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WO2025011754A1 - Compositions photodurcissables et durcissables thermiquement appropriées pour un durcissement à basse température - Google Patents

Compositions photodurcissables et durcissables thermiquement appropriées pour un durcissement à basse température Download PDF

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Publication number
WO2025011754A1
WO2025011754A1 PCT/EP2023/069092 EP2023069092W WO2025011754A1 WO 2025011754 A1 WO2025011754 A1 WO 2025011754A1 EP 2023069092 W EP2023069092 W EP 2023069092W WO 2025011754 A1 WO2025011754 A1 WO 2025011754A1
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cycloalkyl
alkyl
group
alkoxy
aryl
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PCT/EP2023/069092
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English (en)
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Leonhard Feiler
Kaori Sameshima
Peter Nesvadba
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Basf Se
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Priority to PCT/EP2023/069092 priority Critical patent/WO2025011754A1/fr
Publication of WO2025011754A1 publication Critical patent/WO2025011754A1/fr

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    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • the present invention relates to photocurable as well as Thermally Curable Compositions Suitable for Low Temperature Curing Description
  • the present invention relates to photocurable as well as thermally curable compositions com- prising (i) at least one compound or oligomer carrying at least one ethylenically unsaturated group (A), (ii) at least one thermal radical initiator (B) and (iii) at least one photoinitiator (C), to processes forming either a cured layer or a cured pattern on a substrate using these composi- tions, to the cured layer and the cured pattern, and to devices, preferably printed circuit boards, integrated circuits, color filter arrays, liquid crystal displays, organic light emitting diode (OLED) displays or white organic light emitting diode (WOLED) displays, comprising the cured layer or the cured pattern.
  • OLED organic light emitting diode
  • WOLED white organic light emitting diode
  • compositions that are photocurable as well as thermally curable usually comprise at least one photoinitiator, at least one thermal radical initiator and polymerizable monomers or oligomers carrying ethylenically unsaturated groups. These compositions have many applications for ex- ample as coating composition for wood or can coatings, as adhesive composition, as ink com- position, as 3D-printing composition and as photoresist composition. These compositions are usually first cured by light treatment followed by heat treatment.
  • compositions in particular for coating compositions and photo- resist compositions, that form layers, that are photocurable as well as thermally curable, and which layers can be cured in a process comprising a light treatment and a heat treatment step, wheren the heat treatment step can be performed at temperatures of below 150 °C, or even of below 120 °C.
  • a rather low temperature in the heat treatment step which is generally the step of highest temperature of the whole process, allows the use of heat sensitive substrates such as plastic substrates and/or heat-sensitive composition components such as heat-sensitive dyes.
  • Photoresist compositions used in photolithographic processes for the preparation of components such as printed circuit boards (PCBs), integrated circuits (ICs) (also commonly called “chips”) and color filter arrays (CFAs) used in display applications such as liquid-crystal displays (LCDs), organic light emitting diode (OLED) displays or white organic light emitting diode (WOLED) displays.
  • PCBs printed circuit boards
  • ICs integrated circuits
  • CFAs color filter arrays
  • LCDs liquid-crystal displays
  • OLED organic light emitting diode
  • WOLED white organic light emitting diode
  • Photo- lithographic processes comprise the steps of application of the photoresist composition on a substrate to form a layer, light treatment of the layer through a mask, removing either the light- treated parts (positive photoresist) or the not light-treated parts (negative photoresist) of the layer by treatment with a developer to form a pattern, and heat treatment of the pattern on the substrate to increase the resistance, the stability as well as the mechanical strength of the pat- tern.
  • the heat treatment step is commonly also referred to as “post-baking” step. Although it is desired that the temperature of the post-baking step is below 150 °C, or even of below 120 °C, the photoresist composition should also not cure under conditions usually used to remove any solvent prior to the light treatment step.
  • Color filter arrays are composed of various tiny color filters of different color, for example of red, green and blue, which are usually separated by a black matrix, on a transparent substrate. Each color filter array corresponds to one pixel of the displayed image.
  • RGB red, green, blue
  • a black matrix is usually formed on a transparent substrate in a photolithographic process using a black photo-resist composition, then red, green and blue color filters are formed, color-by-color, on the transparent substrate in the gaps of the black matrix in photolithographic processes using a red, a green and a blue, respectively, photoresist composition.
  • JP 2003-015288 describes a colored photoresist composition for forming color filters, wherein the composition comprising azo compounds, organic peroxide or hydrogen peroxide as thermal radical initiator.
  • the composition comprising azo compounds, organic peroxide or hydrogen peroxide as thermal radical initiator.
  • azobisbutyronitrile was used as thermal radical initiator and the post-baking step was performed at 150 °C for 30 minutes.
  • Resist compositions comprising aliphatic azo compounds, organic peroxide or hydrogen perox- ide as thermal radical initiator are often not stable and explosive, and thus, the storage and the transport of these compositions require additional safety measures.
  • JP2003-330184 describes a colored photoresist composition for forming color filters, wherein the composition comprises a thermal radical initiator having an oxadiazole structure or a triazine structure containing a trihalomethyl groups.
  • the post-baking step was performed at 200 °C for 30 minutes.
  • WO2010/108835 describes a photoresist composition for forming color filters, wherein the com- position comprises a hydroxylamine ester as thermal radical initiator.
  • the exemplified blue color filter photoresist was post-baked at 180 °C for 30 minutes.
  • W02012/101245 describes photoresist composition for forming color filters, wherein the com- position comprises an oxime sulfonate as thermal radical initiator.
  • the exemplified blue color filter photoresists were post-baked at temperatures of at least 180 °C, for example at 180 °C for 30 minutes.
  • Iminooxytriazine compounds are known in the art WO2014/064064 describes iminooxytriazine compounds and their use as radical initiator.
  • Vari- ous radically polymerizabe compositions comprising iminooxytriazine compounds, but not pho- toinitiator, are exemplified.
  • Compositions comprising oxime ester photoinitiators are also known in the art.
  • US6596445, WO2002/100903, WO2012/045736 and US2015/0111152 describe compositions comprising oxime ester photoinitiators.
  • compositions that are photocurable as well as thermally curable and which compositions can be cured in processes comprising a light treatment and a heat treatment step, wherein the heat treatment step is performed at a temper- ature of below 120 °C.
  • This object is solved by the composition of claim 1, the processes of claims 11 and 12, the cured layer of claim 14, the cured pattern of claim 15, and the device of claim 16.
  • composition of the present invention comprises (i) at least one compound or oligomer carrying at least one ethylenically unsaturated group (A), (ii) at least one thermal radical initiator (B) of formula wherein n is 1 or 2 R 1 and R 2 independently from each other are H, NR 6 R 7 , COR 6 , COOR 6 , CONR 6 R 7 , CN, Y- R 10 , C1-18-alkyl, C3-12-cycloalkyl, C6-14-aryl or C2-14-heteroaryl, wherein said C3-12-cycloalkyl, C6-14-aryl, C2-14-heteroaryl is unsubstituted or substituted with one or more substituents se- lected from the group consisting of C1-12-alkyl, C5-8-cycloalkyl, phenyl, halogen and C1-12- alkoxy, wherein Y is O or S, R 10 is C 1-18 -alkyl, C
  • C1-12-alkyl, C1-18-alkyl and C1-20-alkyl can be branced or unbranched.
  • Examples of C1-12-alkyl are methyl, ethyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 1,1- dimethyl-3,3-dimethylbutyl, nonyl, decyl, undecyl and dodecyl.
  • Examples of C1-18-alkyl are C1-12- alkyl and tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.
  • Examples of C 1- 20-alkyl are C1-18-alkyl and nonadecyl and eicosyl.
  • C 2-18 -alkenyl and C 2-18 -alkinyl can be branched or unbranched.
  • Examples of C 2-18 -alkenyl are viny and allyl.
  • Examples of C5-8-cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Examples of C 3-12 -cycloalkyl are C 5-8 -cycloalkyl and cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl.
  • Examples of C6-14-aryl are phenyl and naphthyl.
  • Examples of C2-14-heteroaryl are thiophenyl, tetrahydrofuryl, .
  • Examples of halogen are F, Cl, Br and I.
  • Examples of C1-6-alkoxy are methoxy, ethoxy, butoxy, iso-butoxy, sec-butoxy, tert-butoxy, pent- oxy, isopentoxy and hexoxy.
  • C 1-12 -alkoxy are C 1-6 -alkoxy, heptoxy, octoxy, 1,1- dimethyl-3,3-dimethylbutoxy, nonyl, decyl, undecyl and dodecyl.
  • Examples of a 4 to 12 membered carbocyclic or heterocyclic saturated or unsaturated rings formed by R 1 and R 2 together with the C-atom, to which R 1 and R 2 are connected, and which is marked with * are wherein R 6 and R 11 are independently from each other H, C1-18-alkyl, C3-12-cycloalkyl, C6-14-aryl or C 2-14 -heteroaryl, wherein said C 3-12 -cycloalkyl, C 6-14 -aryl, C 2-14 -heteroaryl is unsubstituted or substituted with one or more substituents selected from the group consisting of C 1-12 -alkyl, C 5-8 - cycloalkyl, phenyl, halogen and C1-12-alkoxy.
  • C1-18-alkylene examples include methylene, ethylene, butylene, iso-butylene, sec-butylene, tert- butylene, pentylene, isopentylene, hexylene, heptylene, octylene, 1,1-dimethyl-3,3- dimethylbutylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene and octadecylene.
  • Examples of C3-12-cycloalkylene are cyclopropylene cyclobutylene, cyclopentylene, cyclo- hexylene, cycloheptylene, cyclooctylene, cyclononylene, cyclodecylene, cycloundecylene and cyclododecylene.
  • Examples of C6-14-arylene are phenylene and 1,2-napthylene. Examples of 5 to 8 membered heterocyclic saturated or unsaturated ring formed by R 8 and R 9 together with the N-atom, to which R 8 and R 9 are connected, are .
  • the compound or oligomer carrying at least one ethylenically unsaturated group (A) can be any compound or oligomer carrying at least one ethylenically unsaturated group (A).
  • the compound or oligomer carrying at least one ethylenically unsaturated group (A) preferably has an average weight molecular weight of below 1500 g/mol, more preferably below 1000 g/mol, and most preferably below 800 g/mol.
  • the compound or oligomer carrying at least one ethylenically unsaturated group (A) preferably does not carry acidic groups. Examples of acidic groups are COOH groups, SO3H groups and hydroxy aryl groups.
  • the ethylenically unsaturated group can be any ethylenically unsaturated group that can poly- merize by free radical mechanism. Examples of ethylenically unsaturated groups are acryloyl and methacryloyl groups as well as ethylenically unsaturated groups other than acryloyl and methacrylyol such as vinyl and allyl groups.
  • (meth)acryloyl comprises acryloyl and methacryolyl
  • (meth)acrylate comprises acrylate and methacrylate
  • (meth)acrylic acid com- prises acrylic acid and methacrylic acid.
  • Examples of compounds or oligomers carrying at least one ethylenically unsaturated group, wherein the ethylenically unsaturated groups are (meth)acryloyl groups are: C1-20-alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (methacrylate), sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, 2-methylbutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, heptyl (methacrylate, octyl (meth)acrylate, 2-
  • Examples of compounds carrying at least two ethylenically unsaturated groups, which ethyleni- cally unsaturated group are not a (meth)acryloyl group are: styrene, styrene carrying alkyl groups such as p-tert-butylstyrene, p-methylstyrene and o- methylstyrene, styrene carrying hydroxy groups such as 4-hydroxystyrene, styrene carrying halogen groups such as 2-chlorostyrene, 2-vinylnaphthalene, divinylstyrene, butadiene, iso- prene, chloroprene, ethylene, propylene, 1-butene, 2-butene, isobutene, cylopentene, cyclo- hexene, cyclododecene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, N
  • Preferred compounds and oligomers (A) are compounds and oligomers carrying at least one ethylenically unsaturated group, wherein the ethylenically unsaturated group is selected from the group consisting of acryloyl and methacryloyl groups.
  • More preferred compounds and oligomers (A) are compounds and oligomers carrying at least one acryloyl group.
  • Even more preferred compounds and oligomers (A) are compounds and oligomers carrying at least two acryloyl groups selected from the group consisting of esters of diols with acrylic acid, esters of mono- or poly(ethoxylated) and/or mono- or poly(propoxylated) diols with acrylic acid, partial and full esters of polyols with acrylic acid, wherein hydroxy groups of the polyols not es- terified with acrylic acid can be otherwise modified, partial and full esters of mono- or poly(ethoxylated) and/or mono- or poly(propoxylated) polyols with acrylic acid, and reaction products of compounds and oligomers carrying epoxide groups with acrylic acid.
  • Most preferred compounds and oligomers (A) are compounds and oligomers carrying at least three acryloyl groups selected from the group consisting of pentaerythritol triacrylate, pentae- rythritol tetraacrylate, di(1 , 1 ,1 -trimethylolpropane) tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and tris(2-hydroxyethyl)isocyanurate triacrylate.
  • Particular preferred compounds and oligomers (A) are dipentaerythritol pentaacrylate and di- pentaerythritol hexaacrylate.
  • the thermal radical initiator (B) is preferably of formula wherein n A is 1 or 2 R 1A and R 2A independently from each other are H, COR 6A , COOR 6A , CONR 6A R 7A , CN, Y A - R 10A , C 1-18 -alkyl, C 3-12 -cycloalkyl, C 6-14 -aryl or C 2-14 -heteroaryl, wherein said C 3-12 -cycloalkyl, C6-14-aryl, C2-14-heteroaryl is unsubstituted or substituted with one or more substituents se- lected from the group consisting of C 1-12 -alkyl, C 5-8 -cycloalkyl, phenyl, halogen and C 1-12 - alkoxy, wherein Y A is O or S, R 10A is C1-18-alkyl, C3-12-cycloalkyl, C6-14-aryl or C2-14-heteroaryl,
  • Examples of 4 to 12 membered heterocyclic saturated or unsaturated rings formed by R 7B and R 2B together with the N-atom, to which R 7B is connected, and together with the C-atom, to which R 2B is connected, and which is marked with * are wherein R 6 and R 11 are independently from each other H, C1-18-alkyl, C3-12-cycloalkyl, C6-14-aryl or C 2-14 -heteroaryl, wherein said C 3-12 -cycloalkyl, C 6-14 -aryl, C 2-14 -heteroaryl is unsubstituted or substituted with one or more substituents selected from the group consisting of C1-12-alkyl, C5-8- cycloalkyl, phenyl, halogen and C 1-12 -alkoxy.
  • Examples of 4 to 12 membered carbocyclic saturated or unsaturated ring formed by R 1A and R 2A together with the C-atom, to which R 1A and R 2A are connected, and which is marked with * are .
  • n A is 1 or 2
  • R 1A and R 2A independently from each other are H, C1-18-alkyl, C3-12-cycloalkyl, C6-14-aryl or C2-14- heteroaryl, wherein said C3-12-cycloalkyl, C6-14-aryl, C2-14-heteroaryl is unsubstituted or substitut- ed with one or more substituents selected from the group consisting of C1-12-alkyl, C5-8- cycloalkyl, phenyl, halogen and C1-12-alkoxy, or R 1A and R 2A together with the C-atom, to which R 1A and R 2A are connected, and which is marked with *, form a 4 to 12
  • n A is 1 R 1A and R 2A independently from each other are C 1-18 -alkyl or C 3-12 -cycloalkyl, wherein said C 3-12 - cycloalkyl is unsubstituted or substituted with one or more C1-12-alkyl, R 1A and R 2A together with the C-atom, to which R 1A and R 2A are connected, and which is marked with *, form a 4 to 12 membered carbocyclic saturated ring, which ring is unsubstituted or sub- stituted with one or more substituted with one or more C1-12-alkoxy, R 8A and R 9A are independently from each other are C1-18-alkyl or C3-12-cycloalkyl, or R 8A and R 9A together with the N-atom, to which R 8A and R 9A are connected, form a 5 to 8 membered hetero- cyclic saturated or unsaturated ring, which
  • thermal radical initiators (B) of formula 1A are (1A-a) and .
  • n B is 1 or 2
  • R 6B and R 7B are independently from each other H, C1-18-alkyl, C3-12-cycloalkyl, C6-14-aryl or C2-14- heteroaryl, wherein said C 3-12 -cycloalkyl, C 6-14 -aryl, C 2-14 -heteroaryl is unsubstituted or substitut- ed with one or more substituents selected from the group consisting of C1-12-alkyl, C5-8- cycloalkyl, phenyl, halogen and C 1-12 -alkoxy, or R 6B and R 7B together with the N-atom, to which R 6B and R 7B are connected, form a 5 to 8 mem- bered heterocyclic saturated or unsaturated ring, which ring is unsubstituted or substituted with one or more substituents selected
  • n c is 1 or 2
  • R 1c and R 2c independently from each other are C1-18-alkyl, C3-12-cycloalkyl, C6-14-aryl or C2-14- heteroaryl, wherein said C 3-12 -cycloalkyl, C 6-14 -aryl, C 2-14 -heteroaryl is unsubstituted or substitut- ed with one or more substituents selected from the group consisting of C 1-12 -alkyl, C 5-8 - cycloalkyl, phenyl, halogen and C1-12-alkoxy, or R 1c and R 2C together with the C-atom, to which R 1C and R 2C are connected, and which is marked with *, form a 4 to 12 membered carbocyclic or heterocyclic saturated or unsaturated ring, which ring is unsubstituted or substituted with one or more substituent selected from the group con- sisting of C 1-12
  • thermal radical initiators (B) of formula 1C n c is 1, R 1c and R 2c independently from each other are C1-18-alkyl, C3-12-cycloalkyl, wherein said C3-12- cycloalkyl is unsubstituted or substituted with one or more C 1-12 -alkyl, or R 1c and R 2C together with the C-atom, to which R 1C and R 2C are connected, and which is marked with *, form a 4 to 12 membered carbocyclic or heterocyclic saturated or unsaturated ring, which ring is unsubstituted or substituted with one or more C1-12-alkyl, X C is O, R 5c is C 1-18 -alkyl or C 3-12 -cycloalkyl, wherein said C 3-12 -cycloalkyl is unsubstituted or substituted with one or more substituents C1-12-alkyl, L c is C1-18-alkylene, C3-12-cycloal
  • n D is 1 or 2 Z D is S
  • R 7D is C 6-14 -aryl or C 2-14 -heteroaryl, wherein said C 6-14 -aryl and C 2-14 -heteroaryl is unsubstituted or substituted with one or more substituents selected from the group consisting of C1-12-alkyl, C5- 8 -cycloalkyl, phenyl, halogen and C 1-12 -alkoxy
  • R 2D is C1-18-alkyl, C3-12-cycloalkyl, C6-14-aryl or C2-14-heteroaryl, wherein said C3-12-cycloalkyl, C6- 14 -aryl, C 2-14 -heteroaryl is unsubstituted or substituted with one or more substituents selected from the group consisting of C1-12-alkyl, C5-8-cycloalkyl, phenyl, halogen and
  • thermal radical initiator (B) of formulae 1D is (1D-a)
  • the thermal radical initiator (B) is more preferably of formula wherein R 7B , R 6B , R 2B , R 3B , R 4B and n B are as outlined above.
  • the thermal radical initiator (B) is even more preferably of formulae wherein n B” is 1 or 2 R 6B” is H, C1-18-alkyl, C3-12-cycloalkyl, C6-14-aryl or C2-14-heteroaryl, wherein said C3-12-cycloalkyl, C 6-14 -aryl, C 2-14 -heteroaryl is unsubstituted or substituted with one or more substituents selected from the group consisting of C1-12-alkyl, C5-8-cycloalkyl, phenyl, halogen and C1-12-alkoxy, and R 7B” and R 2B” together with the N-atom, to which R 7B” is connected, and together with the C- atom, to which R 2B” is connected, and which is marked with *, form a 4 to 12 membered hetero- cyclic saturated or unsaturated ring, which ring is unsubstituted or substituted with one or more substituent selected from the group consist
  • the thermal radical initiator (B) is most preferably of formulae or n B” is 1 or 2
  • R 6B” is C1-18-alkyl, C3-12-cycloalkyl, wherein said C3-12-cycloalkyl is unsubstituted or substituted with one or more substituents C 1-12 -alkyl, and R 7B” and R 2B” together with the N-atom, to which R 7B” is connected, and together with the C- atom, to which R 2B” is connected, and which is marked with *, form a 4 to 12 membered hetero- cyclic saturated or unsaturated ring, which ring is unsubstituted or substituted with one or more substituent selected from the group consisting of C 1-12 -alkyl and C 5-8 -cycloalkyl
  • the thermal radical initiator (B) is even most preferably of formulae wherein n B” is 1 or 2 R 6B” is C 1-18 -alkyl or C 3-12 -cycloalkyl, wherein said C 3-12 -cycloalkyl is unsubstituted or substituted with one or more substituents C1-12-alkyl, and R 7B” and R 2B” together with the N-atom, to which R 7B” is connected, and together with the C- atom, to which R 2B” is connected, and which is marked with *, form a 4 to 12 membered hetero- cyclic saturated or unsaturated ring, which ring is of formulae Wherein R 11B ” is is C 1-18 -alkyl or C 3-12 -cycloalkyl, wherein said C 3-12 -cycloalkyl is unsubstituted or substituted with one or more substituents C1-12-alkyl, R 3B” is F, Cl, -(L B” )m
  • the thermal radical initiators (B) can be prepared by methods known in the art.
  • thermal radical initiators (B) The preparation of thermal radical initiators (B) is also described on page 7, line 35 to page 9, line 2 of WO2014064064.
  • the photoinitiator (C) can be any photoinitiator.
  • photoinitiators are acetophenone, benzophenone, 2,4,6-trimethylbenzophenone, 2- methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-methoxycarbonyl- benzophenone, 4,4’-bis(chloromethyl)benzophenone, 4-chlorobenzophenone, 4-phenylbenzo- phenone, 3,3’-dimethyl-4-methoxy-benzophenone, [4-(4-methylphenylthio)phenyl]-phenyl- methanone, methyl-2-benzoylbenzoate, 3-methyl-4’-phenylbenzophenone, 2,4,6-trimethyl-4’- phenylbenzophenone, 4,4’-bis(dimethylamino)benzophenone, 4,4’-bis(diethyl- amino)benzophenone, alpha amino acetophenones such as (4-methylthiobenzoyl)-1-methyl-1 -morpholinoe
  • EP126541 monoacyl phosphine oxides such as (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (Omni- rad® TPO), ethyl (2,4,6 trimethylbenzoyl phenyl) phosphinic acid ester, bisacylphosphine oxides such as bis(2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad® 819), bis(2,4,6- trimethylbenzoyl)-2,4-dipentoxyphenylphosphine oxide, trisacylphosphine oxides, bis(2,4,6- trimethylbenzoyl)-phenylphosphine oxide (Omnirad® 819) of formula halomethyltriazines such as 2-[2-(4-methoxy-phenyl)
  • Preferred photoinitiators (C) are compounds carrying at least one oxime ester group.
  • Photoinititaors carrying oxime ester groups are known in the art and are, for example, described in US6596445B1, W02002100903, WO2012045736, US20150111152, WO200762963, W02007071497, W02005080337, JP2019519518, US20210198193, WO2018196619, W02019120081 , CN110806676, CN109957349, CN109134710, W02019088055, JP2010- 049238, W02008078678, JP2010015025 and JP2010049238.
  • photoinitiators carrying at least one oxime ester group are:
  • More preferred photoinitiators (C) are compounds carrying (i)at least one oxime ester group of formula wherein R 20 is C1-18-alkyl, C3-12-cycloalkyl, C6-14-aryl or C2-14-heteroaryl wherein said C 1-18 -alkyl is unsubstituted or substituted with one or more substitutents selected from the group consisting of C5-8-cycloalkyl, 5 to 8 membered heterocyclic saturated or unsatu- rated ring, halogen, C 1-12 -alkoxy, S-C 1-12 -alkyl, wherein said C 5-8 -cycloalkyl, C 1-12 -alkoxy and S-C 1-12 -alkyl are unsustituted or subsitituted with one or more halogen or C1-6-alkoxy, wherein R 40 , R 41 and R 42 are selected from the group consisting of H, C 5-8 -cycloalkyl, halogen,
  • Even more preferred photoinitiators (C) are compounds carrying (i) at least one oxime ester group of formula wherein R 20 is C1-18-alkyl or C6-14-aryl, wherein said C 1-18 -alkyl is unsubstituted or substituted with one or more substitutents selected from the group consisting of C5-8-cycloalkyl, halogen, C1-12-alkoxy and S-C1-12-alkyl, wherein said C 5-8 -cycloalkyl, C 1-12 -alkoxy and S-C 1-12 -alkyl are unsustituted or subsitituted with one or more halogen or C1-6-alkoxy, wherein said C6-14-aryl is unsubstituted or substituted with one or more substitutents selected from the group consisting of C1-12-alkyl, C5-8-cycloalkyl, halogen, C1-12-alkoxy and S-C1-12-alkyl, wherein said C
  • R 20 is C 1-18 -alkyl or C 6-14 -aryl, wherein said C1-18-alkyl is unsubstituted or substituted with one or more C5-8-cycloalkyl, wherein said C 6-14 -aryl is unsubstituted or substituted with one or more substitutents selected from the group consisting of C1-12-alkyl and C1-12-alkoxy, wherein said C1-12-alkyl, and C1-12- alkoxy is unsubstituted or substituted with one or more halogen or C 1-6 -alkoxy, R 21 is C 1-18 -alkyl, C 3-12 -cycloalkyl or C 6-14 -aryl, R 23 is C1-18-alkyl, R 24 and R 25 are independently C1-18-alkyl or C2-18-alkenyl, R 26 is C6-14-aryl, C2-14-heteroaryl or wherein C 6-14 -aryl and C 2-14 -heter
  • oxime esters photoinitiators are known in the art and is, for example, de- scribed in US6596445B1, WO2002100903, WO2012045736, US20150111152, WO200762963, WO2007071497, WO2005080337, JP2019519518, US20210198193, WO2018196619, WO2019120081, CN110806676, CN109957349, CN109134710, WO2019088055, JP2010- 049238, WO2008078678, JP2010015025 and JP2010049238.
  • the photoinitiator C4 can be prepared according to the process described in example 1 of US6596445B1 using 1-(4-phenylsulfanyl-phenyl)-1-octanone in the first step and benzoyl chlo- ride in the second step.
  • Photoinitiator C5 can be prepared according to the process described in example 1 of WO02100903 using ortho-toluoylchloride and octanoylchloride in the first step and benzoyl chloride in the first step.
  • Photoinitiator C6 can be prepared according to the process described in example 18 of WO2012045736 using 4-(2,2-difluoro-3,3-difluoro-propyl)-benzoyl chloride.
  • C22 can be repared as outlined in example 2 of US20150111152.
  • the composition of the present invention preferably also comprises at least one oligomer or polymer (D), which is soluble in alkaline solution.
  • Alkaline solution is a solution of a base in water.
  • the alkaline solution has preferably a pH in the range from 9 to 12, more preferably in the range of 10 to 12.
  • Oligomer and polymer (D) have preferably an average weight molecular weight of at least 800 g/mol, more preferably at least 1000 g/mol, and most preferably at least 1500 g/mol.
  • the maxi- mum average wight molecular weight is 2000000 g/mol, more preferably 1000000 g/mol.
  • the average weight molecular weight of oligomer and polymer (D) can be determined using gel permeation chromatography calibrated to a polystyrene standard.
  • Oligomer and polymer (D) usually carry acidic groups that render them soluble in alkaline solu- tion such as COOH, SO3H, aromatic hydroxyl groups and anhydride groups.
  • Oligomer and polymer (D) can optionally also carry ethylenically unsaturated groups.
  • oligomer and polymer (D) are oligomers and polymers obtainable by polymeriza- tion of at least one ethylenically unsaturated anhydride and another ethylenically unsaturated monomer (Y) carrying no COOH groups.
  • oligomer and polymer (D) carrying COOH groups are oligomer and polymer (D1) carrying COOH groups and no ethylenically unsaturated group and oligomer and polymer (D2) carrying COOH groups and ethylenically unsaturated groups.
  • oligomer and polymer (D) carrying aromatic hydroxyl groups groups are oligomer and polymer (D3) carrying aromatic hydroxyl groups and no ethylenically unsaturated group and no COOH group, and oligomer or polymer (D4) carrying aromatic hydroxyl groups and ethyleni- cally unsaturated groups and no COOH group.
  • Oligomer and polymer (D1) carrying COOH groups and no ethylenically unsaturated group can be any oligomer and polymer carrying COOH groups and no ethylenically unsaturated group.
  • Oligomer and polymer (D1) carrying COOH groups and no ethylenically unsaturated group can carry other groups such as SO 3 H and aromatic hydroxyl groups.
  • oligomers and polymers can, for example, be obtained by polymerization of at least one ethylenically unsaturated mon- omer (X) carrying at least one COOH group with at least one ethylenically unsaturated mono- mer (Y) not carrying a COOH group.
  • Examples of ethylenically unsaturated monomers (X) carrying at least one COOH group are (meth)acrylic acid, COOH-group carrying esters of (meth)acrylic acid 2-carboxyethyl (meth)acrylic acid and 2-carboxypropyl (meth)acrylic acid, alpha, beta unsaturated C4-10 carbox- ylic acids other than (meth)acrylic acid such as crotonic acid and cinnamic acid, alpha, beta unsaturated C4-io-dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and 2-methyleneglutaric acid, half esters of alpha, beta unsaturated C4-10 carboxylic acids such as maleic acid monomethylester, maleic acid monoethylester, maleic acid monobutylester, mono[2-(meth)acryloyloxyethyl] maleate, mono[2-(meth)acryloy
  • Examples of ethylenically unsaturated monomers (X) carrying at least one COOH group are also bicyclic compounds such as 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6- dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6- ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene and 5-carboxy-6- ethylbicyclo[2.2.1]hept-2-ene.
  • Examples of ethylenically unsaturated monomers (X) carrying at least one anhydride group are cyclic bicompounds such as 5,6-dicarboxybicyclo[2.2.1]hept-2- ene anhydride.
  • esters of (meth)acrylic acid such methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, hydrox- yethyl (meth)acrylate, hydroxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxy- butyl (meth)acrylate, glycerol mono(meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, allyl (meth) acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, 4-methoxyphenyl (meth)acrylate, 2-methoxyethyl (meth)acrylate
  • Preferred oligomers and polymers (D1) carrying COOH groups and no ethylenically unsaturated group are (meth)acrylic polymers carrying COOH groups and no ethylenically unsaturated group obtainable by polymerization of (meth)acrylic acid and at least one ester of (meth)acrylate and optionally other ethylenically unsaturated monomers not carrying a COOH group.
  • Examples of (meth)acrylic polymers carrying COOH groups and no ethylenically unsaturated group obtainable by polymerization of (meth)acrylic acid and at least one ester of (meth)acrylate and optionally other ethylenically unsaturated monomers not carrying a COOH group are copolymers are copolymers of methyl (meth)acrylate and (meth)acrylic acid, copolymers of ben- zyl (meth)acrylate and (meth)acrylic acid, copolymers of methyl (meth)acrylate, ethyl (meth)acrylate and (meth)acrylic acid, copolymers of benzyl (meth)acrylate, (meth)acrylic acid and styrene, copolymers of benzyl (meth)acrylate, (meth)acrylic acid and hydroxyethyl (meth)acrylate, copolymers of benzyl (meth)acrylate, (meth)acryl
  • More preferred oligomers and polymers (D1) carrying COOH groups and no ethylenically un- saturated group are acrylic polymers carrying COOH groups and no ethylenically unsaturated group, obtainable by polymerization of acrylic acid and at least one ester of acrylate and option- ally other ethylenically unsaturated monomers not carrying a COOH group.
  • acrylic polymers carrying COOH groups and no ethylenically unsaturated group obtainable by polymerization of acrylic acid and at least one ester of acrylate and optionally oth- er ethylenically unsaturated monomers not carrying a COOH group are copolymers obtained by polymerization of acrylic acid and styrene, copolymers obtained by polymerization of acrylic acid and benzyl acrylate, copolymers obtained by polymerization of acrylic acid, methyl acrylate and benzyl acrylate, copolymers obtained by polymerization of acrylic acid, benzyl acrylate and sty- rene, copolymers obtained by polymerization of acrylic acid, benzyl acrylate and 2-hydroxyethyl acrylate, copolymers obtained by polymerization of acrylic acid, benzyl acrylate, styrene and 2- hydroxyethyl acrylate, copolymers obtained by polymerization of acrylic acid, styren
  • Oligomer and polymer (D2) carrying COOH groups and ethylenically unsaturated groups can be any compound, oligomer and polymer (D) carrying COOH groups and ethylenically unsaturated groups. These compounds, oligomer and polymer can carry other groups such as SO3H and aromatic hydroxyl groups.
  • Oligomer and polymer (D2) carrying COOH groups and ethylenically unsaturated groups can, for example, be obtained by reacting an oligomer or polymer (E) carrying epoxide groups with at least one ethylenically unsaturated compound (Z) carrying one COOH group, followed by reac- tion with at least one anhydride.
  • Preferred oligomers and polymers (E) carrying epoxide groups are reaction products of novolak resins with epichlorohydrine. The reaction can result in full or partial conversion of the aromatic hydroxyl groups of the novolak resin.
  • novolak resins are resins obtained from phe- nol and formaldehyde and resins obtained from cresol and formaldehyde.
  • Preferred ethylenically unsaturated compounds (Z) carrying one COOH group are acrylic acid and methacrylic acid.
  • Anhydrides are usually derived from a compound carrying at least two COOH groups.
  • Preferred anhydrides are ethylenically unsaturated anhydrides such as maleic anhydride, itaconic anhy- dride, citraconic anhydride, tetrahydrophthalic anhydride, endo-methylenetetrahydrophthalic anhydride, methyl-endomethylene tetrahydrophthalic anhydride, chlorendic anhydride, methyl- tetrahydrophthaic anhydride and 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1 ,2- dicarboxylic anhydride, aromatic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride and benzophenone tetracarboxylic dianhydride, and saturated anhydride such as succinic anhydride, hexahydrophthalic anhydride, methyl
  • Examples of oligomer and polymer (D2) so-obtained are the reaction poducts obtained by first reacting the reaction product of novolak resin and epichlorohydrine with acrylic acid, followed by reaction with maleic anhydride.
  • Oligomer and polymer (D2) carrying COOH groups and ethylenically unsaturated groups can, for example, also be obtained by reaction of part of the COOH groups of an oligomer and poly- mer (D1) carrying COOH groups and no ethylenically unsatuated groups with ethylenically un- saturated monomer (V) carrying one epoxide group.
  • the oligomer and polymer (D1) carrying COOH groups and no ethylenically unsaturated group are described above.
  • Examples of the ethylenically unsaturated monomer (V) carrying one epoxide group are the monomers of formula V-1 to V-15 wherein R50 is hydrogen or methyl group, M3 is substituted or unsubstituted alkylene having 1 to 10 carbon atoms.
  • An example of a compound of formula V-1 is glycidyl (meth)acrylate.
  • Preferred oligomer and polymer (D2) so-obtained are products obtained by the reaction of co- polymers of styrene and acrylic acid with 3,4-epoxycyclohexylmethyl acrylate, products obtained by the reaction of copolymers of styrene, a-methylstyrene and acrylic acid with 3,4- epoxycyclohexylmethyl acrylate, products obtained by the reaction of copolymers of methyl acrylate and acrylic acid with 3,4-epoxycyclohexylmethyl acrylate, products obtained by the re- action of copolymers obtained by polymerization of acrylic acid and benzyl acrylate with glycidyl acrylate, products obtained by the reaction of copolymers obtained by polymerization of acrylic acid, methyl acrylate and benzyl acrylate with glycidyl acrylate.
  • R is benzyl or methyl
  • Oligomer and polymer (D2) carrying COOH groups and ethylenically unsaturated groups can, for example, also be obtained by reaction of part or all of the COOH groups of an oligomer and polymer (D1) carrying COOH groups and no ethylenically unsaturated group with at least one ethylenically unsaturated monomer (V) carrying one epoxide group, followed by reaction with at least one anhydride.
  • the oligomer and polymer (D1) carrying COOH groups and no ethylenically unsaturated group is described above.
  • the ethylenically unsaturated monomer (V) carrying one epoxide group is also described above.
  • Anhydrides are also described above.
  • Examples of oligomers and polymer (D2) so-obtained are reaction products obtained by first reacting a copolymer of acrylic acid and benzyl acrylate with glycidyl acrylate, followed by reac- tion with tetrahydrophthalic anhydride, reaction products obtained by first reacting a copolymer of acrylic acid and methyl acrylate with glycidyl acrylate, followed by reaction with tetrahydroph- thalic anhydride, reaction products obtained by first reacting a copolymer of acrylic acid, benzyl acrylate and methyl acrylate with glycidyl acrylate, followed by reaction with tetrahydrophthalic anhydride, reaction products obtained by first reacting a copolymer of acrylic acid, benzyl acry- late, methyl acrylate and styrene with glycidyl acrylate, followed by reaction with tetrahydroph- thalic anhydride.
  • Oligomer and polymer (D2) carrying COOH groups and ethylenically unsaturated groups can, for example, also be obtained by reaction of part of the COOH groups of an oligomer and poly- mer (D1) carrying COOH groups and no ethylenically unsaturated group with an ethylenically unsaturated compound (F) carrying one hydroxyl group.
  • the oligomer and polymer (D1) carry- ing COOH groups and no ethylenically unsaturated group are described above.
  • An example of ethylenically unsaturated monomer (F) carrying at least one hydroxyl group is 2-hydroxyethyl (meth)acrylate.
  • Oligomer and polymer (D2) carrying COOH groups and ethylenically unsaturated groups can, for example, also be obtained by reaction of oligomers and polymers (G) obtained by polymeri- zation of at least one ethylenically unsaturated anhydride and another ethylenically unsaturated monomer (Y) carrying no COOH groups, with at least one ethylenically unsaturated compound (F) carrying one hydroxy group.
  • G oligomers and polymers
  • G obtained by polymeri- zation of at least one ethylenically unsaturated anhydride and another ethylenically unsaturated monomer (Y) carrying no COOH groups
  • Y ethylenically unsaturated monomer carrying no COOH groups
  • Oligomer and polymer (D2) carrying COOH groups and ethylenically unsaturated groups can, for example, also be polyestes obtained by reaction of at least one ethylenically unsaturated diol (H) with at least one compound (I) carrying at least three COOH groups.
  • ethyleni- cally unsaturated diol (H) are reaction product of Ci-so-diols with glycidyl (meth)acrylate.
  • Exam- ples of compound (I) carrying at least three COOH groups are di(3,4-dicarboxyphenyl) ketone.
  • Oligomer and polymer (D2) carrying COOH groups and ethylenically unsaturated groups can, for example, also be polyesters obtained by reaction of at least one ethylenically unsaturated diol (H) with at least one compound (I) carrying at least three COOH groups, followed by reac- tion with an anhydride.
  • Oligomer and polymer (D2) carrying COOH groups and ethylenically unsaturated groups can also be polyimides carrying COOH groups and ethylenically unsaturated groups.
  • oligomer and polymer (D3) carrying aromatic hydroxyl groups and no ethylenically unsaturated group and and no COOH group are novolac resins, poly(4-hydroxystyrene), as wells as oligomers and polymers obtainable by polymerization of an ethylenically unsaturated monomer carrying a hydroxyl aryl group and no COOH group with other ethylenically unsaturat- ed monomers (Y) not carrying a COOH group.
  • An example of an ethylenically unsaturated monomer carrying a hydroxyl aryl group and no COOH group is 4-hydroxystyrene. Examples of other ethylenically unsaturated monomers (Y) not carrying a COOH group are given above.
  • Preferred oligomer or polymer (D) are oligomer or polymer, which are soluble in alkaline solu- tion.
  • More preferred oligomer and polymer (D) are oligomers or polymers, which are soluble in alka- line solution, and which oligomers or polymers carry COOH groups.
  • oligomers and polymer (D) are oligomers or polymers, which are soluble in alkaline solution, which oligomers or polymers carry COOH groups, and which oligomers or pol- ymers have an acid number in the range of 50 to 600 mg KOH/g.
  • oligomer and polymer (D) are oligomers or polymers, which are soluble in alka- line solution, which oligomers or polymers carry COOH groups, and which oligomers or poly- mers have an acid number in the range of 100 to 300 mg KOH/g.
  • the acid number can be determined by DIN EN 12634.
  • oligomer and polymer (D) are oligomers or polymers, which are soluble in alkaline solution, which oligomers or polymers carry COOH groups, and which oligomers or pol- ymers have an acid number in the range of 100 to 300 mg KOH/g and which are either (i) (meth)acrylic polymers carrying COOH groups and no ethylenically unsaturated group obtainable by polymerization of (meth)acrylic acid and at least one ester of (meth)acrylic acid and optionally other ethylenically unsaturated monomers not carrying a COOH group,
  • (ii) (meth)acrylic polymers carrying COOH groups and ethylenically unsaturated groups obtainable by treatment of (meth)acrylic polymers carrying COOH groups and no ethylenically unsaturated group, obtainable by polymerization of (meth)acrylic acid and at least one ester of (meth)acrylic acid and optionally other ethylenically un- saturated monomers not carrying a COOH group, with an ethylenically unsatuated compound carrying one epoxide group, optionally followed by treatment with an anhydride,
  • composition can also comprise a solvent.
  • solvent comprises “single solvent” and “mixtures of solvents”.
  • ketones are methyl ethyl ketone, isobutyl methyl ketone, 2-heptanone, 2- pentanone, cyclopentanone and cyclohexanone.
  • lactam N-methylpyrrolidone
  • esters are ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether ace- tate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4- methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3- ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl ace- tate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 4-
  • Preferred solvents are esters and mixtures of esters with ketones, lactams and ethers.
  • composition can also comprise a least one additive.
  • additives examples include colorants, dispersing agents, polymeric synergists, surfactants, tex- ture improving agents, adhesion improving agents, photosensitizers, accelerators, additional thermal rqadical initiators, inhibitors and crosslinking agents.
  • composition can also comprise at least one colorant.
  • the colorant can be any pigment or dye.
  • pigment includes “single pigments” as well as “pigment mixtures”.
  • pigments examples include red, gree, blue, black, yellow, magenta and cyan pigments.
  • Preferred red pigments are anthraquinone type pigments such as C. I. Pigment Red 177 and diketopyrolopyrole type pigments such as C. I. Pigment Red 254, mixtures of red anthra- quinone type pigments such as C. I. Pigment Red 177 and red diketopyrolopyrole type pigments such as C. I. Pigment Red 254, as well as mixtures consisting of at least one red pigment se- lected from the group consisting of red anthraquinone type pigment C. I. Pigment Red 177 and red diketopyrolopyrole type pigment such as C. I. Pigment Red 254 and at leat one bisazo type yellow pigment such C. I. Pigment Yellow 83 or at least one isoindoline type yellow pig- ment such as C. I. Pigment Yellow 139.
  • C. I. Pigment Red 177 and diketopyrolopyrole type pigments such as C. I. Pigment
  • red pigments are C.l. Pigment Red 9, 97, 105, 122, 123, 144, 149, 168, 176, 179, 180, 185, 202, 206, 207, 209, 214, 222, 224, 244, 255, 264, 272 and C.l.
  • Preferred green pigments are halogenated phthalocyanine type pigments such C. I. Pigment Green 7, C. I. Pigment Green 36 and C.l. Pigment 58, as well as mixtures of at least one green pigment selected from the group consisting of C. I. Pigment Green 7, C. I. Pigment Green 36, C.l. Pigment Green 58, C.l. Pigment Green 59, C.l. Pigment Green 62 and C.l. Pigment Green 63, with at least one bisazo type yellow pigment such as C. I. Pigment Yellow 83, at least one quinophthalone type yellow pigment such as Pigment Yellow 138, at least one isoindoline type yellow pigment such as C. I. Pigment Yellow 139 or awith at least one metal complex type yel- low pigment such as C. I. Pigment Yellow 150.
  • green pigments are C.l. Pigment Green 15, 25 and 37.
  • Preferred blue pigments are blue phthalocyanine type pigments such as C. I. Pigment Blue 15:6, and mixtures of at least one blue phthalocyanine type pigments such as C. I. Pigment Blue 15:6 with a dioxazine type violet pigmenst such as C. I. Pigment Violet 23.
  • blue pigments are C. I. Pigment Blue 15, 15:1 , 15:2, 15:3, 15:4, 16, 22, 28, 60, 64 and 66., and C. I. Pigment Violet 1 , 1 :1 , 2, 2:2, 3, 3:1 , 5, 5:1 , 14,15, 16, 19, 23, 25, 27, 29, 31 , 32, 37, 39, 42, 44, 47, 49, 50 and 177.
  • black pigments are carbon black, titanium black, iron oxide, lactone-type black pigment, lactame-type black pigment, black perylene-based pigments, C. I. Pigment Black 1 , 6, 7, 12, 20, 31 and 32, C. I. Mordant black 7 and C. I. Reactive black 5, and mixtures thereof.
  • the preferred black pigment is carbon black.
  • yellow pigments examples include bisazo type yellow pigment such C. I. Pigment Yellow 83, iso- indoline type yellow pigment such as C. I. Pigment Yellow 139, quinophthalone type yellow pigment such as Pigment Yellow 138 and metal complex type yellow pigments such as C. I. Pigment Yellow 150.
  • magenta pigments examples include C. I. Pigment Red 122, 144, 146, 169, 177, C. I. Pigment Violet 19 and 23.
  • cyan pigments examples include aluminum phthalocyanine pigments, titanium phthalocyanine pigments, cobalt phthalocyanine pigments, and tin phthalocyanine pigments.
  • the pigment When the composition is a color filter composition, the pigment usually has a mean particle size of below 400 nm, preferably below 100 nm.
  • the mean particle size is usually determined using transmission electron microscopy.
  • dyes are red, green, blue, black, yellow, magenta and cyan dyes.
  • red dyes are C.
  • green dyes are C. I. Acid Green 3, 9, 16, 25, C. I. Direct Green 28, 59, C. I. Basic Green 1 and 4.
  • blue dyes are methane type dyes, anthraquinone type dyes, azo type dyes, metal complex azo type dyes, triaryl methane type dyes and phthalocyanine type dyes.
  • blue dyes are C. I. Solvent Blue 11, 25, 37, 45,49, 68, 78, 94, C. I. Direct Blue 25, 86, 90, 108, C. I. Acid Blue 1, 3, 7, 9, 15, 29, 83, 90, 103, 104, 158, 161, 249, C. I. Basic Blue 1 , 3, 5, 7, 9, 24, 25, 26, 41, 105, C. I. Reactive blue 19, 49, and C. I. Disperse Blue 56, 60, 165, 198, C. I. Vat Blue 4, 5, and C. I. Mordant Blue 1.
  • yellow dyes examples include C. I. Solvent Yellow 2, 5, 14, 15, 16, 19, 21 , 33, 56, 62, 77, 83, 93, 162, 104, 105, 114, 129, 130, 162, C. I. Disperse Yellow 3, 4, 7, 31, 42, 54, 61 , 64, 201 , C. I. Reactive Yellow 2, C. I. Mordant Yellow 5, C. I. Direct Yellow 1 , 11, 12, 28, C. I. Acid Yellow 1, 3, 11, 17, 23, 38, 40, 42, 76, 98, C. I. Basic Yellow 1 ,
  • magenta dyes examples include C. I. Solvent Violet 2, 10, 13, 33, 45, 46, C. I. Disperse Violet 22, 24, 26, 28, 31, C. I. Acid Violet 9, 49, C. I. Basic Violet 1 , 2, 3, 7, 10, 14,
  • black dyes examples include Solvent Black 3, 5, 7, 27, 28, 29, 35, 45 and 46.
  • the colorant is a pigment.
  • the colorant is a red, green, blue or black pigment.
  • the term “dispersing agent” comprises “single dispersing agents” and “mixtures of dispersing agnts”.
  • the dispersing agent can be any dispersing agent, such as a polymeric dispersing agent.
  • polymeric dispersing agents are random, block or comb-type copolymers obtained by polymerization of suitable monomers such styrene derivatives, (meth)acrylates and (meth)acrylamides, and optional modification after polymerization.
  • polymer- ic dispersing agents are polyethylenimines, polyethyleneimines crafted to polyesters, polyam- ines, polyamines crafted to polyesters, polyurethanes and modified polyurethanes
  • polymeric dispersing agents are BYK’s DISPERBYK® 101 , 115, 130, 140, 160, 161 , 162, 163, 164, 166, 168, 169, 170, 171 , 180, 182, 2000, 2001 , 2009, 2020, 2025, 2050, 2090, 2091 , 2095, 2096, 2150, EFKA® 4008, 4009, 4010, 4015, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4310, 4330, 4340, 4400, 4401 , 4402, 4403, 4406, 4500, 4510, 4520, 4530, 4540, 4550, 4560, Ajisper PB®711 , 821 , 822, 823, 824, 827, SOLSPERSE® 1320, 13940, 17000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32500, 32550, 32600, 33500, 34750
  • the dispersing agent is preferably a polymeric dispersing agent, and more preferably selected from the group consisting of EFKA® 4046, 4047, 4060, 4300, 4310, 4330, 4340, DISPERBYK® 161 , 162, 163, 164, 165, 166, 168, 169, 170, 2000, 2001 , 2020, 2050, 2090, 2091 , 2095, 2096, 2105, 2150, Ajisper PB®711 , 821 , 822, 823, 824, 827, SOLSPERSE® 24000, 31845, 32500, 32550, 32600, 33500, 34750, 36000, 36600, 37500, 39000, 41090, 44000, 53095 and mixtures thereof.
  • polymeric synergist includes “single polymeric synergists” as well as “polymeric syn- ergist mixtures”.
  • the polymeric synergist improves the dispersion stability of a pigment in the composition.
  • polymeric synergists examples include opper phthalocyanine derivatives such as EFKA® 6745, SOLSPERSE® 5000, 12000, BYK’s SYNERGIST 2100 and azo derivatives such as EFKA® 6750, SOLSPERSE® 22000 and SYNERGIST 2105.
  • surfactant includes “single surfactants” as well as “surfactant mixtures”.
  • the surfactant can be any surfactant.
  • surfactants are anionic surfactants such as alkylbenzene- or alkylnaphthalene- sulfonates, alkylsulfosuccinates or naphthalene formaldehyde sulfonates, cationic surfactants such as quaternary salts, for example benzyl tributyl ammonium chloride, amphoteric surfac- tants such alkyl betaines or amidopropyl betaines and non-ionic surfactants.
  • anionic surfactants such as alkylbenzene- or alkylnaphthalene- sulfonates, alkylsulfosuccinates or naphthalene formaldehyde sulfonates
  • cationic surfactants such as quaternary salts, for example benzyl tributyl ammonium chloride, amphoteric surfac- tants such alkyl betaines or amidopropyl betaines
  • non-ionic surfactants are polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate, sorbitan fatty acid esters and fatty acid modified polyesters and tertiary amine modi- fied polyurethanes and polyethyleneimines.
  • polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether
  • polyoxyethylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether
  • polyethylene glycol diesters such as polyethylene glyco
  • texture improving agent includes “single texture improving agent” as well as “texture improving agent mixtures”.
  • the texture improving agent can be any texture improving agent.
  • texture improving agents are fatty acids such as stearic acid or behenic acid, fatty amines such as laurylamine or stearylamine, fatty alcohols, ethoxylated fatty alcohols, polyols such as aliphatic 1 ,2-diols or epoxidized soybean oil, waxes, resin acids and resin acid salts.
  • adhesion improving agent includes “single adhesion improving agent” as well as “adhesion improving agent mixtures”.
  • the adhesion improving agent can be any adhesion im- proving agent.
  • the adhesion improving agent usually increases the adhesion of the coated composition to the substrate.
  • adhesion improving agents are silane coupling agents and titanium cou- pling agents.
  • photosensitizer includes “single photosensitizers” as well as “photosensitizer mix- tures”.
  • the photosensitizer can be any photosensitizer.
  • photosensitizers are aromatic compounds such as benzophenone and derivatives thereof, thioxanthone and derivatives thereof, anthraquinone and derivatives thereof, coumarin and derivatives thereof, phenothiazine and derivatives thereof, 3-(aroylmethylene)thiazolines, rhodanines, camphorquinone, eosine, rhodamine, erythrosine, xanthene, thioxanthene, acri- dine, e.g. 9-phenylacridine, 1 ,7-bis(9-acridinyl)heptane, 1 ,5-bis(9-acridinyl)pentane, cyanine and merocyanine dyes.
  • aromatic compounds such as benzophenone and derivatives thereof, thioxanthone and derivatives thereof, anthraquinone and derivatives thereof, coumarin and derivatives thereof, phenothiazine and derivatives thereof, 3-
  • thioxanthone derivatives are 2-isopropylthioxanthone, 2-chlorothioxanthone, 1- chloro-4-propoxythioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4- dimethylthioxanthone, 1 -methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3-(2- methoxyethoxycarbonyl)-thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7- methylthioxanthone, 1-cyano-3chlorothioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, 1- ethoxycarbonyl-3-ethoxythioxanthone, 1 -ethoxycarbonyl-3-aminothioxanthone, 1 - ethoxycarbonyl
  • benzophenone derivatives are 4-phenyl benzophenone, 4-methoxy benzophe- none, 4,4’-dimethoxy benzophenone, 4,4’-dimethyl benzophenone, 4,4’-dichlorobenzophenone 4,4’-bis(dimethylamino)benzophenone, 4,4’-bis(diethylamino)benzophenone, 4,4’- bis(methylethylamino)benzophenone, 4,4’-bis(p-isopropylphenoxy)benzophenone, 4-methyl benzophenone, 2,4,6-trimethylbenzophenone, 4-(4-methylthiophenyl)-benzophenone, 3,3’- dimethyl-4-methoxy benzophenone, methyl-2-benzoylbenzoate, 4-(2-hydroxyethylthio)- benzophenone, 4-(4-tolylthio)benzophenone, 1 -[4-(4-benzoyl-phenyls
  • Examples of coumarin derivatives are Coumarin 1 , Coumarin 2, Coumarin 6, Coumarin 7, Cou- marin 30, Coumarin 102, Coumarin 106, Coumarin 138, Coumarin 152, Coumarin 153, Couma- rin 307, Coumarin 314, Coumarin 314T, Coumarin 334, Coumarin 337, Coumarin 500, 3- benzoyl coumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3- benzoyl-5,7-dipropoxycoumarin, 3-benzoyl-6,8-dichlorocoumarin, 3-benzoyl-6-chloro-coumarin, 3,3’-carbonyl-bis[5,7-di(propoxy)coumarin], 3,3’-carbonyl-bis(7-methoxycoumarin), 3,3’- carbonyl-bis(7-diethylamino-coumarin), 3-isobutyloylcoumarin, 3-benzoyl-5,7-d
  • 3-(aroylmethylene)-thiazolines are 3-methyl-2-benzoylmethylene-p- naphthothiazoline, 3-methyl-2-benzoylmethylene-benzothiazoline and 3-ethyl-2- propionylmethylene-p-naphthothiazoline.
  • rhodanines are 4-dimethylaminobenzalrhodanine, 4-diethylaminobenzalrhodanine, 3-ethyl-5-(3-octyl-2-benzothiazolinylidene)-rhodanine, the rhodanine derivatives, formulae [1], [2], [7], disclosed in JP08-305019A.
  • photosensitizers are acetophenone, 3-methoxyacetophenone, 4- phenylacetophenone, benzil, 4,4’-bis(dimethylamino)benzil, 2-acetylnaphthalene, 2- naphthaldehyde, dansyl acid derivatives, 9,10-anthraquinone, anthracene, pyrene, aminopy- rene, perylene, phenanthrene, phenanthrenequinone, 9-fluorenone, dibenzosuberone, curcu- min, xanthone, thiomichler’s ketone, a-(4-dimethylaminobenzylidene) ketones, e.g.
  • N-phenylglycine ethyl 4-dimethylaminobenzoate, butoxyethyl 4- dimethylaminobenzoate, 4-dimethylaminoacetophenone, triethanolamine, methyldiethanola- mine, dimethylaminoethanol, 2-(dimethylamino)ethyl benzoate, poly(propylenegylcol)-4- (dimethylamino) benzoate.
  • Preferred photosensitizers are selected from the group consisting of benzophenone and its de- rivatives, thioxanthone and its derivatives, anthraquinone and its derivatives, and coumarin and its derivatives.
  • ac- celerator includes “single accelerators” as well as “accelerator mixtures”.
  • the ac- celerator can be any accelerator.
  • the accelerator usually accelerates the photopolymerization.
  • accelerators are amines, for example triethanolamine, N-methyldiethanolamine, ethyl-p-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, 2-ethylhexyl-p- dimethylaminobenzoate, octyl-para-N,N-dimethylaminobenzoate, N-(2-hydroxyethyl)-N-methyl- para-toluidine or Michler’s ketone.
  • the accelerative effect of the amines can be intensified by the addition of aromatic ketones of the benzophenone type.
  • amines which can be used as oxygen scavengers are substituted N,N-dialkylanilines, as are described in EP339841.
  • Other accelerators are thiols, thioethers, disulfides, phosphonium salts, phosphine oxides or phosphines, as described, for example, in EP438123, in GB2180358 and in JP KokaiHei 6- 68309.
  • ditional thermal radical initiator includes “single additional thermal radical initiator” as well as “additional thermal radical initiator mixtures”.
  • the additional thermal radical initiator can be any thermal radical initiator different from the thermal radical initiator (B)
  • thermal radical initiators examples include organic peroxides, azo derivatives, benzoin derivatives, benzoin ether derivatives, acetophenone derivatives, hydroxylamine esters, oxime derivatives such as oxime sulfonates, and hydrogen peroxides.
  • peroxides examples include dilauroyl, 1 ,1 ,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert- butyl peroxy-2-ethylhexanoate, 1,1-di(tert-butylperoxy)-2-methylcyclohexane, 1 ,1-di(tert- hexylperoxy)-3,3,5-trimethylcyclohexane, tert-butylperoxymaleic acid, tert-butyl peroxylaurate, tert-butyl peroxy 2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, tert-butyl peroxyace- tate, tert-butyl peroxybenzoate, dicymyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert- butylperoxy)
  • azo derivatives are 2,2’-azobis(isobutyronitrile), 2,2’-azobis(2-methylbutyronitrile), 1 , 1 ’-azobis(cyclohexane-1 -1 -carbonitrile), (2,4-dimethylvaleronitrile) , 1 -[(1 -cyano-1 - methylethyl)azo]formamide, 2,2’-azobis(2-amidinopropane) dihydrochloride, 2,2’-azobis[N-(2- propenyl)-2-methylpropionamide], 2,2’-azobis(N-butyl-2-methylpropionamide), 2,2’-azobis[2-(2- imidazolin-2-yl)propane], 2,2’-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], Dimethyl 2,2’- azobis(isobutyrate), and the azo compounds described in JP2003015288.
  • oxime sulfonates are described by W02012/101245 and W016/030790.
  • hydroxylamine esters are described by W02001090113, WO03029332 and WO1 0108835.
  • composition of the present invention preferably does not include peroxide and aza com- pounds.
  • inhibitor includes “single inhibitator” as well as “inhibitor mixtures”.
  • the inhibitor can be any inhibitor. Inhibitors usually prevent premature polymerization.
  • thermal inihibitors examples include hydroquinone, hydroquinone derivatives, p-methoxyphenol, P-naphthol and sterically hindered phenols, such as 2,6-di-t-butyl-p-cresol.
  • inhibitors that increase the stability on storage in the dark are copper compounds, such as copper naphthenate, stearate or octoate, phosphorus compounds, for example tri- phenylphosphine, tributylphosphine, triethylphosphine, triphenyl phosphate or tribenzyl phos- phate, quaternary ammonium compounds, for example tetramethylammonium chloride or trime- thylbenzylammonium chloride, or hydroxylamine derivatives, for example N- diethylhydroxylamine.
  • copper compounds such as copper naphthenate, stearate or octoate
  • phosphorus compounds for example tri- phenylphosphine, tributylphosphine, triethylphosphine, triphenyl phosphate or tribenzyl phos- phate
  • quaternary ammonium compounds for example tetramethylammonium
  • inhibitors that exclude atmospheric oxygen during the polymerization by migrating to the surface in the beginning of polymerization and form a transparent surface layer which prevents the ingress of air, are paraffin or similar wax-like substances which, being of inade- quate solubility in the polymer.
  • inhibitors are light stabilizers such as UV absorbers, for example those of the hydroxyphenylbenzotriazole, hydroxyphenyl-benzophenone, oxalamide or hydroxyphenyl-s- triazine type. These compounds can be used individually or in mixtures, with or without sterically hindered amines (HALS).
  • UV absorbers for example those of the hydroxyphenylbenzotriazole, hydroxyphenyl-benzophenone, oxalamide or hydroxyphenyl-s- triazine type.
  • HALS sterically hindered amines
  • Inhibitors may also prevent deterioration of color properties like transparency.
  • examples of these inhibitors preventing deterioration are thermal inhibitors such as phenol derivatives and sterically hindered phenols as are described, for example, by US4994628, JP6128195, JP7206771 and WO0198249
  • inhibitors are latent thermal inhibitors which are antioxidants and prevent premature polymerization or discoloration.
  • the latent thermal inhibitors are usually compounds having a protective group capable of being desorbed by heating and developing an antioxidant function.
  • Preferred latent thermal inhibitors are compounds which are synthesized with a combination of phenol derivatives and acid anhydride, Boc reagent such as di-tert-butyl dicarbonate, acid chlo- ride, alkyl halide derivatives, allyl ether derivatives or cyclochloride derivatives such as decribed in W014021023W017043353, W02016056290, JP2017008219, JP2017066370, J P201513937 WO2018062105
  • crosslinking agent includes “single crosslinking agent” as well as “crosslinking agent mixtures”.
  • the crosslinking agent can be any crosslinking agent. Examples of crosslinking agents which are activated by an acid or a base are those described in JP10221843, epoxy resins and oxetane compounds.
  • epoxy resind examples include bisphenol S type epoxy resins bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol fluorene type epoxy resins, diglycidyl phthalate resins, heterocyclic epoxy resins, bixylenol type epoxy resins, biphenol type epoxy resin, tetraglycidyl xylenoylethane resins, novolak type epoxy resins, novolak type epoxy resin of bisphenol A, che- late type epoxy resins, glyoxal type epoxy resins, rubber-modified epoxy resins, silicone- modified epoxy resins, as well as partially esterified products thereof
  • oxetane compounds are 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), 2- ethylhexyloxetane, xylene bisoxetane and 3-ethyl-3[[(3-ethyloxetane-3-yl)methoxy]- methyl]oxetane,
  • crosslinking agents are crosslinking agents which generate acid or base thermally or by actinic radiation and which activates a crosslinking reaction
  • crosslinking agents are cationic photo- or thermal initiators such as sul- fonium-, phosphonium- or iodonium salts, for example Omnicat®250, cyclopentadienyl-arene- iron(ll) complex salts, for example (r
  • sul- fonium-, phosphonium- or iodonium salts for example Omnicat®250
  • cyclopentadienyl-arene- iron(ll) complex salts for example (r
  • composition of the present composition preferably comprises from
  • thermal radical initiator (B) 0.1 to 20% by weight of thermal radical initiator (B), and
  • photoinitiator (C) 0.1 to 20% by weight of photoinitiator (C) based on the weight of the solids of the composition of the present invention.
  • the percentage given above refers to the sum of all components (A), the sum of all components (B) and the sum of all components (C), respectively.
  • “2 to 80% by weight of compound or oligomer carrying at least one ethylenically unsaturated group (A) based on the weight of the solids of the composition of the present invention” means “2 to 80% by weight of all compounds or oligomers carrying at least one ethylenically unsaturated group (A) based on the weight of the solids of the composition of the present invention”.
  • composition of the present composition more preferably comprises from 10 to 60% by weight of compound or oligomer carrying at least one ethylenically unsaturated group (A),
  • thermal radical initiator (B) 0.5 to 10% by weight of thermal radical initiator (B) and
  • photoinitiator (C) 0.5 to 10% by weight of photoinitiator (C) based on the weight of the solids of the composition of the present invention.
  • the composition of the present invention preferably also comprises an oligomer or polymer (D) which is soluble in an alkaline solution.
  • the composition comprises an oligomer or polymer (D), which is soluble in alkaline solution
  • the composition preferably comprises from 2 to 98% by weight of oligomer and polymer (D) which is soluble in alkaline solution, more preferably from 4 to 90%, and most preferably from 5 to 75% by weight based on the weight of the solid of the composition.
  • the amount of oligomer or polymer (D), which is soluble in alkaline solution is usually in the range of 2 to 40% by weight if a pigment is present and in the range of 30 to 98% by weight if no pigment is present, based on the weight of the solid of the composition
  • composition of the present invention usually also comprises a solvent. If the composition comprises a solvent, the composition preferably has a solid content in the range of from 5 to 50% by weight based on the weight of the composition, more preferably in the range of from 10 to 45% by weight.
  • composition of the present invention comprises a pigment
  • the composition of the present invention preferably also comprises at least one additive selected from the group consisting of dispersing agent, polymeric synergist and surfactant and mixtures thereof.
  • compositions of the present composition comprising a pigment preferably comprise from 2 to 80% by weight compounds or oligomers carrying at least one ethylenically unsaturated group (A),
  • At least one additive selected from the group consisting of dispersing agent, polymeric synergist and surfactant and mixtures thereof, based on the weight of the pigment.
  • compositions of the present composition comprising a pigment more preferably comprise from 10 to 60% by weight of compound or oligomer carrying at least one ethylenically unsaturated group (A),
  • oligomer or polymer (D) which is alkaline soluble 20 to 60% by weight of pigment based on the weight of the solids of the composition of the present invention, and from 10 to 60% by weight at least one additive selected from the group consisting of dispersing agent, polymeric synergist and surfactant and mixtures thereof, based on the weight of the pig- ment.
  • compositions of the present invention can be prepared by mixing the at least one com- pound or oligomer carrying at least one ethylenically unsaturated group (A), the at least one thermal radical initiator (B) and the at least one photoinitiator (C).
  • component (A), (B) and (C) are mixed with at least one oligomer or oligomer (D), which is soluble in alkaline solution, and a solvent.
  • composition of the present invention comprises at least one pig- ment, usually a pigment dispersion comprising pigment, solvent and additives such as dispers- ing agents and polymeric synergists is prepared first, and then components (A), (B), (C), (D) and optionally solvent are added to the pigment dispersion and dispersed.
  • a pigment dispersion comprising pigment, solvent and additives such as dispers- ing agents and polymeric synergists is prepared first, and then components (A), (B), (C), (D) and optionally solvent are added to the pigment dispersion and dispersed.
  • composition of the present invention is preferably suitable as photoresist composition.
  • composition of the present invention also comprising at least one oligomer or oligomer (D), which is soluble in alkaline solution, is preferably suitable as negative photoresist composition.
  • Also part of the present invention is a process for forming a cured layer on a substrate, which processes comprises the steps of
  • step (iii) treating the layer of step ((ii) with light, followed by heat treatment, or heating the layer of step (ii), followed by light treatment.
  • step (iii) the layer of step ((ii) is first treated with light, followed by heat treatment,
  • Also part of the present invention is a process for forming a cured pattern on a substrate, which processes comprises the steps of
  • composition of the present invention (i) applying composition of the present invention on a substrate to form a layer
  • step (iii) treating the layer of step (ii) with light using a mask to form a layer comprising light- treated and not light-treated parts
  • step (iv) treating the layer of step (iii) with a developer to form a pattern
  • the substrate can be any suitable substrate such as glass, or a plastic substrate such as poly- ethersulfone, polycarbonate, polysulfone, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).
  • the composition of the present invention can be applied to the substrate by any technique known in the art.
  • the composition is applied by liquid processing techniques such as spin coating, knife coating, curtain pouring, brush application, blading, slot-die coating, drop- casting, spray-coating, ink-jetting, reverse roll coating, or soaking of the substrate in the compo- sition.
  • the composition is applied by spin-coating.
  • the layer is dried by part or complete removal of the solvent present in the layer. Drying is usu- ally performed, for example, by heating the substrate with the layer at a temperature in the range of 30 to 80°C, more preferably at a temperature in the range of 40 to 70°C, for 1 to 60 minutes, preferably for 5 to 20 minutes.
  • the drying step can be performed, for example, using a convection oven.
  • the dried layer on the substrate can have a thickness in the range of 0.1 micrometer to 2000 micrometer, such as in the range of 0.5 to 500 micrometer, or in the range of 0.5 to 10 microme- ter.
  • the light used to treat the layer can have any suitable wavelength (or mixture of wavelengths).
  • the light has a wavelength in the range of from 150 to 2500 nm, more preferably in the range of from 200 to 650 nm, and most preferably in the rang of from 200 to 450 nm.
  • any suitable light source or mixtue of light sources can be used.
  • light sources are low-pressure mercury vapor lamps, medium-pressure mercury vapor lamps, high-pressure mer- cury vapor lamps, lasers, pulsed lamps (flashlight), halogen lamps, excimer lamps, arc lamps and light emitting diodes.
  • the total light exosure dose is normally chosen to yield sufficient curing.
  • the total light exposure dose can be, for example, in the range of 5 to 3000 mJ/cm 2 , preferably in the range of 5 to 300 mJ/cm 2 , and as low as in the range of 50 to 150 mJ/cm 2 .
  • the developer can be any developer known in the art.
  • the develop- er is an alkaline solution.
  • the layer can be treated with the developer by any method known in the art, such as soaking the substrate with the layer in a developer bath or spraying the devel- oper onto the substrate. Usually, the developer is sprayed onto the layer. Usually, the treatment of the layer with the developer is performed at a temperature in the range of 18 to 40°C. Usual- ly, the treatment of the layer with the developer is performed for 1 second to 15 minutes.
  • the heat treatment is usually performed at a temperature of below 150 °C, preferably at a tem- perature of below 120 °C, more preferably at a temperature in the range of 80 to 115 °C and most preferably at a temperature in the range of 90 to 110 °C.
  • the heat treatment is usually performed for 1 to 300 minutes, preferably for 30 to 180 minutes.
  • a cured layer formed by the process of the present inven- tion is also part of the present invention.
  • a device comprising at least one cured layer of the present invention or at least one cured pattern of the present invention.
  • the device is preferably a print- ed circuit board, an integrated circuit, a color filter array, a liquid crystal display, an organic light emitting diode (OLED) display or a white organic light emitting diode (WOLED) display.
  • compositions comprising (i) at least one compound or oligomer carrying at least one ethyleni- cally unsaturated group (A) and (ii) at least one photoinitiator (C), which is a compound carrying at least one oxime ester group, for increasing the light induced curing of the ethylenically un- saturated groups.
  • the thermal radical initiator (B) is of formula or wherein n B ", R 6B “, R 7B “, R 2B “, R 3B “, R 4B “ and R 6B# , R 7B# and R 2B# are as outlined above.
  • the photoinitiator (C) is a compound having a benzohenone skeleton and carrying at least one oxime ester group.
  • the ethylenically unsaturated groups of compound or oligomer (A) carrying at least one ethylenically unsaturated group are selected from the group consisting of acryloyl and methacryloyl groups.
  • compositions of the present invention are advantageous in that the presence of a photoin- itiator (C) allows photopatterning of the layer formed from the composition.
  • C photoin- itiator
  • the composi- tions of the present invention are suitable for use in photolithographic processes.
  • compositions of the present invention are advantageous in that they can form sufficiently cured layers or, in case of photolithographic processes, cured patterns on a substrate in a pro- cess comprising a light treatment and a heat treatment step, wherein the heat treatment step is performed at a temperature of below 120 °C, preferably at a temperature of below 110 °C.
  • the compositions of the present invention allow the use of heat sensitive substrates such as plastic substrates and/or heat-sensitive composition components.
  • the compos- tions allow the use of processes for forming a cured layer or cured pattern which processes re- quire less energy.
  • compositions of the present invention are also advantageous in that the layer formed from the compositions show a high effectiveness of the heat-initated curing, although the heat treat- ment step is performed at a temperature of below 120 °C, preferably at a temperature of below 110 °C.
  • a high effectiveness of heat-initiated curing is advantageous as it leads to higher chemical re- sistance of the cured pattern and higher adhesion of the cured pattern to the substrate.
  • a high chemical resistance of the cured pattern and high adhesion of the cured pat- tern to the substrate is of upmost importance in the alkaline development steps of subsequent photolithographic processes.
  • compositions of the present invention comprising at least a thermal radical initiator of for- mula 1B such as 1B-a, 1B-b, 1B-c, 1B-d, 1B-e, 1B-f, 1B-g, 1B-h, 1B-j and 1B-k, and at least one photoinitiator carrying at least one oxime ester group, such as C4, C5, C6 and C22, are in particular advantageous in that the effectiveness of the light-initiated curing is increased in the light-treatment step.
  • the combination of at least one thermal radical initiator of formula 1B and at least one photoinitiator carrying at least one oxime ester group shows a synergistic effect regarding the effectiveness of light-initated curing.
  • a higher effectiveness of light-initiated curing is advantageous as it allows the reduction of the amount of photoinitiator used in the composition and/or the reduction of the exposure dose of the light used in the light treatment step.
  • PGMEA propylene glycol monomethyl ether acetate
  • DPHA mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate
  • Example 1.1 Preparation of compound 2b Triethylamine (11.24 g, 0.11 mol) was added to a dispersion of hydroxylamine hydrochloride (7.64 g, 0.11 mol) in methanol (40 mL).
  • Example 1.3 Preparation of compound 2e Ethyl acetohydroxamate (7.15 g, 0.069 mol) was mixed with morpholine (18.13 mL, 0.208 mol) and the resulting orange solution was heated to 85 °C under stirring for 24 hours. Morpholine and other solvents formed were evaporated and 9.5 g (95% yield) compound 2e was obtained and used without further purification.
  • 1 H-NMR (CDCl3) ⁇ 8.15ppm (br., 1H, OH), 3.60 (m, 4H, OCH2), 2.98 / 2.78 (m, 4H, E/Z-Isomer, NCH2), 1.86 / 1.85 (s, 3H, E/Z-Isomer, CH3).
  • Example 1.4 Preparation of compound 2g
  • Dimethylamine hydrochloride (42.03g, 0.5 mol) was dissolved in 170 mL DMF (170 mL), the resulting solution was cooled to 0°C.
  • triethylamin (67.3 g, 0.66 mol) was added slowly in 30 minutes.
  • the resulting slighly milky solution was stirred for 30 minutes at 0°C.
  • o-Toluoyl chlo- ride (26.3 g) was added slowly in 15 minutes at 0°C. After stirring for further 15 minutes the then white suspension was warmed to room temperature.
  • the suspension was added to a mixture of demineralized water (500 mL) and ethyl acetate (350 mL) under strong stirring.
  • the organic phase was seperated, the aqueous phase was extracted 2 times with ethyl acetate.
  • the com- bined organic phases were extracted five times with 200ml of brine and were then dried over magnesium sulfate. After evaporation of the solvent 20.35 g of a clear oil was obtained.
  • the oil was extracted 3 times with brine, diluted afterwards with ethyl acetate, dried over magnesium sulfate and evaporated.12.7 g (47%) N,N-dimethyl-o-toluoylamide was obtained as clear oil.
  • N,N-Dimethyl-2-toluoylamide (9.5 g, 0.06 mol) dissolved in dichloro- methane (3 mL) was added and the solution was stirred for 30 minutes at -10°C. Then the solu- tion was slowly warmed to room temperature, some evolution of gas could be observed. The solution was heated to 40 °C and stirred for 18 hours. Hydroxylamin hydrochloride (6.6 g, 0.09 mol) was suspended in methanol (31 mL), then triethylamin (9.5 g, 0.09 mol) was added at 0 °C. To the such-prepared white suspension the above prepared suspension was added slowly and simultaneously with triethylamine (13.7 g, 0.14 mol).
  • cyanurchloride 37.6 g, 0.2 mol was added to the stirred mixture, and the thick suspension was diluted with iso-propanol (5 mL). The obtained suspension was heated to 45 °C for 5 hours. The white mixture was cooled to room temperature and added to demineral- ised water (40 mL) under strong stirring. After standing some time at room temperature the or- ganic phase was separated and the aqueous phase extracted twice with tert-butyl methyl ether. The separated organic phase and the tert-butyl methyl ether extracts were combined and dried over sodium sulfate.
  • Example 3.1 Preparation of thermal radical initiator 1-a (1-a) Thermal radical initiator 1-a was prepared as described in example 1 of WO2014064064A1.
  • Example 4.1 Preparation of thermal radical initiator 1A-a (1A-a) Thermal radical initiator 1A-a was prepared as described in example 13 of WO2014064064A1.
  • Example 4.2 Preparation of thermal radical initiator 1A-b 5.22 g (28mmol) Cyanurchloride was added slowly to a stirred solution of 6.94 g (70 mmol) 2i in 20 mL acetone at -9 °C. Then, 30 mL acetone was added to dissolve the precipitate formed.
  • the resulting brownish oil was dissolved in dichloromethane, subse- quently extracted with demineralised water, 5% sodium hydroxide, 2% lithium hydroxide, and twice with demineralsed water and dried over magnesium sulfate.
  • the solvent of the organic phase was evaporated, and a brownish residue was obtained.
  • the residue was dispersed in tert-butyl methyl ether, filtered, and the solvent of the filtrate was almost evaporated.
  • a precipi- tate was formed, which was filtered, washed with some tert-butyl methyl ether and dried to yield 2.52g (25%) 1A-b as lightly beige crystals.
  • Example 4.3 Preparation of thermal radical initiator 1A-c A suspension of 9.30 g (0.05 mol) 3a in 80 mL acetonitrile was added slowly during 5 minutes to a suspension of 17.94 g (0.1575 mol) 2k in 70 mL acetonitrile at 0 °C. Then, 22.5 mL (0.16 mol) triethylamine was added so that 15 °C was not surpassed. After the addition the mixture was first stirred for 45 minutes and subsequently heated to 40 °C for 19 hours. Then, the mixture was cooled to room temperature and the precipitate was filtered off. The mother liquor was evaporated, and a brown oil was obtained.
  • Example 5.1 Preparation of thermal radical initiator 1B-a Compound 2b (2.7 g, 15.7mol, purity 75%), prepared as described in example 1.1, was dis- solved in a mixture of THF (10 mL) and demineralised water (10 mL). To this solution potassium carbonate (2.77 g, 15.7 mmol) was added and a turbid yellowish solution was obtained. Com- pound 3c (1.18 g, 5.2 mmol), prepared as described in example 2.1, was added, and the mix- ture was heated to 40°C for 48 hours. The mixture was poured into demineralised water and the resulting yellow solution was extracted three times with dichloromethane. The combined organic phases were dried over magnesium sulfate and evaporated.
  • thermal radcal initiator 1B-a was obtained as off-white crystals.
  • 1 H-NMR (CDCl3) ⁇ 5.39 ppm (sept, 1H, CH(CH3)2), 3.31-3.23 (m, 8H, N-CH2), 3.17/3.15 (s, 6H, N-CH3), 2.82/2.81 (m, 6H, N-CH3), 1.38 (d, 6H, CH(CH 3 ) 2 ).
  • Thermal radical initiator 1B-c was prepared as described in example 11 of W02014064064A1.
  • Thermal radical initiator 1B-d was prepared as described in example 9 of W02014064064A1.
  • Example 5.5
  • Thermal radical initiator 1B-e was prepared as described in example 10 of W02014064064A1.
  • Example 5.7 Preparation of thermal radical initiator 1B-g
  • the obtained yellow suspension was allowed to warm to room temperature and stirred for 20 hours.
  • the resulting slightly brownish suspension was poured into demineralised water and stirred for 30 minutes.
  • the obtained precipitate was filtered off, washed with water and dried under vakuum at room temperature to yield 8.36 g (86% yield) thermal initiator 1B-g as white crystals.
  • Example 5.9 Preparation of thermal radical initiator 1B-i (1B-i) 4.99 g (0.044 mol) potassium tert-butylate was added to a suspension of 5.74 g (0.044 mol) recrystallised 2b in 50 mL THF. The mixture was diluted with additional 100 mL THF, and the hardly stirrable mixture obtained was heated for 2 h 20 min at 38 °C. After cooling to room tem- perature 4.68 g (0.02 mol) 3e, obtained as described in example 2.2, was added slowly during 10 min at below 31 °C. The yellowish milky suspension thus formed was stirred at room tem- perature overnight. The solvent was evaporated.
  • Example 5.11 Preparation of thermal radical initiator 1B-j 0.686 g (5.3 mmol) of 2b was added portionwise during 5 minutes to a solution of 0.50 g (1.2 mmol) 3f, obtained as described in example 2.3, in 10 mL dichloromethane. Subsequently 6 ml 1M NaOH was added during 6 minutes under vigorous stirring. The mixture was stirred for 3 h at 30 °C. After cooling to room temperature, the organic layer was separated and extracted with 10 mL water and subsequently three times with 10 mL 1N hydrochloric acid. The hydrochloric acid fractions were combined, and the pH value was adjusted to around 10 by using 1M sodium hydroxide.
  • Example 6.2 Preparation of thermal radical initiator 1C-b A solution of 4.99 g (44 mmol) potassium tert-butylate in 25 ml dried THF was added to a solu- tion of 4.41 g (44 mmol) 2i in 5 ml dried THF. The formed white suspension was diluted with 50 mL dried THF and cooled to 14 °C using an ice bath.4.68g of 3e, prepared as described in ex- ample 2.2, was added slowly during 10 min while keeping the temperature at around 15 °C. The resulting slightly reddish suspension was heated to 38 °C and stirred for 90 minutes. The heat- ing was discontinued, and the mixture was stirred over night at room temperature.
  • Example 7.1 Preparation of blue photo-curable and thermally curable compositions comprising the thermal radical initiator of examples 3.1, 4.1, 4.2, 4.3, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 5.10, 6.1, 6.2 and 10.1 respectively, and photoinitiator C6
  • a blue pigment dispersion was prepared by mixing the following components and dispersing them by using a paint conditioner (SKANDEX): 5.6 parts by weight PB15:6, Blue E provided by Toyo Ink (blue pigment) 0.6 parts by weight PV23, Cromophtal Violet GA provided by BASF (violet pigment) 2.6 parts by weight Ajisper PB821 provided by Ajinomoto Fine Techno (dispersing agent) 0.4 parts by weight EFKA6745 provided by BASF (polymeric synergist)
  • Ripoxy SPC-2000 provided by Shoko Highpolymer (38.8% solution of an acrylic polymer (made from benzyl acrylate, methyl acylate, acrylic acid) carrying COOH groups (alkaline solution soluble polymer solution)
  • Photoinitiator C6 was prepared according to the process described in example 18 of WO2012/045736 using 4-(2,2-difluoro-3,3-difluoro-propyl)-benzoyl chloride.
  • Blue pigment dispersion was prepared by mixing the following components and dispersing them by using a paint conditioner (SKANDEX).
  • Ripoxy SPC-2000 provided by Shoko Highpolymer (37.8% solution of an acrylic polymer (made from benzyl acrylate, methyl acrylate, acrylic acid) carrying COOH groups (alkaline solution soluble polymer solution)
  • Photoinitiator C4 was prepared according to the process described in example 1 of US6596445B1 using 1-(4-phenylsulfanyl-phenyl)-1-octanone in the first step and benzoyl chlo- ride in the second step.
  • a blue pigment dispersion was prepared by mixing the following components and dispersing them by using a paint conditioner (SKANDEX):
  • Ripoxy SPC-2000 provided by Shoko Highpolymer (38.8% solution of an acrylic polymer (made from benzyl acrylate, methyl acylate, acrylic acid) carrying COOH groups (alkaline solution soluble polymer solution)
  • Blue pigment dispersion was prepared by mixing the following components and dispersing them by using a paint conditioner (SKANDEX).
  • Ripoxy SPC-2000 provided by Shoko Highpolymer (37.8% solution of an acrylic polymer (made from benzyl acrylate, methyl acrylate, acrylic acid) carrying COOH groups (alkaline solution soluble polymer solution)
  • Photoinitiator C5 was prepared according to the process described in example 1 of
  • a comparative blue composition was prepared in analogy to the blue photocurable and thermal- ly curable compositions of example 7.1, but not comprising a thermal radical initiator.
  • compositions of example 7.1 comprising thermal radical initiator 1 -a, 1A-a, 1A-b, 1A-c, 1B- a, 1B-b, 1B-c, 1B-d, 1B-e, 1 B-f , 1B-g, 1B-h, 1 B-i, 1 B-j, 1B-k, 1C-a, 1C-b and 1D-a, respec- tively, and 2.25 weight% photoinitiator C6 based on the solids of the composition as well as the compositions of example 7.4 comprising thermal radical initiator 1B-a and 1 B-j, respectively, and 2.25 weight% photoinitiator C22 based on the solids of the composition form layers on a substrate, wherein
  • compositions of the present invention are suitable for use in photolithographic processes.
  • compositions of example 7.1 comprising the thermal radical initiator 1B-a, 1B-b, 1B-c, 1B-d 1B-e, 1 B-f , 1B-g, 1B-h, 1 B-i and 1 B-j, respectively, and 2.25 weight% photoinitiator C6 based on the solids of the composition as well as the compositions of example 7.4 comprising thermal radical initiator 1B-a and 1 B-j, respectively, and 2.25 weight% photoinitiator C22 based on the solids of the composition not only form layers on a substrate, wherein
  • compositions of example 7.1 comprising thermal radical initiator 1 -a, 1A-a, 1A-b, 1A-c, 1C-a, 1C-b and 1D-a, respectively, and 2.25 weight% photoinitiator C6 based on the solids of the composition form layers on a substrate, wherein
  • the comparative composition comprising no thermal radical initiator, but only 2.25 weight% photoinitiator C6 based on the solids of the composition form a layer on a sub- strate, wherein
  • thermal radical initiator of formula 1 B such as 1 B-a, 1 B-b, 1 B-c, 1 B-d 1 B-e, 1 B-f , 1 B-g, 1 B-h, 1 B-i and 1 B-j respectively in compositions comprising at least one pho- toinitiator carrying at least one oxime ester group, such as photoinitaitor C6 and C22, increases the effectiveness of the light-initiated curing of the ethylenically unsaturated groups, such as acryloyl groups, present in the composition.
  • thermal radical initiators of formula 1 B and a photoinitiator carrying at least one oxime ester group, such as photoinitaitor C6 and C22 shows a synergistic effect re- garding the effectiveness of light-initated curing of ethylenically unsaturated groups, such as acryloyl groups.
  • Comparative blue compositions were also prepared in analogy to blue photocurable and ther- mally curable compositions of example 7.2, but not comprising the thermal radical initiator 1 B-a of example 5.1.
  • thermal radical initiator 1B-a does not have an effect on the curing in the light treatment step for compositions comprising photoinitiator C2, C7 or C8.
  • thermal radical initiator 1B-a increases the effec- tiveness of the curing in the light treatment step for compositions comprising photoinitiator C6.
  • This effect is achieved although the amount of photoinitiator in the composition of example 7.1 is 2.25% by weight based on the weight of the solids of the composition, whereas the amount of photoinitia- tor in the composition of example 7.2 is 5.0% by weight based on the weight of the solids of the composition.
  • a comparative blue composition was also prepared in analogy the blue photocurable and ther- mally curable compositions of example 7.3, but comprising no thermal radical initiator 1B-a or 1 B-j.
  • a comparative blue composition was also prepared in analogy the blue photocurable and ther- mally curable compositions of example 7.3, but comprising 0.7 weight parts of the photosensiz- izer 2-isopropylthioxanthone (ITX) instead of 0.7 weight parts thermal radical initiator 1B-a or 1 B-j.
  • ITX photosensiz- izer 2-isopropylthioxanthone
  • a comparative blue composition was also prepared in analogy the blue photocurable and ther- mally curable compositions of example 7.5, but comprising no thermal radical initiator 1B-a or 1 B-j.
  • compositions of example 7.3 comprising the thermal radical initiator 1B-a and 1 B-j, respec- tively and 4.5 weight% photoinitiator C4 or C5 based on the solids of the composition not only form layers on a substrate, wherein
  • the comparative composition comprising 4.5 weight% ITX based on the solids of the composi- tion instead of 1B-a or 1 B-j, and photoinitiator C4 form a layer on a substrate, wherein
  • the comparative composition comprising no thermal radical initiator, but only 4.5 weight% photoinitiator C4 or C5 based on the solids of the composition form a layer on a substrate, wherein
  • Exposure to light was carried out using a 250 W super high pressure mercury lamp (LISHIO, USH-250BY, maximum output at wavelength 436, 405, 365 nm and 313 nm) at a distance of 15 cm.
  • a total light exposure dose measured by an optical power meter (ORC UV Light Measure Model LIV-M02 with UV-35 detector) on the glass filter is 70 mJ/cm 2 .
  • the exposed film is developed with an alkaline solution (5 % aqueous solution of DL-A4, YOKOHAMA OILS & FATS) for 30 seconds after break time at 25 °C by using a spray type developer (AD-1200, MIKASA). Break time is the de- velopment time of the unexposed region.
  • a pattern on the glass substrate was obtained, which was baked at 100 °C for 120 minutes in a forced convection oven.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne une composition comprenant (i) au moins un composé ou un oligomère portant au moins un groupe éthyléniquement insaturé (A), (ii) au moins un initiateur radicalaire thermique (B) de formule (1) et (iii) au moins un photoinitiateur (C), des procédés pour la préparation d'une couche durcie ou d'un motif durci à l'aide de ces compositions, la couche durcie et le motif durci formés par le procédé respectif, et des dispositifs comprenant au moins une couche durcie ou un motif durci.
PCT/EP2023/069092 2023-07-10 2023-07-10 Compositions photodurcissables et durcissables thermiquement appropriées pour un durcissement à basse température WO2025011754A1 (fr)

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