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WO2011069947A1 - Photoinitiateurs pour compositions durcissables par del uv et encres - Google Patents

Photoinitiateurs pour compositions durcissables par del uv et encres Download PDF

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Publication number
WO2011069947A1
WO2011069947A1 PCT/EP2010/068940 EP2010068940W WO2011069947A1 WO 2011069947 A1 WO2011069947 A1 WO 2011069947A1 EP 2010068940 W EP2010068940 W EP 2010068940W WO 2011069947 A1 WO2011069947 A1 WO 2011069947A1
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WIPO (PCT)
Prior art keywords
group
photoinitiator
hydrogen
radiation curable
formula
Prior art date
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Ceased
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PCT/EP2010/068940
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English (en)
Inventor
Johan Loccufier
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.)
Agfa Gevaert NV
Agfa Gevaert AG
Original Assignee
Agfa Gevaert NV
Agfa Gevaert AG
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Application filed by Agfa Gevaert NV, Agfa Gevaert AG filed Critical Agfa Gevaert NV
Priority to EP10790390.8A priority Critical patent/EP2509948B1/fr
Priority to CA2780036A priority patent/CA2780036C/fr
Priority to BR112012013779-4A priority patent/BR112012013779B1/pt
Priority to AU2010330044A priority patent/AU2010330044B2/en
Priority to CN201080055158.9A priority patent/CN102639501B/zh
Priority to US13/511,375 priority patent/US8957224B2/en
Publication of WO2011069947A1 publication Critical patent/WO2011069947A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • 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

  • the present invention relates to a new class of photoinitiators, especially suited for UV LED curable compositions.
  • Photoinitiators are frequently used in polymerizable compositions, such as UV-curable inks, to initiate the polymerization of monomers when exposed to UV radiation.
  • Bathochromic photoinitiators absorbing in the region between 365 nm and 395 nm, are required to make full use of the recent development of UV-LEDs with increasing power.
  • Thioxanthones and acyl phosphine oxides are photoinitiators absorbing in this spectral region.
  • Thioxanthones are prone to yellowing upon exposure, thereby forming degradation products with a limited stability. As a result, the original yellowing shifts upon storage. Especially in imaging, e.g. inkjet printing, this unstable yellowing behaviour makes control of the image tone in the final image difficult. On top of that, certain applications, predominantly packaging applications, prefer thioxanthone free radiation curable compositions.
  • Bis-keto-carbazoles have been disclosed in photochemical applications as sensitizers for acyl oxime and oxime based photoinitiators in negative resist application (JP 2007219362 (TOYO INK) ) and radiation curable applications JP 2007112930 (TOYO INK) and JP 2005187678 (TOYO INK) ). They have further been disclosed as sensitizing agents for cationic radiation curable formulations in US 2005113483 (KONICA) , JP
  • a specific carbazole based photoinitiator provided radiation curable compositions with high curing speed upon exposure to UV radiation in the range between 365 nm and 395 nm.
  • alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1 ,1 -dimethyl-propyl, 2,2-dimethylpropyl and 2- methyl-butyl etc.
  • substituted in, for example substituted alkyl, means that the substituent contains at least one atom different from carbon or hydrogen.
  • the substituent may be a single atom (e.g. a halogen) or a group of atoms containing at least one atom different from carbon or hydrogen (e.g. an acrylate group).
  • a photoinitiator according to present invention has as chemical structure the Fo
  • R1 selected from the group consisting of a group according to S1 ,-CN, - COR4 and a group, according to Formula (II):
  • R3 is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkaryl group and a
  • R4 is selected from the group consisting of a hydrogen a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynynl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkaryl group, a substituted or unsubstituted aryl or heteroaryl group and W-R6;
  • Q and X independently represent O or N-R7;
  • W,V and Y independently represent O or N-R8;
  • R6 and R8 independently are selected from the group consisting of hydrogen a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkaryl group and a substituted or unsubstituted aryl or heteroaryl group;
  • R7 is selected from the group consisting a hydrogen a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkaryl group, a substituted or unsubstituted aryl or heteroaryl group and O-R9;
  • R9 is selected from the group consisting of hydrogen a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkaryl group, a substituted or unsubstituted aryl or heteroaryl group and an acyl group;
  • n and m independently represent an integer from 1 to 3;
  • R1 to R3 comprizes a branched, substituted or unsusbtituted alkyl, alkenyl, alkynyl, aralkyl or alkaryl group.
  • R1 is selected from the group consisting of hydrogen, -COR4 and a functional group according to Formula (II).
  • Q an X represent O.
  • Si and S 2 represent hydrogen.
  • R3 represents a branched alkyl group.
  • the photoinitiator is a diffusion hindered photoinitiator selected from the group consisting of a polymerisable photoinitiator, a multifunctional photoinitiator and a polymeric or an oligomeric photoinitiator.
  • Preferred polymeric photoinitiators, according to the present invention are selected from the group consisting of star polymers, dendritic polymers and hyperbranched polymers, polyesters and polyethers being particularly preferred.
  • R1 , R3, Si, S 2 , n and m are defined as for Formula (I);
  • L is a divalent linking group comprising 1 to 15 carbon atoms
  • R10 represents a hydrogen or a C1 to C4 alkyl group, a hydrogen and a methyl group being particularly preferred and a hydrogen being most preferred.
  • Suitable examples of photoinitiators according to Formula (I) are given by Table 1 , without being limited thereto.
  • n par cu ar or oo pac ag ng app ca ons, e photoinitiator is preferably a so-called diffusion hindered photoinitiator.
  • a diffusion hindered photoinitiator is a photoinitiator which exhibits a much lower mobility in a cured layer of the curable liquid or ink than a
  • monofunctional photoinitiator such as benzopnenone.
  • Several methods can be used to lower the mobility of the photoinitiator.
  • One way is to increase the molecular weight of the photoinitiator so that the diffusion speed is reduced, e.g. polymeric photoinitiators.
  • Another way is to increase its reactivity so that it is built into the polymerizing network, e.g. multifunctional photoinitiators and polymerizable photoinitiators.
  • the diffusion hindered photoinitiator is preferably selected from the group consisting of non-polymeric multifunctional photoinitiators, polymeric photoinitiators and polymerizable photoinitiators.
  • multifunctional photoinitiators are considered to have a molecular weight between 300 and 900 Dalton.
  • Non-polymerizable monofunctional photoinitiators with a molecular weight in that range are not diffusion hindered photoinitiators. Most preferably the diffusion hindered
  • photoinitiator is a polymerizable initiator.
  • Suitable polymerizable photoinitiators according to Formula (I) are given in Table 1 by the photoinitiators INI-12 to INI-16.
  • a preferred amount of photoinitiator is 0.1 - 50 wt%, more preferably 0.1 - 20 wt%, and most preferably 0.3 - 15 wt% of the total weight of the curable pigment dispersion or ink.
  • the photoinitiators according to the present invention can be any photoinitiators according to the present invention.
  • the radiation curable composition is a radiation curable inkjet ink, especially an inkjet ink curable by UV LEDs emitting at in the spectral region of 365 nm to 395 nm. Due to their compactness, UV LEDs can be built into inkjet printers more easily than other UV light sources such as doped mercury lamps.
  • the radiation curable inkjet ink is part of an inkjet ink set, preferably an inkjet ink set including two or more inkjet inks in accordance with the invention.
  • the radiation curable inkjet ink form preferably part of a CMY(K) inkjet ink set.
  • the CMY(K) inkjet ink set may also be extended with extra inks such as red, green, blue, violet and/or orange to further enlarge the colour gamut of the image.
  • the CMY(K) ink set may also be extended by the combination of full density and light density inks of both colour inks and/or black inks to improve the image quality by lowered graininess.
  • the inkjet ink can be advantageously used in an inkjet printing method comprising the steps: a) providing a radiation curable inkjet ink according to the present invention.
  • the radiation curable composition according to the present invention may further also contain at least one surfactant to control the homogenous spreading of the pigment dispersion on a substrate.
  • the surfactant is important to control the dot size of the ink droplet on a substrate.
  • the viscosity of a radiation curable inkjet ink is preferably lower than 30 mPa.s, more preferably lower than 15 mPa.s, and most preferably between 2 and 10 mPa.s at a shear rate of 100 s "1 and a jetting
  • the radiation curable composition according to the present invention is preferably prepared according to a method comprising the steps of:
  • composition b) adding to said composition at least one co-initiator selected from the group consisting of an aliphatic tertiary amine and a dialkyl aniline derivative; and at least one photoinitiator according to Formula (I).
  • co-initiator selected from the group consisting of an aliphatic tertiary amine and a dialkyl aniline derivative; and at least one photoinitiator according to Formula (I).
  • composition contains a co-initiator.
  • co-initiators can be categorized in 3 groups:
  • aromatic amines such as amylparadimethylaminobenzoate, 2-n- butoxyethyl-4-(dimethylamino) benzoate, 2-(dimethylamino)ethylbenzoate, ethyl-4-(dimethylamino)benzoate, and 2-ethylhexyl-4- (dimethylamino)benzoate; and
  • (meth)acrylated amines such as dialkylamino alkyl(meth)acrylates (e.g., diethylaminoethylacrylate) or N-morpholinoalkyl-(meth)acrylates (e.g., N-morpholinoethyl-acrylate).
  • dialkylamino alkyl(meth)acrylates e.g., diethylaminoethylacrylate
  • N-morpholinoalkyl-(meth)acrylates e.g., N-morpholinoethyl-acrylate
  • the preferred co-initiators are aminobenzoates.
  • composition according to the present invention are preferably diffusion hindered for safety reasons, in particular for food packaging applications.
  • a diffusion hindered co-initiator is preferably selected from the group
  • the diffusion hindered co-initiator is selected from the group consisting of polymeric co-initiators and polymerizable co-initiators. Most preferably the diffusion hindered co-initiator is a polymerizable co-initiator having at least one (meth)acrylate group, more preferably having at least one acrylate group.
  • Preferred diffusion hindered co-initiators are the polymerizable co-initiators disclosed in EP 2053101 A (AGFA GRAPHICS) in paragraphs [0088] and [0097].
  • Preferred diffusion hindered co-initiators include a polymeric co-initiator having a dendritic polymeric architecture, more preferably a hyperbranched polymeric architecture.
  • Preferred hyperbranched polymeric co-initiators are those disclosed in US 2006014848 (AGFA) incorporated herein as a specific reference.
  • the curable pigment dispersion or ink preferably comprises the diffusion hindered co-initiator in an amount of 0.1 to 50 wt%, more preferably in an amount of 0.5 to 25 wt%, most preferably in an amount of 1 to 10 wt% of the total weight of the ink.
  • the monomers and oligomers used in radiation curable compositions and inks, especially for food packaging applications are preferably purified compounds having no or almost no impurities, more particularly no toxic or carcinogenic impurities.
  • the impurities are usually derivative compounds obtained during synthesis of the polymerizable compound. Sometimes, however, some compounds may be added deliberately to pure
  • Any monomer or oligomer capable of free radical polymerization may be used as polymerizable compound.
  • a combination of monomers, oligomers and/or prepolymers may also be used.
  • the monomers, oligomers and/or prepolymers may possess different degrees of functionality, and a mixture including combinations of mono-, di-, tri-and higher functionality
  • the viscosity of the radiation curable compositions and inks can be adjusted by varying the ratio between the monomers and oligomers.
  • Particularly preferred monomers and oligomers are those listed in [0106] to [01 15] in EP 1911814 A (AGFA GRAPHICS) incorporated herein as a specific reference.
  • a preferred class of monomers and oligomers are vinyl ether acrylates such as those described in US 6310115 (AGFA) , incorporated herein by reference. Particularly preferred compounds are 2- (2-vinyloxyethoxy)ethyl (meth)acrylate, most preferably the compound is 2- (2-vinyloxyethoxy)ethyl acrylate.
  • Colorants used in the radiation curable compositions and inks may be any colorants used in the radiation curable compositions and inks.
  • the colorant is preferably a pigment or a
  • polymeric dye most preferably a pigment.
  • the pigments may be black, white, cyan, magenta, yellow, red, orange, violet, blue, green, brown, mixtures thereof, and the like.
  • This colour pigment may be chosen from those disclosed by HERBST, Willy, et al. Industrial Organic Pigments, Production, Properties, Applications. 3rd edition. Wiley - VCH , 2004. ISBN 3527305769.
  • Suitable pigments include mixed crystals of the above particular preferred pigments.
  • Mixed crystals are also referred to as solid solutions.
  • different quinacridones mix with each other to form solid solutions, which are quite different from both physical mixtures of the compounds and from the compounds themselves.
  • the molecules of the components enter into the same crystal lattice, usually, but not always, that of one of the components.
  • the x-ray diffraction pattern of the resulting crystalline solid is characteristic of that solid and can be clearly differentiated from the pattern of a physical mixture of the same components in the same proportion. In such physical mixtures, the x-ray pattern of each of the components can be
  • Cinquasia Magenta RT-355-D from Ciba Specialty Chemicals.
  • mixtures of pigments may be used in the UV curable inks.
  • a neutral black inkjet ink is preferred and can be obtained, for example, by mixing a black pigment and a cyan pigment into the ink.
  • the inkjet application may also require one or more spot colours, for example for packaging inkjet printing or textile inkjet printing. Silver and gold are often desired colours for inkjet poster printing and point-of-sales displays.
  • Non-organic pigments may be used in the radiation curable compositions and inks.
  • Particular preferred pigments are C.I. Pigment Metal 1 , 2 and 3.
  • Illustrative examples of the inorganic pigments include red iron oxide (III), cadmium red, ultramarine blue, prussian blue, chromium oxide green, cobalt green, amber, titanium black and synthetic iron black.
  • Pigment particles in inkjet inks should be sufficiently small to permit free flow of the ink through the inkjet-printing device, especially at the ejecting nozzles. It is also desirable to use small particles for maximum colour strength and to slow down sedimentation.
  • the numeric average pigment particle size is preferably between 0.050 and 1 ⁇ , more preferably between 0.070 and 0.300 ⁇ and particularly preferably between 0.080 and 0.200 ⁇ . Most preferably, the numeric average pigment particle size is no larger than 0.150 ⁇ . An average particle size smaller than 0.050 ⁇ is less desirable for decreased light- fastness, but mainly also because very small pigment particles or individual pigment molecules thereof may still be extracted in food packaging applications.
  • the average particle size of pigment particles is determined with a Nicomp 30 Submicron Particle Analyzer based upon the principle of dynamic light scattering. The ink is diluted with ethyl acetate to a pigment concentration of 0.002 wt%.
  • the numeric average particle diameter of the white pigment is preferably from 50 to 500 nm, more preferably from 150 to 400 nm, and most preferably from 200 to 350 nm. Sufficient hiding power cannot be obtained when the average diameter is less than 50 nm, and the storage ability and the jet-out suitability of the ink tend to be degraded when the average diameter exceeds 500 nm.
  • the determination of the numeric average particle diameter is best performed by photon correlation spectroscopy at a wavelength of 633 nm with a 4mW HeNe laser on a diluted sample of the pigmented inkjet ink.
  • a suitable particle size analyzer used was a Malvern nano-S available from Goffin-Meyvis.
  • a sample can, for example, be prepared by addition of one drop of ink to a cuvet containing 1 .5 ml_ ethyl acetate and mixed until a homogenous sample was obtained.
  • the measured particle size is the average value of 3 consecutive measurements consisting of 6 runs of 20 seconds.
  • Suitable white pigments are given by Table 2 in [01 16] of WO
  • the white pigment is preferably a pigment with a refractive index greater than 1 .60.
  • the white pigments may be employed singly or in combination.
  • titanium dioxide is used as pigment with a refractive index greater than 1 .60.
  • Suitable titanium dioxide pigments are those disclosed in [01 17] and in [01 18] of WO 2008/074548 (AGFA GRAPHICS) .
  • the pigments are present in the range of 0.01 to 10 % by weight,
  • the white pigment is preferably present in an amount of 3% to 30% by weight of the ink composition, and more preferably 5% to 25%. An amount of less than 3% by weight cannot achieve sufficient covering power and usually exhibits very poor storage stability and ejection property.
  • pigments are stabilized in the dispersion medium by dispersing agents, such as polymeric dispersants.
  • dispersing agents such as polymeric dispersants.
  • the surface of the pigments can be modified to obtain so-called “self-dispersible” or
  • the dispersant is preferably a polymeric dispersant.
  • Typical polymeric dispersants are copolymers of two monomers but may contain three, four, five or even more monomers.
  • the properties of polymeric dispersants depend on both the nature of the monomers and their distribution in the polymer.
  • Suitable copolymeric dispersants have the following polymer compositions:
  • alternating polymerized monomers e.g. monomers A and B polymerized into ABABABAB
  • block copolymers e.g. monomers A and B polymerized into AAAAABBBBBB wherein the block length of each of the blocks (2, 3, 4, 5 or even more) is important for the dispersion capability of the polymeric dispersant;
  • graft copolymers consist of a polymeric backbone with polymeric side chains attached to the backbone; and mixed forms of these polymers, e.g. blocky gradient copolymers.
  • the polymeric dispersant has preferably a number average molecular weight Mn between 500 and 30000, more preferably between 1500 and 10000.
  • the polymeric dispersant has preferably a weight average molecular
  • the polymeric dispersant has preferably a polydispersity PD smaller than 2, more preferably smaller than 1 .75 and most preferably smaller than 1 .5.
  • polymeric dispersants are the following:
  • Particularly preferred polymeric dispersants include SolsperseTM
  • GMBH GMBH.
  • Particularly preferred dispersants are SolsperseTM 32000, 35000 and 39000 dispersants from NOVEON.
  • the polymeric dispersant is preferably used in an amount of 2 to 600 wt%, more preferably 5 to 200 wt% based on the weight of the pigment.
  • a dispersion synergist usually consists of an anionic part and a cationic part.
  • the anionic part of the dispersion synergist exhibiting a certain molecular similarity with the colour pigment and the cationic part of the dispersion synergist consists of one or more protons and/or cations to compensate the charge of the anionic part of the dispersion synergist.
  • the synergist is preferably added in a smaller amount than the polymeric dispersant(s).
  • the ratio of polymeric dispersant/dispersion synergist depends upon the pigment and should be determined experimentally. Typically the ratio wt% polymeric dispersant/wt% dispersion synergist is selected between 2:1 to 100:1 , preferably between 2:1 and 20:1 .
  • Suitable dispersion synergists that are commercially available include
  • Particular preferred pigments for the magenta ink used are a diketopyrrolo- pyrrole pigment or a quinacridone pigment.
  • Suitable dispersion synergists include those disclosed in EP 1790698 A (AGFA GRAPHICS) , EP
  • Cu-phthalocyanine dispersion synergist e.g. SolsperseTM 5000 from NOVEON is preferred.
  • Suitable dispersion synergists for yellow inkjet inks include those disclosed in EP 1790697 A (AGFA GRAPHICS) .
  • the radiation curable compositions and inks may contain a surfactant.
  • the surfactant(s) can be anionic, cationic, non-ionic, or zwitter-ionic and are usually added in a total quantity less than 10 wt% based on the total weight of the radiation curable composition or ink and particularly in a total less than 5 wt% based on the total weight of the radiation curable composition or ink .
  • Suitable surfactants include those disclosed in paragraphs [0283] to [0291] of WO 2008/074548 (AGFA GRAPHICS) incorporated herein as a specific reference.
  • the UV curable compositions and inks may contain a polymerization
  • Suitable polymerization inhibitors include phenol type
  • antioxidants hindered amine light stabilizers, phosphor type antioxidants, hydroquinone monomethyl ether commonly used in (meth)acrylate monomers, and hydroquinone, t-butylcatechol, pyrogallol, 2,6-di-tert.butyl- 4-methylphenol may also be used.
  • Suitable commercial inhibitors are, for example, SumilizerTM GA-80,
  • SumilizerTM GM and SumilizerTM GS produced by Sumitomo Chemical Co. Ltd.; GenoradTM 16, GenoradTM 18 and GenoradTM 20 from Rahn AG; IrgastabTM UV10 and IrgastabTM UV22, TinuvinTM 460 and CGS20 from Ciba Specialty Chemicals; FloorstabTM UV range (UV-1 , UV-2, UV-5 and UV-8) from Kromachem Ltd, AdditolTM S range (S100, S1 10, S120 and S130) from Cytec Surface Specialties.
  • the inhibitor is preferably a polymerizable inhibitor.
  • the amount capable of preventing polymerization is determined prior to blending.
  • polymerization inhibitor is preferably lower than 5 wt%, more preferably lower than 3 wt% of the total radiation curable composition or ink.
  • the average particle size and distribution of a colour pigment is an
  • the inkjet ink may be prepared by precipitating or milling the pigment in the dispersion medium in the presence of the dispersant.
  • Mixing apparatuses may include a pressure kneader, an open kneader, a planetary mixer, a dissolver, and a Dalton Universal Mixer.
  • Suitable milling and dispersion apparatuses are a ball mill, a pearl mill, a colloid mill, a high-speed disperser, double rollers, a bead mill, a paint conditioner, and triple rollers.
  • the dispersions may also be prepared using ultrasonic energy.
  • the grinding media can comprise particles, preferably substantially spherical in shape, e.g. beads consisting essentially of a polymeric resin or yttrium stabilized zirconium oxide beads.
  • each process is performed with cooling to prevent build up of heat, and as much as possible under light conditions in which actinic radiation has been substantially excluded.
  • the inkjet ink may contain more than one pigment, and may be prepared using separate dispersions for each pigment, or alternatively several pigments may be mixed and co-milled in preparing the dispersion.
  • the dispersion process can be carried out in a continuous, batch or semi- batch mode.
  • the preferred amounts and ratios of the ingredients of the mill grind will vary widely depending upon the specific materials and the intended applications.
  • the contents of the milling mixture comprise the mill grind and the milling media.
  • the mill grind comprises pigment, polymeric dispersant and a liquid carrier.
  • the pigment is usually present in the mill grind at 1 to 50 wt%, excluding the milling media.
  • the weight ratio of pigment over polymeric dispersant is 20:1 to 1 :2.
  • the milling time can vary widely and depends upon the pigment
  • pigment dispersions with an average particle size of less than 100 nm may be prepared.
  • the milling media is separated from the milled particulate product (in either a dry or liquid dispersion form) using conventional separation techniques, such as by filtration, sieving through a mesh screen, and the like. Often the sieve is built into the mill, e.g. for a bead mill.
  • the milled pigment concentrate is preferably separated from the milling media by filtration.
  • the inkjet ink is adjusted to the desired viscosity, surface tension, colour, hue, saturation density, and print area coverage for the particular application.
  • DPGDA is dipropyleneglycoldiacrylate from SARTOMER.
  • TMPTA is trimethylolpropane triacrylate available as SartomerTM SR351 from SARTOMER.
  • VEEA is 2-(vinylethoxy)ethyl acrylate, a difunctional monomer available from NIPPON SHOKUBAI, Japan.
  • EPD is ethyl 4-dimethylaminobenzoate, available under the trade name of GenocureTM EPD from RAHN AG.
  • IC127 is an abbreviation used for IrgacureTM 127, supplied by Ciba Specia
  • IC907 is an abbreviation used for Irgacure 907 is 2-methyl-1 -[4- (methylthio)phenyl]-2-morpholino-propan-1 -one, a photoinitiator available from CIBA SPECIALTY CHEMICALS.
  • IC379 is an abbreviation used for IrgacureTM 379 is a photoinitiator available from CIBA SPECIALTY having as chemical structure:
  • ITX is an abbreviation used for Darocur ITX , an isomeric mixture of 2- and 4-isopropylthioxanthone from CIBA SPECIALTY CHEMICALS.
  • TPO is an abbreviation used for 2,4,6-trimethylbenzoyl-diphenyl- phosphineoxide available under the trade name DarocurTM TPO from CIBA SPECIALTY CHEMICALS.
  • GenoradTM 16 is a polymerization inhibitor from RAHN AG.
  • GENOSOL is a 50wt% solution of GenoradTM 16 in DPGDA.
  • PB15:4 is an abbreviation used for HostapermTM Blue P-BFS, a cyan pigment (C.I. Pigment Blue 15:4) available from CLARIANT.
  • DB162 is an abbreviation used for the polymeric dispersant DisperbykTM
  • DB162sol is a 30 wt% solution of DB162 in DPGDA.
  • S35000 is an abbreviation used for SOLSPERSETM 35000, a
  • polyethyleneimine-polyester hyperdispersant from NOVEON polyethyleneimine-polyester hyperdispersant from NOVEON.
  • S35000SOL is a 40 wt% solution of S35000 in DPGDA.
  • BykTM UV3510 is a polyethermodified polydimethylsiloxane wetting agent available from BYK CHEMIE GMBH.
  • the curing speed on a Fusion DRSE-120 conveyer was defined as the percentage of the maximum output of the lamp needed to cure the samples. The lower the number the higher curing speed. A sample was considered as fully cured at the moment scratching with a Q-tip caused no visual damage.
  • a percentage of more then 100 % of the maximum output of the lamp means that the speed of the conveyer belt had to be reduced to get the sample fully cured at the maximum output of the lamp. The higher the percentage, the more the belt had to be slowed down.
  • a curing speed of 160% means a belt speed of 12.5 m/min at the maximum output of the lamp.
  • a percentage between 150% and 200% is considered as at the edge of practical use.
  • a percentage above 200% is considered out of the range for practical use and no higher percentages are measured.
  • the curing degree was tested on a coating immediately after curing with UV light.
  • the cured coating is rubbed with the means of a Q-tip. When the surface is not damaged, the coating is fully cured. When some of the cured coating can be damaged, the coating is only partly cured. When the whole cured coating is damaged, the coating is not cured.
  • the particle size of pigment particles in an inkjet ink was determined by photon correlation spectroscopy at a wavelength of 633 nm with a 4mW HeNe laser on a diluted sample of the pigmented inkjet ink.
  • the particle size analyzer used was a MalvernTM nano-S available from Goffin-Meyvis.
  • the sample was prepared by addition of one drop of ink to a cuvette
  • the measured particle size is the average value of 3 consecutive measurements consisting of 6 runs of 20 seconds.
  • the average particle size of the dispersed particles is below 200 nm, preferably between 70 and 150 nm.
  • the degree of conversion i.e. the percentage of converted functional groups, may be determined by for example RT-FTIR (Real-Time Fourier Transform Infra-Red Spectroscopy).
  • composition was coated on a PGA-paper, using a bar coater and a 10 ⁇ wired bar.
  • the coated sample was mounted on a belt, transporting the samples under a Phoseon 4W 395 nm LED at a speed specified in the examples.
  • ratiOref leio(ref)/li728(ref)
  • I corresponds to the respective peak heights.
  • Curing% 100 - (ratio cur ing / ratio re f) * 100
  • a full cure is defined as a degree of conversion wherein the increase in the percentage of converted functional groups, with increased exposure to radiation (time and/or dose), is negligible.
  • a full cure corresponds with a conversion percentage that is within 10%, preferably 5%, from the maximum conversion percentage defined by the horizontal asymptote in the RT-FTIR graph (percentage conversion versus curing energy or curing time).
  • EXAMPLE 1 [0097] This example illustrates the simplicity of the method for preparing a photoinitiator according to the present invention.
  • the pooled organic fractions were dried over MgSO 4 and the solvent was evaporated under reduced pressure to obtain a brown oil.
  • the crude 9-(2- ethyl-hexyl)-9H-carbazole was purified on a Merck SVP D40 Column using n-hexane as eluent. Evaporation of the pooled fractions yielded 85 g of 9- (2-Ethyl-hexyl)-9H-carbazole.
  • the residual oil was purified on a Prochrom LC80 using dichloromethane as eluent. Evaporation of pooled fractions yielded 3.8 g of INI-3 (Rf : 0.6, eluent : 100% methylene chloride, Merck Kieselgel 60 F 2 5 4 ).
  • the organic fraction was isolated, extracted with brine and twice with 200 ml of a saturated NaHCO3 solution.
  • the intermediate diester precipitated from the organic fraction and was isolated by filtration. The filtrate was evaporated under reduced pressure and the residue was treated with toluene, yielding a second crop of the diester.
  • the fractions were pooled and 52.8 g (43.6 %) of the diester was isolated (R f : 0.23, eluent 70/30 hexane/ethyl acetate on Merck Kieselgel 60 F 2 5 4 .). The intermediate was used without further purification.
  • INI-6 was isolated by preparative column chromatography on a Prochrom LC80 column, using Kromasil Si 60A 10 ⁇ and a gradient elution from 100% methylene chloride to methylene chloride/ethyl acetate 94/6 at a flow rate of 150 ml/min. (R f : 0.35, eluent MeOH/NaCI 90/10, Partisil KC18F ).
  • N-sec.butyl-carbazole was isolated by preparative column chromatography on a Prochrom LC80 column, using Kromasil Si60 10 ⁇ and n. hexane/methylene chloride 93/7 as eluent. 8.7 g (26 %) of N-sec. butyl carbazole was isolated.
  • Photoinitiator INI-16 14 Acrylic acid 4-(3-(2-[6-benzoyl-9-(2-ethyl-hexyl)-9H-carbazol-3-yl]-2-oxo- acetoxy)-2-hydroxy-propoxy)-butyl ester was synthesized according to the following synthesis scheme:
  • INI-8 was synthesized according to the following synthesis scheme:
  • the intermediate oxime was isolated by preparative column chromatography on a Prochrom LC80 column, using Kromasil Si 60A 10 ⁇ and a gradient elution from n.-hexane/ethyl acetate 70/30 to n.- hexane/ethyl acetate 50/50 at a flow rate of 150 ml/min. 1 .4 g of the intermediate bis-oxime was isolated (Rf : 0.5, eluent n.-hexane/ethyl acetate 50/50, Merck Kieselgel 60 F 25 4)-
  • INI-8 was purified by crystallisation from n.- hexane/ethyl acetate 60/40 (Rf : 0.25, eluent : n.-hexane/ethyl acetate 50/50, Merck Kieselgel 60 F 25 4).
  • This example illustrates the need for introducing a branched substituent on the nitrogen of the carbazole photoinitiators according to the present invention and further illustrates their high photoreactivity and excellent yellowing behaviour.
  • the mixture was circulated over the mill for 7 hours and 45 minutes at a flow rate of about 2 L per minute and a rotation speed in the mill of about 15 m/s. During the complete milling procedure the content in the mill was cooled to a temperature of 42° C. After milling, the concentrated pigment dispersion DISP-1 was discharged into another 125 L vessel. The resulting
  • concentrated pigment dispersion DISP-1 according to Table 2 exhibited an average particle size of 1 10 nm.
  • the mixture was circulated over the mill for 1 hour and 50 minutes at a flow rate of about 5 L per minute and a rotation speed in the mill of about 15 m/s. During the complete milling procedure the content of the mill was cooled to a temperature of 54° C. The concentrated pigment dispersion DISP-2 was discharged into another 60 L vessel. The resulting
  • concentrated pigment dispersion DISP-2 according to Table 3 exhibited an average particle size of 1 19 nm.
  • the crude (6- ethoxyoxalyl-9-ethyl-9H-carbazol-3-yl)-oxo-acetic acid ethyl ester was purified on a Merck SVP D40 Column using n-hexane/dichloromethane (50/50) as eluent.. After evaporation of the pooled fractions, the residue was dissolved in dichloromethane and n-hexane was added.
  • the comparative radiation curable compositions COMP-1 toCOMP-4 and the inventive radiation curable compositions INV-1 to INV-4 were prepared according to Table 4.
  • the weight% (wt%) was based on the total weight of the radiation curable compositions.
  • Genorad I 16 0.8 0.8 0.8 0.9 0.9 0.9 0.8 0.8
  • the comparative radiation curable compositions COMP-1 and COMP-2 and inventive radiation curable compositions INV-1 to INV-4 were coated on PGA-paper, using a bar coater and a 10 ⁇ wired bar.
  • the coated samples were mounted on a belt, transporting the samples under a Phoseon 4W 395 nm LED. The number of passes at a given belt speed to completely cure the samples was determined. The Q-tip method was used to determine complete cure. The results are summarized in Table 5.
  • the radiation curable compositions INV-1 to INV-4 and COMP-2 were cured on a Fusion DRSE-120 conveyer equipped with Fusion VPS/1600 lamp at 20m/min at full power of the lamp.
  • a second sample was cured with a Phoseon 4W 395 nm LED, passing the sample 4 times under the LED at a speed of 5 m/min.
  • the stability of the image tone under both curing conditions was quantified by measuring the shift in b-value between the freshly printed sample and the sample stored for 7 days at ambient temperature. The results are summarized in Table 8.
  • the comparative radiation curable compositions COMP-5 and COMP-6 and the inventive radiation curable compositions INV-5 to INV-7 were prepared according to Table 7.
  • the weight% (wt%) was based on the total weight of the radiation curable compositions.
  • Genorad I 16 0.8 0.9 0.8 0.9 0.9 0.9
  • the comparative radiation curable compositions COMP-7 and COMP-8 and the inventive radiation curable compositions INV-8 to INV-12 were prepared according to Table 9.
  • the same concentrated pigment dispersions DISP-1 and DISP-2 of EXAMPLE 3 were used.
  • the weight% (wt%) was based on the total weight of the radiation curable compositions.
  • VEEA 24.5 - 26.5 - 24.5 30.0 -
  • Genorad I 16 0.8 0.8 0.8 0.9 0.8 0.9 0.9 0.9
  • the comparative radiation curable compositions COMP-7 and COMP-8 and inventive radiation curable compositions INV-8 to INV-12 were coated on PGA-paper, using a bar coater and a 10 ⁇ wired bar.
  • the coated samples were mounted on a belt, transporting the samples under a Phoseon 4W 395 nm LED at a speed of 5 m/min and 10 m/min
  • the radiation curable compositions INV-9 and INV-1 1 and COMP-8 were cured with a Phoseon 4W 395 nm LED, passing the sample 4 times under the LED at a speed of 5 m/min.
  • the stability of the image tone was quantified by measuring the shift in b-value between the freshly printed sample and the sample stored for 7 days at ambient temperature. The results are summarized in Table 1 1 .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne un type spécifique de photoinitiateur au carbazole capable de donner des compositions durcissables au rayonnement pouvant être durcies par des DEL UV et ne montrant pas de comportement de jaunissement instable dans une image lors du stockage comme c'est le cas avec l'ITX.
PCT/EP2010/068940 2009-12-07 2010-12-06 Photoinitiateurs pour compositions durcissables par del uv et encres Ceased WO2011069947A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP10790390.8A EP2509948B1 (fr) 2009-12-07 2010-12-06 Photo-initiateurs pour compositions durcissables à uv-del et encres
CA2780036A CA2780036C (fr) 2009-12-07 2010-12-06 Photoinitiateurs pour compositions durcissables par del uv et encres
BR112012013779-4A BR112012013779B1 (pt) 2009-12-07 2010-12-06 fotoiniciadores para composições e tintas curáveis por meio de led de uv
AU2010330044A AU2010330044B2 (en) 2009-12-07 2010-12-06 Photoinitiators for UV-LED curable compositions and inks
CN201080055158.9A CN102639501B (zh) 2009-12-07 2010-12-06 用于uv-led可固化组合物和墨水的光引发剂
US13/511,375 US8957224B2 (en) 2009-12-07 2010-12-06 Photoinitiators for UV-LED curable compositions and inks

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EP09178164.1 2009-12-07
EP09178164 2009-12-07
US26746809P 2009-12-08 2009-12-08
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WO2015031927A1 (fr) * 2013-09-06 2015-03-12 Durst Phototechnik Digital Technology Gmbh Photo-initiateur
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WO2018041935A1 (fr) * 2016-09-02 2018-03-08 Igm Group B.V. Glyoxylates polycycliques utilisés en tant que photo-initiateurs
EP3597669A1 (fr) 2018-07-20 2020-01-22 Clariant International Ltd Composition de résine photodurcissable pour impression 3d
EP3597668A1 (fr) 2018-07-20 2020-01-22 Clariant International Ltd Composition de résine photodurcissable pour impression 3d
JP2020055992A (ja) * 2018-07-17 2020-04-09 奇▲たい▼科技股▲ふん▼有限公司 液体光開始化合物とその用途
CN113024690A (zh) * 2020-12-30 2021-06-25 艾坚蒙(安庆)科技发展有限公司 光引发剂组合物、光固化组合物及光固化产品
WO2022238591A1 (fr) * 2021-10-08 2022-11-17 Igm Resins Italia S.R.L. Nouveaux photo-initiateurs

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WO2018041935A1 (fr) * 2016-09-02 2018-03-08 Igm Group B.V. Glyoxylates polycycliques utilisés en tant que photo-initiateurs
US10597515B2 (en) 2016-09-02 2020-03-24 Igm Group B.V. Polycyclic glyoxylates as photoinitiators
JP2020055992A (ja) * 2018-07-17 2020-04-09 奇▲たい▼科技股▲ふん▼有限公司 液体光開始化合物とその用途
WO2020015964A1 (fr) 2018-07-20 2020-01-23 Clariant International Ltd Composition de résine photodurcissable pour impression 3d
WO2020015966A1 (fr) 2018-07-20 2020-01-23 Clariant International Ltd Composition de résine photodurcissable pour impression 3d
EP3597668A1 (fr) 2018-07-20 2020-01-22 Clariant International Ltd Composition de résine photodurcissable pour impression 3d
EP3597669A1 (fr) 2018-07-20 2020-01-22 Clariant International Ltd Composition de résine photodurcissable pour impression 3d
CN113024690A (zh) * 2020-12-30 2021-06-25 艾坚蒙(安庆)科技发展有限公司 光引发剂组合物、光固化组合物及光固化产品
CN113024690B (zh) * 2020-12-30 2023-08-11 艾坚蒙(安庆)科技发展有限公司 光引发剂组合物、光固化组合物及光固化产品
WO2022238591A1 (fr) * 2021-10-08 2022-11-17 Igm Resins Italia S.R.L. Nouveaux photo-initiateurs
WO2022207945A3 (fr) * 2021-10-08 2022-12-01 Igm Resins Italia S.R.L. Nouveaux photo-initiateurs

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CN103435722A (zh) 2013-12-11
AU2010330044B2 (en) 2014-08-28
CA2780036C (fr) 2017-08-22
US20120309861A1 (en) 2012-12-06
BR112012013779A8 (pt) 2017-12-05
CN103435722B (zh) 2015-07-01
CA2780036A1 (fr) 2011-06-16
BR112012013779B1 (pt) 2020-11-03
BR112012013779A2 (pt) 2015-09-15
CN102639501A (zh) 2012-08-15
EP2509948B1 (fr) 2017-05-03
CN102639501B (zh) 2015-04-29
AU2010330044A1 (en) 2012-05-10
EP2509948A1 (fr) 2012-10-17

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