-h]-9-sec-butyl carbazole:
[00169] 7,7'-Acetyl-1 , 1 '-dimethyl-bisindeno[3,2-b:2',3'-h]-9-sec-butyl carbazole (5.40 g, 10.0 mmol) was added into a solution mixture containing 120 mL of 1 ,3-dioxane, sodium acetate (2.46 g, 30.0 mmol), hydroxylammonium chloride (2.08 g, 30.0 mmol) and water (80 mL). The reaction mixture was stirred at room temperature overnight, cooled to room temperature, and then poured into water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried over MgSC , and concentrated to give a residue, which was further dried in a vacuum oven at 40°C. The product thus obtained was used for the next step without further purification.
( c) Synthesis of 7, 7'-Acetyloxime-0-acetate-1 , 1 '-dimethyl-bisindeno[3, 2-b:2 ', 3 '-h]-9-sec-butyl carbazole:
[00170] Triethylamine (4.18 mL, 30.0 mmol) was slowly added into 100 mL of a tetrahydrofuran solution containing 7,7'-acetyloxime-1 , 1'-dimethyl-bisindeno[3,2-b:2',3'-h]-9-sec-butyl carbazole (5.70 g, 10.0 mmol) and acetyl chloride (2.13 mL, 30.0 mmol) at 0°C under nitrogen atmosphere. After 5 hours stirring at room temperature, the reaction mixture was poured in water. The product was extracted with ethyl acetate. The combined organic layer was washed twice with water, dried with MgS04, and concentrated by vacuum evaporation to give a residue, which was purified by flash chromatography on silica gel with ethyl acetate and hexane as eluents. The solvent was removed using vacuum evaporation to give a white powder product with 76% yield and 99% purity.
Examples 1.11 and fallowings [00171] The syntheses of the photoinitiators of Examples 1.11 and following were performed in a flame dried glass wares, which were equipped with mechanical stirrer, water condenser, heating mental, nitrogen gas inlet and temperature controller. The obtained products and intermediates were characterized by FTIR spectrophotometer (Perkin Elmer, Model Spectrum 100), NMR (Nicolet 500 MHz), UV-Vis Spectrophotometer (Perkin Elmer, Model Lambda 25), DSC (TA Instruments, Model Q2000), TGA (TA Instrument, Model Q500), and HPLC (Waters, Model Breeze 2).
Example 1.11 - 2,7,12 Triacetyloxime-O-acetate-5,5',10,10',15,15'-hexahexyltruxene
[00172] The synthesis of 2,7, 12 Triacetyloxime-O-acetate-5,5', 10, 10', 15, 15'-hexahexyltruxene was performed as follows.
(a) Synthesis of 2, 7, 12-triacetyloxime-5,5', 10, 10', 15, 15'-hexahexyltruxene:
[00173] 2,7, 12-Triacetyl-5,5', 10, 10', 15, 15'-hexahexyltruxene (prepared according to Example 1.16 below) was dissolved in 180 mL of dioxane in a 500 mL flask. Sodium acetate (283 mg) and hydroxylamine HCI (256 mg) were dissolved in 60 mL of water in a 100 mL flask. This solution was added to the tnacetylhexahexyltruxene solution, which was then heated at reflux overnight. Most of the dioxane was removed under low pressure (the product precipitated), then 300 mL of water were added. The suspension was stirred for 30 minutes at room temperature, and then filtered to afford 950 mg (91 %) of a yellowish powder.
[00174] H1NMR (500 MHz, CDCI3) δ: 8.51 -8.46 (m, 3H); 8.12-8.07 (m, 3H); 7.84-7.79 (m, 3H); 3.05-2.92 (m, 6H); 2.70-2.60 (m, 9H); 2.65-2.57 (m, 6H); 2.32-2.17 (m, 36H); 1.05-0.82 (m, 18H); 0.65-0.49 (m, 12H).
(b) Synthesis of 2, 7, 12-triacetyloxime-0-acetate-5,5', 10, 10', 15, 15'-hexahexyltruxene:
[00175] 2,7, 12-Triacetyloxime-5,5', 10, 10',15,15'-hexahexyltruxene was dissolved in 60 mL of THF in a flame dried 100 mL flask under N2. The solution was cooled down to 0°C in an ice bath. Triethylamine (225 uL) was added, and then acetyl chloride (120uL) was slowly added. A white precipitate formed. The reaction was monitored with TLC using 15% EtOAc in hexane. After 2 hours at room temperature, the reaction mixture was extracted using EtOAc and water, dried over MgSC , carefully dried under vacuum, and then suspended in methanol. This suspension was sonicated for 30 minutes and then filtered to afford 235 mg (32%, HPLC purity +99%) of a white powder.
Figure imgf000091_0001
[00176] H1NMR (500 MHz, CDCI3) δ 8.42 (d, J = 8.5 Hz, 3H); 7.88 (dd, J1 = 1.7 Hz, J2 = 8.4 Hz, 3H); 7.82 (d, J = 1.7 Hz, 3H); 2.97-2.91 (m, 6H); 2.54 (s, 9H); 2.35 (s, 9H); 2.18-2.1 1 (m, 6H); 0.98-0.80 (m, 36H); 0.62 (I, J = 7.2 Hz, 18H); 0.52-0.45 (m, 12H).
Example 1.12 - 3A13-Triacetyl-5M15-trihexyl-10, 15-dihydro-5H-5,10,15
fluorene tnoxime tri-O-acetate (2E)
[00177] The synthesis of 3,8, 13-triacetyl-5, 10, 15-trihexyl-10, 15-dihydro-5H-5, 10, 15-triazadiindeno [1 ,2-a; 1 ',2'-c]fluorene trioxime tri-O-acetate was performed as follows.
(a) Synthesis of 3,8, 13-triacetyl-5, 10, 15-trihexyl-10, 15-dihydro-5H-5, 10, 15-triazadiindeno[1,2-a;1 -c\- fluorene trioxime:
[00178] 3,8, 13-Triacetyl-5, 10, 15-trihexyl-10, 15-dihydro-5H-5, 10, 15-triazadiindeno[1 ,2-a; 1 ',2'-c]fluorine (800 g, 1.10 mmol, from Example 1.17 below) was dissolved in 1 ,4-dioxane (120 mL) under nitrogen. The reaction mixture was gently heated to dissolve the solid. A solution of sodium acetate (285 mg, 4.32 mmol) and hydroxyl ammonium chloride (255 mg, 3.67 mmol) in water (40 ml) was added to the reaction mixture, which was then refluxed for 24 h. The reaction was monitored by TLC using ethyl acetate (20 %) and hexane (80 %) as eluent. After the reaction was completed, the product was precipitated in cold water (200 mL). A beige solid product was obtained by vacuum filtration, copiously washed with water and dried under vacuum at 30°C until constant weight (790 mg, 93% yield).
(b) Synthesis of 3,8, 13-triacetyl-5, 10, 15-trihexyl-10, 15-dihydro-5H-5, 10, 15-triazadiindeno[1,2-a;1 -c\- fiuorene trioxime tn-O-acetate:
[00179] Acetyl chloride (167 μί, 2.34 mmol) was slowly added into a tetrahydrofuran solution (500 mL) containing 3,8, 13-triacetyl-5, 10, 15-trihexyl-10, 15-dihydro-5H-5, 10, 15-triazadiindeno[1 ,2-a; 1 ',2'-c]fluorene trioxime (500 mg, 0.65 mmol) and triethylamine (312 μί, 2.24 mmol). The reaction mixture was stirred overnight. Then solvent was evaporated under reduced pressure to give a dark brown oil. It was purified by column chromatography using silica gel mobile phase and a mixture of ethyl acetate and hexanes as eluent. The solvent was evaporated under vacuum to give a pale brown solid (207 mg, 40 %). The melting point and decomposition temperature were determined by differential scanning calorimeter and thermal gravimetric analysis to be around 124°C and 260°C, respectively.
Figure imgf000092_0001
[00180] 1H NMR (500 MHz, CDCI3) δ 8.71 (s, 3 H), 7.88 (d, J = 8.6 Hz, 3H), 7.66 (d, J = 8.6 Hz, 3H), 4.98 (t, J = 7.5 Hz, 6H), 2.60 (s, 9H), 2.36 (s, 9H), 1.95 (p, J = 6.6 Hz, 6H), 1.20-1.1 1 (m, 18H), 0.76 (t, J = 7.1 Hz, 9H).
Example 1.13 - 4,9,13-triethoxyacetyloxime-O-triacetatetruxenone
[00181] The synthesis of 4,9, 13-triethoxyacetyloxime-O-triacetatetruxenone was performed according to the scheme shown in Figure 1 1.
(a) Synthesis of 4, 9, 13-triethoxyacetyltruxenone (3B):
[00182] Aluminum trichloride (1.47 g, 11.02 mmol) was slowly added into a solution containing dichloromethane (10 mL) and truxenone (3A, 1.29 g, 3.35 mmol). The solution turned dark red. Then, ethoxyacetyl chloride (1.81 g, 14.75 mmol) was added dropwise over a period of 2 minutes. The reaction was continued for 36 hours. Then, the reaction mixture was quickly filtered, and concentrated under vacuum to obtain a sticky product. Anhydrous ethanol (15 mL) was added to form a slurry, which was placed in a sonic bath for 30 minutes. The solid product was filtered, copiously washed with ethanol and dried under high vacuum at 30°C overnight to afford a pale yellow solid (1.83 g, 85% yield).
(b) Synthesis of 4, 9, 13-triethoxyacetyioximetruxenone (3C):
[00183] 4,9, 13-Triethoxyacetyltruxenone (707 mg, 1.10 mmol) was dissolved in 1 ,4-dioxane (120 mL) under nitrogen. The reaction mixture was gently heated to dissolve of the solid. A solution of sodium acetate (285 mg, 4.32 mmol) and hydroxyl ammonium chloride (255 mg, 3.67 mmol) in water (40 ml) was added to the reaction mixture, which was then refluxed for 24 h. The reaction was monitored by TLC using ethyl acetate (20 %) and hexane (80 %) as eluent. After the reaction was completed, the product was precipitated in cold water (200 mL). A beige solid product was obtained by vacuum filtration, copiously washed with water and dried under vacuum at 30°C until constant weight (680 mg, 90% yield).
( c) Synthesis of 4,9, 13-triethoxyacetyloxime-O-triacetatetivxenone (3D):
[00184] Acetyl chloride (167 μΙ_, 2.34 mmol) was slowly added into tetrahydrofuran solution (500 mL) containing 4,9, 13-triethoxyacetyloximetruxenone (447 mg, 0.65 mmol) and triethylamine (312 μΙ_, 2.24 mmol). The reaction mixture was stirred overnight. Then, the solvent was evaporated under reduced pressure to give a dark brown oil. It was purified by column chromatography using a silica gel mobile phase and a mixture of ethyl acetate and hexanes as eluent. The solvent was evaporated under vacuum to give a pale solid product (158 mg, 30 %).
Example 1.14 - 3,8, 13-trihexanoyl-5, 10, 15-trihexyl-10, 15-dihydro-5H-5, 10, 15-triazadiindeno[1,2-a;1',2'-c] fluorene tiioxime tri-O-acetate
[00185] The synthesis of 3,8, 13-trihexanoyl-5, 10, 15-trihexyl-l 0, 15-dihydro-5H-5, 10, 15-triazadiindeno [1 ,2-a; 1 ',2'-c]fluorene trioxime tri-O-acetate (shown below) was performed similarly to Example 1.11 with the exception that acetyl chloride was re laced with hexanoyl chloride in step (b).
Figure imgf000093_0001
[00186] 3,8, 13-Trihexanoyl-5, 10, 15-trihexyl-10, 15-dihydro-5H-5, 10, 15-triazadiindeno[1 ,2-a; 1 ',2'-c]fluorene trioxime tri-O-acetate was obtained as a white solid product with a 28 % overall yield.
[00187] 1H NMR (500 MHz, CDCI3) δ: 8.69 (s, 3 H), 7.83 (d, J = 8.4 Hz, 3H), 7.67 (d, J = 8.7 Hz, 3H), 5.00 (t, J = 7.1 Hz, 6H), 3.05 (t, J = 7.8 Hz, 6H), 2.35 (s, 9H), 1.95 (p, J = 7.1 Hz, 6H), 1.72 (p, J = 7.6 Hz, 6H), 1.50-1.44 (m, 6H), 1.41 (p, J = 7.4 Hz, 6H), 1.25-1.13 (m, 18H), 0.94 (t, J = 7.3 Hz, 9H), 0.76 (t, J = 7.1 Hz, 9H).
[00188] The UV-Vis spectrum of 3,8, 13-Triacetyl-5, 10, 15-trihexyl-10, 15-dihydro-5H-5, 10, 15- triazadiindeno[1 ,2-a; 1 ',2'-c]fluorene trioxime tri-O-acetate is shown in Figure 12. This spectrum shows strong absorption bands between 300 and 400 nm. More particularly, the spectrum shows a strong absorption at 365 nm followed by a sharp decline. This enhances sensitivity, while avoiding color interference.
Example 1.15 - 2, 7, 12-Tii(4-acetylphenyl)-5,5, 10, 10, 15, 15-hexahexyl-10, 15-άΐΗγάΓθ-5Η-άϋηάβηο[1,2-3;ΐ;2·- c] fluorene trioxime tii-O-acetate
(a) Synthesis of 2, 7, 12-Tri(4-acetylphenyl)-5,5, 10, 10, 15, 15-hexahexyl-10, 15-dihydro-5H-diindeno[1,2- a;T,2'-c]fluorene trioxime
[00189] In a 100mL 3-necks flask, 2,7, 12-tri(4-acetylphenyl)-5,5', 10, 10', 15, 15'-hexahexyltruxene (6g) was dissolved in dioxane (50mL) under nitrogen. A solution of hydroxylammonium chloride (346mg) and sodium acetate (329mg) in water (15mL) was added to this solution. The reaction mixture was refluxed for 12h. The reaction was monitored by TLC using 5% ethyl acetate in toluene. The solvent was evaporated under reduced pressure. Then water (250mL) was added and the compound was filtered off to afford a sticky solid. The product was purified by recrystallization in methanol and left at -20°C overnight. The compound (shown below) was filtered to afford 4g (65%) of a white powder.
Figure imgf000094_0001
[00190] 1H NMR (500 MHz, CDCI3) δ 8.52-8.50 (m, 3H); 8.03-7.94 (m, 6H); 7.91-7.85 (m, 6H); 7.79-7.73 (m, 6H); 3.05 (s, 6H); 2.71 (s, 9H); 2.22 (s, 6H); 0.96-0.90 (m, 36H); 0.63-0.61 (m, 30H).
(b) 2, 7, 12-Tri(4-acetylphenyl)-5,5, 10, 10, 15, 15-hexahexyl-10, 15-dihydro-5H-diindeno[1,2-a;1 ',2'-c]fluorene tnoxime tri-O-acetate
[00191] In a flame dried 1 L 3-neck flask was added dry tetrahydrofuran and 2,7, 12-Tri(4-acetylphenyl)- 5,5, 10, 10, 15, 15-hexahexyl-10, 15-dihydro-5H-diindeno[1 ,2-a; 1 ',2'-c]fluorene trioxime (3g) under nitrogen. The reaction was allowed to cool down to 0°C in an ice bath before the addition of triethylamine (1.1 mL). The reaction was stirred for 5min before the slow addition of acetyl chloride (0.591 mL). The reaction was stirred 2h at 0°C and monitored on TLC using 5% ethyl acetate in toluene as eluent. The reaction mixture was extracted in ethyl acetate and water, dried over magnesium sulphate and the solvent evaporated under reduced pressure. Then methanol (500mL) was added to the crude product and the solution was heated and filtered. The crude product was dissolved in 2-propanol, the solution was heated, and left at -20°C for 1 h then filtered to afford 2g (60%) of a white powder.
Figure imgf000095_0001
(Truxe-12)
[00192] 1H NMR (500 MHz, CDCI3) δ 8.48 (d, J = 8.4 Hz, 3H); 7.94 (d, J = 8.6 Hz, 6H); 7.84 (d, J = 8.6 Hz, 6H); 7.74-7.72 (m, 6H); 3.08-3.01 (m, 6H); 2.50 (s, 9H); 2.34 (s, 9H) 2.24-2.15 (m, 6H); 1.03-0.85 (m, 36H); 0.64-0.58 (m, 30H).
[00193] UV-Vis (THF): 338 nm. DSC: 124°C. IR (KBr): 2955, 2924, 2855, 1772, 1603, 1478, 1364, 1318, 1 199, 984, 933, 890, 830, 808.
[00194] Figure 13 shows the UV spectra of Carba-05 (which is Irgacure OXE-02 from BASF), aHd-Truxe-08T and Truxe-07 (from above), [My T: Which Examples above are Truxe -08 and -07?1 and Truxe-12 (from Example 1.15). The spectra have been normalized so that the maximum absorption of Carba-05 is 1. In this figure, Carba-05 is the curve with a maximum absorption at 277 nm and a relative absorption at 365 nm or 0.161. Truxe-08 has two absorption peaks at 304 and 333 nm with a relative absorption at 365 nm of 0.754. Truxe-07 has one absorption peak at 325 nm and a relative absorption at 365 nm of 0.043. Finally, Truxe-12 has an absorption peak at 338 nm and a relative absorption at 365 nm of 0.666. It should be noted that Truxe-12 has a higher absorption than OXE-02.
Example 1.16 - 2,7,12-triacetyl-5,5',10,10',15,15'-hexahexyltruxene (INDENO 332)
[00195] The synthesis of 2,7, 12-triacetyl-5,5', 10,10',15, 15'-hexahexyltruxene was effected by dissolving 4.3 grams of 5,5', 10,10', 15,15'-hexahexyltruxene in a 250 mL flame dried flask containing 50 mL of dichloromethane under N2. Acetyl chloride (1.83 mL) was added, and then aluminum chloride (3.27 g) was slowly added over a period of 15 minutes. The reaction mixture was stirred at room temperature overnight. The reaction was monitored by TLC using 2.5% EtOAc in toluene as eluent. An extraction was performed using dichloromethane and water. The mixture was then dried over magnesium sulfate. The crude product was carefully dried under high vacuum, precipitated in methanol and then filtered to afford an off white powder (5.5g, 72%).
Figure imgf000096_0001
[00196] H1NMR (500 MHz, CDCI3) δ 8.49 (d, J = 8.4 Hz, 3H); 8.12 (d, J = 1.7 Hz, 3H); 8.07 (dd, J1 = 1.7, J2 = 8.3 Hz, 3H); 3.00 2.94 (m, 6H); 2.76 (s, 9H); 2.25 2.19 (m, 6H); 0.98 0.79 (m, 36H); 0.61 (t, J = 7.1 , 18H); 0.52 0.44 (m, 12H).
[00197] The maximum absorption peak and absorption coefficient of 2,7,12-triacetyl-5,5', 10, 10', 15, 15'- hexahexyltruxene in tetrahydrofuran solution are 332 nm and 8.66 x 104 L / mol .cm, respectively. The melting point was measured to be 217 °C by DSC.
Example 1.17 - 3 ,13-triacetyl-5,10,154rihexyl-10,15 ihydro-5H-5,10,154riaza
[1,2-3;1·,2·-ο]-ίΙυοΓβηβ (INDENO 336)
[00198] The synthesis of 3,8, 13-triacetyl-5, 10, 15-trihexyl-10, 15-dihydro-5H-5, 10, 15-triazadiindeno[1 ,2-a; 1 ',2'-c]- fluorene was done by slowly adding aluminum trichloride (1.47 g, 1 1.02 mmol) into a solution containing dichloromethane (10 mL) and 5, 10, 15-trihexyl-10, 15-dihydro-5/-/-5, 10, 15-triazadiindeno[1 ,2-a;1 ',2'-c]fluorene (2 g, 3.35 mmol). The solution turned dark red. Then, acetyl chloride (750 μΙ_, 14.75 mmol) of was added dropwise over a period of 2 minutes. The reaction was monitored by TLC using a mixture of ethyl acetate (30 %) and hexane (70 %) as an eluent. After the reaction was completed, the reaction mixture was quickly filtered and concentrated under vacuum to obtain a sticky red product. Anhydrous ethanol (15 mL) was added to form a slurry, which was placed in a sonic bath for 30 minutes. The solid product was filtered, copiously washed with ethanol and dried under high vacuum at 30°C overnight to afford a pale red solid (1.93 g, 80% yield).
Figure imgf000097_0001
[00199] 1H NMR (500 MHz, CDCI3) δ 9.02 (s, 3 H), 8.13 (d, J = 8.6 Hz, 3H), 7.66 (d, J = 8.5 Hz, 3H), 5.00 (t, J = 7.7 Hz, 6H), 2.80 (s, 9H), 1.99 (p, J = 7.6 Hz, 6H), 1.33 (p, J = 7.3 Hz, 6H), 1.26-1.17 (m, 12H), 0.78 (t, J = 7.1 Hz, 9H).
[00200] The maximum absorption peak and absorption coefficient of 3,8, 13-triacetyl-5, 10, 15-trihexyl-10, 15- dihydro- 5H-5, 10, 15-triazadiindeno[1 ,2-a; 1 ',2'-c]-fluorene in tetrahydrofuran solution are 336 nm and 7.40 x 104 L mo crrr1, respectively.
Example 1.18 - 2,7, 12-tri(4-acetylphenyl)-5,5', 10,10', 15,15'-hexahexyltruxene
[00201] TRUXE-03 [MY T: What is Truxo 03? Do you moan TRUXE 3H, TRUXE 3Br or TRUXE 3F?] (8.5g), 4-acetylphenylboronic acid (4.2g) and toluene (500mL) were introduced in a 500mL flask, flushed with nitrogen. Potassium carbonate (28g) dissolved in water (l OOmL) was added to this mixture. The reaction mixture was bubbled with nitrogen for 30min. Then, palladium acetate (52mg) and triphenylphosphine (62mg) were added to the solution. The reaction mixture was heated at reflux for 2 days before adding 4-acetylphenylboronic acid (4.2g). The reaction was once again refluxed for 2 days before the final addition of 4-acetylphenylboronic acid (4.2g). The reaction was then refluxed for 4 days. The reaction was monitored using 100% toluene as eluent. The reaction mixture was washed three times with water, dried over magnesium sulphate and concentrated under reduced pressure. The mixture was quickly passed over a silica gel pad using 100% toluene as eluent to afford 7g (75%) of the desired product.
Figure imgf000098_0001
[00202] 1H NMR (500 MHz, CDCI3) δ 8.50 (d, J = 8.3 Hz, 3H); 8.14 (d, J = 8.6 Hz, 6H); 7.89 (d, J = 8.5 Hz, 6H); 7.77-7.75 (m, 6H); 3.08-3.02 (m, 6H); 2.72 (s, 9H); 2.25-2.19 (m, 6H); 1.05-0.85 (m, 36H); 0.64-0.58 (m, 30H).
[00203] The maximum absorption peak and absorption coefficient of 2C in tetrahydrofuran solution are 340 nm and 12.64 x 104 L moMcrrr1, respectively. The melting point is 85°C.
Example 1.19 - 2J,12-tri-(o-toluloyl)-5,5 10,10 15,15'-hexahexyltruxene (INDENO 337)
[00204] 5,5', 10, 10', 15, 15'-Hexahexyltruxene (1.1 g) was dissolved in 10 mL of CH2CI2 in a 100 mL flask under N2. o-Toluloyl chloride (638 mg, 3.20 eq) was added, and then aluminium chloride (525 mg, 3.05 eq) was added slowly over a period of 15 minutes. The reaction mixture was stirred at room temperature overnight. The reaction was monitored by TLC using 100% toluene as eluent. If necessary, aluminium chloride (130 mg, 0.76 eq) and o-toluloyl chloride (160 mg, 0.80 eq) were added to the reaction mixture and the reaction was stirred at room temperature overnight. The reaction was quenched by the careful and slow addition of water. An extraction was performed using CH2CI2 and water. The mixture was then dried over MgS04. The crude product was purified on a silica gel column using 50% hexanes in toluene to 100% toluene. The resulting thick oil was triturated in methanol and filtered to afford a light yellow powder (720 mg, 46%).
Figure imgf000099_0001
[00205] 1H NMR (500 MHz, CDCI3) δ 8.42 (d, J = 8.4 Hz, 3H), 7.99 (d, J = 1.5 Hz, 3H), 7.80 (dd, ^ = 1.4 Hz, J2 = 8.3 Hz, 3H), 7.47-7.41 (m, 6H), 7.35 (d, J = 7.6 Hz, 3H), 7.31 (t, J = 7.4 Hz, 3H), 2.95-2.86 (m, 6H), 2.40 (s, 9H), 2.17-2.09 (m, 6H), 0.97-0.79 (m, 36H), 0.61 (t, J = 7.0 Hz, 18H), 0.53-0.44 (m, 12H).
[00206] The maximum absorption peak and absorption coefficient of 2, 7, 12-tri-(o-toluloyl)-5,5', 10, 10', 15, 15'- hexahexyltruxene in tetrahydrofuran solution are 336 nm and 7.90 x 104 L mo crrr1, respectively. The melting point is 125°C.
Example 1.20 - 2,7,12-Tri-(phenoyl)-5,5',10,10',15,15'-hexahexyltruxene (INDENO 333)
[00207] 5,5', 10, 10', 15, 15'-Hexahexyltruxene (5.0 g) was dissolved in 50 mL of CH2CI2 in a 100 mL flask under N2. Benzoyl chloride (2.6 g, 3.20 eq) was added, and then aluminium chloride (3.3 g, 3.05 eq) was slowly added over a period of 5 minutes. The reaction mixture was stirred at room temperature for two days. The reaction was monitored by HPLC (peak at 8 min.) and TLC using 100% toluene as eluent. If necessary, aluminium chloride (825 mg, 0.76 eq) and benzoyl chloride (650 mg, 0.80 eq) were added to the reaction mixture and the reaction was stirred at room temperature overnight. The reaction was quenched by the careful and slow addition of water (WARNING: highly exothermic). An extraction was performed using CH2CI2 and water. The organic layer was washed with a 1 M solution of NaHC03 and then dried over MgS04. The solution was concentrated under reduced pressure. The resulting tarry solid was triturated in methanol for 1 h and filtered. After filtration, the crude product was recrystalized from 2-propanol to afford 3.3g (48%, 100% : 6.84g). Further purification, when desired, was achieved on a silica gel column using 50% hexanes in toluene to 100% toluene (started with 500 mg, recovered 60 mg, 12%).
Figure imgf000100_0001
[00208] 1H NMR (500 MHz, CDCI3) δ 8.48 (d, J = 8.4 Hz, 3H), 7.96 (d, J = 1.6 Hz, 3H), 7.93-7.88 (m, 9H), 7.65 (tt, J, = 7.5 Hz, J2 = 1.3 Hz, 3H), 7.55 (t, J = 7.7 Hz, 6H), 3.00-2.92 (m, 6H), 2.21 -2.13 (m, 6H), 1.00-0.83 (m, 36H), 0.63 (t, J = 7.3 Hz, 18H), 0.58-0.50 (m, 12H).
[00209] The maximum absorption peak and absorption coefficient of 2, 7, 12-tri-(phenoyl)- 5,5', 10, 10', 15, 15 -hexahexyltruxene in tetrahydrofuran solution are 332 nm and 8.55 x 104 L mo crrr1, respectively. The melting point is 155°C.
Example 1.21 - 2,7, 12-tri-(2-thienyloyl)-5,5', 10,10', 15,15'-hexahexyltruxene
[00210] 5,5', 10, 10', 15, 15'-Hexahexyltruxene (5.0 g) was dissolved in 50 mL of CH2CI2 in a 100 mL flask under N2. 2-thiophenecarbonyl chloride (2.8 g, 3.20 eq) was added, and then aluminium chloride (3.3 g, 3.05 eq) was slowly added over a period of 5 minutes. The reaction mixture was stirred at room temperature for two days. The reaction was monitored by HPLC (peak at 5 min.) and TLC using 100% toluene as eluent. If necessary, aluminium chloride (825 mg, 0.76 eq) and 2-thiophenecarbonyl chloride (700 mg, 0.80 eq) were added to the reaction mixture and the reaction was stirred at room temperature overnight. The reaction was quenched by the careful and slow addition of water (WARNI NG: highly exothermic). An extraction was performed using CH2CI2 and water. The organic layer was washed with a 1 M solution of NaHC03 and then dried over MgSC . The solution was concentrated under reduced pressure. The resulting tarry solid was triturated in methanol for 1 h and filtered. After filtration, the crude product was recrystalized from 2-propanol to afford 580 mg (8%, 100% : 6.95 g) of a compound suitable for analysis and 1.6g (23%) of acceptably pure compound. Both fractions showed only one peak by HPLC but the 1.6 g fraction showed a small impurity on TLC.
Figure imgf000101_0001
[00211] 1H NMR (500 MHz, CDCI3) δ 8.51 (d, J = 8.2 Hz, 3H), 8.03-7.99 (m, 6H), 7.78 (dd, J, = 4.9 Hz, J2 = 1.1 Hz, 3H), 7.77 (dd, J, = 3.8 Hz, J2 = 1.1 Hz, 3H), 7.24 (dd, J, = 4.8 Hz, J2 = 3.8 Hz, 3H), 3.00-2.95 (m, 6H), 2.24- 2.17 (m, 6H), 1.01 -0.82 (m, 36H), 0.62 (t, J = 7.0 Hz, 18H), 0.58-0.49 (m, 12H).
[00212] The maximum absorption peak and absorption coefficient of 2,7, 12-tri-(2-thienyloyl)- 5,5', 10, 10', 15, 15'-hexahexyltruxene in tetrahydrofuran solution are 338 nm and 8.53 x 104 L mo crrr1, respectively. The melting point is 125°C.
Example 1.22 - 2,7, 12-tri-(4-methoxyphenyloyl)-5,5', 10,10', 15,15'-hexahexyltruxene
[00213] 5,5', 10, 10', 15, 15'-Hexahexyltruxene (5.0 g) was dissolved in 50 mL of CH2CI2 in a 100 mL flask under N2. 3-methoxybenzyol chloride (3.2 g, 3.20 eq) was added, and then aluminium chloride (3.3 g, 3.05 eq) was slowly added over a period of 5 minutes. The reaction mixture was stirred at room temperature for two days. The reaction was monitored by HPLC (peak at 6 min.) and TLC using 2% ethyl acetate in toluene as eluent. If necessary, aluminium chloride (825 mg, 0.76 eq) and 3-methoxybenzyol chloride (800 mg, 0.80 eq) were added to the reaction mixture and the reaction was stirred at room temperature overnight. The reaction was quenched by the careful and slow addition of water (WARNING : highly exothermic). An extraction was performed using CH2CI2 and water. The organic layer was washed with a 1 M solution of NaHC03 then dried over MgSC . The solution was concentrated under reduced pressure. The resulting tarry solid was triturated in methanol for 1 h and filtered. After filtration, the crude product was recrystalized from 2-propanol to afford 700 mg (9%, 100% : 7.37 g). Further purification, when desired, was achieved on a silica gel column using 100% toluene to 10% ethyl acetate in toluene (recovered 30 mg).
Figure imgf000102_0001
[00214] 1H NMR (500 MHz, CDCI3) δ 8.48 (d, J = 8.4 Hz, 3H), 7.95 (d, J, = 1.5 Hz, 3H), 7.93 (dd, J, = 8.3 Hz, J2 = 1.6 Hz, 3H), 7.46-7.42 (m, 9H), 7.21-7.18 (m, 3H), 3.91 (s, 9H), 3.00-2.93 (m, 6H), 2.20-2.13 (m, 6H), 1.00-0.82 (m, 36H) 0.63 (t, J = 7.0 Hz, 18H), 0.59-0.48 (m, 12H).
[00215] The maximum absorption peak and absorption coefficient of 2, 7, 12-tri-(4-methoxyphenyloyl)- 5,5', 70, 70', 75, 75'-hexahexyltruxene in tetrahydrofuran solution are 333 nm and 8.55 x 104 L moMcrrr1, respectively. The melting point is 137°C.
Example 1.23 - 2,7,12 tri-(2-acetylphenyl)-5,5',10,10',15,15' hexahexyltruxene
[00216] 2,7, 12-tribromo-5,5', 10, 10', 15, 15'-hexahexyltruxene (1.7g), 2-acetylphenylboronic acid (0.84g) and toluene (lOOmL) were introduced in a 500mL flask, flushed with nitrogen. Sodium carbonate (5.6g) dissolved in water (20mL) and tetrabutylammonium bromide (100mg) were added to this mixture. The reaction mixture was bubbled with nitrogen for 30min. Then, palladium acetate (48mg) and triphenylphosphine (60mg) were added to the solution. The reaction mixture was heated at reflux for 2 days. The reaction mixture was washed with water three times, dried over magnesium sulphate and concentrated under reduced pressure. The mixture was quickly passed over a silica gel using 100% toluene, then 1 to 3% acetone in toluene as eluent to afford 500mg (27%) of the desired product.
Figure imgf000103_0001
[00217] 1H NMR (500 MHz, CDCI3) δ 8.42 (d, J = 8.2 Hz, 3H), 7.61 -7.55 (m, 9H), 7.48-7.45 (m, 6H), 7.42 (dd, J1 = 8.2 Hz, J2 = 1.7 Hz, 3H), 3.04-2.96 (m, 6H), 2.15-2.07 (m, 6H), 2.01 (s, 9H), 1.00-0.80 (m, 36H), 0.60 (t, J = 7.3 Hz, 18H), 0.58-0.52 (m, 12H).
[00218] The maximum absorption peak and absorption coefficient of 2, 7, 12-tri-(2-acetylphenyl)- 5,5', 70, 70', 75, 75'-hexahexyltruxene in tetrahydrofuran solution are 323 nm and 9.20 x 104 L moMcrrr1, respectively. The melting point is 136°C.
[00219] Figure 13 shows the relative UV-Vis absorbance of the photoinitiators of Examples 1.16 and 1.18 to 1.23.
RED, GREEN, BLUE AND BLACK COLOR FILTER RESISTS
Examples 2.1 to 2.10 and Comparative Example 1
[00220] Red, green, and blue color filter resists and black matrix with different photoinitiators were prepared by mixing 1.0 part of photoinitiators, 13 parts of resist vehicles, 6.0 parts of the corresponding pigment dispersions, i.e., Red-254, Green-36, Blue-15 and Black-250, respectively, using a high shear mixer for 2 hours. The resulting mixtures were filtered through a 1 μηι pore filter. The pigmented solutions were coated on glass using a spin coater, dried at 100°C for 2 minutes to produce uniform films having a thickness around 3 μηι.
[00221] The color resist films were exposed using a 250 W super high pressure mercury lamp under air with a dose of 1 ,000 mJ/cm2 through a 21 -gray-scale step target mask (Stouffer Graphic Arts T21 15). The exposed films were developed using aqueous potassium hydroxide solution (pH 12), washed copiously with de-ionized water, and then dried at 100°C for 30 minutes. The results are summarized in the table below.
Examples Photoinitiators Sensitivity (mJ/cm2 Red Green Blue Black
2.1 Example 1.1 32 82 90 107
2.2 Example 1.2 32 82 90 107
2.3 Example 1.3 36 89 97 120
2.4 Example 1.4 38 91 105 115
2.5 Example 1.5 28 74 89 107
2.6 Example 1.6 18 42 51 65
2.7 Example 1.7 12 37 42 49
2.8 Example 1.8 18 46 54 67
2.9 Example 1.9 39 94 98 117
2.10 Example 1.10 15 41 49 57
Comparative Example 1 Irgacure OXE-2 34 86 98 1 15
[00222] In this table, the value reported for the sensitivity is the minimum dose required to fully cure the color resist films. It was calculated from the transmittance of the highest step number remaining after development. It is desirable that the minimum dose (mJ/cm2) required be as small as possible, which indicates a highly sensitive compound. Generally, the more sensitive the photoinitiator, the less time it takes to cure the composition.
[00223] It can be seen from the above table that the compounds of the invention are about as sensitive as Irgacure OXE-2 and sometimes even more sensitive.
Examples 2.11 to 2.18 and Comparative Examples (CE) 2 to 5
[00224] Red, green, blue and black color resists were prepared by mixing the pigment dispersion, resist vehicle and the photoinitiators of Examples 1.1 1 and 1.12 using a high shear mixer for 2 hours. The resulting mixture was filtered through a 1 μηι pore filter. The pigmented solutions were coated on glass using spin coater, dried at 100°C for 2 minutes to produce a uniform film having a thickness around 3 μηι. For comparison, commercially available photoinitiator, Irgacure OXE-02 was also used.
[00225] The color resist films were exposed using a 250 W super high pressure mercury lamp under air with a dose of 1 ,000 mJ/cm2 through a 21 -gray-scale step target mask (Stouffer Graphic Arts T21 15). The exposed films were developed using aqueous potassium hydroxide solution (pH 12), copiously washed with de-ionized water, and then dried at 100°C for 30 minutes. The results are summarized in the table below.
[00226] In this table, the value reported for photosensitivity is the minimum dose required to fully cure the color resist films. It was calculated from the transmittance of the highest step number remaining after development. It is desirable that the minimum dose (mJ/cm2) required be as small as possible, which indicates a highly sensitive compound. Generally, the more sensitive the photoinitiator, the less time it takes to cure the composition. EXAMPLES
Ingredients (Solid weight in grams)
2.11 2.12 CE 2 2.13 2.14 CE 3 2.15 2.16 CE 4 2.17 2.18 CE 5
Red-254 6.0 6.0 6.0
Green-30 5.0 5.0 5.0
Yellow-150 1.0 1.0 1.0
Blue-15 6.0 6.0 6.0
Black-250 6.0 6.0 6.0
Resist vehicle 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0
Photoinitiator 1.0 1.0 1.0 1.0
of Example 1.11
Photoinitiator 1.0 1.0 1.0 1.0 of Example 1.12
Irgacure® OXE02 1.0 1.0 1.0 1.0
Sensitivity (mJ/cm2) 29 25 34 74 67 86 83 75 98 97 86 115
[00227] As can be seen from the above, the compounds of the invention tested are, in all cases, more senstive that Irgacure OXE-02.
LITHOGRAPHIC OFFSET PRINTING PLATES
Example 3.1
[00228] A coating composition was prepared by mixing 250 g of BR10-010, 67 g of UR07-009, 1.0 g of basic green 4, 33 g of Blue-15, and 5.0 g of photoinitiator from Example 1.7, and 900 g of cyclohexanone solution using a high shear mixer for 5 hours. The resulted solution was filtered through a 5 μηι pore filter. It was coated on an anodized aluminum substrate, which was postreated with phosphate fluoride (PF) using a wire-wound rod, then dried in a hot air oven at 100 °C for 5 minutes.
[00229] The plate was exposed using a 250 W super high pressure mercury lamp under air with an energy density of 100 mJ/cm2 through a 21-gray-scale step target mask (Stouffer Graphic Arts T2115). The exposed plate was developed with aqueous solution containing 1 % soap solution using a Tung Sung 800 processor at 25°C and 20 seconds dwell time to give a high resolution image.
The developed plate was placed on a Heidelberg 46 press using black ink (Toyo Black) and fountain solution (UF300, available from Mylan Group, Vietnam) and produced 20,000 copies with good quality.
Example 3.2
[00230] A printing plate was prepared in a manner similar to that described in Example 3.1 excepted that the photoinitiator from Example 1.10 was used to replace the photoinitiator from Example 1.7.
[00231] The plate was exposed using a 250 W super high pressure mercury lamp under air with an energy density of 100 mJ/cm2 through a 21-gray-scale step target mask (Stouffer Graphic Arts T2115). The exposed plate was developed with aqueous solution containing 1 % soap solution using a Tung Sung 800 processor at 25°C and 20 seconds dwell time to give high resolution image.
[00232] The developed plate was placed on a Heidelberg 46 press using black ink (Toyo Black) and fountain solution (UF300, available from Mylan Group, Vietnam) and produced 20,000 copies with good quality
Example 3.3
[00233] A coating composition was prepared by mixing 250 g of BR10-010, 67 g of UR07-009, 1.0 g of basic green 4, 33 g of Blue-15, and 5.0 g of photoinitiators 1 E (Example 1.1 1) and 900 g of 2-methoxypropanol solution using a high shear mixer for 5 hours. The resulted solution was filtered through a 5 μηι pore filter. It was coated on an anodized aluminum substrate, which was postreated with phosphate fluoride (PF) using a wire-wound rod, then dried in a hot air oven at 100 °C for 5 minutes.
[00234] The plate was exposed using a 250 W super high pressure mercury lamp under air with an energy density of 100 mJ/cm2 through a 21-gray-scale step target mask (Stouffer Graphic Arts T2115). The exposed plate was developed with aqueous solution containing 1 % Mr. Clean soap solution using a Tung Sung 800 processor at 25°C and 20 seconds dwell time to give high resolution image.
[00235] The developed plate was placed on a Heidelberg 46 press using black ink (Toyo Black) and fountain solution (UF300, available from Mylan Group, Vietnam) to produce 20,000 copies with good quality.
Example 3.4
[00236] The printing plate was prepared similar to Example 3.3 except that the photoinitiator from Example 1.12 was used instead of that of Example 1.1 1.
[00237] The plate was exposed using a 250 W super high pressure mercury lamp under air with an energy density of 100 mJ/cm2 through a 21-gray-scale step target mask (Stouffer Graphic Arts T2115). The exposed plate was developed with aqueous solution containing 1 % Mr. Clean soap solution using a Tung Sung 800 processor at 25°C and 20 seconds dwell time to give high resolution image.
[00238] The developed plate was placed on a Heidelberg 46 press using black ink (Toyo Black) and fountain solution (UF300, available from Mylan Group, Vietnam) to produce 20,000 copies with good quality.
UV CURABLE INKJET PRINTING INKS
Examples 4.1 to 4.4 [00239] Ultra-violet radiation curable inkjet printing inks having the compositions shown in the table below were prepared by using a high shear mixer to form uniform solutions. These solutions were filtered throught a 1.0 μηι propylene filter. The filtered inks were printed on polyester films with different testing patterns and 300 DPI resolution using the Richol G4 print heads, which were jetted at 50 °C. The printed patterns were cured with a UV-LED curing unit (Model: 8 Watt/cm2 Fireline, available from Phoseon Technology, Oregon, USA) at a speed of ten meter per minute. The UV-LED curing unit was placed 5 cm about the printed films. Fully cured printing patterns from inkjet inks comprising the invented photoinitiators were obtained with high resolution and good adhesion to the polyester substrate.
EXAMPLES
Ingredients (gram)
4.1 4.2 4.3 4.4
ADD-2204 3.50 3.50 3.50 3.50
ADD-9984 10.0 10.0 10.0 10.0
ADD-9991 10.0 10.0 10.0 10.0
ADD-9992 8.00 8.00 8.00 8.00
ADD-9995 10.0 10.0 10.0 10.0
ADD-2614 10.0 10.0 10.0 10.0
POL-0138 2.50 2.50 2.50 2.50
POL-1001 10.0 10.0 10.0 10.0
POL-0137 1.00 1.00 1.00 1.00
600-B307 1.00 1.00 1.00 1.00
COL-1829 8.40 8.40 8.40 8.40
ADD-9993 20.6 20.6 20.6 20.6
Photoinitiator of Example 1.16 5.00 0.00 0.00 0.00
Photoinitiator of Example 1.17 0.00 5.00 0.00 0.00
Photoinitiator of Example 1.21 0.00 0.00 5.00 0.00
Photoinitiator of Example 1.18 0.00 0.00 0.00 5.00
Total 100 100 100 100
Viscosity at 25 °C (cPs) 23.6 23.4 23.2 23.5 OXYGEN SCAVENGING PLASTIC FILMS
[00240] The oxygen scavenging activity of the polymeric films comprising photoinitiators of the invention was demonstrated by monitoring the reduction in oxygen concentration as a result of consumption of oxygen by the prepared film sample. Thus, 1.0 gram of film sample made from acetal copolymer comprising cyclohexane pendant groups (PACH-001), cobalt (II) oleate salt and a photoinitiator was placed in a glass bottle. The glass bottle was sealed with a homemade cap containing an oxygen fluorescent probe. The glass bottle was then flushed with nitrogen gas containing around 21 % of oxygen. The bottle was then sealed and activated by exposure to a UV light at 254 nm at room temperature with a dosage of 100 mJ/cm2. The reduction in oxygen concentration over time was monitored using an Oxysense's GEN III 5000 non-invasive oxygen monitoring and permeation system.
Example 4.1
[00241] One hundred parts of an acetal copolymer comprising cyclohexane pendant group (PACH-001) was dissolved in 1 ,3-dioxane to make up a 20% solution. To this solution were added 0.1 parts of cobalt (II) oleate salt and 0.1 parts of the photoinitiator of Example 1.16. When the solution became clear, it was poured onto a flat Teflon surface and the solvent was allowed to evaporate at room temperature. The obtained polymer film was further dried in a vacuum overnight, which gave an optically clear film having a thickness of around 200 μηι. This film was used for the subsequent demonstration for oxygen scavenging activity. Results of the reduction of oxygen versus time are shown in Figure 15
[00242] For comparative purposes, a similar PACH-001 film was prepared without the photoinitiator of Example 1.16. The oxygen scavenging activity was also monitored and is also shown in Figure 15
EXAMPLE 4.2:
[00243] One hundred parts of PACH-001 was dissolved in a solvent mixture comprising equal amounts of tetrahydrofuran and 2-methoxy propanol to make up a 20% solution. To this solution were added 0.1 parts of cobalt II oleate salt and 0.2 parts of the photoinitiator of Example 1.17. After the solution became clear, it was poured onto a flat Teflon surface and the solvent was allowed to evaporate at room temperature. The obtained polymer film was further dried in a vacuum overnight, which gave an optically clear film having a thickness of around 200 μηι. This film was used for the subsequent demonstration for oxygen scavenging activity. Results of the reduction of oxygen versus time are shown in Figure 16s
[00244] The results of Examples 4.1 and 4.2 indicate that truxene photoinitiators are very effective in the oxygen scavenging compositions.
[00245] The scope of the claims should not be limited by the preferred embodiments set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole. REFERENCES
[00246] The content of the following documents is herein incorporated by reference in their entirety.
Kura ef a/., "New Oxime Ester Photoinitiators U.S. Pat. No. 3,558,309;
for Color Filter Resists", Radtech Report, U.S. Pat. No. 4,255,513;
May/June 2004, p30-35;
U.S. Pat. No. 4,575,330;
Odian, "Principles of Polymerization", 4th
U.S. Pat. No. 4,776, 152;
Edition, Wiley-lnterscience;
U.S. Pat. No. 5,840,465
EP 320,264;
U.S. Pat. No. 5,853,446
EP 678,534;
U.S. Pat. No. 6,051 ,367;
EP 855,731 ;
U.S. Pat. No. 6,949,678;
EP 863,534;
U.S. Pat. No. 7,449,574;
DE 19700064 ;
U.S. Pat. No. 7,556,910;
JP 05-67405-A;
U.S. Pat. Publication No. 2009/0023085;
JP 05-271576-A;
U.S. Pat. Publication No. 2010/0210749;
JP 08-171863-A;
PCT Pat. Publication No. WO 02/100903; and
JP 09-244230-A;
PCT Pat. Publication No. WO 2006/018405.
JP 10-62980-A;

Claims

CLAIMS:
1. A compound comprising optionally substituted
Figure imgf000110_0001
(FORMULA I) fused with one or
two optionally substituted
Figure imgf000110_0002
(FORMULA II), wherein A and E each independently represent -CH2-, -NH-, -0-, -S-, or -C(=0)- and B represents a bond, -CH2-, -NH-, -0-, -S-, or -C(=0)-, said compound having directly or indirectly attached thereto at least one oxime ester and/or acyl group.
2. The compound of claim 1 , wherein the oxime ester group is -CR6=N-0-(C=0)-R7 or =N-0-(C=0)-R7, wherein R6 and R7 are the same or different substituents.
3. The compound of claim 2, wherein R6 represents:
■ hydrogen;
■ C1-C12 alkyl optionally substituted with one or more:
o phenyl,
o halogen,
Figure imgf000110_0003
o -0-L, and/or
o -S-L;
■ C4-C10 cycloalkyi, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, or C4-C10 cycloalkenyl, each of which being optionally substituted by alkyl and/or -0-L; or
■ phenyl optionally substituted with one or more:
o Ci-C6 alkyl,
o halogen,
o nitrile,
o alkyloxy,
Figure imgf000110_0004
o C2-C12 alkylcarboxyl,
wherein L is hydrogen or C1-C6 alkyl and wherein each of Rs, Rg and R10 is independently hydrogen, C1-C12 alkyl; C4-C10 cycloalkyi; C1-C12 alkenyl; C4-C10 cycloalkenyl; C2-C12 alkynyl; C4-C10 cycloalkynyl; C1-C12 haloalkyl; or optionally substituted aryl.
4. The compound of claim 3, wherein R6 is alkyl optionally substituted with -O-C1-6 alkyl.
5. The compound of claim 4, wherein R6 is methyl or butyl.
6. The compound of claim 5, wherein R6 is methyl.
7. The compound of any one of claims 2 to 6, wherein R7 represents alkyl, cycloalkyi, alkenyl, or cycloalkenyl, each of which being optionally substituted with aryl or halogen, or R7 is aryl optionally substituted with alkyl or halogen.
8. The compound of claim 7, wherein R7 represents C1-C12 alkyl optionally substituted with phenyl; C4-C10 cycloalkyi; or phenyl optionally substituted with C1-C6 alkyl.
9. The compound of claim 8, wherein R7 is C1-C12 alkyl; C4-C10 cycloalkyi; or phenyl.
10. The compound of claim 9, wherein R7 is methyl.
1 1. The compound of any one of claims 1 to 10, wherein the acyl group is -C(=0)-R3o, wherein R30 is optionally substituted alkyl, cycloalkyi, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, or aryl, each of which optionally comprising one or more oxygen atom, sulfur atom, nitrogen atom, carbonyl group, carbamate group, carbamide group, and/or ester group.
12. The compound of claim 11 , wherein said alkyl, cycloalkyi, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, and aryl in R30 is substituted with one or more
■ polyethylene glycol chain,
■ C1-C12 alkyl optionally substituted with one or more:
Figure imgf000111_0001
o -O-L,
o -S-L, and/or
o phenyl optionally substituted with one or more: C1-C6 alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
■ C4-C10 cycloalkyi, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, C4-C10 cycloalkynyl, each of which being optionally substituted by alkyl and/or -O-L, and/or
■ aryl, such as phenyl, thiophenyl, biphenyl and naphthyl, each of which being optionally substituted with one or more:
o Ci-C6 alkyl,
o halogen,
o nitrile,
o alkyloxy,
Figure imgf000111_0002
o C2-C12 alkylcarboxyl.
wherein L, Re, Rg and R10 are as defined in claim 3.
13. The compound of claim 12, wherein R30 is linear alkyl, phenyl or thiophenyl, all of which being optionally substituted with a linear alkyl or with -O-L.
14. The compound of claim 13, wherein R30 is methyl, 2-methylphenyl, phenyl, thiophenyl, or 4-methoxyphenyl.
15. The compound of any one of claims 1 to 14, wherein at least one of the oxime ester group and/or acyl groups is attached to the compound through a linker -LK-.
16. The compound of claim 15, wherein -LK- is optionally substituted alkylene, cycloalkylene, alkenylene, cycloalkenylene, alkynylene, cycloalkynylene, arylene, -S-arylene, -NH-arylene, or -N(aryl)-arylene, each of which optionally comprising one or more oxygen atom, sulfur atom, nitrogen atom, carbonyl group, carbamate group, carbamide group, and/or ester group.
17. The compound of claim 16, wherein the alkylene, cycloalkylene, alkenylene, cycloalkenylene, alkynylene, cycloalkynylene, arylene, -S-arylene, -NH-arylene, and -N(aryl)-arylene are substituted with one or more:
■ polyethylene glycol chain,
■ C1-C12 alkyl optionally substituted with one or more:
Figure imgf000112_0001
o -O-L,
o -S-L, and/or
o phenyl optionally substituted with one or more: C1-C6 alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
■ C4-C10 cycloalkyl, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, C4-C10 cycloalkynyl, each of which being optionally substituted by alkyl and/or -O-L, and/or
■ aryl, such as phenyl, biphenyl and naphthyl, or aryloyl, such as benzoyl, each of which being optionally substituted with one or more:
o Ci-C6 alkyl,
o halogen,
o nitrile,
o alkyloxy,
Figure imgf000112_0002
o C2-C12 alkylcarboxyl.
wherein L, f¾, Rg and R10 are as defined in claim 3.
18. The compound of any one of claims 1 to 17, wherein FORMULA I and/or either or both FORMULA II are independently substituted by one or more of the following substituents:
■ C1-C12 alkyl, C1-C12 alkyloxy, C4-C10 cycloalkyl, C1-C12 alkenyl, C4-C10 cycloalkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, and/or C4-C10 cycloalkynyl, each of which being optionally substituted with one or more:
Figure imgf000112_0003
o -O-L,
o -S-L, and/or
o phenyl optionally substituted with one or more Ci alkyl, halogen atom, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl; and/or
■ phenyl, biphenyl and/or naphthyl, each of which being optionally substituted with one or more: o Ci-C6 alkyl,
o halogen atom,
o nitrile,
o alkyloxy,
Figure imgf000113_0001
o C2-C12 alkylcarboxyl,
wherein L, f¾, Rg and R10 are as defined in claim 3.
19. The compound of any one of claims 1 to 18 comprising one optionally substituted FORMULA I
20. The compound of claim 19 comprising optionally substituted
Figure imgf000113_0002
T
Figure imgf000113_0003
he compound of claim 20 comprising optionally substituted fused with
optionally substituted
22. The compound of c
Figure imgf000113_0004
laim 20 comprising optionally substituted fused with optionally substituted
23. The compound of cl
Figure imgf000114_0001
aim 20 comprising optionally substituted fused with
optionally substituted
24. The compound of cl
Figure imgf000114_0002
aim 20 comprising optionally substituted fused with
optionally substituted
25. The compound of c
Figure imgf000114_0003
laim 20 com rising optionally substituted fused with
optionally substituted
Figure imgf000114_0004
26. The compound of any one of claims 1 to 18 comprising two optionally substituted FORMULA I
27. The compound of cl fused with
optionally substituted
Figure imgf000114_0005
and with optionally substituted
28. The compound of claim 26 comprising optionally substituted
Figure imgf000114_0006
fused with optionally substituted
Figure imgf000115_0001
and with optionally substituted
29. The com ound of any one of claims 1 to 18 being:
Figure imgf000115_0002
f¾, f¾, RV and R5' are optional and independently represent, in the case of R4 and R5, one to four and, in the case of RV and R5', one or two:
o C 1 -C 12 alkyi or alkyloxy, said alkyi and alkyloxy being optionally substituted with one or more :
■ -NR8R9,
■ -O-L or -S-L, and/or ■ phenyl optionally substituted with one or more: Ci alkyl, halogen atom, nitrile, alkyloxy, COOR10, and/or C2 to C12 alkylcarboxyl;
C4-C10 cycloalkyl, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, C4-C10 cycloalkynyl, each of which being optionally substituted by alkyl and/or -O-L, and/or phenyl, biphenyl and naphthyl, each of which being optionally substituted with one or more:
Ci-C6 alkyl,
halogen,
nitrile,
alkyloxy,
Figure imgf000116_0001
C2-C12 alkylcarboxyl,
are op ndently represent one to four acyl groups and/or oxime ester
groups of formula
Figure imgf000116_0002
each of X, Y and Z independently represent
Figure imgf000116_0003
' o Λ oΡr Q4 "* , wherein:
, f¾, and Ra each independently represent:
■ a hydrogen atom;
■ C1-C12 alkyl optionally substituted with one or more:
• -NRsRg,
• -O-L,
• -S-L, and/or
• phenyl optionally substituted with one or more Ci alkyl, halogen, nitrile, alkyloxy, -COOR10, and/or C2-C12 alkylcarboxyl;
■ C4-C10 cycloalkyl, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, C4-C10 cycloalkynyl, each of which being optionally substituted by alkyl and/or -O-L, and/or ■ phenyl, biphenyl or naphthyl, each of which being optionally substituted with one or more:
• Ci-C6 alkyl,
• halogen,
• nitrile,
• alkyloxy,
Figure imgf000117_0001
• C2-C12 alkylcarboxyl,
o me ester group of formula:
o
Figure imgf000117_0002
, and o Ar is a linker -LK- as defined in any one of claims 15 to 17,
wherein L, f¾, Rg and R10 are as defined in claim 3, and wherein R6 and R7 are as defined in any one of claims 2 to 10 .
30. The com ound of claim 29 being:
Figure imgf000117_0003
117
Figure imgf000118_0001
118
Figure imgf000119_0001
Figure imgf000120_0001
R2 R3 Ar R2 R3 wherein Qi, Q2, Q3, Q4, Ri, R2, R3, R4, R5, and Ar are as defined in claim 29.
31. The compound of claim 29 or 30, wherein -Ar- is optionally substituted arylene, said arylene optionally comprising one or more oxygen atom, sulfur atom, nitrogen atom, carbonyl group, carbamate group, carbamide group, and/or ester group.
32. The compound of claim 31, wherein the substituents of the arylene are one or more:
■ C1-C12 alkyl optionally substituted with one or more:
Figure imgf000120_0002
o -O-L,
o -S-L,
o phenyl optionally substituted with one or more: Ci alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
■ C4-C10 cycloalkyl, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, C4-C10 cycloalkynyl, each of which being optionally substituted by alkyl and/or -O-L, and/or
■ phenyl, biphenyl and naphthyl, each of which being optionally substituted with one or more: o Ci-C6 alkyl,
o halogen,
o nitrile,
o alkyloxy,
Figure imgf000121_0001
o C2-C12 alkylcarboxyl.
wherein L, f¾, Rg and R10 are as defined in claim 3.
33. The com ound of any one of claims 29 to 32, wherein each -Ar-Ch independently represents
Figure imgf000121_0002
wherein Rn and R^ are optional and independently represent one or more:
■ C1-C12 alkyl optionally substituted with one or more:
Figure imgf000121_0003
o -O-L,
o -S-L, and/or o phenyl optionally substituted with one or more: Ci alkyl, halogen, nitrile, alkyloxy, COOR10, and/or C2-C12 alkylcarboxyl;
■ C4-C10 cycloalkyl, C2-C12 alkenyl, C4-C10 cycloalkenyl, C2-C12 alkynyl, and/or C4-C10 cycloalkynyl, each of which being optionally substituted by alkyl and/or -O-L; and/or
■ phenyl, biphenyl and naphthyl, each of which being optionally substituted with one or more:
o Ci-C6 alkyl,
o halogen,
o nitrile,
o alkyloxy,
Figure imgf000122_0001
o C2-C12 alkylcarboxyl.
wherein L, f¾, f¾ and R10 are as defined in claim 3.
34. The compound of any one of claims 29 to 33 being:
Figure imgf000122_0002
Figure imgf000123_0001
wherein:
R4 and R5 are optional and independently represent one C1-C12 alkyl or C1-C12 alkyloxy, optional and independently represent one oxime ester group of formula
Figure imgf000123_0002
Ri, R2, and Ra each independently represent a hydrogen atom or C1-C12 alkyl,
Q3 represents a hydrogen atom or an oxime ester group of formula:
Figure imgf000123_0003
Q4 represents an oxime ester of formula:
Ar represents , and
■ R6 and R7 independently represents alkyl.
35. The compound of claim 34 being:
H 5r-C 2 i CHn
Figure imgf000124_0001
Figure imgf000124_0002
124
Figure imgf000125_0001
Figure imgf000126_0001
36. The compound claim 26, being truxene, truxenone, triazatruxene or a derivative thereof, said truxene, truxenone, triazatruxene or derivative thereof having attached thereto, directly or indirectly, at least one acyl and/or oxime ester group.
37. The com ound of claim 36 being:
truxene:
truxenone
Figure imgf000126_0002
Figure imgf000127_0001
the truxene, truxenone, triazatruxene, or derivative thereof having attached thereto at least one of -Ei, -LK-Ei, -LK-(Ei)2 or =E2,
-Ei representing an acyl group of formula-C(=0)-R3o or an oxime ester group of formula -CR6=N-0-(C=0)-R7, and =E2 representing an oxime ester group of formula =N-0-(C=0)-R7,
wherein LK is as defined in any one of claims 15 to 17, f¾ and R7 are as defined in any one of claims 2 to 10 and R30 is as defined in any one of claims 11 to 14.
38. The com ound of claims 36 or 37 being of formula:
Figure imgf000127_0002
or
Figure imgf000128_0001
wherein:
each Q independently represents 1 to 4:
■ hydrogen;
Figure imgf000128_0002
■ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
■ C1-C12 haloalkyl;
■ C4-C8 cycloalkenyl;
■ C2-C12 alkynyl;
■ phenyl or -N(Rig)-phenyl, each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl;
■ benzoyl, naphthoyi, phenyloxycarbonyl, or naphtyloxycarbonyl, each of which being optionally substituted by one or more C1-C20 alkyl, C1-C4 haloalkyl, -SR19 , -OR19 , -NR19R20, halogen, phenyl, -COOR19, -CONR19R20, -CN, -NO2 and/or C3-C10 cycloalkyl, wherein the C3-C10 cycloalkyl may be interrupted by -0-, -(C=0)- or -N(Ri9)-;
Figure imgf000128_0003
■ thiophene carbonyl or pyrrolidinyl, each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl, and
each R21 independently represents:
■ hydrogen;
Figure imgf000128_0004
■ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
■ C4-C8 cycloalkenyl; ■ C2-C12 alkynyl; or
■ phenyl optionally substituted with one or more C1-C6 alkyl, nitrile, alkyloxy, -COOR16, and/or C2-C12 alkylcarboxyl,
and/or two R21 attached to the same carbon atom represent =0 or =E2,
wherein:
L represents a hydrogen atom or C1-C6 alkyl,
R16 and Ri7 independently represent:
■ hydrogen,
■ C1-C12 alkyl optionally substituted with one or more -NR19R20, -0-L and/or -S-L;
■ C4-C10 cycloalkyl;
■ C4-C10 cycloalkenyl;
■ C2-C12 alkynyl;
■ C1-C12 haloalkyl; or
■ phenyl or benzoyl, each of which optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl group, and
Rig and R20 independently represent hydrogen, C1-C12 alkyl; C1-C12 haloalkyl; C4-C8 cycloalkenyl; or C2-C12 alkynyl,
provided that the compound comprises at least one oxime ester or acyl group, and provided that when R21 is attached to a nitrogen atom and R21 is -Ei, -Ei is not -CR6=N-0-(C=0)-R7.
39. The com ound of claim 38 being of formula:
Figure imgf000129_0001
1
Formula 2', or
Figure imgf000130_0001
wherein:
each of Qn, Q12 and Q13 independently represent:
■ hydrogen;
Figure imgf000130_0002
■ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
■ C1-C12 haloalkyi;
■ C4-C8 cycloalkenyl;
■ C2-C12 alkynyl;
■ phenyl or -N(Rig)-phenyl, each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl;
■ benzoyl, naphthoyi, phenyloxycarbonyl, or naphtyloxycarbonyl, each of which being optionally substituted by one or more C1-C20 alkyl, C1-C4 haloalkyi, -SR19 , -OR19 , -NR19R20, halogen, phenyl, -COOR19, -CONR19R20, -CN, -NO2 and/or C3-C10 cycloalkyl, wherein the C3-C10 cycloalkyl may be interrupted by -0-, -(C=0)- or -N(Ri9)-;
■ thiophene carbonyl or pyrrolidinyl, each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl,
each R22 independently represents:
■ hydrogen;
■ C1-C12 alkyl optionally substituted with one or more -NR19R20, -O-L and/or -S-L;
■ C1-C12 haloalkyl;
■ C4-C8 cycloalkenyl;
■ C2-C12 alkynyl;
■ phenyl or -N(Rig)-phenyl, each of which being optionally substituted with one or more C1-C6 alkyl, halogen, nitrile, alkyloxy, -COOR19, and/or C2-C12 alkylcarboxyl; or
■ benzoyl, naphthoyl, phenyloxycarbonyl, or naphtyloxycarbonyl, each of which being optionally substituted by one or more C1-C20 alkyl, C1-C4 haloalkyl, -SR19 , -OR19 , -NR19R20, halogen, phenyl, -COOR9, -CONR19R20, -CN, -NO2 and/or C3-C10 cycloalkyl, wherein the C3-C10 cycloalkyl is interrupted by -0-, -(C=0)- or -N(Ri9)-,
wherein R16, R17, R19, R20, R21, and L are as defined in claim 38,
provided that the compound comprises at least one oxime ester or acyl group, and provided that when R21 is attached to a nitrogen atom and R21 is -Ei, -Ei is not -CR6=N-0-(C=0)-R7.
40. The com ound according to claim 38 or 39, wherein -LK-E1 represents:
Figure imgf000131_0001
wherein R18 is hydrogen or C1-C12 alkyl optionally substituted with one or more -O-L and/or -S-L, and wherein L, R16 and R17 are as defined in claim 38.
41. The compound of any one of claims 38 to 40, wherein ■ each Q, Qi, Cfe, and Q3, when present, represents one -Ei of formula -CR6=N-0-(C=0)-R7, wherein R6 represents C1-C12 alkyl optionally substituted with -O-L, wherein L is C1-C6 alkyl, and R7 represents Ci- C12 alkyl;
■ all R22, when present, represent hydrogen; and
■ all R21, when present, represent hydrogen or C1-C12 alkyl.
42. The compound of any one of claims 38 to 40, wherein:
■ each Q, Qn, Q12, and Q13, when present, represents one -LK-E1, wherein Ei is of formula -CR6=N-0-(C=0)-R7, wherein R6 represents C1-C12 alkyl optionally substituted with -O-L, wherein L is C1-C6 alkyl, and R7 represents C1-C12 alkyl;
■ all R22, when present, represent hydrogen;
■ all R when present, represents hydrogen or C1-C12 alkyl; and
Figure imgf000132_0001
wherein R16 is hydrogen or benzoyl substituted with C1-C6 alkyl, R17 represents hydrogen and R18 represents C1-C12 alkyl.
43. The compound of any one of claims 38 to 40, wherein each of Qn, Q12, and Q13, when present, represents hydrogen, each of Q and R22, when present, represents one -N(Rig)-phenyl wherein R19 represents C1-C12 alkyl, and every pair of R21 attached to a common carbon atom represent =E2 wherein R7 represents C1-C12 alkyl.
44. The compound of any one of claims 38 to 40, wherein
■ each Q, Qi, Cfe, and Q3, when present, represents one -LK- Ei or -Ei, wherein Ei is of formula -C(=0)- R30, wherein R30 represents C1-C12 linear alkyl, phenyl, phenyl substituted with alkyl or alkyloxy, or thiophenyl;
■ all R22, when present, represent hydrogen;
■ all R21, when present, represent C1-C12 alkyl, and
■ -LK- represents 2-phenylene or 4-phenylene.
45. The compound of any one of claims 36 to 40, being of formula:
Figure imgf000133_0001
Figure imgf000133_0002
133
Figure imgf000134_0001
Figure imgf000134_0002
134
Figure imgf000135_0001
Figure imgf000135_0002
135
Figure imgf000136_0001
Figure imgf000136_0002
136
Figure imgf000137_0001
137
Figure imgf000138_0001
Figure imgf000138_0002
Figure imgf000138_0003
Figure imgf000139_0001
46. The compound of any one of claims 1 to 45 for use as a photoinitiator in a photopolymenzable composition.
47. The compound of any one of claims 1 to 45 being comprised in a photopolymenzable composition.
48. The compound of claim 46 or 47, wherein the photopolymenzable composition is a lithographic printing plate composition.
49. The compound of claim 46 or 47, wherein the photopolymenzable composition is a color filter resist composition.
50. The compound of claim 46 or 47, wherein the photopolymenzable composition is a black matrix resin composition.
51. The compound of claim 46 or 47, wherein the photopolymenzable composition is a photosetting or photocuring ink.
52. The compound of claim 46 or 47, wherein the photopolymenzable composition is an oxygen scavenging film composition.
53. A photopolymenzable composition comprising a compound according to any one of claims 1 to 45.
54. The photopolymenzable composition of claim 53 being a lithographic printing plate composition.
55. The photopolymenzable composition of claim 53 being a color filter resist composition.
56. The photopolymenzable composition of claim 53 being a black matrix resin composition.
57. The photopolymenzable composition of claim 53 being a photosetting or photocuring ink.
58. The photopolymenzable composition of claim 53 being an oxygen scavenging film composition.
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