EP4352033A1 - Nouveaux mélanges de sels de diaryliodonium en tant que photo-initiateurs de faible poids moléculaire ayant un comportement de cristallisation réduit au minimum et une solubilité élevée - Google Patents

Nouveaux mélanges de sels de diaryliodonium en tant que photo-initiateurs de faible poids moléculaire ayant un comportement de cristallisation réduit au minimum et une solubilité élevée

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Publication number
EP4352033A1
EP4352033A1 EP22777184.7A EP22777184A EP4352033A1 EP 4352033 A1 EP4352033 A1 EP 4352033A1 EP 22777184 A EP22777184 A EP 22777184A EP 4352033 A1 EP4352033 A1 EP 4352033A1
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EP
European Patent Office
Prior art keywords
diaryliodonium salt
salt mixtures
diaryliodonium
butyl
mixture
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EP22777184.7A
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German (de)
English (en)
Inventor
Dietmar Keil
Philipp Gehrmann
Kai Licha
Frank Lerch
Saija WERNER
Christopher Simpson
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FEW Forschungs- und Entwicklungsgesellschaft Wolfen mbH
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FEW Forschungs- und Entwicklungsgesellschaft Wolfen mbH
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Publication of EP4352033A1 publication Critical patent/EP4352033A1/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/08—Saturated oxiranes
    • C08G65/10—Saturated oxiranes characterised by the catalysts used
    • C08G65/105—Onium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/20—Tetrahydrofuran
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials

Definitions

  • Novel diaryliodonium salt mixtures as low molecular weight photoinitiators with minimized crystallization behavior and elevated solubility
  • the invention relates to novel diaryliodonium salt mixtures as low molecular weight photoinitiators with minimized crystallization behavior and elevated solubility, advantageous methods for their synthesis and manufacturing, as well as their application in compositions for coatings, varnishes, layers, and printing plates.
  • PRG photoradical generators
  • PAG photoacid generators
  • this invention employs alkyliodonium salts of low molecular weight, corresponding to short chain alkyl substituents (1 to 7 carbon atoms, branched or unbranched) for Ri and R.2 in the general formula I. It is well known that with decreasing molecular weight and corresponding increased impact of the cationic charge to the chemical structure of diaryliodonium salts, the solubility in nonpolar solvents will become lower. In turn, melting points and ability to crystallize will be increased, which may cause unwanted effects of crystallization in polymeric materials, coatings, layers, and surfaces.
  • the surprisingly found solution to this limitation is based on the utilization of impurities being part of the diaryliodonium salts.
  • This is achieved by iodonium salt mixtures, as further detailed below, yielding to improved physicochemical properties while maintaining low molecular weight.
  • This is achieved by performing a synthesis of diaryliodoniums salts with more than one purified starting material of alkyl substituted aryls, yielding a synthesis mixture composed of a plurality of both asymmetric and symmetric iodonium salt structures.
  • the relative constituents are formed based on principles of the synthesis reaction mechanism (see detailed description).
  • arylalkyl (R-Ar) aromatic compounds serve as starting materials to enable an electrophilic substitution at the Ar moiety, leading to a mixture of diaryliodonium salts, as outlined below in detail.
  • the invention concerns novel diaryliodonium salt mixtures useful as photoinitiators with improved properties, advantageous methods for their preparation, as well as their application especially for the manufacturing of coatings, varnishes, layers, and printing plates.
  • Diaryliodonium structures are obtained by two or three synthetic steps, as known to a person skilled in the art.
  • a first step in the reaction mechanism an iodoaryl moiety is oxidized to an iodine (Ill)-complex.
  • a ligand exchange with aryl or aryl-metal-organyl yields a diaryliodonium cation (with counter anion depending on the reagents used). The counter anion can finally be exchanged by a desired other anion.
  • hypervalent iodine(III) reagents see Figure 2
  • Optimized pathways were developed by B ERINGER et al by utilizing hypervalent iodo moieties such as iodosylaryls, (diacetoxyiodo)aryls and iodoxyaryls in the presence of strong acids (F. M. Beringer et al. , J. Am. Chem. Soc. 1959, 81, 342 & 1953, 75, 2705; J. V. Crivello, J. H. W. Lam, J. Org. Chem. 1978, 43, 3055). This enabled increased yields by supporting the expected mechanism of aromatic electrophilic substitution (SE).
  • SE aromatic electrophilic substitution
  • aryls (+M and/or +I-effect of a residue R at the aryl Ar-R) direct into their 2- and 4-position (ortho/para position), with preference for the 4-position due to steric hindrance in the 2-position, usually increasing with sterically more demanding substituents at the aryl (Ar-R).
  • KOSER et al. developed a method enabling selective access to defined non- symmetric iodonium salts by applying hydroxy(tosyloxy)iodobenzene (Koser‘s reagent) with arylsilanes and then also arylstannates (G. F. Koser et al., J. Org. Chem. 1980, 45, 1543; C.
  • diaryliodonium salt bromides obtained by reaction of monofunctional arenes (Ar- R) in the presence of potassium iodate, acetic acid and acetic anhydride and sulfuric acid.
  • Ar- R monofunctional arenes
  • reactive iodosylsulfate is formed in-situ, followed by treatment with aqueous KBr solution and recrystallization from methanol.
  • the avoidance of pre-synthesized, expensive aryliodides makes this method economic, and further allows to identify inventive iodonium salt mixtures with surprising behavior, when applying different, multiple aryl compounds in the reaction.
  • Diaryliodonium structures have been applied already back in the early 1980s as radical initiators in the area of polymerization under UV and thermal conditions, such as for the manufacturing of printing plates and coatings. This went along with substituting more expensive and toxic Pd-, Hg- und Pb-based organyls as catalysts.
  • diaryliodonium salts have emerged as crucial components in the chemical composition of printing plates for Computer- to-plate offset methods (CtP; Bromme et al. Chem. Eng. Technol. 2016, 39, No. 1, 13-25).
  • diaryliodonium salts are often applied as mixtures generated by previously synthesized, pure single compounds (WO 2017/11959 Al). This type of physically generated mixtures leads to decreased ability to crystallize and better solubility (based on known principles of eutectic mixing), but has often shown to be not sufficient for long time storage of coatings and manufacturing of printing plates.
  • the synthesis of diaryliodonium salt mixtures according to the method in Fig. 2.
  • aryl chains of 8 to 20 carbon atoms are essential to suppress the tendency to from crystals, and in particular, solubility of the mixture is improved by increasing the length of the alkyl chain substituents in iodonium salts.
  • the inventors of the present application demonstrate that an increased solubility of the respective iodonium mixtures impedes their isolation unfavorably, with difficulties to obtain solid materials, often yielding oils. This is a drawback regarding economic manufacture and purification.
  • WO2017131959 Al discloses diaryliodonium salts which were applied for lithographic printing plates. The compounds were combined as mixtures into the coating formulations, utilizing known effects of avoiding crystallization by enhancing complexity of mixtures. However, it does not provide information about synthetic procedures to iodonium salts and does not describe mixtures derived from a single synthetic procedure leading to statistical compositions. The current drawbacks and deficiencies of the relevant prior art lead to the invention of novel iodonium salt mixtures with improved properties for a broad technological field, and to methods of an efficient synthesis and manufacture.
  • the invention relates to novel diaryliodonium salt mixtures according to Formula (A) as low molecular weight photoinitiators with minimized crystallization behavior and elevated solubility, advantageous methods for their synthesis and manufacturing, as well as their application in compositions for coatings, varnishes, layers, and printing plates.
  • diaryliodonium salt mixtures shall be understood as a material composed of a plurality of different chemical diaryliodonium structures, which are formed together in one synthetic procedure, thereby yielding a synthetic mixture.
  • technically mixed diaryliodonium salts are defined derived from a number of single and pure compounds, each previously and independently synthesized and purified, followed by their weighting and mixing together, thereby generating a technical mixture.
  • the synthetic mixtures according to the invention comprise three or more different diaryliodonium cations each neutralized with an anion (thereby forming an iodonium salt), wherein the aryl moieties are substituted with alkyl or alkoxy substituents, giving a diaryliodonium salt mixture constituted of at least
  • n number of different structures of substituted aryls R-Ar) different compounds when only assuming the reaction mechanism of 4-substitution (para-substitution).
  • Two or more different Aryls (R-Ar) are used for the synthesis, yielding a diaryliodonium salt mixture of general formula (A), constituted of at least three defined single structures, wherein at least one of these single structures comprises R 1 and R 2 being different substituents.
  • the number of components in the mixture can be enhanced considering 2- and 4-positions of the carbon-iodine bond formation relative to the alkyl position in R-Ar (ortho and para-position), which is mechanistically favored with +M and/or +I-activating substituents.
  • the 2-position (ortho-position) is disfavored, due to steric hindrance.
  • a mixture will contain para/para-structures as major components, followed by ortho/para-structures and ortho/ortho-structures in different ratios depending on the steric demands of the R substituents.
  • diaryliodonium salts For example, the use of three differently substituted arylalkyl (R-Ar) aromatic compounds as suitable starting material for conducting an electrophilic substitution at the Ar moiety, leads to a mixture of diaryliodonium salts.
  • the analysis of the composition obtained by the reaction procedures can be conducted by usual analytical methods (HPLC, mass spectroscopy, NMR).
  • the relative composition can be quantified by HPLC, as known to the skilled person, e.g. by integrating all detected peaks.
  • Mass spectrometry can qualitatively show existence of all possible molecular weight generated, independent of the o/p- substitution pattern.
  • diaryliodonium salt mixtures contain the structures (I), (V) and (VIII). That means, components include all possible symmetric and non-symmetric structures for each pair of R 1 and R 2 , formed with the predominant para- substitution, with usually non-symmetric components in higher relative amount compared to the respective symmetric compounds with equal R1 and R2.
  • mixtures containing at least one structure selected from an ortho/ para -pattern of formula (II), (III), (VI) or (IX), or an ortho/ortho pattern of formula (IV), (VII) or (X), in addition to the predominant components of type (I), (V) and (VIII). Even more preferred are such mixtures, containing at least two identified structures selected from an ortho/para-pattern of formula (II), (III), (VI) or (IX), or an ortho/ortho pattern of formula (IV), (VII) or (X).
  • the quantification of the relative amounts of components within the mixture can be conducted with techniques known to the skilled person, such as HPLC.
  • Substituents R 1 and R 2 can be linear or branched Ci to Cyalkyl or alkoxy groups. Maximal efficacy by generated radicals per mass is achieved, when residues are as small as possible. According to the invention, diaryliodonium salt mixtures with linear or branched Ci to C4-alkyl or alkoxy groups lead to increased solubility and decreased melting points compared to pure compounds of similar molecular weight, and are thus preferred embodiment.
  • residues R 1 and R 2 in the diaryliodonium salt mixtures are selected from the group of t-butyl, s-butyl, n-butyl, i-propyl, n-propyl, ethyl, methyl, t- butyloxy, s-butyloxy, n-butyloxy, i-propyloxy, n-propyloxy, ethoxy and methoxy.
  • R 1 and R 2 in the diaryliodonium salt mixtures being selected from the group of t-butyl, s-butyl, n-butyl, i-propyl, n-propyl, ethyl, methyl, t-butyloxy, s- butyloxy, n-butyloxy, i-propyloxy, n-propyloxy, ethoxy and methoxy. More preferred are R 1 and R 2 being selected from the group methyl, ethyl, i-propyl, t- butyl, s-butyl, n-butyl and methoxy. Even more preferred are R 1 and R 2 being selected from the group methyl, ethyl, i-propyl, t-butyl, s-butyl, n-butyl.
  • R H
  • diaryliodonium salts comprise improved solubility in non-polar solvents or matrices and a decreased melting point (see data in examples).
  • Decreasing melting points for diaryliodonium salts was reported to be possible only by long chain alkyl substituents (such as dodecyl), as taught by W020100128649.
  • This publication describes alkyl substituents of 8 to 20 carbon atoms. Confirmatory own work using > 8 carbon atoms showed substantial difficulties in the isolation of such diaryliodonium salt mixtures as solid materials, making purification disadvantageous. Thus, the technical feasibility for industrial manufacturing is limited.
  • diaryliodonium salt mixtures with substituents R not exceeding 7 carbon atoms could be isolated as solid materials for different counteranions, while exhibiting decreased melting points and enhanced solubility in non-polar solvents at the same time (see Examples for methods and analytical data).
  • the combination of lowest possible molecular weight of the diaryliodonium cations of the mixture with the ability to obtain the products as solid materials is a surprisingly found feature of the invention.
  • efficacy of photoinitiation when given by radicals per mass, is higher for low molecular weight mixtures of the embodiment.
  • the solubility in nonpolar solvents such as ketones, ethers, esters
  • Anions according to the invention can be organic, organometallic or inorganic anions. Preferred are anions selected from the group of chloride, bromide, iodide, perchlorate, tosylate, dodecylphenylsulfonate, hydrogensulfate, hexafluorophosphate, tris(pentafluoroethyl)-trifluorophosphate, hexafluoroantimonate, bis(trifluoromethanesulfonyl)imide (NTf2; (CF3S02)2l ⁇ T), tris(trifluoromethanesulfonyl)methide (triflide; CTf3; (CF3S02)3C ⁇ ), tetrafluoroborate, tetraphenylborate, triphenylmonoalkylborate, tetraki
  • diaryliodonium salt mixtures containing one single type of counteranion for all different diaryliodonium cations.
  • Preferred diaryliodonium salt mixtures within the embodiment of formulas (I) - (X) are summarized in the following table with entries 1 - 60, each entry comprising a synthetic mixture containing the components of formula (I), (V) and (VIII). More preferred are entries 1, 2, 7, 8, 13, 14, 19, 20, 25, 26, 31, 32, 37, 38, 43, 44, 49, 50, 55, 56 as photoradical generators. Entries 3, 4, 9, 10, 15, 16, 19, 21, 22, 27, 28, 33, 34, 39, 40, 45, 46, 51, 52, 57, 58 are more preferred as photoacid generators.
  • diaryliodonium salt mixtures wherein the obtained composition contains more than one additional component, even more preferred more than two additional components, selected from the formula (II), (III), (IV), (VI), (VII), (IX), (X), as outlined above.
  • the cationic component in the diaryliodonium salt mixtures can be synthesized as published (see section state-of-the-art).
  • the technical mixing of previously synthesized, pure iodonium salts of single structure is not scope of the embodiment, as defined above.
  • a preferred method to synthesize diaryliodonium salt mixtures is the mixing of a number of n different alkylaryls or alkoxyaryls with linear or branched alkyl or alkoxy substituents of up to 7 carbon atoms, and performing a reaction in the presence of an iodate salt, or periodate, or m- chloroperbenzoic acid (see examples), forming a salt with hydrogensulfate as counteranion.
  • the synthesis is accomplished by mixing two or more alkylaryls and/or alkoxyaryls together with alkalimetal iodate or alkalimetal periodate salt, in acetic anhydride, acetic acid and sulfuric acid, and performing the reaction under temperature control.
  • the reaction solution is quenched with ice/water and the resulting solution is extracted with solvents, such as dichloromethane or chloroform.
  • solvents such as dichloromethane or chloroform.
  • the organic phase can be further washed and dried. Precipitation with a suitable solvent yields the desired diaryliodonium salt mixtures with hydrogensulfate as counteranion.
  • the final product with a desired counterion is obtained by using aqueous solutions of respective salts, yielding the diaryliodonium salt mixtures according to the invention as solid materials (see picture below).
  • a preferred method for the synthesis comprises the pathway described above, with performing the isolation of the diaryliodonium salt mixture with hydrogen sulfate as solid precipitate, thereby allowing an intermediate step of purification.
  • Preferred aqueous solutions to convert the hydrogen sulfate- based solid intermediates into the desired products with respective counteranions are those with KI, KBr, NaBPhu, Li ⁇ AI[OC(CF3)3]4> and KPF6, yielding diaryliodonium salt mixtures with iodide, bromide, tetraphenylborate, hexafluorophosphate or tetrakisperfluoro-tert-butoxyaluminate as counteranion.
  • EP 2428501A1 describes a similar method for the synthesis of diaryliodonium salt mixtures with long alkyl chains and obtaining them as bromide and iodide salts only by adding aqueous KBr- or respectively KI-solutions to the reaction mixture. The precipitated products were then recrystallized.
  • Such initiators with bromides and iodides are known to exhibit higher crystallization tendency and less solubility, making them less useful and technically applicable as photoinitiators, in particular in offset printing plates.
  • Direct isolation of diaryliodonium mixtures in the form of hydrogen sulfate salts has proven to be surprisingly advantageous by giving highly pure products as crystalline materials, including all given subsequent products with exchanged counteranion. Even mixtures of > 6 different components could be transferred into solid compositions from oily intermediates.
  • the topic of the invention is also the use of the diaryliodonium salt mixtures as initiators for polymerization procedures in chemical and material applications, particularly for polymerization processes based on radical and/or cationic reaction mechanisms.
  • Preferred use of the compounds according to the invention is as photoinitiators for methods of photopolymerization, as known for the skilled person (i.e. Baumann et al.: Imaging Technology, 3.
  • Photopolymerization can be initiated at different wavelengths of the spectral range from UV to near-IR, optionally supported combining the photoinitiators by sensitizing dyes. Photocuring in 3D printing technologies is described by Quan H. et al.; Bioactive Materials 5 (2020) 110-115. Applications for hologram storage and waveguide formation are described by Malallah R. et al. Polymers 2017, 9, 337.
  • the compounds as photoinitiators encompass those compounds of formula (I) - (X), wherein the anion Z ⁇ influences the mechanistic pathway of photopolymerization.
  • the anion Z- is preferably selected from the group comprising tetraphenyl borate, triphenyl-monoalkylborate. Accordingly, more preferred is the use of diaryliodonium salt mixtures comprising the anions tetraphenyl borate or triphenyl- monoalkylborate as photoinitiators for photopolymerization based on radicalic mechanisms.
  • Preferred anions efficient for cationic photopolymerization are selected from the group comprising hexafluorophosphate, tetrakis(perfluoro-te/t-butoxy)aluminate [((CF 3 )3C-0)4A
  • Preferred anions to achieve increased thermal stability are selected from the group comprising tris(pentafluoroethyl)trifluorophosphate and bis(trifluoromethansulfonyl)imide (NTf2; (CF3S02)2l ⁇ l ⁇ ).
  • support is used herein to refer to an aluminum-containing material (web, sheet, foil, or other form) that can be then treated or coated to prepare a "substrate” that refers to a hydrophilic article having a hydrophilic surface upon which various layers, including the infrared radiation-sensitive imageable layer, and optional hydrophilic overcoat are coated.
  • infrared radiation absorber refers to compounds or materials that are sensitive to wavelengths of infrared radiation.
  • infrared refers to radiation having a Amax of at least 750 nm and higher. In most instances, the term “infrared” is used to refer to the "near- infra red" region of the electromagnetic spectrum that is defined herein to be at least 750 nm and up to and including 1400 nm.
  • polymer is used to describe compounds with relatively large molecular weights formed by linking together many small reacted monomers. As the polymer chain grows, it folds back on itself in a random fashion to form coiled structures. With the choice of solvents, a polymer can become insoluble as the chain length grows and become polymeric particles dispersed in the solvent medium. These particle dispersions can be very stable and useful in infrared radiation-sensitive imageable layers described for use in the present invention. In this invention, unless indicated otherwise, the term “polymer” refers to a non- crosslinked material.
  • crosslinked polymeric particles differ from the non- crosslinked polymeric particles in that the latter can be dissolved in certain organic solvents of good solvating property whereas the crosslinked polymeric particles may swell but do not dissolve in the organic solvent because the polymer chains are connected by strong covalent bonds.
  • copolymer refers to polymers composed of two or more different repeating or recurring units that are arranged along the polymer backbone.
  • backbone refers to the chain of atoms in a polymer to which a plurality of pendant groups can be attached.
  • An example of such a backbone is an "all carbon" backbone obtained from the polymerization of one or more ethylenically unsaturated polymerizable monomers.
  • arranged randomly means that blocks of recurring units are not intentionally incorporated into the polymeric binders, but that recurring units are incorporated into the backbone in a random fashion using known polymerization procedures that do not encourage the formation of block copolymers.
  • Recurring units in polymeric binders described herein are generally derived from the corresponding ethylenically unsaturated polymerizable monomers used in a polymerization process, which ethylenically unsaturated polymerizable monomers can be obtained from various commercial sources or prepared using known chemical synthetic methods.
  • weight % refers to the amount of a component or material based on the total solids of a composition, formulation, or layer. Unless otherwise indicated, the percentages can be the same for either a dry layer or the total solids of the formulation or composition.
  • the term "layer” or “coating” can consist of one disposed or applied layer or a combination of several sequentially disposed or applied layers.
  • the layer is considered infrared radiation-sensitive and negative-working, it is both sensitive to infrared radiation as described above and negative-working in the formation of lithographic printing plates.
  • the present invention is useful for preparing lithographic printing plates by imagewise exposing and processing the exposed precursor off-press using a suitable developer or on a suitable printing press using a lithographic printing ink, a fountain solution, or both a lithographic printing ink and a fountain solution as described below.
  • the lithographic printing plate precursors of the present invention are prepared with the structure and components described as follows.
  • the substrate that is present in the precursors generally has a hydrophilic surface, or at least a surface that is more hydrophilic than the applied infrared radiation- sensitive imageable layer on the imaging side of the substrate.
  • the substrate comprises a support that can be composed of any material that is conventionally used to prepare lithographic printing plate precursors.
  • One useful substrate is composed of an aluminum support that can be treated using techniques known in the art, including roughening of some type by physical (mechanical) graining, electrochemical graining, or chemical graining, usually followed by anodizing.
  • Anodizing is typically done using phosphoric or sulfuric acid and conventional procedures.
  • Anodized aluminum support can be treated further to seal the oxide pores and to hydrophilize its surface using known post-anodic treatment (PAT) processes, such as treatments in aqueous solutions of poly(vinyl phosphonic acid) (PVPA), vinyl phosphonic acid copolymers, poly[(meth)acrylic acid], or acrylic acid copolymers, mixtures of phosphate and fluoride salts, or sodium silicate.
  • PVPA poly(vinyl phosphonic acid)
  • vinyl phosphonic acid copolymers poly[(meth)acrylic acid]
  • acrylic acid copolymers mixtures of phosphate and fluoride salts, or sodium silicate.
  • Useful treatment processes include dipping with rinsing, dipping without rinsing, and various coating techniques such as extrusion coating.
  • the thickness of a substrate can be varied but should be sufficient to sustain the wear from printing and thin enough to wrap around a printing form.
  • Useful embodiments include a treated aluminum foil having a thickness of at least 100 pm and up to and including 700 pm.
  • the backside (nonimaging side) of the substrate can be coated with antistatic agents, a slipping layer, or a matte layer to improve handling and "feel" of the precursor.
  • Infrared Radiation-Sensitive Imageable Layer The precursors of the present invention can be formed by suitable application of a negative-working infrared radiation-sensitive composition as described below to a suitable substrate (as described above) to form an infrared radiation- sensitive imageable layer that is negative-working on that substrate.
  • the infrared radiation-sensitive composition (and resulting infrared radiation-sensitive imageable layer) comprises one or more free radically polymerizable compounds, one or more infrared radiation absorbers, an initiator composition that provides free radicals upon exposure to imaging infrared radiation, and optionally a polymeric binder.
  • the infrared radiation-sensitive imageable layer There is generally only a single infrared radiation-sensitive imageable layer in the precursor. It is generally the outermost layer in the precursor, but in some embodiments, there can be an outermost water-soluble hydrophilic overcoat (also known as a topcoat or oxygen barrier layer) disposed over the one or more infrared radiation-sensitive imageable layers.
  • the infrared radiation-sensitive imageable layers provided in precursors preferably comprises one or more polymeric binders that can be selected from a number of materials known in the art.
  • some useful primary polymeric binders comprise recurring units having side chains comprising polyalkylene oxide segments such as those described in U.S. Patent 6,899,994 (Huang et al.).
  • Other useful polymeric binders comprise two or more types of recurring units having different side chains comprising polyalkylene oxide segments as described in Japanese Patent Publication 2015-202586 (Kamiya et al.).
  • Some of such polymeric binders can further comprise recurring units having pendant cyano groups as those described in U.S. Patent 7,261,998 (Hayashi et al.).
  • Some useful polymeric binders are present in particulate form, that is, in the form of discrete particles (non-agglomerated particles). Such discrete particles can have an average particle size of at least 10 nm and up to and including 1500 nm, or typically of at least 80 nm and up to and including 600 nm, and that are generally distributed uniformly within the infrared radiation-sensitive imageable layer. Average particle size can be determined by various known methods including measuring the particles in electron scanning microscope images and averaging a set number of measurements.
  • the polymeric binders also can have a backbone comprising multiple (at least two) urethane moieties as well as pendant groups comprising the polyalkylenes oxide segments.
  • Useful polymeric binders also include those that comprise polymerizable groups such as acrylate ester group, methacrylate ester group, vinyl aryl group and allyl group and those that comprise alkali soluble groups such as carboxylic acid. Some of these useful primary binders are described in U.S. Patent Application Publication 2015/0099229 (Simpson et al.) and U.S. Patent 6,916,595 (Fujimaki et al.).
  • Polymeric binders generally have a weight average molecular weight (M n ) of at least 2,000 and up to and including 500,000, or at least 20,000 and up to and including 300,000, as determined by Gel Permeation Chromatography (polystyrene standard).
  • M n weight average molecular weight
  • Useful polymeric binders can be obtained from various commercial sources or they can be prepared using known procedures and starting materials, as described for example in publications described above.
  • the total polymeric binders are generally present in the infrared radiation-sensitive imageable layer in an amount of at least 10 weight % and up to and including 70 weight %, or more likely in an amount of at least 20 weight % and up to and including 50 weight %, based on the total dry weight of the infrared radiation- sensitive imageable layer.
  • the infrared radiation-sensitive composition (and infrared radiation-sensitive imageable layer) comprises one or more free radically polymerizable compounds, each of which contains one or more free radically polymerizable groups (and two or more of such groups in some embodiments) that can be polymerized using free radical initiation.
  • the infrared radiation-sensitive imageable layer comprises two or more free radically polymerizable components having different numbers of free radically polymerizable groups in each molecule.
  • Useful free radically polymerizable components can contain one or more free radical polymerizable monomers or oligomers having one or more addition polymerizable ethylenically unsaturated groups (for example, two or more of such groups). Similarly, crosslinkable polymers having such free radically polymerizable groups can also be used. Oligomers or prepolymers, such as urethane acrylates and methacrylates, epoxide acrylates and methacrylates, polyester acrylates and methacrylates, polyether acrylates and methacrylates, and unsaturated polyester resins can be used. In some embodiments, the free radically polymerizable component comprises carboxyl groups.
  • Free radically polymerizable components include urea urethane (meth)acrylates or urethane (meth)acrylates having multiple (two or more) polymerizable groups. Mixtures of such compounds can be used, each compound having two or more unsaturated polymerizable groups, and some of the compounds having three, four, or more unsaturated polymerizable groups.
  • a free radically polymerizable component can be prepared by reacting DESMODUR® N100 aliphatic polyisocyanate resin based on hexamethylene diisocyanate (Bayer Corp., Milford, Conn.) with hydroxyethyl acrylate and pentaerythritol triacrylate.
  • Useful free radically polymerizable compounds include NK Ester A-DPH (di pentaerythritol hexaacrylate) that is available from Kowa American, and Sartomer 399 (dipentaerythritol pentaacrylate), Sartomer 355 (di-trimethylolpropane tetraacrylate), Sartomer 295 (pentaerythritol tetraacrylate), and Sartomer 415 [ethoxylated (20)trimethylolpropane triacrylate] that are available from Sartomer Company, Inc.
  • useful free radically polymerizable components are also described in EP1182033A1 (Fujimaki et al.), beginning with paragraph [0170], and in U.S Patents 6,309,792 (Hauck et al.), 6,569,603 (Furukawa), and 6,893,797 (Munnelly et al.).
  • Other useful free radically polymerizable components include those described in U.S. Patent Application Publication 2009/0142695 (Baumann et al.), which radically polymerizable components include lH-tetrazole groups.
  • the one or more free radically polymerizable compounds are generally present in an infrared radiation-sensitive imageable layer in an amount of at least 10 weight % and up to and including 70 weight %, or typically of at least 20 weight % and up to and including 50 weight %, all based on the total solids in the noted layer.
  • the infrared radiation-sensitive composition (and imageable layer) also comprises one or more infrared radiation absorbers to provide desired radiation sensitivity.
  • the total amount of one or more infrared radiation absorbers is at least 0.5 weight % and up to and including 30 weight %, or typically of at least 1 weight % and up to and including 15 weight %, based on the infrared radiation-sensitive composition (or imageable layer) total solids.
  • Some useful infrared radiation absorbers are sensitive to both infrared radiation (typically of at least 700 nm and up to and including 1400 nm) and visible radiation (typically of at least 450 nm and up to and including 700 nm).
  • Useful infrared radiation absorbers are described in U.S. Patent No. 7,429,445 (Munnelly et al.).
  • the present invention comprises one or more infrared radiation absorbers that are sensitive only to near-infrared or infrared radiation having a wavelength of at least 750 nm.
  • useful infrared radiation absorbers include but are not limited to, azo dyes, squarilium dyes, croconate dyes, triarylamine dyes, thioazolium dyes, indolium dyes, oxonol dyes, oxazolium dyes, cyanine dyes, merocyanine dyes, phthalocyanine dyes, indocyanine dyes, indotricarbocyanine dyes, oxatricarbocyanine dyes, thiocyanine dyes, thiatricarbocyanine dyes, cryptocyanine dyes, naphthalocyanine dyes, polyaniline dyes, polypyrrole dyes, polythiophene dyes, chalcogenopyrylo- arylid
  • Suitable dyes are also described in U.S. Patents 5,208,135 (Patel et al.), 6,153,356 (Urano et al.), 6,264,920 (Achilefu et al.), 6,309,792 (Hauck et al.), 6,569,603 (Furukawa), 6,787,281 (Tao et al.), 7,018,775 (Tao), 7,135,271 (Kawaushi et al.), WO 2004/101280 (Munnelly et al.), and EP1182033A1 (noted above).
  • At least one infrared radiation absorber in the infrared radiation-sensitive imageable layer be a cyanine dye comprising a tetraary I borate anion such as a tetraphenylborate anion.
  • the infrared radiation-sensitive imageable layer essentially comprises an initiator composition according to invention as described above.
  • the essential compounds of the diaryl iodonium salt mixture are individually and collectively capable of generating free radicals sufficient to initiate polymerization of the various free radically polymerizable compounds described above upon exposure to imaging infrared radiation.
  • the initiator composition is generally responsive, for example, to electromagnetic radiation of at least 750 nm and up to and including 1400 nm or at least 750 nm and up to and including 1250 nm.
  • the initiator composition can be used for any of the noted infrared radiation exposures or for multiple infrared radiation exposures.
  • the initiator composition is present in the infrared radiation-sensitive imageable layer sufficient to provide a total (cumulative) amount of compounds of formula (I) to (X) of at least 3 weight % and up to and including 30 weight %, or typically of at least 5 weight % and up to and including 18 weight %, or even at least 7 weight % and up to and including 15 weight %, all based on the total solids in the infrared radiation-sensitive imageable layer.
  • Additional additives to the infrared radiation-sensitive imageable layer can include dye precursors and color developers as are known in the art.
  • Useful dye precursors include but are not limited to, phthalide and fluoran leuco dyes having a lactone skeleton with an acid dissociation property, such as those described in U.S. Patent 6,858,374 (Yanaka).
  • the infrared radiation-sensitive imageable layer can include crosslinked polymer particles having an average particle size of at least 3 pm and up to and including 20 pm as described for example in U.S. Serial No. 14/642,876 (filed March 10, 2015 by Hayakawa et al.) and in U.S.
  • the infrared radiation-sensitive imageable layer can also include a variety of other optional compounds including but not limited to, dispersing agents, humectants, biocides, plasticizers, surfactants for coatability or other properties, viscosity builders, pH adjusters, drying agents, defoamers, preservatives, antioxidants, development aids, rheology modifiers, adhesion promoters, or combinations thereof, or any other addenda commonly used in the lithographic art, in conventional amounts.
  • the infrared radiation-sensitive imageable layer is the outermost layer with no layers disposed thereon
  • the precursors could be designed with a hydrophilic overcoat (or oxygen-barrier layer or topcoat) disposed directly on the infrared radiation-sensitive imageable layer (no intermediate layers between these two layers).
  • a hydrophilic overcoat or oxygen-barrier layer or topcoat
  • Such precursors could be developed on-press as well as off-press using any suitable developer as described below.
  • this hydrophilic overcoat is generally the outermost layer and thus, when stacked with other precursors, the hydrophilic overcoat of one precursor would be in contact with the backside of the substrate of the precursor immediately above it.
  • Such hydrophilic overcoats can comprise one or more film-forming water-soluble polymeric binders in an amount of at least 60 weight % and up to and including 98 weight %, based on the total dry weight of the hydrophilic overcoat.
  • filmforming water-soluble (or hydrophilic) polymeric binders can include a modified or unmodified poly(vinyl alcohol) having a saponification degree of at least 30%, or a degree of at least 75%, or a degree of at least 90%, and a degree of up to and including 99.9%.
  • one or more acid-modified poly(vinyl alcohol)s can be used as filmforming water-soluble (or hydrophilic) polymeric binders in the hydrophilic overcoat.
  • at least one modified poly(vinyl alcohol) can be modified with an acid group selected from the group consisting of carboxylic acid, sulfonic acid, sulfuric acid ester, phosphonic acid, and phosphoric acid ester groups.
  • acid group selected from the group consisting of carboxylic acid, sulfonic acid, sulfuric acid ester, phosphonic acid, and phosphoric acid ester groups.
  • examples of such materials include but are not limited to, sulfonic acid-modified poly(vinyl alcohol), carboxylic acid-modified poly(vinyl alcohol), and quaternary ammonium salt-modified poly(vinyl alcohol), glycol-modified poly(vinyl alcohol), or combinations thereof.
  • the optional hydrophilic overcoat can also include crosslinked polymer particles having an average particle size of at least 3 pm and up to and including 20 pm as described for example in U.S. Serial No. 14/642,876 (filed March 10, 2015 by Hayakawa et al.) and in U.S. Patents 8,383,319 (Huang et al.) 8,105,751 (Endo et al).
  • the hydrophilic overcoat is provided at a dry coating coverage of at least 0.1 g/m 2 and up to but less than 4 g/m 2 , and typically at a dry coating coverage of at least 0.15 g/m 2 and up to and including 2.5 g/m 2 .
  • the dry coating coverage is as low as 0.1 g/m 2 and up to and including 1.5 g/m 2 or at least 0.1 g/m 2 and up to and including 0.9 g/m 2 , such that the hydrophilic overcoat layer is relatively thin for easy removal during off-press development or on-press development.
  • the hydrophilic overcoat can optionally comprise organic wax particles dispersed, generally uniformly, within the one or more film-forming water-soluble (or hydrophilic) polymeric binders as described for example in U.S. Patent Application Publication 2013/0323643 (Balbinot et al.).
  • Negative-working Infrared Radiation-sensitive Lithographic Printing Plate Precursors The negative-working infrared radiation-sensitive compositions described above can be applied to a substrate as a solution or dispersion in a coating liquid using any suitable equipment and procedure, such as spin coating, knife coating, gravure coating, die coating, slot coating, bar coating, wire rod coating, roller coating, or extrusion hopper coating. They can also be applied by spraying onto a suitable support. Typically, the negative-working infrared radiation-sensitive composition is applied and dried to form an infrared radiation- sensitive imageable layer.
  • Such manufacturing methods can include mixing the various components needed for the imaging chemistry in a suitable organic solvent or mixtures thereof [such as methyl ethyl ketone (2-butanone), methanol, ethanol, l-methoxy-2-propanol, iso-propyl alcohol, acetone, y-butyrolactone, n-propanol, tetrahydrofuran, and others readily known in the art, as well as mixtures thereof], applying the resulting solution to a substrate, and removing the solvent(s) by evaporation under suitable drying conditions.
  • a suitable organic solvent or mixtures thereof such as methyl ethyl ketone (2-butanone), methanol, ethanol, l-methoxy-2-propanol, iso-propyl alcohol, acetone, y-butyrolactone, n-propanol, tetrahydrofuran, and others readily known in the art, as well as mixtures thereof
  • the dry coating coverage of the infrared radiation-sensitive imageable layer is generally at least 0.1 g/m 2 and up to and including 4 g/m 2 or at least 0.4 g/m 2 and up to and including 1.8 g/m 2 .
  • Distinct non-imageable layers can also be present under the infrared radiation-sensitive imageable layer and disposed directly on the hydrophilic substrate to enhance developability or to act as thermal insulating layers. However, unless a hydrophilic overcoat layer is present, there are no layers disposed over the infrared radiation-sensitive imageable layer.
  • a suitable aqueous-based hydrophilic overcoat formulation (as described above) can be applied to the dried infrared radiation-sensitive imageable layer in a suitable manner, and then dried in a suitable manner.
  • a negative-working infrared radiation- sensitive lithographic printing plate precursor of this invention can be exposed to a suitable source of exposing radiation depending upon the infrared radiation absorber present in the infrared radiation-sensitive imageable layer to provide specific sensitivity that is at a wavelength of at least 750 nm and up to and including 1400 nm, or of at least 800 nm and up to and including 1250 nm using an appropriate energy source.
  • imaging can be carried out using imaging or exposing radiation from an infrared radiation-generating laser (or array of such lasers). Imaging also can be carried out using imaging radiation at multiple wavelengths at the same time if desired.
  • the laser used to expose the precursor is usually a diode laser, because of the reliability and low maintenance of diode laser systems, but other lasers such as gas or solid-state lasers can also be used.
  • diode laser because of the reliability and low maintenance of diode laser systems, but other lasers such as gas or solid-state lasers can also be used.
  • gas or solid-state lasers can also be used.
  • the combination of power, intensity and exposure time for infrared radiation laser imaging would be readily apparent to one skilled in the art.
  • the imaging apparatus can be configured as a flatbed recorder or as a drum recorder, with the negative-working infrared radiation-sensitive lithographic printing plate precursor mounted to the interior or exterior cylindrical surface of the drum.
  • An example of useful imaging apparatus are available as models of KODAK ® Trendsetter platesetters (Eastman Kodak Company) that contain laser diodes that emit near infrared radiation at a wavelength of about 830 nm.
  • Other suitable imaging apparatus includes the Screen PlateRite® 4300 series or 8600 series platesetter (available from Screen USA, Chicago, IL) that operates at a wavelength of 810 nm.
  • Imaging with infrared radiation can be carried out generally at imaging energies of at least 30 mJ/cm 2 and up to and including 500 mJ/cm 2 and typically at least 50 mJ/cm 2 and up to and including 300 mJ/cm 2 depending upon the sensitivity of the infrared radiation-sensitive imageable layer.
  • processing (Development) and Printing: After imagewise exposing, the exposed negative-working infrared radiation-sensitive lithographic printing plate precursors having exposed regions and non-exposed regions in the infrared radiation- sensitive imageable layer are processed in a suitable manner to remove the non- exposed regions (and any hydrophilic overcoat over such regions). As noted above, processing can be carried out off-press using any suitable developer in one or more successive applications (treatments or developing steps) of the same or different processing solution.
  • Such one or more successive processing treatments can be carried out with exposed precursors for a time sufficient to remove the non-exposed regions of the infrared radiation-sensitive imageable layer to reveal the hydrophilic surface of the substrate, but not long enough to remove significant amounts of the exposed regions that have been hardened in the same layer.
  • the revealed hydrophilic substrate surface repels inks while the remaining exposed regions accept lithographic printing ink.
  • the exposed precursors can be subjected to a "pre-heating" process to further harden the exposed regions in the infrared radiation-sensitive imageable layer.
  • Such optional pre-heating can be carried out using any known process and equipment generally at a temperature of at least 60°C and up to and including 180°C.
  • the exposed precursor can be washed (rinsed) to remove any hydrophilic overcoat that is present.
  • washing can be carried out using any suitable aqueous solution (such as water or an aqueous solution of a surfactant) at a suitable temperature and for a suitable time that would be readily apparent to one skilled in the art.
  • aqueous solution such as water or an aqueous solution of a surfactant
  • Useful developers can be ordinary water or can be formulated.
  • the formulated developers can comprise one or more components selected from surfactants, organic solvents, alkali agents, and surface protective agents.
  • Useful organic solvents include the reaction products of phenol with ethylene oxide and propylene oxide [such as ethylene glycol phenyl ether (phenoxyethanol)], benzyl alcohol, esters of ethylene glycol and of propylene glycol with acids having 6 or less carbon atoms, and ethers of ethylene glycol, diethylene glycol, and of propylene glycol with alkyl groups having 6 or less carbon atoms, such as 2- ethylethanol and 2-butoxyethanol.
  • phenol ethylene oxide and propylene oxide
  • benzyl alcohol esters of ethylene glycol and of propylene glycol with acids having 6 or less carbon atoms
  • ethers of ethylene glycol, diethylene glycol, and of propylene glycol with alkyl groups having 6 or less carbon atoms such as 2- ethylethanol and 2-butoxyethanol.
  • an aqueous processing solution can be used off-press to both develop the imaged precursor by removing the non-exposed regions and also to provide a protective layer or coating over the entire imaged and developed (processed) precursor printing surface.
  • the aqueous solution behaves somewhat like a gum that is capable of protecting (or "gumming") the lithographic image on the printing plate against contamination or damage (for example, from oxidation, fingerprints, dust, or scratches).
  • the resulting lithographic printing plate can be mounted onto a printing press without any contact with additional solutions or liquids. It is optional to further bake the lithographic printing plate with or without blanket or floodwise exposure to UV or visible radiation.
  • printing can be carried out by putting the exposed and processed lithographic printing plate on a suitable printing press.
  • Printing can be carried out by applying a lithographic printing ink and fountain solution to the printing surface of the lithographic printing plate in a suitable manner.
  • the fountain solution is taken up by the surface of the hydrophilic substrate revealed by the exposing and processing steps, and the lithographic ink is taken up by the remaining (exposed) regions of the imageable layer.
  • the lithographic ink is then transferred to a suitable receiving material (such as cloth, paper, metal, glass, or plastic) to provide a desired impression of the image thereon.
  • a suitable receiving material such as cloth, paper, metal, glass, or plastic
  • an intermediate "blanket” roller can be used to transfer the lithographic ink from the lithographic printing plate to the receiving material (for example, sheets of paper).
  • On-Press Development and Printing Alternatively, an imaged negative-working infrared radiation-sensitive lithographic printing plate precursor is mounted onto a printing press and the printing operation is begun. The non-exposed regions in the infrared radiation-sensitive imageable layer are removed by a suitable fountain solution, lithographic printing ink, or a combination of both, when the initial printed impressions are made.
  • Typical ingredients of aqueous fountain solutions include pH buffers, desensitizing agents, surfactants and wetting agents, humectants, low boiling solvents, biocides, antifoaming agents, and sequestering agents.
  • Varn Litho Etch 142W + Varn PAR (alcohol sub) (available from Varn International, Addison, IL).
  • Varn Litho Etch 142W + Varn PAR alcohol sub
  • the dampening roller is engaged first and supplies fountain solution to the mounted imaged precursor to swell the exposed infrared radiation-sensitive imageable layer at least in the non-exposed regions.
  • the inking rollers are engaged, and they supply lithographic printing ink(s) to cover the entire printing surface of the lithographic printing plates.
  • printing sheets are supplied to remove the non- exposed regions of the infrared radiation-sensitive imageable layer as well as materials on a blanket cylinder if present, using the formed ink-fountain emulsion.
  • Example 6 of the present application demonstrates that printing plates utilizing iodonium compounds for the initiation of photopolymerization may suffer from crystallization and can be improved in terms of damage related to crystal growth by utilization of mixtures of iodonium compounds, which is current state of the art also applied in WO2017131959 Al.
  • the diaryliodonium salts applied in comparative Example 5 of the present application, according to inventive Example 3 of Hayashi et al. in WO2017131959 Al were synthesized as pure compounds and subjected to the manufacturing of printing plates by physical mixing of previously pure compounds.
  • example 6 of this invention was set to include a tentative 25:50:25 composition of physical mixing according to example 3 in WO2017131959 Al. Accordingly, example 6-1 states no damage by crystallization for iodonium salt mixture (compound 1 / example 1), compared to this comparative preparation (comparative compound mixture 5) yielding trace damage.
  • cationic polymerization is mainly understood as ring-opening polymerization, as known to the skilled person.
  • Polymerizable monomers or oligomers are usually epoxides (oxiranes), vinylethers, thiiranes (episulfides), oxetanes, aziridines, lactames, lactones, lactids, glycolids, tetrahydrofuran, organopolysiloxanes containing epoxy groups, organopolysiloxanes containing alkenyloxy groups.
  • Highest relevance in the application have monomeric or oligomeric epoxides. Materials and methods are known to the skilled person, as published by Sangermano M.; Macromolecular Materials and Engineering 2014, 299 (7), 775-793.
  • the diaryliodonium salt mixtures are applied in combination with epoxy resins of the types established for diverse industrial applications, such as bisphenol A types. These include several trades, such as SU- 8 novolack, EPON, EPALLOY, DER, ARALDITE, ECN cresol analogs.
  • the application is meant to be conducted together with usual reactive additives, thinners, solvents, fillers, initiators, stabilizers, modifiers, as needed for the respective material to be obtained.
  • starting materials depicted are alkylaryl compounds t-butylbenzene, i-propylbenzene (Cumene), and toluene.
  • the mixture contains para/para- structures (4-substitution), ortho/para-structures (2- and 4-substitution) and ortho/ortho-structures (2-substitution).
  • starting materials depicted are alkylaryl compounds t-butylbenzene, i-propylbenzene (Cumene), and toluene.
  • the mixture contains para/para- structures (4-substitution), ortho/para-structures (2- and 4-substitution) and ortho/ortho-structures (2-substitution).
  • Figure 2 Possible iodonium cations formed as components
  • diaryliodonium salt mixtures from four starting components (t- butylbenzene, i-propylbenzene, ethylbenzene, toluene) yielding the product mix as hydrogen sulfate salts (possible o/p- and o/o-isomers not depicted; theoretical number of all possible isomers is 56).
  • Figure 6 H-NMR spectrum and HPLC chromatogram of diaryliodonium mixture from starting components t-butylbenzene, i-propylbenzene with hexafluorophosphate anion (compound 3).
  • Figure 6A shows H-NMR (DMSO-d6, 700 MHz) and
  • Figure 6B shows HPLC chromatogram (RP-C18 Purospher, phosphate-buffer/acetonitrile gradient, detection 254 nm). * indicates entities with o/p or o/o-substitution
  • FIG. 7A shows H-NMR (DMSO-d6, 700 MHz) of compound 15 (hexafluorophosphate anion) and
  • Figure 7B shows HPLC chromatogram (RP-C18 Purospher, phosphate-buffer/acetonitrile gradient, detection 254 nm) of compound 13 (tetraphenyl borate anion).
  • Example 1 Synthesis of a diaryliodonium mixture based on tert-butylbenzene and /so-propylbenzene.
  • Example 1.1 Synthesis of diaryliodonium mixtures as hydrogen sulfates 0.31 mol (48 ml, 41.9 g) tert-butylbenzene, 0.31 mol (43.5 ml, 37.6 g) isopropylbenzene, 1.06 mol (100 ml, 108 g) acetic anhydride and 1.75 mol (100 ml, 105 g) acetic acid were mixed in a 500 ml flask. To this solution 0.31 mol (61.9 g) NaI03 was added in small portions. The resulting suspension was cooled to 5 °C. Then, 0.68 mol (35 ml, 64.4 g) cone.
  • H2SO4 was added dropwise while the reaction temperature must be kept below 20 °C. After adding cone. H2SO4 the cooling bath was removed, and the reaction mixture was stirred overnight. The suspension was subsequently added to a mixture of 400 g ice and 250 ml CHCb. The resulting 2- phase mixture was stirred intensely for 1 h. The organic phase was separated and neutralized via adding 500 ml of saturated Na2C03-solution. The subsequently separated organic phase was dried over Na2S04. After filtration, the filtrate was added to 1.25 I Et20 and the diaryliodonium salt mixture as hydrogen sulfate precipitated in the form of white crystals.
  • the oxidizing agent NaI03 may be replaced by potassium iodate or sodium periodate with comparable yields.
  • the diaryliodonium salt mixture was also synthesized as iodide, bromide, hexafluorophosphate (compound 3) and tetrakisperfluoro-tert- butoxyaluminate (compound 4). All yields obtained after anion exchange were at 85.0 - 97%.
  • Example 2 Synthesis of diaryliodonium salt mixture based on tert-butylbenzene, /so-propylbenzene and toluene.
  • diaryliodonium salt mixtures based on tert- butylbenzene, /so-propylbenzene and toluene as iodide, bromide, hexafluorophosphate, tetraphenyl borate and tetrakisperfluoro-tert- butoxyaluminate
  • Example 3 Synthesis of diaryliodonium salt mixture based on tert-butylbenzene, /so-propylbenzene and methoxybenzene (anisole). 0.31 mol (48 ml, 41.9 g) tert-butylbenzene, 0.31 mol (43.5 ml, 37.6 g) /so- propylbenzene, 0.31 mol (34 ml, 33.9 g) methoxybenzene, 1.06 mol (100 ml, 108 g) acetic anhydride and 1.75 mol (100 ml, 105 g) acetic acid were mixed in a 500 ml flask.
  • Example 4 Synthesis of diaryliodonium salt mixture based on tert-butylbenzene, /so-propylbenzene, ethylbenzene and toluene.
  • diaryliodonium salt mixture based on tert- butylbenzene, /so-propylbenzene, toluene and ethylbenzene as bromide, iodide, hexafluorophosphate, tetraphenyl borate and tetrakisperfluoro-tert- butoxyaluminate
  • Example 5 Comparative synthesis of diaryliodonium salt mixture based on Cio - Ci3 alkyl substituted benzenes
  • Negative-working, infrared radiation-sensitive lithographic printing plate precursors were prepared using a substrate that was composed of an aluminum sheet that had been subjected to an electrolytic roughening treatment in a hydrochloric acid solution to achieve an average roughness (Ra) of 0.4 mhi.
  • the aluminum sheet was then subjected to an anodizing treatment in an aqueous phosphoric acid solution to form 1.1 g/m 2 of an oxide film and then coated with a post-treatment aqueous solution of poly(acrylic acid) to give a dry thickness of 0.03 g/m 2 .
  • an infrared radiation-sensitive imageable layer is formed using a formulation shown in the following TABLE 1.
  • Each formulation comprised a specific iodonium salt mixture shown in the TABLE 3 below.
  • Each formulation was coated onto the substrate using a bar coater, dried at 50°C for 60 seconds, and then cooled to room temperature to give a dry coating weight of 0.9 g/m 2 of the resulting infrared radiation-sensitive imageable layer, thus forming a negative-working, infrared radiation-sensitive lithographic printing plate precursor with each formulation.
  • Example 6 Components of the IR-sensitive imageable layer TABLE 3 / Example 6: Iodonium salt mixtures
  • the negative-working, infrared radiation-sensitive lithographic printing plate precursors prepared in this manner were each imagewise exposed on a Kodak Magnus® 800 image setter to deliver a dose of 120 mJ/cm 2 in a solid area and thus formed exposed precursors having both exposed areas and unexposed areas in the infrared radiation-sensitive imageable layer.
  • On-press Developability Each of the lithographic printing plate precursors was exposed at 15 to 150 mJ/cm 2 using a Kodak Trendsetter 3244x. The exposed plate precursor was mounted on a MAN Roland Favorit 04 press machine. Fountain solution (Varn Supreme 6038) and printing ink (Gans Cyan) were supplied, and printing was performed. The on press developability was evaluated by counting the number of printed paper sheets needed to receive a clean background.
  • Photospeed, and hence press durability, is sufficient for all examples and comparative examples with iodonium salt initiators having low molecular weights, indicating their good photochemical properties irrespective of the complexity of their mixture, as long as the effective number of radicals formed per mass unit remains sufficient. This is not the case for comparative example 6 applying the iodonium salt mixture received in example 5, although crystallization propensity of the mixture is as good as that of the inventive mixture.
  • a sol-gel coating solution consisting of 15% TEOS, 5% epoxy-modified silanes, 75% organic solvents, and 5% water was prepared according to protocols known (R.B. Figueira et al.; Journal of Coatings Technology and Research 2015, 12, 1- 35). To 10 g of this coating solution were added 0.05 g of photoinitiator test compounds (see Table 5/example 7), followed by 1 hour of stirring at room temperature. This solution was applied to a PET foil at a wet thickness of 30 pm by a doctor blade device. This material was illuminated at 254 nm for 2 min or for 5 min (UV-Crosslinker device; UVP).
  • abrasion resistance 500 cycles was determined with a standard method (taber-abraser) and the decrease in gloss was measured. Results are summarized in Table 7. Coatings with Compound 1 showed best abrasion resistance (lowest decrease in gloss) in comparison to controls. In addition, Compound 1 showed better solubility in the coating and layer, while the single component bis-(4-tert.-butyl-phenyl)-iodonium tetrakis(perfluoro-tert.- butoxy)aluminate lead to visible precipitates and spots in the coat.

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Abstract

L'invention concerne de nouveaux mélanges de sels de diaryliodonium en tant que photo-initiateurs de faible poids moléculaire ayant un comportement de cristallisation réduit au minimum et une solubilité élevée, des procédés avantageux pour leur synthèse et leur fabrication, ainsi que leur application dans des compositions pour revêtements, vernis, couches et plaques d'impression.
EP22777184.7A 2021-06-10 2022-05-02 Nouveaux mélanges de sels de diaryliodonium en tant que photo-initiateurs de faible poids moléculaire ayant un comportement de cristallisation réduit au minimum et une solubilité élevée Pending EP4352033A1 (fr)

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EP21178716.3A EP4101830A1 (fr) 2021-06-10 2021-06-10 Nouveaux mélanges de sels de diaryliodonium comme photoinitiateurs de faible poids moléculaire à comportement de cristallisation réduit et à solubilité élevée
PCT/EP2022/061669 WO2022258259A1 (fr) 2021-06-10 2022-05-02 Nouveaux mélanges de sels de diaryliodonium en tant que photo-initiateurs de faible poids moléculaire ayant un comportement de cristallisation réduit au minimum et une solubilité élevée

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EP22777184.7A Pending EP4352033A1 (fr) 2021-06-10 2022-05-02 Nouveaux mélanges de sels de diaryliodonium en tant que photo-initiateurs de faible poids moléculaire ayant un comportement de cristallisation réduit au minimum et une solubilité élevée

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