EP1080118A1 - Nouveaux photoamorceurs et leurs applications - Google Patents

Nouveaux photoamorceurs et leurs applications

Info

Publication number
EP1080118A1
EP1080118A1 EP99916703A EP99916703A EP1080118A1 EP 1080118 A1 EP1080118 A1 EP 1080118A1 EP 99916703 A EP99916703 A EP 99916703A EP 99916703 A EP99916703 A EP 99916703A EP 1080118 A1 EP1080118 A1 EP 1080118A1
Authority
EP
European Patent Office
Prior art keywords
photoinitiator
photoinitiators
present
radiation
admixture
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.)
Withdrawn
Application number
EP99916703A
Other languages
German (de)
English (en)
Inventor
Ronald Sinclair Nohr
John Gavin Macdonald
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.)
Kimberly Clark Worldwide Inc
Kimberly Clark Corp
Original Assignee
Kimberly Clark Worldwide Inc
Kimberly Clark 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 Kimberly Clark Worldwide Inc, Kimberly Clark Corp filed Critical Kimberly Clark Worldwide Inc
Publication of EP1080118A1 publication Critical patent/EP1080118A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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

Definitions

  • the present invention relates to a novel photoinitiators and methods for generating a reactive species using the photoinitiators.
  • the present invention further relates to methods of polymerizing or photocuring polymerizable unsaturated material using the above- mentioned photoinitiators.
  • Polymers have served essential needs in society. For many years, these needs were filled by natural polymers. More recently, synthetic polymers have played an increasingly greater role, particularly since the beginning of the 20th century. Especially useful polymers are those prepared by an addition polymerization mechanism, i.e., free radical chain polymerization of unsaturated monomers, and include, by way of example only, coatings and adhesives. In fact, the majority of commercially significant processes is based on free-radical chemistry. That is, chain polymerization is initiated by a reactive species which often is a free radical. The source of the free radicals is termed an initiator or photoinitiator. Improvements in free radical chain polymerization have focused both on the polymer being produced and the photoinitiator.
  • Whether a particular unsaturated monomer can be converted to a polymer requires structural, thermodynamic, and kinetic feasibility. Even when all three exist, kinetic feasibility is achieved in many cases only with a specific type of photoinitiator. Moreover, the photoinitiator can have a significant effect on reaction rate which, in turn, may determine the commercial success or failure of a particular polymerization process or product.
  • a free radical-generating photoinitiator may generate free radicals in several different ways. For example, the thermal, homolytic dissociation of an initiator typically directly yields two free radicals per initiator molecule.
  • a photoinitiator i.e., an initiator which absorbs light energy, may produce free radicals by either of two pathways:
  • the photoinitiator undergoes excitation by energy absorption with subsequent decomposition into one or more radicals
  • the photoinitiator undergoes excitation and the excited species interacts with a second compound (by either energy transfer or a redox reaction) to form free radicals from the latter and/or former compound(s).
  • x is an integer from 1 to 4, and R and R2 each independently
  • O N— represent H- ; ⁇ ' ; (R)2N- where R is an alkyl group having from one to six carbon atoms; a chalcone; HSO3-; and NaSC»3- .
  • the present invention is directed to photoinitiators having the following formula:
  • x is an integer from 1 to 4.
  • the present invention is directed to the above-described photoinitiators, compositions containing the same, and methods for generating a reactive species which includes providing one or more of the photoinitiators and irradiating the one or more photoinitiators.
  • One of the main advantages of the photoinitiators of the present invention is that they efficiently generate one or more reactive species under extremely low energy lamps, such as excimer lamps, as compared to prior art photoinitiators.
  • the present invention is further directed to methods of using the above-described photoinitiators to polymerize and/or photocure a polymerizable material.
  • the photoinitiators of the present invention result in rapid curing times in comparison to the curing times of prior art photoinitiators, even with relatively low output lamps.
  • the present invention includes a method of polymerizing an unsaturated monomer by exposing the unsaturated monomer to radiation in the presence of the efficacious wavelength specific photoinitiator composition described above. When an unsaturated oligomer/ monomer mixture is employed in place of the unsaturated monomer, curing is accomplished.
  • the present invention further includes a film and a method for producing a film, by drawing an admixture of unsaturated polymerizable material and one or more photoinitiators of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition.
  • the admixture may be drawn into a film on a nonwoven web or on a fiber, thereby providing a polymer-coated nonwoven web or fiber, and a method for producing the same.
  • the present invention is also directed to an adhesive composition comprising an unsaturated polymerizable material admixed with one or more photoinitiators of the present invention.
  • the present invention includes a laminated structure comprising at least two layers bonded together with the above- described adhesive composition, in which at least one layer is a nonwoven web or film. Accordingly, the present invention provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition.
  • the present invention is directed to energy-efficient reactive photoinitiators and methods for utilizing the same. More particularly, the present invention is directed to new photoinitiators having the following general formula:
  • x is an integer from 1 to 4, and Ri and R2 each independently
  • the photoinitiator comprises bis-phthaloylglycine sulfide compounds having the following formula: O O C(S) X C CH 2 O
  • x is an integer from 1 to 4.
  • the present invention also includes a method of polymerizing an unsaturated polymerizable material by exposing the unsaturated material to radiation in the presence of one or more of the photoinitiators described above. Further, the present invention is directed to a film and a method for producing a film, by drawing an admixture of unsaturated polymerizable material and one or more of the photoinitiators described above, into a film and irradiating the film with an amount of radiation sufficient to polymerize the admixture.
  • the present invention is further directed to an adhesive composition comprising an unsaturated polymerizable material admixed and one or more photoinitiators of the present invention.
  • the present invention includes a laminated structure comprising at least two layers bonded together with the above- described adhesive composition.
  • the present invention further provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition.
  • reactive species is used herein to mean any chemically reactive species including, but not limited to, free-radicals, cations, anions, nitrenes, and carbenes. Illustrated below are examples of several of such species.
  • carbenes include, for example, methylene or carbene, dichlorocarbene, diphenylcarbene, alkylcarbonylcarbenes, siloxycarbenes, and dicarbenes.
  • nitrenes include, also by way of example, nitrene, alkyl nitrenes, and aryl nitrenes. Cations (sometimes referred to as carbocations or
  • 5 carbonium ions include, by way of illustration, primary, secondary, and tertiary alkyl carbocations, such as methyl cation, ethyl cation, propyl cation, /--butyl cation, f-pentyl cation, £-hexyl cation; allylic cations; benzylic cations; aryl cations, such as triphenyl cation; cyclopropylmethyl cations; methoxymethyl cation; triarylsulphonium cations; and acyl cations.
  • primary, secondary, and tertiary alkyl carbocations such as methyl cation, ethyl cation, propyl cation, /--butyl cation, f-pentyl cation, £-hexyl cation
  • allylic cations such as methyl cation, ethyl cation, prop
  • Cations also include those formed from various metal salts, such as tetra-n-butylammonium tetrahaloaurate(III) salts; sodium tetrachloroaurate(III); vanadium tetrachloride; and silver, copper(I) and (II), and thallium(I) triflates.
  • metal salts such as tetra-n-butylammonium tetrahaloaurate(III) salts; sodium tetrachloroaurate(III); vanadium tetrachloride; and silver, copper(I) and (II), and thallium(I) triflates.
  • anions include, by way of example, alkyl anions, such as ethyl anion, npropyl anion, isobutyl anion, and neopentyl anion; cycloalkyl anions, such as cyclopropyl anion, cyclobutyl anion, and cyclopentyl anion; allylic anions; benzylic anions; aryl cations; and sulfur- or phosphorus-containing alkyl anions.
  • alkyl anions such as ethyl anion, npropyl anion, isobutyl anion, and neopentyl anion
  • cycloalkyl anions such as cyclopropyl anion, cyclobutyl anion, and cyclopentyl anion
  • allylic anions such as cyclopropyl anion, cyclobutyl anion, and cyclopentyl anion
  • benzylic anions such as
  • organometallic photoinitiators include titanocenes, fluorinated diaryltitanocenes, iron arene complexes, manganese decacarbonyl, and methyl cyclopentadienyl manganese tricarbonyl.
  • Organometallic photoinitiators generally produce free radicals or cations.
  • quantum yield is used herein to indicate the efficiency of a photochemical process. More particularly quantum yield is a measure of the probability that a particular molecule will absorb a quantum of light during its interaction with a photon. The term expresses the number of photochemical events per photon absorbed. Thus, quantum yields may vary from zero (no absorption) to 1.
  • polymerization is used herein to mean the combining, e.g. covalent bonding, of large numbers of smaller molecules, such as monomers, to form very large molecules, i.e., macromolecules or polymers.
  • the monomers may be combined to form only linear macromolecules or they may be combined to form three-dimensional macromolecules, commonly referred to as crosslinked polymers.
  • curing means the polymerization of functional oligomers and monomers, or even polymers, into a crosslinked polymer network.
  • curing is the polymerization of unsaturated monomers or oligomers in the presence of crosslinking agents.
  • unsaturated monomer “functional oligomer”
  • crosslinking agent is used herein with their usual meanings and are well understood by those having ordinary skill in the art. The singular form of each is intended to include both the singular and the plural, i.e., one or more of each respective material.
  • unsaturated polymerizable material is meant to include any unsaturated material capable of undergoing polymerization.
  • the term encompasses unsaturated monomers, oligomers, and crosslinking agents.
  • the singular form of the term is intended to include both the singular and the plural.
  • the term "fiber” as used herein denotes a threadlike structure.
  • the fibers used in the present invention may be any fibers known in the art.
  • the term "nonwoven web” as used herein denotes a web-like matter comprised of one or more overlapping or interconnected fibers in a nonwoven manner. It is to be understood that any nonwoven fibers known in the art may be used in the present invention.
  • Photoinitiators of the Present Invention The present invention is directed to new photoinitiators having the following general formula:
  • x is an integer from 1 to 4, and Ri and R2 each independently
  • O N— represent H- ; ⁇ ' ; (R)2N- where R is an alkyl group having from one to six carbon atoms; a chalcone; HSO3-; and NaS ⁇ 3- .
  • the photoinitiator comprises bis- m-morpholinobenzoyl trisulfide having the following formula:
  • the photoinitiator comprises a bis-dialkylaminobenzoyl trisulfide having the following formula:
  • the photoinitiator comprises bis-m-dimethylaminobenzoyl trisulfide having the following formula:
  • the photoinitiator comprises a water-soluble photoinitiator having the following structure:
  • the photoinitiator comprises bis-phthaloylglycine trisulfide having the following formula:
  • the photoinitiators of the present invention may be prepared by any reaction mechanism known to those of ordinary skill in the art.
  • special reagents, used to prepare the photoinitiators of the present invention are produced by reacting sulfur with a desired amount of lithium triethylborohydride to produce lithium sulfide compounds. The above-described reaction is shown by the following mechanism:
  • lithium sulfide compounds may be produced by the above- described reaction including, but not limited to, Li2S, Li2S2, and U2S3.
  • y is an integer from 1 to 4.
  • y is an integer from 1 to 4.
  • the above-described reaction results in a variety of lithium sulfide compounds wherein y varies from 1 to 3.
  • these compounds may be separated using separation techniques known to those of ordinary skill in the art if desired.
  • the lithium sulfide compounds may be further reacted with a substituted benzoyl chloride, a phthaloylglycine chloride or other carbonyl chloride compounds to produce one or more photoinitiators of the present invention.
  • a substituted benzoyl chloride a phthaloylglycine chloride or other carbonyl chloride compounds to produce one or more photoinitiators of the present invention.
  • a morpholinobenzoyl chloride is reacted with one or more lithium sulfide compounds to produce one or more morpholinobenzoyl sulfide compounds.
  • phthaloylglycine chloride is reacted with one or more lithium sulfide compounds to produce one or more phthaloylglycine sulfide compounds.
  • the resulting photoinitiators are stable at room temperature (from about 15 C to 25°C) and normal room humidity (from about 30% to 60%). However, upon exposure to radiation, the photoinitiators efficiently produce one or more free radicals.
  • the photoinitiators of the present invention have a high intensity of absorption.
  • the photoinitiators of the present invention may have a molar extinction coefficient greater than about 2,000 liters per mole per cm (1 mole " lcm " l) at an absorption maximum.
  • the photoinitiators of the present invention may have a molar extinction coefficient (absorptivity) greater than about 5,000 1 mole ' lcm ' l.
  • the photoinitiators of the present invention may have a molar extinction coefficient (absorptivity) greater than about 10,000 l mole ' lcm "1 .
  • the photoinitiators of the present invention will have a molar extinction coefficient greater than about 20,000 1 mole " 1 1 cm -1.
  • the present invention is also directed to a method of generating a reactive species.
  • the method of generating a reactive species involves generating a reactive species by exposing one or more of the above-described photoinitiators to radiation. The exposure of the photoinitiators to a radiation source triggers a photochemical process.
  • quantum yield is used herein to indicate the efficiency of a photochemical process. More particularly, quantum yield is a measure of the probability that a particular molecule (photoinitiator) will absorb a quantum of light during its interaction with a photon. The term expresses the number of photochemical events per photon absorbed. Thus, quantum yields may vary from zero (no absorption) to 1.
  • the photoinitiators of the present invention absorb photons having a specific wavelength and transfers the absorbed energy to one or more excitable portions of the molecule.
  • the excitable portion of the molecule absorbs enough energy to cause a bond breakage, which
  • the photoinitiators of the present invention desirably will have a quantum yield greater than about 0.5. More desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.6. Even more desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.7. Still more desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.8, with the most desirable quantum yield being greater than about 0.9.
  • the photoinitiators of the present invention may be employed in any situation where reactive species are required, such as for the polymerization of an unsaturated monomer and the curing of an unsaturated oligomer/ monomer mixture.
  • the unsaturated monomers and oligomers may be any of those known to one having ordinary skill in the art.
  • the polymerization and curing media also may contain other materials as desired, such as pigments, extenders, amine synergists, and such other additives as are well known to those having ordinary skill in the art.
  • examples of unsaturated monomers and oligomers include ethylene, propylene, vinyl chloride, isobutylene, styrene, isoprene, acrylonitrile, acrylic acid, methacylic acid, ethyl acrylate, methyl methacrylate, vinyl acrylate, allyl methacrylate, tripropylene glycol diacrylate, trimethylol propane ethoxylate acrylate, epoxy acrylates, such as the reaction product of a bisphenol A epoxide with acrylic acid; polyester acrylates, such as the reaction product of acrylic acid with an adipic acid/ hexanediol-based polyester, urethane acrylates, such as the reaction product of hydroxypropyl acrylate with diphenylmethane-4,4'-diisocyanate, and polybutadiene diacrylate oligomer.
  • the types of reactions that various reactive species enter into include, but are not limited to, addition reactions, including poly
  • the present invention also comprehends a method of polymerizing an unsaturated monomer by exposing the unsaturated monomer to radiation in the presence of the efficacious photoinitiators of the present invention described above.
  • an unsaturated oligomer /monomer mixture is employed in place of the unsaturated monomer, curing is accomplished.
  • the polymerizable material admixed with the photoinitiators of the present invention is to be admixed by means known in the art, and that the mixture will be irradiated with an amount of radiation sufficient to polymerize the material.
  • the amount of radiation sufficient to polymerize the material is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiators, the identity and amount of the polymerizable material, the intensity and wavelength of the radiation, and the duration of exposure to the radiation.
  • radiation exposure results in the generation of free radicals from the photoinitiators of the present invention by one or more of the following: cleavage of a sulfur-sulfur bond resulting in two sulfur-terminated free radicals; and cleavage of a carbon-sulfur bond resulting in a carbon-terminated free radical and a sulfur- terminated free radical.
  • the present invention further includes a film and a method for producing a film, by drawing an admixture of unsaturated polymerizable material and one or more photoinitiators of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition.
  • the unsaturated polymerizable material is an unsaturated oligomer /monomer mixture
  • curing is accomplished.
  • Any film thickness may be produced, as per the thickness of the admixture formed, so long as the admixture sufficiently polymerizes upon exposure to radiation.
  • the admixture may be drawn into a film on a nonwoven web or on a fiber, thereby providing a polymer-coated nonwoven web or fiber, and a method for producing the same. Any method known in the art of drawing the admixture into a film may be used in the present invention.
  • the present invention also includes an adhesive composition comprising an unsaturated polymerizable material admixed with one or more photoinitiators of the present invention.
  • the present invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition.
  • a laminate is produced wherein at least one layer is a cellulosic or polyolefin nonwoven web or film. Accordingly, the present invention provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition.
  • the adhesive is irradiated to cure the composition.
  • any layers may be used in the laminates of the present invention, on the condition that at least one of the layers allows sufficient radiation to penetrate through the layer to enable the admixture to polymerize sufficiently.
  • any cellulosic or polyolefin nonwoven web or film known in the art may be used as one of the layers so long as they allow radiation to pass through.
  • the amount of radiation sufficient to polymerize the admixture is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiator, the identity and amount of the polymerizable material, the thickness of the admixture, the identity and thickness of the layer, the intensity and wavelength of the radiation, and the duration of exposure to the radiation.
  • the radiation to which the photoinitiators of the present invention may be exposed generally will have a wavelength of from about 4 to about 1,000 nanometers.
  • the radiation may be ultraviolet radiation, including near ultraviolet and far or vacuum ultraviolet radiation; visible radiation; and near infrared radiation.
  • the radiation will have a wavelength of from about 100 to about 900 nanometers. More desirably, the radiation will have a
  • the radiation will be ultraviolet radiation having a wavelength of from about 4 to about 400 nanometers. More desirably, the radiation will have a wavelength of from about 100 to about 390 nanometers, and even more desirably will have a wavelength of from 200 to about 380 nanometers. For example, the radiation may have a wavelength of from about 222 to about 370 nanometers.
  • the radiation desirably will be incoherent, pulsed ultraviolet radiation from a dielectric barrier discharge excimer lamp or radiation from a mercury lamp.
  • Excimers are unstable excited-state molecular complexes which occur only under extreme conditions, such as those temporarily existing in special types of gas discharge.
  • Typical examples are the molecular bonds between two rare gaseous atoms or between a rare gas atom and a halogen atom.
  • Excimer complexes dissociate within less than a microsecond and, while they are dissociating, release their binding energy in the form of ultraviolet radiation.
  • the dielectric barrier excimers in general emit in the range of from about 125 nm to about 500 nm, depending upon the excimer gas mixture.
  • Dielectric barrier discharge excimer lamps (also referred to hereinafter as “excimer lamp”) are described, for example, by U.
  • Lenzburg, Switzerland, and at the present time are available from Heraeus ⁇ oblelight GmbH, Kleinostheim, Germany.
  • the excimer lamp emits incoherent, pulsed ultraviolet radiation.
  • Such radiation has a relatively narrow bandwidth, i.e., the half width is of the order of approximately 5 to 100 nanometers.
  • the radiation will have a half width of the order of approximately 5 to 50 nanometers, and more desirably will have a half width of the order of 5 to 25 nanometers. Most desirably, the half width will be of the order of approximately 5 to 15 nanometers.
  • the ultraviolet radiation emitted from an excimer lamp can be emitted in a plurality of wavelengths, wherein one or more of the wavelengths within the band are emitted at a maximum intensity. Accordingly, a plot of the wavelengths in the band against the intensity for each wavelength in the band produces a bell curve. The "half
  • width of the range of ultraviolet radiation emitted by an excimer lamp is defined as the width of the bell curve at 50% of the maximum height of the bell curve.
  • the emitted radiation of an excimer lamp is incoherent and pulsed, the frequency of the pulses being dependent upon the frequency of the alternating current power supply which typically is in the range of from about 20 to about 300 kHz.
  • An excimer lamp typically is identified or referred to by the wavelength at which the maximum intensity of the radiation occurs, which convention is followed throughout this specification and the claims.
  • excimer lamp radiation is essentially monochromatic.
  • the source of radiation used with the photoinitiators of the present invention may be any radiation source known to those of ordinary skill in the art.
  • a mercury lamp with a D-bulb which produces radiation having an emission peak of 350 nm is used to produce free radicals from the above-described photoinitiators.
  • This radiation source is particularly useful when matched with one or more photoinitiators of the present invention having an absorption maximum of 350 nanometers, corresponding to the emission peak of the mercury lamp.
  • the photoinitiators of the present invention absorbing radiation in the range of about 250 to about 350 nanometers, the photoinitiators of the present invention will generate one or more reactive species upon exposure to sunlight. Accordingly, these photoinitiators of the present invention provides a method for the generation of reactive species that does not require the presence of a special light source.
  • the photoinitiators of the present invention enable the production of adhesive and coating compositions that consumers can apply to a desired object and polymerize or cure upon exposure to sunlight. These photoinitiators also enable numerous industry applications wherein unsaturated polymerizable materials may be polymerized merely upon exposure to sunlight. Therefore, depending upon how the photoinitiator is designed, the photoinitiator of the present invention can eliminate the cost of purchasing and maintaining light sources in numerous industries wherein such light
  • the effective tuning of the photoinitiators of the present invention for a specific wavelength band permits the photoinitiators of the present invention to more efficiently utilize the target radiation in the emission spectrum of the radiating source corresponding to the "tuned" wavelength band, even though the intensity of such radiation may be much lower than, for example, radiation from a narrow band emitter, such as an excimer lamp.
  • a narrow band emitter such as an excimer lamp.
  • the photoinitiators of the present invention may be desirable to utilize a mercury lamp that emits radiation having a wavelength of approximately 350 nm with the substituted benzoyl-containing photoinitiators of the present invention.
  • the effectiveness of the photoinitiators of the present invention is not necessarily dependent upon the availability or use of a narrow wavelength band radiation source.
  • a major advantage of the photoinitiators of the present invention is that they have rapid curing times in comparison to the curing times of the prior art.
  • Another advantage of the present invention is that the photoinitiators of the present invention are highly sensitive photoinitiators and are beneficially used in situations having lower light levels.
  • the above reagents including 25 g of 3-morpholinobenzoic acid and 15.2 g of oxalyl chloride, were mixed in dioxane at 0°C under argon gas. The reaction proceeded for about 2 hours, one hour at 0°C and one hour at room temperature. The solvent was then removed under reduced pressure to yield 22.1 g of 3-morpholinobenzoyl chloride, which was used without further purification.
  • the reaction product was filtered to yield a yellow solid which was washed with water, benzene, and subsequently dried under vacuum.
  • the reaction yielded 3.4 g of bis-m-morpholinobenzoyl trisulfide.
  • the reaction HPLC showed complete reaction after about 30 minutes, yielding two products with retention times respectively of about 10 and about 15 minutes in a ratio of about 25:75.
  • the 75% peak was the bis-m-morpholinobenzoyl trisulfide solid while the 25% peak was in the filtrated liquid.
  • EXAMPLE 9 Photocuring bis-p -morpholinobenzoyl trisulfide in red ⁇ exo resin
  • a 2% wt/wt mixture of bis-p-morpholinobenzoyl trisulfide and 1.0 g of red flexo resin (Gamma Graphics) was mixed for about 5 minutes while stirring at a temperature of about 30 to 40°C.
  • a drop of the mixture was placed on a metal plate and drawn down with a 0 bar.
  • the resulting film was exposed to radiation from a medium pressure mercury lamp for approximately 0.1 seconds to fully cure the film.

Abstract

La présente invention concerne de nouveaux photoamorceurs, efficaces d'un point de vue énergétique, se présentant sous la forme de composés organiques renfermant du soufre. La présente invention concerne également un procédé permettant de produire des espèces réactives, lequel procédé consiste à exposer un ou plusieurs photoamorceurs à un rayonnement de manière à former une ou plusieurs espèces réactives. L'invention concerne aussi des procédés de polymérisation de monomères insaturés, des procédés de photopolymérisation d'un mélange oligomère/monomère insaturé, et des procédés de stratification utilisant les photoamorceurs de la présente invention.
EP99916703A 1998-04-17 1999-04-16 Nouveaux photoamorceurs et leurs applications Withdrawn EP1080118A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US8214398P 1998-04-17 1998-04-17
US82143P 1998-04-17
PCT/US1999/008527 WO1999054363A1 (fr) 1998-04-17 1999-04-16 Nouveaux photoamorceurs et leurs applications

Publications (1)

Publication Number Publication Date
EP1080118A1 true EP1080118A1 (fr) 2001-03-07

Family

ID=22169338

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99916703A Withdrawn EP1080118A1 (fr) 1998-04-17 1999-04-16 Nouveaux photoamorceurs et leurs applications

Country Status (4)

Country Link
EP (1) EP1080118A1 (fr)
JP (1) JP2002512273A (fr)
AU (1) AU3496199A (fr)
WO (1) WO1999054363A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5489616B2 (ja) * 2009-09-28 2014-05-14 富士フイルム株式会社 インク組成物及び印刷物成型体の製造方法
CA2981012A1 (fr) 2017-10-02 2019-04-02 Hydro-Quebec Polymeres et composes soufres et leur utilisation comme materiau actif d'electrode

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5442617B2 (fr) * 1974-12-28 1979-12-15
IT1187703B (it) * 1985-07-23 1987-12-23 Lamberti Fratelli Spa Benzofenoni sostituiti e loro miscele liquide,atti all'impiego come iniziatori di fotopolimerizzazione
US5230982A (en) * 1989-03-09 1993-07-27 The Mead Corporation Photoinitiator compositions containing disulfides and photohardenable compositions containing the same
US5795985A (en) * 1996-03-05 1998-08-18 Ciba Specialty Chemicals Corporation Phenyl alkyl ketone substituted by cyclic amine and a process for the preparation thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9954363A1 *

Also Published As

Publication number Publication date
AU3496199A (en) 1999-11-08
WO1999054363A1 (fr) 1999-10-28
JP2002512273A (ja) 2002-04-23

Similar Documents

Publication Publication Date Title
US5747550A (en) Method of generating a reactive species and polymerizing an unsaturated polymerizable material
US6090236A (en) Photocuring, articles made by photocuring, and compositions for use in photocuring
US5798015A (en) Method of laminating a structure with adhesive containing a photoreactor composition
CA2412607C (fr) Nouveaux photo-initiateurs et leurs applications
US5849411A (en) Polymer film, nonwoven web and fibers containing a photoreactor composition
US5739175A (en) Photoreactor composition containing an arylketoalkene wavelength-specific sensitizer
US5811199A (en) Adhesive compositions containing a photoreactor composition
EP0555058A1 (fr) Complexe d'(oxo)sulfonium, composition polymérisable le contenant et méthode de polymérisation
JP2003533548A6 (ja) 光重合開始剤であるキノイド基を含むキレート
WO2000018750A2 (fr) Nouveaux photoamorceurs et leurs utilisations
US6294698B1 (en) Photoinitiators and applications therefor
EP1080118A1 (fr) Nouveaux photoamorceurs et leurs applications
US6277897B1 (en) Photoinitiators and applications therefor
US6071979A (en) Photoreactor composition method of generating a reactive species and applications therefor
US6008268A (en) Photoreactor composition, method of generating a reactive species, and applications therefor
US6242057B1 (en) Photoreactor composition and applications therefor
MXPA00010170A (en) Novel photoinitiators and applications therefor
KR100711692B1 (ko) 광개시제로서 키노이드기를 포함하는 킬레이트
MXPA00001253A (en) Novel photoinitiators and applications therefor
MXPA01002683A (en) Novel photoinitiators and applications therefor

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20001017

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE CH DE ES FR GB IT LI NL SE

17Q First examination report despatched

Effective date: 20030724

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20031204