Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
  • C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
  • C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
  • C07D295/108—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
  • C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C225/14—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated
  • C07C225/16—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
  • C07C45/46—Friedel-Crafts reactions
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
  • C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
  • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
• • 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
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• This invention is related to clear photopolymerisable systems for the preparation of high thickness coatings, to a procedure for their application and to the solid surfaces coated with them.
• high thickness coating we mean a solid coating having thickness higher than 10 micron.
• the clear photopolymerisable systems of the invention include bifunctional photoinitiators of formula I:
• Riand R 2 are independently linear or branched or cyclic d-C ⁇ alkyl, or together represent C2-C-6 alkylene;
• Z1 is -NR3R4 or -OH, and
• R 3 and R 4 are independently C C ⁇ linear or branched or cyclic alkyl or C2-C6 oxaalkylene.
• Known photopolymerisable systems contains photoinitiators characterised by the presence, within the molecule of a functional group that, by electromagnetic excitation, generally UV radiation, is able to generate radicals.
• photoinitiators characterised by the presence, within the molecule of a functional group that, by electromagnetic excitation, generally UV radiation, is able to generate radicals.
• These compounds are described for example in US 3,715,293, DE 2722264, EP 161463, EP 3002, EP 88050, EP 284561, EP 192967, EP 850253 and are usually used in the polymerisation of unsaturated ethylene systems.
• In order to obtain a good polymerisation both in surface curing and in through curing it is a common practice to associate within the formulation different photoinitiators.
• Riand R 2 are independently linear or branched or cyclic Ci-C ⁇ alkyl, or together represent C 2 -C 6 alkylene; Zi is-NR 3 R4 or -OH, and R 3 and R 4 are independently d-C ⁇ linear or branched or cyclic alkyl or C2-C6 oxaalkylene, in clear photopolymerisable systems useful for the realisation of through cure systems, surprisingly show a particularly high reactivity and an improved solubility within the formulations; clear photopolymerisable systems including these compounds show a better and faster crosslinking with respect to the analogous containing diphenilsulphide derivatives.
• Clear systems including bifunctional compounds of formula I are particularly useful for the preparation of high thickness coatings, preferably having a thickness between 10 and 100 micron; they are a fundamental object of this invention.
• the preferred clear photopolymerisable systems of the present invention include as photoinitiator at least one of the following compounds of formula la, lb, lcor ld:
• Cylear photopolymerisable system and “clear photopolymerisable formulation” mean, in the present text, a mixture of reactive oligomers or monomers with at least a photoinitiator, fillers, dispersants and other additives of general use, devoid of pigments, dyes and/or opacifying agents, and dispersed solids.
• photopolymerisation is intended in a wide sense and include, for example, the polymerisation or crosslinking of polymeric materials, such as for example pre-polymers, the homopolymerisation and the copolymerisation of simple monomers and the combination of this kind of reactions.
• Monomers useful in the described system include for example : acrylonitrile, acrylamide and its derivatives, vinyl ethers, N-vinylpyrroIidone, mono and polyfunctional allyl ethers, such as for example trimethylolpropane diallylether, styrenes and alpha-methyl styrenes, esters of acrylic and methacrylic acid with alyphatic alcohols, with glycols, with polyhydroxylated compounds, as for example pentaerythritoi, trimethylolpropane or aminoalcohols, esters of vinyl alcohol with aliphatic or acrylic acids, derivatives of fumaric or maleic acids.
• the oligomers which are useful for the present invention include, for example, polyesters, polyacrylates, polyurethanes, epoxydic resins, polyethers with acrylic, maleic or fumaric functionalities.
• Compounds of formula I of the present invention acts as photoinitiators and can be used alone or in combination with other photoinitiators as for example benzophenone and its derivatives (such as methylbenzophenone, trimethylbenzophenone), acetophenone and its derivatives, for example ⁇ -hydroxyacetophenones, ⁇ - aminoacetophenones, ketosulphones (as 1 — [4-(4— benzoyl- phenylsulfanyl)-phenyl]-2-methyl-2-(toluene-4-sulfonyl)-propan-1-one), ⁇ - hydroxycycloalkylphenyl ketones, dialcoxyacetophenone, (as oligo - [2- hydroxy-2-methyl-1 -[4-(1 -methylvinyl)phenyl]-propanone], 2-hydroxy-2- methyl-1 -phenyl-propanone, 2-hydroxy-1 -[4-(2- hydroxy-ethoxy-
• thermal stabilisers for example thermal stabilisers, sensitisers, photooxydation stabilisers such as sterically hindered amines, antioxidants, oxygen inhibitors, thermal radicals generators such as organic and inorganic peroxides, peresters, hydroperoxides, benzopinacols, azoderivatives such as azaisobutyronitrile, metallic compounds such as cobalt(ll) salts, manganese, antifoam, fillers, glass and carbon fibres, thixotropic agents and other additives.
• thermal stabilisers such as sterically hindered amines, antioxidants, oxygen inhibitors, thermal radicals generators such as organic and inorganic peroxides, peresters, hydroperoxides, benzopinacols, azoderivatives such as azaisobutyronitrile, metallic compounds such as cobalt(ll) salts, manganese, antifoam, fillers, glass and carbon fibres, thixotropic agents and other additives
• photopolymerisable systems may be chemically inert non photopolymerisable polymers, as for example nitrocellulose, polyacrylic esters, polyolefines etc., or polymers which are crosslinkables with other systems, as for example with peroxides and atmospheric oxygen or acid catalysis or thermal activation, as for example polyisocyanates, urea, melamine or epoxydic resins.
• non photopolymerisable polymers as for example nitrocellulose, polyacrylic esters, polyolefines etc.
• polymers which are crosslinkables with other systems as for example with peroxides and atmospheric oxygen or acid catalysis or thermal activation, as for example polyisocyanates, urea, melamine or epoxydic resins.
• Solid substrates coated with a clear coating having a thickness between 10 and 100 microns obtained by photopolymerisation of a photopolymerisable system including at least one compound of formula la, lb, lc or Id are a further object of the invention.
• the compounds of formula I are generally used in the photopolymerisable system in quantity of 0.01 to 20% in weight, preferably of 0.5 to 5% in weight, on the total weight of the photopolymerisable system and are perfectly compatible with the system, imparting to it an increased photochemical reactivity and light stability.
• the compounds of formula I and particularly compounds la, lb, Ic and Id show an excellent solubility in the common clear photopolymerisable systems.
• the compounds of formula I are very efficient photoinitiators also in pigmented photopolymerisable systems and for example useful for the preparation of photocrosslinkable inks.
• Examples of sources of light useful for the photopolymerisation of the photopolymerisable systems prepared according to the invention are mercury vapour or superactinic or excimers lamps, with emission bands in the UV-visible region until 400 nm.
• NMR 300 MHz, CDCI 3 , ⁇ (ppm): 8.15, d, 2H; 8.07, d, 2H; 7.07, m, 4H, from 2.10 to 1.25, m, 10H; 1.65, s, 6H
• NMR 300 MHz, CDCI 3 , ⁇ (ppm): 8.6, d, 2H; 7.4, m, 2H; 7.24, m, 1 H; 7.1 , d, 2H; 6.95, d, 2H; 3.7, m, 4H; 2.6, m, 4H; 1.35, s, 6H.
• NMR 300 MHz, CDCI 3 , ⁇ (ppm): 8.65, d, 2H; 8.13, d, 2H; 7.05, m, 4H; 4.03, s, 1 H; 3.68, m, 4H; 2.57, m, 4H; 2.55, s, 6H; 1.35, s, 6H.
• NMR 300 MHz, CDCI3, ⁇ (ppm): 8.55, d, 2H; 8.25, d, 2H; 7.4, m, 4H; 3.7, m, 4H; 2.51 , m, 4H; 2.05, s, 6H; 1.35, s, 6H.
• NMR 300 MHz, CDCI3, ⁇ (ppm): 8.65, d, 2H; 8.00, d, 2H; 7.4, m, 4H; 3.95, sb, 1H; 3.68, m, 4H; 2.57, m, 4H; 1.65, s, 6H; 1.30, s, 6H.
• NMR 300 MHz, CDCI 3 , d (ppm): 8.4, d, 2H; 8.1 , d, 2H; 7.0-7.3, m, 9H; 3.22, s, 2H; 2.4, s, 6H; 2.1 , m, 1H; 1.85, m, 1H; 1.65,m, 6H; 0.70, t, 3H
• Ebecryl ® 220 hexafunctional aromatic urethane acrylate from UCB (Belgium)
• OTA 480 ® trifunctional oligomer acrylate derived from glycerol, from UCB, Belgium
• HDDA 1,6-hexanedioldiacrylate
• photoinitiators the following compounds were used: - 2-ethyl-2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyI-propionyl)-phenoxy]- phenyl ⁇ -butan-1-one (la); 2-hydroxy-1- ⁇ 4 ⁇ [4 ⁇ (1-hydroxy-cyclohexanecarbonyl)-phenoxy]-phenyl ⁇ - 2-methyl-propan-1-one (lb); 2 ⁇ hydroxy-2-methyl-1- ⁇ 4-[4-(2-methyl-2-morpholin-4-yl-propionyl)- phenoxy]-phenyl ⁇ -propan-1 -one (Ic); 2-benzyl-2-dimethylamino-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)- phenoxy]-phenyl ⁇ -butan-1 -one (Id); 1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-phenylsuIphanyl]-phenyl
• the evaluation of the photocrosslinkable systems was done by determining the reactivity, through cure, percentage of conversion and yellow and white indexes. fO0149] Reactivity.
• the photopolymerisable system is laid with a thickness of 50 microns on a varnished cardboard using a bar-coater mounted on an electric stretch-film and therefore irradiated at a distance of 26 cm from the light source.
• a Giardina® photopolymerisator was used, equipped with a medium pressure mercury lamp with a power of 80W/cm.
• the thickness of the coating after photocrosslinking is 37 micron (measured with a Minitest 3000 apparatus).
• the photopolymerisation speed measured in m/min, is the maximum possible speed that results in a perfect superficial crosslinking of the system (" tack free”); the superficial crosslinking is assumed to be perfect when the surface is not damaged with the "thumb twist test”.
• the maximum speed (expressed in m/min) that results in a surface resisting to any visible damage after rubbing with abrasive paper was also measured (superficial abrasion).
• the photopolymerisable system is laid with a thickness of 100 micron, with a bar-coater mounted on an electric stretch-film, on a glass support then irradiated at a distance of 26 cm from the light source at a speed of 10 m/min.
• a Giardina® photopolymerisator was used, equipped with a medium pressure mercury lamp with a power of 80W/cm.
• the thickness of the photopolymerisable system after crosslinking is 65 micron (measured with a Minitest 3000 apparatus)
• the photopolymerisable system is laid with a thickness of 100 microns on a varnished cardboard using a bar-coater mounted on an electric stretch- film and then is passed at a distance of 26 cm from the light source and a speed of 10 m/min.
• a Giardina® photopolymerisator was used, equipped with a medium pressure mercury lamp with a power of 80 W/cm.
• White and yellow indexes were measured according to ASTM D1925-70 standard test method. A low value of yellow index and a high value of white index, correspond to a good stability of the colour of the formulation.
• the photopolymerisable system is laid with a thickness of 3 microns on a varnished cardboard using a bar-coater mounted on an electric stretch-film and therefore irradiated at a distance of 26 cm from the light source.
• a Fusion® photopolymerisator was used, equipped with a medium pressure mercury lamp with a power of 120W/cm.
• the photopolymerisation speed measured in m/min, is the maximum possible speed that results in a perfect superficial crosslinking of the system (" tack free”); the superficial crosslinking is assumed to be perfect when the surface is not damaged with the "thumb twist test".
• the matrix for the pigmented photopolymerisable systems to be evaluated was a blue acrylic ink from Piacentini S.p.A.
• the photopolymerisable system is laid with a thickness of 12 micron using a bar-coater mounted on an electric stretch-film on a polyethylene sheet.
• An IR spectra was registered in absorbance and the peak area at 1405 cm “1 was measured, keeping as reference the area of the peak at 1725 cm -1 (Ao).
• the photopolymerisable system is then irradiated with a Fusion photopolymerisator equipped with a medium pressure mercury lamp with a power of 120W/cm at a speed of 50 m/min.

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• 2004
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