WO2025140854A2 - Nouvelle forme solide d'oxyde de bis(2,4,6-triméthylbenzoyl)-n-octyl-phosphine - Google Patents

Nouvelle forme solide d'oxyde de bis(2,4,6-triméthylbenzoyl)-n-octyl-phosphine Download PDF

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WO2025140854A2
WO2025140854A2 PCT/EP2024/085660 EP2024085660W WO2025140854A2 WO 2025140854 A2 WO2025140854 A2 WO 2025140854A2 EP 2024085660 W EP2024085660 W EP 2024085660W WO 2025140854 A2 WO2025140854 A2 WO 2025140854A2
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compound
formula
composition
octyl
weight
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WO2025140854A3 (fr
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Luca BAZZONI
Andrea BERNINI FREDDI
Francesco NETTUNO
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IGM Resins Italia SRL
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IGM Resins Italia SRL
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5337—Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)
    • 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
    • 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
    • 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
    • G03F7/0037—Production of three-dimensional images
    • 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
    • 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

Definitions

  • Bis(2,4,6-trimethylbenzoyl)-n-octyl-phosphine oxide is a known photoinitiator.
  • the role of a photoinitiator (PI) is to convert light to chemical energy in the form of reactive intermediates. Said intermediates are radicals able to initiate radical polymerization of double bonds present in the formulation to be cured.
  • Bis(2,4,6-trimethylbenzoyl)-n-octyl-phosphine oxide has been disclosed in a non-solid form.
  • said compound has been disclosed as a resin in GB2259704 (Compound 7), as an oil in US5534559 (Example 6) and as a viscous oil in WOOO/32612 (Example 10).
  • Figure 1 shows photographs of bis(2,4,6-trimethylbenzoyl)-n-octyl- phosphine oxide of the prior art (A) (viscous oil poured on a surface) and of the invention (B) (solid product).
  • Figure 2 shows the DSC diagram of a compound of formula (I) according to the invention.
  • the present invention relates to bis(2,4,6- trimethylbenzoyl)-n-octyl-phosphine oxide (herein after also referred to as "n-octyl-BAPO") of formula (I) characterized in that is it in a solid form at ambient temperature and pressure.
  • n-octyl-BAPO of the invention is a white/light yellow powder, having a melting point higher than 38°C.
  • n-octyl-BAPO of the invention shows a DSC peak from 40 to 50°C, more preferably from 41 to 48°C, for example at about 41°C, about 42°C, about 43°C, about 44°C, about 45°C, about 46°C, about 47°C or about 48°C.
  • n-octyl-BAPO of the invention is a white/light yellow powder having a HPLC (area%) higher than 99%.
  • n-octyl-BAPO of the invention is a white/light yellow powder, with a melting point higher than 38°C and having a HPLC (area%) higher than 99%.
  • Step 1 is carried out in the presence of water and a phase transfer catalyst, preferably ammonium salts, more preferably tert-butylammonium bromide or tert-butylammonium chloride and a base, such as a tertiary amine or alkali metal base, such as alkali carbonate, alkali hydroxide, e.g. potassium or sodium carbonate, potassium or sodium hydroxide, triethyl amine, preferably potassium carbonate.
  • a phase transfer catalyst preferably ammonium salts, more preferably tert-butylammonium bromide or tert-butylammonium chloride and a base, such as a tertiary amine or alkali metal base, such as alkali carbonate, alkali hydroxide, e.g. potassium or sodium carbonate, potassium or sodium hydroxide, triethyl amine, preferably potassium carbonate.
  • a phase transfer catalyst preferably ammonium salts, more
  • Step 1 is carried out at a temperature ranging from ambient temperature to the reflux temperature of the reaction mixture, preferably from 50°C to the reflux temperature of the reaction mixture, more preferably at 80-95°C, advantageously at 88-90°C.
  • the said base is added to the reaction mixture in the form of an aqueous solution, more preferably dropwise, advantageously over 1 to 3 hours, and subsequently the reaction may be kept at the above temperatures for further 1 to 3 hours at ambient temperature.
  • the mixture is extracted with an organic, preferably non-polar solvent, preferably selected from a C6-C8 alkane and their mixtures, petroleum ether, toluene, xylene and cyclohexane, more preferably with a C6-C8 alkane and their mixtures, for instance n-heptane or heptane mixtures, according to the known methods.
  • an organic, preferably non-polar solvent preferably selected from a C6-C8 alkane and their mixtures, petroleum ether, toluene, xylene and cyclohexane, more preferably with a C6-C8 alkane and their mixtures, for instance n-heptane or heptane mixtures, according to the known methods.
  • step 2 the compound of formula (III) in the organic phase is oxidated with a suitable oxidating agent, preferably an aqueous solution of hydrogen peroxide, preferably at a temperature ranging from ambient temperature to 60°C, preferably from 45°C to 60°C, more preferably at approximately 55- 60°C, then the reaction may be kept at said temperature for approximately 2-4 hours.
  • a suitable oxidating agent preferably an aqueous solution of hydrogen peroxide
  • Suitable oxidating agents may include air.
  • the two phases are separated and the organic phase is preferably washed with water, with a sodium bicarbonate water solution and again with water.
  • the two phases are separated and the organic phase is preferably filtered, optionally concentrated under reduced pressure, then cooled at -5 to 5°C.
  • Compound of formula (I) precipitates, generally in a few hours, in a solid form and is isolated preferably by filtration and optionally washed with the organic solvent previously used.
  • the invention relates to a compound of formula (I) in a solid form, as above defined, obtainable or obtained by the process of the invention.
  • the present invention relates to the use of compound of formula (II) as above defined for the preparation of compound of formula (I), preferably, but not limited to, for the preparation of compound of formula (I) in a solid form.
  • a solid compound is easier to handle, workable at room temperature, while a viscous liquid always needs to be warmed to be poured/used/weighted, etc.
  • the present invention relates to a photopolymerizable composition
  • a photopolymerizable composition comprising: a) from 50 to 99.7%, preferably from 70 to 98.9% by weight, based on the total content of the composition, of at least one ethylenically unsaturated compound; b) from 0.1 to 35%, preferably from 0.1 to 20%, and more preferably from 0.2 to 15% by weight, based on the total content of the composition, of compound of formula (I) as above defined; and c) from 0 to 20% by weight, preferably from 0 to 15%, and more preferably from 0.2 to 15% by weight, based on the total content of the composition, of an accelerator and/or of a coinitiator.
  • % weight amounts of any of the components is calculated with respect to the sum of the weight of all the components of the composition, including any possible further additional components (in addition to a), b) and c) above), but possible water and/or solvents which may be present in the composition are not considered for the calculation of said % weight amounts.
  • the present invention relates to a process for photocuring photopolymerizable compositions coatings, adhesives and inks, which process comprises: i. providing a photopolymerizable composition as above defined; ii. coating or printing said photopolymerizable composition onto a substrate, and iii. photocuring said coated or printed composition with a light source on said substrate.
  • the present invention relates to a process for three-dimensional printing which comprising photocuring with a light source a mixture comprising the composition as above defined.
  • the present invention relates to an article of manufacture obtained by the process of the invention.
  • the photopolymerizable composition used the processes of the invention comprises at least components (a) and (b), more preferably at least (a), (b) and (c).
  • the photoinitiators of the invention can be used in photocurable compositions comprising ethylenically unsaturated compounds (a).
  • Said unsaturated compounds (a) can contain one or more olefinic double bonds. They can be low-molecular weight (monomeric) or high-molecular weight (oligomeric) compounds.
  • suitable low molecular weight monomers (monomeric compounds) having one double bond are alkyl or hydroxyalkyl acrylates or methacrylates, such as methyl-, ethyl-, butyl-, 2-ethylhexyl-,2-hydroxyethyl- or isobornyl-acrylate; and methyl or ethyl methacrylate.
  • resins modified with silicon or fluorine e.g. silicone acrylates.
  • Examples of monomers having more than one double bond are the ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate, bisphenol A diacrylate, 4,4'-bis-(2- acryloyloxyethoxy)-diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinyl benzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris-(2-acryloylethyl) isocyanurate.
  • high-molecular weight (oligomeric) polyunsaturated compounds are acrylated epoxy resins, acrylated or vinyl-ether- or epoxy-group- containing polyesters, acrylated polyurethanes or acrylated polyethers.
  • unsaturated oligomers are unsaturated polyester resins which are usually prepared from maleic acid, phthalic acid and one or more diols and which have molecular weights of from approximately 500 Da to 3,000 Da. Such unsaturated oligomers can also be referred to as prepolymers.
  • Examples of compounds (a) which are particularly suitable for the implementation of the present invention, are esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers containing ethylenically unsaturated groups in the chain or in side groups, e.g. unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, alkyl resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers having (meth)acrylic groups in side chains, as well as mixtures thereof.
  • esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides and polymers containing ethylenically unsaturated groups in the chain or in side groups, e.g. unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, alkyl resins, polybut
  • unsaturated carboxylic acids or anhydrides useful for the preparation of the above esters, are acrylic acid, methacrylic acid, maleic anhydride, crotonic acid, itaconic acid, cinnamic acid and unsaturated fatty acids such as linolenic acid and oleic acid.
  • Acrylic and methacrylic acid are preferred.
  • polyols which can also be esterified, are aromatic and aliphatic and cycloaliphatic polyols, preferably aliphatic and cycloaliphatic polyols.
  • Aromatic polyols are, for example, hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di(4-hydroxyphenyl) propane, as well as novolaks and resoles.
  • Polyepoxides, which can be esterified include those based on the said polyols, especially the reaction products between aromatic polyols and epichlorohydrin.
  • polystyrene resin polystyrene resin
  • polystyrene resin polystyrene resin
  • polymethacrylic acid hydroxyalkyl esters or copolymers thereof polymethacrylic acid hydroxyalkyl esters or copolymers thereof.
  • oligoesters carrying hydroxyl terminal groups are also suitable as polyols.
  • ethylenically unsaturated compounds (a) are unsaturated polyamides obtained from unsaturated carboxylic acids and aromatic, aliphatic and cycloaliphatic polyamines having preferably from 2 to 6, preferably from 2 to 4, amino groups.
  • polyamines examples include: ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4- butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylene diamine, 1,4-diaminocyclohexane, isophoronediamine, phenylene diamine, bisphenylenediamine, di-(p- aminoethyl) ether, diethylene triamine, triethylenetetramine and di(p- aminoethoxy)- and di(p-aminopropoxy)ethane.
  • suitable polyamines are polymers and copolymers which may contain additional amino groups in the side chain and oligoamides containing amino end groups.
  • unsaturated polyamides are methylenebisacrylamide, 1,6-hexamethylene bisacrylamide, diethylenetriamine trismethacrylamide, bis(methacrylamidopropoxy) ethane and N-[(p-hydroxyethoxy)ethyl]-acrylamide.
  • Unsaturated polyurethanes are also suitable for the implementation of the present invention as components (a), for example those derived from saturated or unsaturated diisocyanates and unsaturated or saturated diols. Polybutadiene and polyisoprene and copolymers thereof may also be used.
  • Suitable monomers include, for example, olefins, such as ethylene, propene, butene and hexene, (meth)acrylates, acrylonitrile, styrene and vinyl chloride.
  • Polymers having unsaturated (meth)acrylate groups in the side chain can also be used as component (a). They may typically be reaction products of epoxy resins based on novolac with (meth)acrylic acid; homo- or copolymers of vinyl alcohol or hydroxyalkyl derivatives thereof that have been esterified with (meth)acrylic acid; and homo- and co-polymers of (meth)acrylates that have been esterified with hydroxyalkyl (meth)acrylates.
  • the photocurable composition further comprises a coinitiators (c), also referred to as accelerators.
  • a coinitiators also referred to as accelerators.
  • accelerators/coinitiators (c) are alcohols, thiols, thioethers, amines or ethers that have an available hydrogen, bonded to a carbon adjacent to the heteroatom, disulfides and phosphines, e.g. as described in EP 438 123 and GB 2 180 358.
  • amine accelerators/co-initiators include, but are not limited to, aliphatic, cycloaliphatic, aromatic, aryl-aliphatic, heterocyclic, oligomeric or polymeric amines. They can be primary, secondary or tertiary amines, for example butyl amine, dibutyl amine, tributyl amine, cyclohexyl amine, benzyldimethyl amine, di-cyclohexyl amine, N-phenyl glycine, triethyl amine, phenyl-diethanol amine, triethanolamine, piperidine, piperazine, morpholine, pyridine, quinoline, esters of dimethylamino benzoic acid, Michler's ketone (4,4'-bis-dimethyl aminobenzophenone) and derivatives thereof.
  • an amine-modified acrylate compound can be used as the amine accelerators/co-initiators; examples of such amine-modified acrylate include acrylates modified by reaction with a primary or secondary amine that are described in US 3,844,916, EP 280222, US 5,482,649 or US 5,734,002.
  • Multifunctional amine and polymeric amine derivatives are also suitable as co-initiators some examples are those presently marketed as Omnipol® ASA from IGM Resins B.V., Genopol® AB-2 from Rahn A.G., Speedcure® 7040 from Lambson Limited or those described in US2013/0012611.
  • compositions of the present invention can also be formulated in compositions further comprising water and/or solvents, such as organic solvents.
  • Photosensitizers (d) can be present in an amount comprised between 0.01 and 15% by weight, based on the total content of the composition, preferably between 0.01 and 10% by weight.
  • photosensitizers are those commonly used in the art, aromatic carbonyl compounds, e.g. benzophenones, thioxanthones, anthraquinones, coumarins and 3-acylcoumarin derivatives, terphenyls, styryl ketones, and 3- (aroylmethylene)-thiazolines, camphorquinones and also eosin, rhodamine and erythrosine dyes.
  • aromatic carbonyl compounds e.g. benzophenones, thioxanthones, anthraquinones, coumarins and 3-acylcoumarin derivatives, terphenyls, styryl ketones, and 3- (aroylmethylene)-thiazolines, camphorquinones and also eosin, rhodamine and erythrosine dyes.
  • thioxanthones examples include thioxanthone, 2-isopropyl thioxanthone, 2- chloro thioxanthone, 2-dodecyl thioxanthone, 2,4-diethyl thioxanthone, 2,4- dimethyl thioxanthone, 1-methoxycarbonyl thioxanthone, 2-ethoxycarbonyl thioxanthone, 3-(2-methoxyethoxycarbonyl) thioxanthone, 4- butoxycarbonyl thioxanthone, 3-butoxycarbonyl-7-methyl thioxanthone, 1- cyano-3-chloro thioxanthone, l-ethoxycarbonyl-3-chloro thioxanthone, 1- ethoxycarbonyl-3-ethoxy thioxanthone, l-ethoxycarbonyl-3-amino thioxanthone, l-e
  • polymeric thioxanthone derivatives e.g. those presently marketed as Omnipol® TX from IGM Resins B.V., Genopol® TX-1 from Rahn A.G., Speedcure® 7010 from Lambson Limited.
  • 3-(aroylmethylene) thiazolines are 3-methy-l,2- benzoylmethylene-p-benzo thiazoline, 3-methyl-2-benzoyl methylene- benzo thiazoline, 3-ethyl-2-propionylmethylene-p-benzo thiazoline.
  • aromatic carbonyl compounds examples include acetophenone, 3- methoxyacetophenone, 4-phenylacetophenone, benzil, such as that described in WO 2013/164394, 2-acetylnaphthalene, 2-naphthaldehyde, 9,10-anthraquinone, 9-fluorenone, dibenzosuberone, xanthone, 2,5-bis(4- diethylaminobenzylidene) cyclopentanone, a-(para-dimethylamino benzylidene), ketones, such as 2-(4-dimethylamino-benzylidene)-indan-l- one or 3-(4-dimethylaminophenyl)-l-indan-5-yl-propenone, 3- phenylthiophthalimide, N-methyl-3,5-di(ethylthio) phthalimide.
  • benzil such as that described in WO 2013/164394
  • thioxanthones particularly preferred are thioxanthones, coumarins and 3-acylcoumarins.
  • compositions have the special advantage that an appropriate choice of the photosensitizer (d) allows the spectral sensitivity of photoinitioator (b) to be shifted to any desired wavelength region.
  • the skilled in the art is able to select the suitable photosensitizer (d) to make the photoinitiator(s) (b) work at any desired wavelength region.
  • ketosulfones e.g l-[4-[(4-benzoyl-phenyl)-thio]-phenyl]-2- methyl-2-[(4-methyl-phenyl)-sulfonyl]-propan-l-one (Esacure® 1001, from IGM Resins B.V.), 3-ketocoumarins, for example as described in EP2909243 and WO2017216699, phenylglyoxylates and derivatives thereof, dimeric phenyl glyoxylates, peresters, e.g.
  • acylphosphine photoinitiators which can be selected from mono-acylphosphine oxides, bisacylphosphine oxides, tris-acylphosphine oxides and multifunctional mono- or bisacylphosphine oxides
  • halomethyltriazines hexaaryl bisimidazole/coinitiator systems, e.g.
  • Examples of a- hydroxy ketones and a-aminoketones are 1-hydroxy cyclohexylphenyl ketone, 2-hydroxy-2-methyl-l-phenyl-propane-l-one, 1- [4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-l-propane- 1-one, 2- hydroxy-l- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl ⁇ -2- methyl-propane-l-one), 2-hydroxy-l- ⁇ 4-[4-(2-hydroxy-2-methyl- propionyl)-phenoxy]-phenyl ⁇ -2-methyl-propan- 1-one, 2-methyl-l-(4- methylthiophenyl)-2-morpholinopropane-l-one), 2-benzyl-2- di methylam ino-l-(4-morpholi nophenyl)- butane- 1-one, and (2-
  • O-acyloxime ester photoinitiators are l,2-octanedione,l-[4- (phenylthio)phenyl]-2-(O-benzoyloxime), ethanone 1- [9-ethyl-6-(2- methylbenzoyl)-9H-carbazole-3-yl] l-(O-acetyloxime) or those described in GB 2339571.
  • acylphosphine photoinitiators include, but are not limited to, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6- dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide, bis(2,4,6- trimethylbenzoyl)-(2,4-dipentyloxyphenyl), 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, and phenyl(2,4,6-trimethylbenzoyl)phosphinic acid glycerol ethoxylated triester (Omnipol TP from IGM Resins B.V.).
  • halomethyltriazines based photoinitiators 2-[2-(4- methoxy-phenyl)-vinyl]-4,6-bis-trichloromethyl [l,3,5]triazine, 2-(4- methoxy-phenyl)-4,6-bis-trichloromethyl [l,3,5]triazine, 2-(3,4- dimethoxyphenyl)-4,6-bis-trichloromethyl [l,3,5]triazine, 2-methyl-4,6-bis- trichloromethyl [1,3,5] triazine.
  • Cationic photoinitiators can be also used as the further photoinitiators (e), when the photocurable compositions according to the invention are used in hybrid systems (which in this connection mean mixtures of free- radically and cationically curing systems).
  • suitable cationic photoinitiators are aromatic sulfonium, phosphonium or iodonium salts, as described e.g. in US4,950,581, or cyclopentadienylarene-iron(II) complex salts, e.g.
  • the photocuring composition according to the invention may also comprise conventional additives, from 0 to 10% based on the total content of the composition.
  • Additives (f) can be, for example, thermal initiators, binders, stabilizers, and mixture thereof.
  • additives The choice of additives is governed by the field of use in question and the properties desired for that field.
  • the additives (f) described above are known in the art and are accordingly used in the amounts conventionally used in the art.
  • the composition may also comprise, as additional additive (f), a thermal initiator, a compound that forms free radicals when heated, e.g. an azo compounds, such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), a triazene, diazosulfide, pentazadiene or a peroxy compound, for example a hydroperoxide or peroxycarbonate, e.g. tert-butyl hydroperoxide, as described e.g. in EP 245 639.
  • a thermal initiator e.g. an azo compounds, such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), a triazene, diazosulfide, pentazadiene or a peroxy compound, for example a hydroperoxide or peroxycarbonate, e.g. tert-butyl hydroperoxide, as described e.g. in EP 245 639.
  • Binders may also be added to the photocurable composition of the invention.
  • the addition of binders is particularly advantageous when the photocurable compounds are liquid or viscous substances.
  • the amount of binder may be, for example, from 5 to 60% by weight, preferably from 10 to 50% by weight, based on the total content of the composition, excluding possible water and solvents.
  • the choice of binder is made in accordance with the field of use and the properties required therefor, such as developability in aqueous and organic solvent systems, adhesion to substrates and sensitivity to oxygen.
  • Suitable binders are, for example, polymers having a weight average molecular weight (Mw) of approximately from 5,000 Da to 2,000,000 Da, preferably from 10,000 Da to 1,000,000 Da.
  • Illustrative examples are: homo- and copolymers of acrylates and methacrylates, e.g. copolymers of methyl methacrylate/ethyl acrylate/methacrylic acid, poly(methacrylic acid alkyl esters), poly(acrylic acid alkyl esters); cellulose esters and ethers, such as cellulose acetate, cellulose acetate butyrate, methylcellulose, ethylcellulose, polyvinylbutyral, polyvinylformal, cyclised rubber, polyethers such as polyethylene oxide, polypropylene oxide, polytetrahydrofuran, polystyrene, polycarbonates, polyurethanes, chlorinated polyolefins, e.g.
  • polyvinyl chloride co-polymers of vinyl chloride/vinylidene chloride, co-polymers of vinylidene chloride with acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, co-poly (ethylene/vinyl acetate), polymers such as polycaprolactam and poly(hexamethylene adipamide), polyesters such as poly(ethylene glycol terephthalate) and poly(hexamethylene glycol succinate).
  • Suitable stabilizers are, for example, thermal inhibitors, such as hydroquinone, hydroquinone derivatives, p-methoxyphenol, p-benzol or sterically hindered phenols, e.g. 2,6-di(tert-butyl)-p-cresol, which prevent premature polymerization.
  • thermal inhibitors such as hydroquinone, hydroquinone derivatives, p-methoxyphenol, p-benzol or sterically hindered phenols, e.g. 2,6-di(tert-butyl)-p-cresol, which prevent premature polymerization.
  • copper compounds such as copper naphthenate, stearate or octoate
  • phosphorus compounds for example triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl phosphite or tribenzyl phosphite
  • quaternary ammonium compounds e.g. tetramethylammonium chloride or trimethylbenzylammonium chloride
  • hydroxylamine derivatives e.g. N,N-diethylhydroxylamine.
  • the photocurable compositions according to the invention may also comprise, as further additives (f), photoreducible dyes, e.g. a xanthene, benzoxanthene, benzothioxanthene, thiazine, pyronin, porphyrin or acridine dye, and/or radiation cleavable trihalomethyl compounds.
  • photoreducible dyes e.g. a xanthene, benzoxanthene, benzothioxanthene, thiazine, pyronin, porphyrin or acridine dye
  • radiation cleavable trihalomethyl compounds are described, for example, in EP445624.
  • customary additives (f) are, depending upon the intended use, optical brighteners, fillers, pigments, both white and colored pigments, colorants, antistatics, wetting agents or flow improvers. Additives conventionally used in the art, e.g. antistatics, flow improvers and adhesion enhancers, can also be used.
  • chain-transfer reagents conventionally used in the art to be added to the compositions according to the invention.
  • chain-transfer reagents conventionally used in the art to be added to the compositions according to the invention.
  • examples are mercaptans, amines and benzothiazole.
  • composition of the invention may also comprise colorants and/or colored pigments.
  • inorganic and organic pigments may be used.
  • Such additives are well known to the person skilled in the art; some examples are carbon black, iron oxides, such as iron oxide yellow, iron oxide red, chromium yellow, chromium green, nickel titanium yellow, ultramarine blue, cobalt blue, bismuth vanadate, cadmium yellow and cadmium red.
  • organic pigments are mono- or bis-azo pigments, and also metal complexes thereof, phthalocyanine pigments, polycyclic pigments, e.g.
  • pigments may be used in the formulations on their own or in admixture. Depending upon the intended use, the pigments can be added to the formulations in amounts conventionally used in the art, for example in an amount from 0.1 to 30% by weight or from 10 to 25% by weight, based on the total weight of the composition.
  • the composition may also comprise, for example, organic colorants of an extremely wide variety of classes.
  • organic colorants of an extremely wide variety of classes. Examples are azo dyes, methine dyes, anthraquinone dyes and metal complex dyes. Usual concentrations are, for example, from 0.1 to 20% wt, especially from 1 to 5% wt, based on the total weight of the composition.
  • the photocurable compositions of the invention may comprise water.
  • An article comprising a compound of formula (I) or comprising a photocurable composition of the invention represents a further subject-matter of the invention.
  • the article obtained by applying said photopolymerizable composition to said substrate by said means of coating or printing, and photopolymerizing by said light source, with or without further elaboration of the article by further coating or printing, represents a further subject-matter of this invention.
  • Heptane mixture was purchased from VWR International.
  • the photopolymerizable compositions for the test were prepared by dissolving the Pls at the concentration of 4% by weight in a solution of Photomer 3016 (Bisphenol A epoxy diacrylate) 50%, Photomer 4335 (PETIA) 15%, Photomer 4600 (DPHA) 15%, Photomer 4172 (PPTTA) 20%.
  • the Pls were tested with:
  • the photopolymerizable composition is spread with a thickness of 12 g/m 2 on a BYK coated cardboard.

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Abstract

La présente invention concerne une nouvelle forme physique d'oxyde de bis(2,4,6-triméthylbenzoyl)-n-octyl-phosphine, un procédé pour sa préparation et son utilisation en tant que photo-initiateur dans des compositions de photopolymérisation. L'invention concerne également un procédé de photopolymérisation de compositions contenant ledit photo-initiateur ainsi que son utilisation dans des articles manufacturés, notamment des ensembles imprimés, revêtus et fabriqués.
PCT/EP2024/085660 2023-12-28 2024-12-11 Nouvelle forme solide d'oxyde de bis(2,4,6-triméthylbenzoyl)-n-octyl-phosphine Pending WO2025140854A2 (fr)

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IT102023000028218 2023-12-28
IT102023000028218A IT202300028218A1 (it) 2023-12-28 2023-12-28 Nuova forma solida di bis(2,4,6-trimetilbenzoil)-n-ottilfosfina ossido

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WO2025140854A2 true WO2025140854A2 (fr) 2025-07-03
WO2025140854A3 WO2025140854A3 (fr) 2025-09-04

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Citations (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3844916A (en) 1972-09-18 1974-10-29 Desoto Inc Radiation curable non-gelled michael addition reaction products
US4136055A (en) 1974-06-21 1979-01-23 Raychem Corporation Compositions of antioxidants of reduced volatility
US4450598A (en) 1982-08-30 1984-05-29 Blue Giant Equipment Of Canada Ltd. Lip construction for dock leveller
EP0126541A1 (fr) 1983-04-26 1984-11-28 Nippon Oil And Fats Company, Limited Initiateur de photopolymérisation et méthode de photopolymérisation avec usage de cet initiateur
US4575330A (en) 1984-08-08 1986-03-11 Uvp, Inc. Apparatus for production of three-dimensional objects by stereolithography
GB2180358A (en) 1985-07-16 1987-03-25 Mead Corp Photosensitive microcapsules and their use on imaging sheets
EP0245639A2 (fr) 1986-04-12 1987-11-19 Bayer Ag Procédé de préparation de revêtements pigmentés durcissables aux rayons UV
US4950581A (en) 1987-07-06 1990-08-21 Fuji Photo Film Co., Ltd. Photopolymerizable composition
EP0438123A2 (fr) 1990-01-16 1991-07-24 Showa Denko Kabushiki Kaisha Initiateur de polymérisation utilisable dans l'infrarouge proche
EP0445624A2 (fr) 1990-03-09 1991-09-11 Hoechst Aktiengesellschaft Composition photopolymérisable et matériau d'enregistrement produit de cela
GB2259704A (en) 1991-09-23 1993-03-24 Ciba Geigy Ag Alkylbisacylphosphine oxides
EP0678534A1 (fr) 1994-04-22 1995-10-25 BASF Aktiengesellschaft Gels ayant des caractéristiques thermotropiques
US5482649A (en) 1992-08-05 1996-01-09 Bayer Aktiengesellschaft Aminoacrylates and a process for their preparation
US5534559A (en) 1993-03-18 1996-07-09 Ciba-Geigy Corporation Daylight curing compositions containing bisacylphosphine oxide photoinitiators
DE19700064A1 (de) 1996-01-13 1997-07-17 Basf Ag Gele mit thermotropen Eigenschaften
US5734002A (en) 1995-03-09 1998-03-31 Basf Aktiengesellschaft Amino-modified urethaneacrylates
GB2339571A (en) 1998-06-26 2000-02-02 Ciba Sc Holding Ag O-Acyloxime compounds as photoinitiators
WO2000010972A1 (fr) 1998-08-19 2000-03-02 Ciba Specialty Chemicals Holding Inc. Nouveaux derives d'oxime insatures et leur utilisation comme acides latents
WO2000026219A1 (fr) 1998-10-29 2000-05-11 Ciba Specialty Chemicals Holding Inc. Derives d'oxime et leur utilisation en tant qu'acides latents
WO2000032612A1 (fr) 1998-11-30 2000-06-08 Ciba Specialty Chemicals Holding Inc. Procedes pour l'elaboration d'acylphosphines et derives
GB2348644A (en) 1999-03-31 2000-10-11 Ciba Sc Holding Ag Oxime derivatives as latent acids in photoresist compositions
US20130012611A1 (en) 2010-03-25 2013-01-10 Robert Stephen Davidson Synergists
WO2013164394A1 (fr) 2012-05-03 2013-11-07 Lamberti Spa Alpha-dicétones destinées au photodurcissement de del
EP2909243A1 (fr) 2012-10-22 2015-08-26 Lamberti SpA 3-cétocoumarines pour photodurcissement à diode électroluminescente (del)
WO2017216699A1 (fr) 2016-06-17 2017-12-21 Igm Group Bv Nouvelles 3-cétocoumarines, procédé pour leur préparation et leur utilisation comme photo-initiateurs dans des réactions de photopolymérisation
US9938231B2 (en) 2014-04-23 2018-04-10 Sun Chemical Corporation Liquid arylbenzoyl benzoic acid ester derivatives for energy curable compositions

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3706355A1 (de) 1987-02-27 1988-09-08 Basf Ag Additionsprodukte aus acrylaten und aminen sowie deren verwendung in strahlungshaertbaren massen
CN102471150B (zh) * 2010-06-30 2014-05-07 帝斯曼知识产权资产管理有限公司 D1492液体双酰基氧化膦光引发剂及其在可辐射固化组合物中的用途

Patent Citations (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3844916A (en) 1972-09-18 1974-10-29 Desoto Inc Radiation curable non-gelled michael addition reaction products
US4136055A (en) 1974-06-21 1979-01-23 Raychem Corporation Compositions of antioxidants of reduced volatility
US4450598A (en) 1982-08-30 1984-05-29 Blue Giant Equipment Of Canada Ltd. Lip construction for dock leveller
EP0126541A1 (fr) 1983-04-26 1984-11-28 Nippon Oil And Fats Company, Limited Initiateur de photopolymérisation et méthode de photopolymérisation avec usage de cet initiateur
US4575330B1 (fr) 1984-08-08 1989-12-19
US4575330A (en) 1984-08-08 1986-03-11 Uvp, Inc. Apparatus for production of three-dimensional objects by stereolithography
GB2180358A (en) 1985-07-16 1987-03-25 Mead Corp Photosensitive microcapsules and their use on imaging sheets
EP0245639A2 (fr) 1986-04-12 1987-11-19 Bayer Ag Procédé de préparation de revêtements pigmentés durcissables aux rayons UV
US4950581A (en) 1987-07-06 1990-08-21 Fuji Photo Film Co., Ltd. Photopolymerizable composition
EP0438123A2 (fr) 1990-01-16 1991-07-24 Showa Denko Kabushiki Kaisha Initiateur de polymérisation utilisable dans l'infrarouge proche
EP0445624A2 (fr) 1990-03-09 1991-09-11 Hoechst Aktiengesellschaft Composition photopolymérisable et matériau d'enregistrement produit de cela
GB2259704A (en) 1991-09-23 1993-03-24 Ciba Geigy Ag Alkylbisacylphosphine oxides
US5482649A (en) 1992-08-05 1996-01-09 Bayer Aktiengesellschaft Aminoacrylates and a process for their preparation
US5534559A (en) 1993-03-18 1996-07-09 Ciba-Geigy Corporation Daylight curing compositions containing bisacylphosphine oxide photoinitiators
EP0678534A1 (fr) 1994-04-22 1995-10-25 BASF Aktiengesellschaft Gels ayant des caractéristiques thermotropiques
US5734002A (en) 1995-03-09 1998-03-31 Basf Aktiengesellschaft Amino-modified urethaneacrylates
DE19700064A1 (de) 1996-01-13 1997-07-17 Basf Ag Gele mit thermotropen Eigenschaften
GB2339571A (en) 1998-06-26 2000-02-02 Ciba Sc Holding Ag O-Acyloxime compounds as photoinitiators
WO2000010972A1 (fr) 1998-08-19 2000-03-02 Ciba Specialty Chemicals Holding Inc. Nouveaux derives d'oxime insatures et leur utilisation comme acides latents
WO2000026219A1 (fr) 1998-10-29 2000-05-11 Ciba Specialty Chemicals Holding Inc. Derives d'oxime et leur utilisation en tant qu'acides latents
WO2000032612A1 (fr) 1998-11-30 2000-06-08 Ciba Specialty Chemicals Holding Inc. Procedes pour l'elaboration d'acylphosphines et derives
GB2348644A (en) 1999-03-31 2000-10-11 Ciba Sc Holding Ag Oxime derivatives as latent acids in photoresist compositions
US20130012611A1 (en) 2010-03-25 2013-01-10 Robert Stephen Davidson Synergists
WO2013164394A1 (fr) 2012-05-03 2013-11-07 Lamberti Spa Alpha-dicétones destinées au photodurcissement de del
EP2909243A1 (fr) 2012-10-22 2015-08-26 Lamberti SpA 3-cétocoumarines pour photodurcissement à diode électroluminescente (del)
US9938231B2 (en) 2014-04-23 2018-04-10 Sun Chemical Corporation Liquid arylbenzoyl benzoic acid ester derivatives for energy curable compositions
WO2017216699A1 (fr) 2016-06-17 2017-12-21 Igm Group Bv Nouvelles 3-cétocoumarines, procédé pour leur préparation et leur utilisation comme photo-initiateurs dans des réactions de photopolymérisation

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