[go: up one dir, main page]

WO1998033764A1 - Aminobenzophenones et compositions photopolymerisables contenant de tels aminobenzophenones - Google Patents

Aminobenzophenones et compositions photopolymerisables contenant de tels aminobenzophenones Download PDF

Info

Publication number
WO1998033764A1
WO1998033764A1 PCT/US1998/001951 US9801951W WO9833764A1 WO 1998033764 A1 WO1998033764 A1 WO 1998033764A1 US 9801951 W US9801951 W US 9801951W WO 9833764 A1 WO9833764 A1 WO 9833764A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
lower alkyl
benzophenone
hydrogen
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1998/001951
Other languages
English (en)
Inventor
John Gabriel Santobianco
August John Muller
Joseph Stanton Bowers, Jr.
Rajamani Nagarajan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
First Chemical Corp
Original Assignee
First Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by First Chemical Corp filed Critical First Chemical Corp
Priority to AU61407/98A priority Critical patent/AU6140798A/en
Publication of WO1998033764A1 publication Critical patent/WO1998033764A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C07C225/22—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 carbon atoms of six-membered aromatic rings of the carbon skeleton
    • 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

  • This invention relates generally to novel photoactive compounds and methods for using the same. More particularly, this invention relates to aminobenzophenones and methods of using the same in photoactivatable polymerization systems.
  • Ethylenically unsaturated compounds, and in particular acrylate derivatives can be polymerized by irradiation with ultraviolet . light of wavelength between 200 and 450 nanometers (nm) in the presence of a bimolecular photoinitiating system.
  • the photoinitiating system can include, for example, (1) a benzophenone derivative and (2) a coinitiator or synergist, that is, a molecule which serves as a hydrogen atom donor.
  • the coinitiators or synergists are typically alcohols, tertiary amines or ethers which have available hydrogens attached to a carbon adjacent to a heteroatom.
  • Michler's Ketone 4,4'- bis (dimethylamino) benzophenone, also referred to in the art as "Michler's Ketone” .
  • Michler's Ketone has the following structure:
  • Michler's Ketone can be useful as a photoinitiator in radiation curing of polymers, it is typically used little in the industry due to its potentially hazardous characteristics.
  • 4,4' -Bis (diethylamino) benzophenone (also referred to as tetraethyl Michler's Ketone) has been proposed as a possible alternative to Michler's Ketone due to its lower toxicity.
  • this compound does not exhibit good photoinitiating activity and thus has not been widely adopted as an alternative to Michler's Ketone .
  • Other Michler's Ketone derivatives are described, for example, in U.S. Patent No. 4,507,497 to Reilly, Jr., which is directed to water soluble Michler's Ketone analogs which include amino groups substituted by R 1 COOH, in which R 1 is an alkylene group having 1 to 8 carbon atoms.
  • the objects of the present invention are achieved based on the discovery of novel compounds useful in photopolymerization systems.
  • the compounds can display highly active photoinitiation and photopolymerization properties.
  • the compounds of the invention have a structure according to Formula (I) below:
  • each A is independently selected from the group consisting of hydrogen, lower alkyl, cycloalkyl, aryl, lower alkanol, lower alkoxy, halogen, sulfonyl, alkylsulfonyl, trihaloalkyl, trihaloalkoxy, trihaloalkylthio, polymerizable moiety, and oligomeric moiety, with the proviso that no more than three A are the same lower alkyl; each R is independently selected from the group consisting of hydrogen, lower alkyl, cycloalkyl, aryl, lower alkanol, lower alkoxy, halogen, sulfonyl, alkylsulfonyl, trihaloalkyl, trihaloalkoxy, trihaloalkylthio, polymerizable moiety, and oligomeric moiety; and n is an integer from 1 to 4.
  • the present invention also provides photopolymerizable compositions which include the compounds of Formula (I) above as a component thereof, as well as methods for the manufacture of the compounds of Formula (I) and methods for the use of the compounds of Formula (I) in photopolymerization systems.
  • novel compounds of the invention include compounds according to Formula (I) below:
  • each A is independently selected from the group consisting of hydrogen, lower alkyl, cycloalkyl, aryl, lower alkanol, lower alkoxy, halogen, sulfonyl, alkylsulfonyl, trihaloalkyl, trihaloalkoxy, trihaloalkylthio, polymerizable moiety, and oligomeric moiety, with the proviso that no more than three A are the same lower alkyl ; each R is independently selected from the group consisting of hydrogen, lower alkyl, cycloalkyl, aryl, lower alkanol, halogen, lower alkoxy, sulfonyl, alkylsulfonyl, trihaloalkyl, trihaloalkoxy, trihaloalkylthio, polymerizable moiety, and oligomeric moiety; and n is an integer from 1 to 4.
  • lower alkyl refers to linear or branched C1-C8 alkyl, such as but not limited to methyl, ethyl, propyl , isopropyl, n-butyl, t -butyl, and the like, optionally substituted with one or more halogen, aryl, arylalkyl, alkylaryl, cycloalkyl, alkoxy, heteratom, and the like.
  • cycloalkyl refers to C3 to C6 cyclic alkyl, such as but not limited to cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, optionally substituted with one or more halogen, aryl, alkyl, arylalkyl, alkylaryl, cycloalkyl, alkoxy, heteratom, and the like.
  • alkanol refers to lower alkyl substituted with one or more hydroxyl groups.
  • lower alkoxy refers to lower alkyl substituted with one or more oxygen atoms, including but not limited to methoxy, ethoxy, propoxy, butoxy, and the like.
  • alkylsulfonyl refers to lower alkyl substituted with sulfonyl .
  • trihaloalkyl, trihaloalkoxy, and trihaloalkylthio refer to lower alkyl, lower alkoxy and lower alkylthio, respectively, in which hydrogen atoms on the organic group are replaced with halogen, preferably fluorine.
  • aryl refers to C3 to CIO cyclic aromatic groups such as but not limited to phenyl, naphthyl, and the like, optionally substituted with one or more halogen, alkyl, arylalkyl, alkylaryl, cycloalkyl, alkoxy, heteroatom, and the like.
  • heteroatom refers to oxygen, nitrogen, sulfur, or phosphorous.
  • polymerizable moiety refers to ethylenically unsaturated moieties known in the art which are capable of reaction with another compound (for example, by a free radical mechanism) , such as but not limited to, acrylate and methacrylate moieties.
  • A can have the structure
  • n is an integer from 1 to 10 and R is H or lower alkyl.
  • Yet another exemplary polymerizable moiety can be a maleimide moiety
  • R' is selected from the group consisting of -(CH 2 ) n -, wherein n is an integer from 0 to 10, optionally substituted with one or more heteroatom in the -CH 2 - chain; and each R" is independently selected from the group consisting of hydrogen, lower alkyl, and halogen.
  • oligomeric moiety refers to a moiety including two or more monomer units (dimer, trimer, etc.), such as but not limited to an C2-C20 alkylene or polyalkylene polyol, wherein hydroxy groups of the polyol moiety are optionally alkylated, and preferably an alkylene or polyalkylene polyol derived from ethylene glycol .
  • suitable oligomer moieties include C2-C20 alkylene or polyalkylene moieties end capped with trihaloalkyl, and optionally substituted with one or more halogen atoms along the chain, preferably fluorine.
  • Other exemplary oligomeric moieties include C2-C20 alkylene or polyalkylene moieties including carbonate groups and end capped with lower alkyl .
  • each A of the compound of formula (I) is lower alkyl, preferably methyl or ethyl, with the proviso that no more than three As are the same.
  • at least one A is lower alkyl, preferably methyl or ethyl, and at least one other A is a polymerizable moiety or an oligomeric moiety.
  • Exemplary compounds of the invention in accordance with Formula I include without limitation:
  • photopolymerizable compositions which include a compound of Formula (I) above as a photoinitiator .
  • photopolymerizable composition refers to compositions which harden or cure upon exposure to radiation.
  • the compositions of the invention include ethylenically unsaturated compounds, including monomers, oligomers, polymers, prepolymers, resinous materials, optionally dispersed or dissolved in a suitable solvent that is copolymerizable therewith, and mixtures thereof, which are photopolymerizable when exposed to a source of ultraviolet (“UV") radiation.
  • UV ultraviolet
  • the photopolymerizable compounds ' can be monofunctional, or can include two or more terminal polymerizable ethylenically unsaturated groupings per molecule.
  • Exemplary photopolymerizable compounds or precursors include, but are not limited to, reactive vinyl monomers, including acrylic monomers, such as acrylic and methacrylic acids, and their amides, esters, salts and corresponding nitriles.
  • Suitable vinyl monomers include, but are not limited to, methyl acrylate, ethyl acrylate, n- or tert-butylacrylate, isooctyl acrylate, methyl methacrylate, ethylmethacrylate, 2 -ethylhexyl methacrylate, butylacrylate, isobutyl methacrylate, the corresponding acrylates, i.e., hydroxy ethylacrylate, hydroxy propylacrylate, hydroxy ethylhexyl methacrylate, glycol acrylates, i.e., ethylene glycol dimethacrylate, hexamethylene glycol dimethacrylate, the allyl acrylates,
  • ком ⁇ онентs such as vinyl acetate, vinyl and vinylidene halides and amides, i.e., methacrylamide, acrylamide, diacetone acrylamide, butadiene, styrene, vinyl toluene, and the like are also included.
  • Prepolymers include acrylated epoxides, polyesters and polyurethanes, and are typically combined with a suitable monomer for viscosity control.
  • the photopolymerizable compounds may be polymerized to form homopolymers or copolymerized with various other monomers .
  • the photopolymerizable compound can be present in the compositions of the invention in amounts between about 99.8 and about 90 percent by weight of the composition, preferably between about 99.5 and about 95 percent by weight .
  • Formula (I) act as photopolymerization initiators.
  • the compounds of Formula (I) are ' added to the photopolymerizable compound in an amount sufficient to initiate polymerization thereof upon exposure to ultraviolet radiation.
  • the compound of Formula (I) can be one of several photoinitiators in a formulation in which the compounds of Formula (I) may act as sensitizers.
  • the compounds of Formula (I) are present in the photopolymerizable composition in an amount between about 0.2 and about 10 parts by weight of the composition, and more preferably between about 0.5 and about 5 parts by weight, depending on the specific application.
  • compositions of the invention can also include any of the various pigments or extenders, organic and inorganic, known in the art.
  • Exemplary pigments or extenders include, but are not limited to, opacifying pigments such as zinc oxide, titania, e.g., anatase and rutile; basic lead sulfate, magnesium silicate, silica, clays, wollastonite, talcs, mica, chromates, iron pigments, wood fluor, microballoons (or microspheres) , hard polymer particles, glass fiber or flake.
  • Pigments can be present in the compositions of the invention in conventional amounts, i.e., between about 1 and about 40 percent by weight.
  • a coinitiator or synergist that is, a molecule which serves as a hydrogen atom donor.
  • Coinitiators or synergists are known in the art, and are typically alcohols, tertiary amines or ethers which have available hydrogens attached to a carbon adjacent to a heteroatom.
  • Such co-initiators are typically present in an amount between about 0 ' .2 and about 25 percent by weight.
  • Suitable compounds include triethanolamine, methyl-diethanolamine, ethyldiethanolamine and esters of dimethylamino benzoic acid. These compounds behave as co-initiators or accelerators for the primary photoinitiators and can increase the efficiency and speed of the polymerization process.
  • compositions of the present invention may contain polymerization inhibitors, fillers, ultraviolet absorbers and organic peroxides.
  • the compositions of the invention can be applied or deposited to a surface of a substrate using conventional techniques and apparatus.
  • the composition can be applied as a substantially continuous film; alternatively, the composition can be applied in a discontinuous pattern.
  • the compositions of the invention are fluid at ordinary operating temperatures (between ambient and up to about 60°C) .
  • the thickness of the deposited composition can vary, depending upon the desired thickness of the resultant cured product.
  • the composition is applied to the substrate surface in an amount sufficient to provide a cured coating having a thickness between about 1 micron and about 250 mils.
  • the substrate is coated with the uncured photopolymerizable composition and passed under an ultraviolet providing light beam by a conveyer moving at predetermined speeds .
  • the substrate to be coated can be, for example, metal, mineral, glass, paper, plastic, fabric, ceramic, and the like.
  • the active energy beams used in accordance with the present invention may be ultraviolet light or may contain in their spectra both visible and ultraviolet light.
  • the polymerization may be activated by irradiating the composition with ultraviolet light using any of the techniques known in the art for providing ultraviolet radiation, i.e., in the range of about 200 nm and about 450 nm ultraviolet radiation.
  • the radiation may be natural or artificial, monochromatic or polychromatic, incoherent or coherent and should be sufficiently intense to activate the photoinitiators of the invention and thus the polymerization.
  • Conventional radiation sources include fluorescent lamps, mercury, metal additive and arc lamps.
  • Coherent light sources are the pulsed nitrogen, xenon, argon ion- and ionized neon lasers whose emissions fall within or overlap the ultraviolet or visible absorption bands of the compounds of the invention.
  • the composition including the compounds of the invention is exposed to ultraviolet radiation having a wavelength of about 200 to about 450 nm.
  • compositions of the invention When polymerized by exposure to UV radiation, the compositions of the invention give a substantially tack- free product which is durable for ordinary handling.
  • the compositions of the invention are useful in any of the types of applications known in the art for photopolymerizations, including as a binder for solids to yield a cured product in the nature of a paint, varnish, enamel, lacquer, stain or ink.
  • the compositions are particularly useful in the production of photopolymerizable surface coatings in printing processes, such as lithographic printing, screen printing, and the like.
  • the compounds of the invention can be prepared from an aniline compound which may be substituted at any position, preferably at any position except the 4 position.
  • the nitrogen atom of the aniline can be substituted using techniques known in the art .
  • the aniline can be alkylated using known techniques.
  • the aniline may be converted to an N-ethylaniline by reductive alkylation with acetaldehyde by methods reviewed by Rylander in "Catalytic Hydrogenation over Platinum Metals.”
  • the N-ethylaniline may be converted to an N-ethyl, N-methylaniline by subsequent reductive alkylation with formaldehyde.
  • These N-alkylations may also be performed with alcohol reagents by methods known in the art.
  • the order of the N-alkylations may also be reversed in order to firstly form the N-methyl and secondly form the N-ethyl, N-methyl intermediate.
  • the N-ethyl, N-methylaniline may be converted to the
  • the nitrogen atoms can alternatively be hydroxylated as known in the art, or one can start with hydroxy substituted aniline compounds, such as N-alkyl, N 1 -hydroxyalkyl anilines, commercially available, for example, from First Chemical Corporation.
  • the hydroxyl functionality is reacted with suitable reagents as known in the art to provide the desired functionality.
  • a hydroxyl functionality can be reacted with a sulfonyl halide to provide sulfonyl groups.
  • a hydroxyl functionality can alternatively be reacted with acryloyl halide to provide an acrylate group.
  • compounds having at least one maleimide unit can be prepared according to techniques known in the art .
  • a suitably substituted aromatic amine can be reacted with maleic anhydride (or a substituted maleic anhydride, such as citraconic anhydride) in a polar solvent to provide the amic acid.
  • maleic anhydride or a substituted maleic anhydride, such as citraconic anhydride
  • a polar solvent to provide the amic acid.
  • an acid catalyzed ring closure to form the imide .
  • Compounds having maleimide functional groups are described in pending U.S. Provisional Application Serial No. 60/047,729, pending U.S. Application Serial No. 08/917,024, Z.Y. Wang, Synthetic Comm. 20(11) 1607- 1610 (1990); P.O. Tawnet et al .
  • Other compounds which can be converted to a benzophenone include, but are not limited to, N-ethyl-m-toluidine, o-toluidine, m-toluidine, 3-propylaniline, 2, 3-dimethylaniline, 2 , 5-dimethylaniline, 2 , 6-dimethylaniline,
  • Ethyl-aniline is methylated by reductive alkylation with formaldehyde using isopropyl alcohol as a solvent at 100°C under 120 psi of H 2 . After the solvent is stripped the product ethylmethylaniline (NEMA) is purified by distillation at 120°C at a pressure of 21 mm mercury (Hg) . NEMA (80 g, 0.59 mol) is charged to a vessel fitted with a dry-ice condenser and is heated to 50-60°C. Phosgene is transferred from a cylinder to a calibrated trap placed in dry-ice.
  • the trap was connected to the vessel containing NEMA and the phosgene was added over 1 hour. After the addition was complete, the mixture was heated to 120°C and held at this temperature for 1 hour. The mixture was cooled to 50-60°C before 11 g (0.275 mol) of NaOH dissolved in 100 mL of water was added to hydrolyze the unreacted acid chloride. The resulting mixture was then extracted with two 100 mL portions of toluene.
  • Michler's Ketone also tetramethyl Michler's Ketone or TMMK
  • TMMK tetramethyl Michler's Ketone
  • tetraethyl Michler's Ketone also tetraethyl Michler's Ketone
  • the composition included 1% by weight isopropylthioxanthone, 2% ethyl 4-N,N- dimethylaminobenzoate, 4% benzophenone, 1% aminobenzophenone compound, and the balance hexanediol diacrylate.
  • the composition was applied as a 0.15 inch film to a substrate and cured with a Fusion UV Systems "H" bulb with 600 Watts/inch power with a belt speed of 55 feet per minute.
  • MEAB and TMMK both required 10 passes under the lamp to obtain a well-cured hard polymer, and TEMK required 25 passes. This illustrates that MEAB and TMMK have approximately the same activity, and both are much superior to the tetraethyl compound.
  • Michler's ketone is listed by the National Toxicology Program as "reasonably anticipated to be a carcinogen" based on the results of cancer studies in rats and mice. Seventh Annual Report on Carcinogens, U.S. Dept. Health Human Services, p. 259, 1994. Based on comparisons of mutagenicity studies with animal cancer studies, mutagens are more likely to cause cancer, to produce tumors in multiple organs, and to affect multiple species. Gold, L.S. et al . , Mutat . Res. 286, 75-100 (1993) .
  • Mutagenicity can be measured by a variety of assays .
  • the most commonly used method is the Salmonella/Mammalian-Microsome Reverse Mutation Assay (Ames Test) , which commonly uses four or five strains of Salmonella bacteria to detect different types of mutations .
  • Ames Test Salmonella/Mammalian-Microsome Reverse Mutation Assay
  • TMMK, TEMK, and MEAB were evaluated for the ability to induce reverse mutations at the histidine locus in the genome of a specific Salmonella typhimurium tester strain in the presence of an exogenous metabolic activation system of mammalian microsomal enzymes derived from AroclorTM-induced rat liver (S9) .
  • the tester strain used in the mutagenicity assay was Salmonella typhimurium tester strain TA98 with added activation.
  • the assay was conducted using eight doses of the test article, along with the appropriate vehicle and positive controls in the presence of S9 mix (S9 homogenate was purchased from Molecular Toxicology, Inc., Annapolis, MD 21401, Batch 0646, 43.4 mg of protein per ml) . Positive controls were also plated in the absence of S9 mix. All doses of test article, vehicle, and positive controls were plated in triplicate.
  • test article TMMK was stored at room temperature.
  • Acetone (CAS# 67-64-1, Fisher Scientific Co., Lot 961140) was used as the vehicle.
  • the test article formed a clear, light yellow solution.
  • the test article remained a solution in all succeeding dilutions prepared for the mutagenicity assay.
  • the maximum aliquot of acetone which can be used in the test system is 200 ⁇ l .
  • the maximum concentration which could be tested was 4,000 ⁇ g per plate.
  • the test article and vehicle controls were plated using a 200 ⁇ l plating aliquot. Positive control articles were plated using 50 ⁇ l plating aliquot.
  • test article TEMK was stored at room temperature. Acetone (CAS# 67-64-1, Fisher Scientific Co., Lot 961140) was used as the vehicle. At 100 mg per ml, which was the most concentrated stock solution prepared, the test article formed a clear, yellow solution. The test article remained a solution in all succeeding dilutions prepared for the mutagenicity assay.
  • the test article, vehicle controls and positive control articles were plated using a 50 ⁇ l plating aliquot .
  • test article MEAB was stored at room temperature. Acetone (CAS# 67-64-1, Fisher Scientific Co., Lot 961140) was used as the vehicle. At 25 mg per ml, which was the most concentrated stock solution prepared, the test article formed a clear, light yellow solution. The test article remained a solution in all succeeding dilutions prepared for the mutagenicity assay.
  • the test article and vehicle controls were plated using a 200 ⁇ l plating aliquot. Positive control articles were plated using a 50 ⁇ l plating aliquot .
  • the mutagenicity assay results for TMMK, TEMK, and MEAB are presented in Table 1.
  • the data are presented as individual plate counts along with a mean and standard deviation.
  • TMMK was mutagenic.
  • aromatic amino or nitro compounds such as these test materials, very few which were not mutagenic in the Ames test have been found to cause tumors in animal cancer studies.
  • Ashby, J. and Tennant, R.W. Mutat. Res. 257, 229-306 (1991). Therefore, these results suggest that MEAB has a lower potential to cause tumors than TMMK.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne des dérivés benzophénones et des procédés de fabrication et d'utilisation de tels benzophénones. Les composés de l'invention présentent des propriétés caractérisées par une grande activité de photoamorçage et de photopolymérisation.
PCT/US1998/001951 1997-02-04 1998-02-03 Aminobenzophenones et compositions photopolymerisables contenant de tels aminobenzophenones Ceased WO1998033764A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU61407/98A AU6140798A (en) 1997-02-04 1998-02-03 Aminobenzophenones and photopolymerizable compositions including same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US3715597P 1997-02-04 1997-02-04
US60/037,155 1997-02-04

Publications (1)

Publication Number Publication Date
WO1998033764A1 true WO1998033764A1 (fr) 1998-08-06

Family

ID=21892737

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/001951 Ceased WO1998033764A1 (fr) 1997-02-04 1998-02-03 Aminobenzophenones et compositions photopolymerisables contenant de tels aminobenzophenones

Country Status (2)

Country Link
AU (1) AU6140798A (fr)
WO (1) WO1998033764A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9212160B2 (en) 2010-11-12 2015-12-15 Coloplast A/S Photoinitiators
US9353211B2 (en) 2012-05-16 2016-05-31 Coloplast A/S Polymeric photoinitiators and photoinitiator monomers

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2729918A1 (de) * 1977-07-02 1979-01-18 Basf Ag 4,4'-diaminodiphenylmethanderivate
JPS59204850A (ja) * 1983-05-09 1984-11-20 Sumitomo Chem Co Ltd 静電荷像現像用トナ−
US4507497A (en) * 1983-03-03 1985-03-26 Minnesota Mining And Manufacturing Company Water soluble michlers ketone analogs
JPS6281403A (ja) * 1985-10-04 1987-04-14 Nippon Oil & Fats Co Ltd 光重合開始剤組成物
DE3606155A1 (de) * 1986-02-26 1987-08-27 Basf Ag Photopolymerisierbares gemisch, dieses enthaltendes lichtempfindliches aufzeichnungselement sowie verfahren zur herstellung einer flachdruckform mittels dieses lichtempfindlichen aufzeichnungselements
JPS62257969A (ja) * 1986-05-01 1987-11-10 Yamada Chem Co Ltd ジビニル化合物及びそれを使用した発色性記録材料
US5229238A (en) * 1990-04-27 1993-07-20 Takasago International Corporation Electrophotographic photoreceptor comprising a benzodithiafulvene derivative charge transport material
DE4303938A1 (en) * 1992-02-12 1993-08-19 Fuji Electric Co Ltd Electrophotographic photoconductor contg. bis:di:substd.-amino-phenyl cpd. - used as charge transport cpd. in laminated or mono:layer material giving high sensitivity and fatigue resistance
JPH06211759A (ja) * 1993-01-18 1994-08-02 Fuji Photo Film Co Ltd ４，４’−ジアミノベンゾフェノン誘導体
JPH06211758A (ja) * 1993-01-18 1994-08-02 Fuji Photo Film Co Ltd ベンゾフェノン誘導体
US5378519A (en) * 1992-04-28 1995-01-03 Canon Kabushiki Kaisha Electroluminescent device
US5428163A (en) * 1986-12-31 1995-06-27 Mills; Randell L. Prodrugs for selective drug delivery
JPH07325391A (ja) * 1994-05-31 1995-12-12 New Oji Paper Co Ltd 可視光反応性樹脂組成物およびそれを用いたシート状光記録材料

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2729918A1 (de) * 1977-07-02 1979-01-18 Basf Ag 4,4'-diaminodiphenylmethanderivate
US4507497A (en) * 1983-03-03 1985-03-26 Minnesota Mining And Manufacturing Company Water soluble michlers ketone analogs
JPS59204850A (ja) * 1983-05-09 1984-11-20 Sumitomo Chem Co Ltd 静電荷像現像用トナ−
JPS6281403A (ja) * 1985-10-04 1987-04-14 Nippon Oil & Fats Co Ltd 光重合開始剤組成物
DE3606155A1 (de) * 1986-02-26 1987-08-27 Basf Ag Photopolymerisierbares gemisch, dieses enthaltendes lichtempfindliches aufzeichnungselement sowie verfahren zur herstellung einer flachdruckform mittels dieses lichtempfindlichen aufzeichnungselements
JPS62257969A (ja) * 1986-05-01 1987-11-10 Yamada Chem Co Ltd ジビニル化合物及びそれを使用した発色性記録材料
US5428163A (en) * 1986-12-31 1995-06-27 Mills; Randell L. Prodrugs for selective drug delivery
US5229238A (en) * 1990-04-27 1993-07-20 Takasago International Corporation Electrophotographic photoreceptor comprising a benzodithiafulvene derivative charge transport material
DE4303938A1 (en) * 1992-02-12 1993-08-19 Fuji Electric Co Ltd Electrophotographic photoconductor contg. bis:di:substd.-amino-phenyl cpd. - used as charge transport cpd. in laminated or mono:layer material giving high sensitivity and fatigue resistance
US5378519A (en) * 1992-04-28 1995-01-03 Canon Kabushiki Kaisha Electroluminescent device
JPH06211759A (ja) * 1993-01-18 1994-08-02 Fuji Photo Film Co Ltd ４，４’−ジアミノベンゾフェノン誘導体
JPH06211758A (ja) * 1993-01-18 1994-08-02 Fuji Photo Film Co Ltd ベンゾフェノン誘導体
JPH07325391A (ja) * 1994-05-31 1995-12-12 New Oji Paper Co Ltd 可視光反応性樹脂組成物およびそれを用いたシート状光記録材料

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8501, Derwent World Patents Index; Class A89, AN 85-004014, XP002066202 *
DATABASE WPI Section Ch Week 9435, Derwent World Patents Index; Class A41, AN 94-283313, XP002066201 *
DATABASE WPI Section Ch Week 9435, Derwent World Patents Index; Class E13, AN 94-283314, XP002066200 *
DATABASE WPI Section Ch Week 9607, Derwent World Patents Index; Class A89, AN 96-066076, XP002066203 *
LESLIE HELLERMAN ET AL.: "Syntheses of Certain Derivatives of Phenylalanine and of Auramine in Studies of Antimalarial Action", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 68, no. 10, 17 October 1946 (1946-10-17), DC US, pages 1890 - 1893, XP002066198 *
PATENT ABSTRACTS OF JAPAN vol. 011, no. 282 (C - 446) 11 September 1987 (1987-09-11) *
PATENT ABSTRACTS OF JAPAN vol. 012, no. 143 (C - 492) 30 April 1988 (1988-04-30) *
ULF PINDUR ET AL.: "[4+2]Cycloaddition of Indole Derivatives with Bismaleimides: a Route to New Biscarbazoles", JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1, no. 12, 21 June 1997 (1997-06-21), LETCHWORTH GB, pages 1861 - 1867, XP002066199 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9212160B2 (en) 2010-11-12 2015-12-15 Coloplast A/S Photoinitiators
US9353211B2 (en) 2012-05-16 2016-05-31 Coloplast A/S Polymeric photoinitiators and photoinitiator monomers

Also Published As

Publication number Publication date
AU6140798A (en) 1998-08-25

Similar Documents

Publication Publication Date Title
US7709545B2 (en) Benzophenone/thioxanthone derivatives and their use in photopolymerizable compositions
US5837746A (en) Coreactive photoinitiators
KR100698799B1 (ko) 신규한 광개시제 및 블록 공중합체
US6855745B2 (en) Polymerization processes using aliphatic maleimides
JP2518592B2 (ja) 新規芳香族アミノケトンおよびそれよりなるエチレン性不飽和化合物の光重合のための光開始剤
US5145885A (en) Photopolymerizable compositions containing aminoaryl ketone photoinitiators
JPH0635427B2 (ja) 光硬化性着色組成物のための光開始剤
US6048667A (en) Heterogeneous photo-initiators, photopolymerizable compositions and their use
JPH0429681B2 (fr)
JPH10291969A (ja) 新規α−アミノアセトフェノン光開始剤
PL149572B2 (en) Photopolymerizing compound
US6153662A (en) Aromatic maleimides and methods of using the same
JP2012051927A (ja) 粉末の形態での白色固体光開始剤およびその製造
US6797841B2 (en) Aminobenzophenones and photopolymerizable compositions including the same
WO2007092935A1 (fr) Hydroxyalkylaminoalkylthioxanthones
WO1998033764A1 (fr) Aminobenzophenones et compositions photopolymerisables contenant de tels aminobenzophenones
SK4172001A3 (en) Chelates comprising chinoid groups as photoinitiators
WO1988007042A1 (fr) Derives d'acridine substituee et leur utilisation
US20040235976A1 (en) Polymerization processes using alphatic maleimides
JP2724624B2 (ja) 紫外線硬化性樹脂組成物、インキ組成物及びそれらの硬化物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AT AU AZ BA BB BG BR BY CA CH CN CU CZ CZ DE DE DK DK EE EE ES FI FI GB GE GH GM GW HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SK SL TJ TM TR TT UA UG US UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 1998533169

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase