Classifications

• • 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
  • 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
  • C07C45/64—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
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/78—Separation; Purification; Stabilisation; Use of additives
  • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
• • 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

Definitions

• This invention is related to a white solid photoinitiator in the form of powder consisting of 2-hydroxy-1 - ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-phenoxy]- phenyl ⁇ -2-methyl-propan-1-one (COMPOUNDl) and to the procedure for its preparation.
• COMPOUNDl obtained through the procedure of the invention is particularly reactive as photoinitiator in photopolymerizable systems and it is easily and completely soluble in such systems in the quantities useful for the photopolymerization.
• the known photopolymerizable systems contain a photoinitiator possessing in the molecule a functional group that, by electromagnetic excitation, generally UV radiation, produces radicals able to polymerize the system.
• EP 3002 A numerous alpha-hydroxyketons are described together with their uses as photoinitiators; particularly in Example 5 the use as photoinitiator of 2-hydroxy-1 ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)- phenoxy]-phenyl ⁇ -2-methyl-propan-1-one (compound No. 21), obtained in form of wax and with boiling point of 220° C at 0.05 mmHg, is described .
• the white solid photoinitiator in the form of powder, consisting of 2-hydroxy-1- ⁇ 4-[4-(2- hydroxy-2-methyl-propionyl)-phenoxy]-phenyl ⁇ -2-methyl-propan-1-one (COMPOUNDl) and having melting point between 96° and 99°C, product not previously described in the literature.
• the product of the invention is particularly interesting when used as photoinitiator in formulations either of the transparent or pigmented kind, since it allows to obtain very good photocrosslinking rates, notably higher than those of analogous products normally used and commercially available; moreover it provides good colour stability to photopolymerized transparent systems.
• step b) reaction of 2-bromo-1 - ⁇ 4-[4-(2-bromo-2-methyl-propionyl)-phenoxy]- phenyl ⁇ -2-methyl-propan-1 -one (or of 2-chloro-1 - ⁇ 4-[4-(2-chloro-2-methyl- propionyl)-phenoxy]-phenyl ⁇ -2-methyl-propan-1-one) obtained in step a) with hydrated bases, at a temperature comprised between 10°C and 50°C, preferably between 15°C and 40°C, to give 2-hydroxy-1- ⁇ 4-[4-(2- hydroxy-2-methyl-propionyl)-phenoxy]-phenyl ⁇ -2-methyl-propan-1-one dissolved in solvent;
• step a) The Friedel Crafts reaction of step a) is performed preparing a solution of acylating agent and diphenylether, in a molar ratio comprised between 2.0 and 2.2, in dichloromethane or other solvent, as, by way of example, chlorobenzene, and then adding the Lewis acid, preferably AICI3, in portions to the solution, maintaining the temperature between -20°C and 20°C, preferably between -5°C and 5°C.
• the Lewis acid preferably AICI3
• the Friedel Crafts reaction of step a) normally includes a final quenching phase, wherein the reaction mixture is poured in diluted acidic water solution, the separation of phases and the washings of the organic phase (where the reaction product is dissolved) with water or brine; such organic phase can be used as such in step b), or after evaporation of the solvent.
• the reaction mixture of step b) can be indifferently monophasic or biphasic according to the solvent used; whenever the reaction mixture is biphasic, it is preferable to add a phase transfer catalyst such as benzyltriethylammonium chloride (BTEAC).
• BTEAC benzyltriethylammonium chloride
• step a) the solvent of step a) is evaporated before proceeding with step b) and the product of reaction of step a) is dissolved in an aliphatic alcohol miscible with water, particularly in isopropanol.
• the hydrated base commonly used in step b) is selected among NaOH, KOH or Ba(OH) 2 in aqueous solution at 20-50 % w/w; preferably the hydrated base is NaOH.
• COMPOUNDl is directly obtained by crystallization from the reaction mixture.
• COMPOUNDl can be also obtained by precipitation, filtration and drying, by adding to the residue obtained after evaporation of the solvent at the end of step b) one or more solvents selected among: ethyl acetate and toluene, both as such or in mixture with petroleum ether; isopropanol, n- propanol, ethyl alcohol or mixtures thereof, optionally in mixture with water; n-butyl alcohol; isobutyl alcohol; t-butyl alcohol.
• solvents selected among: ethyl acetate and toluene, both as such or in mixture with petroleum ether; isopropanol, n- propanol, ethyl alcohol or mixtures thereof, optionally in mixture with water; n-butyl alcohol; isobutyl alcohol; t-butyl alcohol.
• step b) when the reaction of step b) is performed in an alcohol miscible with water, such as isopropanol, 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-phenoxy]- phenyl ⁇ -2-methyl-propan-1-one is obtained as a white solid in the form of powder with a melting point between 96 and 99°C (COMPOUNDl) by the following phases: addition of from 0.5 to 2.0 parts by weight of water for every part by weight of isopropanol at the end of the reaction of step b); cooling at a temperature between 0°C and 10 °C; collecting by filtration the thus obtained precipitate; drying at a temperature comprised between 20°C and 60°C.
• an alcohol miscible with water such as isopropanol
• COMPOUNDl according to the invention is a white solid photoinitiator in the form of powder having a melting point between 96° and 99°C, it is easily soluble in the photopolymerizable systems in the quantities normally used for photopolymerization, and it mainly consists of the para- para isomer, 2-hydroxy-1 - ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-phenoxy]- phenyl ⁇ -2-methyl-propan-1-one; 300 MHz 1 H-NMR do not indicate the presence of the other isomers.
• photopolymerizable system or "photopolymerizable formulation”
• photopolymerizable formulation we mean a mixture of reactive monomers and/or oligomers, at least a photoinitiator, fillers, dispersants and other additives of general use.
• photopolymerization has a broad meaning and comprises, for example, the further polymerization or crosslinking of polymeric material, for example pre-polymers, the homo-polymerization and the copolymerization of simple monomers and the combination of these types of reactions.
• Useful monomers for photopolymerizable systems include, for example: acrylonitrile, acrylamide and derivatives thereof, vinyl ethers, N-vinylpirrolidone, mono and polyfunctional allyl ethers such as trimethylolpropanediallyl ether, styrene and alpha-methylstyrene, esters of acrylic and methacrylic acid with aliphatic alcohols, with glycols, with polyhydroxylates compounds such as pentaerythritol and trimethylolpropane or with aminoalcohols, esters of vinyl alcohol with aliphatic or acrylic acids, derivatives of fumaric and maleic acid.
• Useful oligomers for photopolymerizable systems are for example: polyesters, polyacrylates, polyurethanes, epoxidic resins, polyethers with acrylic, maleic or fumaric functionality.
• COMPOUNDl of the invention acts as photoinitiator and can be used alone or in combination with other photoinitiators such as for example benzophenone and its derivatives (such as methylbenzophenone, trimethylbenzophenone), acetophenone and its derivatives, for example alpha-hydroxyacetophenones, alpha-ami noacetophenones, di- alkoxyacetophenones, (such as oligo - [2-hydroxy-2-methyl-1-[4-(1- methylvinyl)phenyl]-propanone], 2-hydroxy-2-methyl-1-phenyl-propanone, alpha-hydroxycyclohexyl phenyl ketone, 2-hydroxy-1-[4-(2- hydroxy - ethoxy)-phenyl]-2-methyl-propan-1 -one, 2-dimethylami ⁇ o-2-(4- methylbenzyl)-1-(4-morfolin-4-yl-phenyl)-butan-1-one, 2-benzyl and its
• COMPOUNDl of the invention with tertiary amines (such as the triethylamine, N-methyldiethanolamine, esters of p- dimethylamino benzoic acid), that increase the speed of crosslinking by reducing the inhibitory effect of oxygen, is particularly advantageous.
• tertiary amines such as the triethylamine, N-methyldiethanolamine, esters of p- dimethylamino benzoic acid
• COMPOUNDl of the invention many components can be included in the photopolymerizable systems, for example thermal stabilizers, dyes or pigments, sensitisers, photooxydation stabilizers as sterically hindered amines , antioxidants, oxygen inhibitors, thermal radicals generators such as organic and inorganic peroxides, peresters, hydroperoxides, benzopinacols, azoderivatives such as azaisobutyrronitrile, metallic compounds such as cobalt(ll) salts, manganese, antifoam, fillers, glass and carbon fibres, tixotropic agents.
• thermal stabilizers such as organic and inorganic peroxides, peresters, hydroperoxides, benzopinacols, azoderivatives such as azaisobutyrronitrile, metallic compounds such as cobalt(ll) salts, manganese, antifoam, fillers, glass and carbon fibres, tixotropic agents.
• non-photopolymerizable polymers present as inactive substances, as for example nitrocellulose, polyacrylic esters, polyolefines etc., or polymers that are crosslinkable with other systems (for example with peroxides, atmospheric oxygen, acid catalysts or thermal activation) such as polyisocyanates, urea, melamine or epoxidic resins.
• COMPOUNDl of the invention is generally used in the photopolymerizable system in a quantity of 0.01 to 20% by weight, preferably of 0.5 to 5% by weight, on the total weight of the photopolymerizable system, and it is highly compatible with the system, while imparting to it an increased photochemical reactivity.
• Examples of sources of light useful for the photopolymerization of the photopolymerizable systems prepared according to the invention are mercury vapour or superactinic or excimers lamps, with emission bands in the UV-visible region.
• COMPOUNDl according to the invention acts as an efficient photoinitiator both in transparent systems and, surprisingly, in pigmented systems, and it is for instance useful for the preparation of photocrosslinkable inks, in photopolymerizable formulations for wood coating, paper, plastics, metals, in overprint coating systems, in printing inks, in varnishes, in powder coating, in the electronics, for instance for the production of printed circuits, in microelectronic and in general in all those applications in which it is useful the formation of radicals through electromagnetic radiation.
• a photo-crosslinkable system prepared by dissolution of the white solid photoinitiator in the form of powder having a melting point between 96" and 99°C and consisting of 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2- methyl-propionyl)-phenoxy]-phenyl ⁇ -2-methyl-propan
• Part of the product was crystallized from toluene, obtaining a product with a melting point of 97°-99 °C.
• Ebecryl ® 220 hexafunctional aromatic urethane acrylate from UCB (Belgium);
• OTA 480 ® trifunctional oligomer acrylate derived from glycerol, from UCB, Belgium);
• HDDA (1 ,6-hexanedioldiacrylate from UCB, Belgium);
• TMPTA trimethylolpropanetriacrylate);
• Ebecryl ® 600 epoxyacrylate from UCB, Belgium;
• Ebecryl ® 810 polyyester acrylate from UCB, Belgium);
• TPGDA tripropyleneglycoldiacrylate);
• Ebecryl ® 350 additive from UCB, Belgium
• Irgalite ® Blue BSNF from UCB (Belgium)
• Irgacure ® 184 alpha-hydroxyketone commercialised by Ciba Specialty Chemicals.
• Irgacure ® 907 aromatic aminoketone commercialised by CIBA Specialty Chemicals.
• Four formulations (I, II, III and IV) were prepared mixing respectively (% by weight): [0078] I. Ebecryl ⁇ 600 40%
• the photopolymerizable system is spread with a thickness of 50 microns on a varnished cardboard (3 microns only for the evaluation of the systems IVa and IVb) using a bar-coater and irradiated at a distance of 12 cm from the light source.
• a Fusion® photopolymerizator was used, equipped with a medium pressure mercury lamp with a power of 120W/cm.
• the photopolymerization rate measured in m/min, is the maximum possible speed at which a perfect superficial cure of the system is obtained (Tack Free). The perfect superficial cure is intended when the cured layer doesn't show to suffer damages from the "thumb twist test.”
• the maximum speed (in m/min) at which a damage of the photopolymerized system can't be seen after rubbing with abrasive paper was also measured (Superficial Abrasion); greater is the speed line, greater it is the efficiency of the system.
• the photopolymerizable system is spread with a thickness of 50 microns on a varnished cardboard using a bar-coater mounted on an electric stretch-film and therefore is passed at a distance of 12 cm from the light source at a speed of 10 m/mins.
• a Fusion® photopolymerizator was used, equipped with a medium pressure mercury lamp with a power of 120W/cm.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Physics & Mathematics (AREA)
• Medicinal Chemistry (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Health & Medical Sciences (AREA)
• Crystallography & Structural Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Polymerisation Methods In General (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Paints Or Removers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Treatments Of Macromolecular Shaped Articles (AREA)

Priority Applications (7)

Applications Claiming Priority (2)

Publications (1)

Family

ID=34509528

Family Applications (1)

Country Status (11)

Cited By (1)

Families Citing this family (13)

Citations (2)

Family Cites Families (11)

• 2003
  • 2003-10-27 IT IT000040A patent/ITVA20030040A1/it unknown
• 2004
  • 2004-10-14 AT AT04791220T patent/ATE450494T1/de not_active IP Right Cessation
  • 2004-10-14 CN CNB2004800315364A patent/CN100436394C/zh not_active Expired - Lifetime
  • 2004-10-14 US US10/577,194 patent/US7482392B2/en not_active Expired - Lifetime
  • 2004-10-14 CA CA2541993A patent/CA2541993C/en not_active Expired - Fee Related
  • 2004-10-14 JP JP2006537276A patent/JP4889496B2/ja not_active Expired - Lifetime
  • 2004-10-14 ES ES04791220T patent/ES2337691T3/es not_active Expired - Lifetime
  • 2004-10-14 DE DE602004024442T patent/DE602004024442D1/de not_active Expired - Lifetime
  • 2004-10-14 WO PCT/EP2004/052532 patent/WO2005040083A1/en not_active Ceased
  • 2004-10-14 BR BRPI0415828-8A patent/BRPI0415828B1/pt not_active IP Right Cessation
  • 2004-10-14 EP EP04791220A patent/EP1692088B1/en not_active Expired - Lifetime
• 2011
  • 2011-10-21 JP JP2011232028A patent/JP2012051927A/ja active Pending

Patent Citations (2)

Also Published As

Similar Documents

Legal Events