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WO2005089957A1 - Procede de production de couches adherant fortement - Google Patents

Procede de production de couches adherant fortement Download PDF

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Publication number
WO2005089957A1
WO2005089957A1 PCT/EP2005/050994 EP2005050994W WO2005089957A1 WO 2005089957 A1 WO2005089957 A1 WO 2005089957A1 EP 2005050994 W EP2005050994 W EP 2005050994W WO 2005089957 A1 WO2005089957 A1 WO 2005089957A1
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WO
WIPO (PCT)
Prior art keywords
process according
process step
group
alkyl
chemically active
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/EP2005/050994
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English (en)
Inventor
Thomas Bolle
Giorgio Macor
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.)
BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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Filing date
Publication date
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Publication of WO2005089957A1 publication Critical patent/WO2005089957A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5209—Coatings prepared by radiation-curing, e.g. using photopolymerisable compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0045—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or film forming compositions cured by mechanical wave energy, e.g. ultrasonics, cured by electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams, or cured by magnetic or electric fields, e.g. electric discharge, plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
    • 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
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • G03F7/0955—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer one of the photosensitive systems comprising a non-macromolecular photopolymerisable compound having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/068—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using ionising radiations (gamma, X, electrons)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/08—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by flames
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/546—No clear coat specified each layer being cured, at least partially, separately
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/12—Preparation of material for subsequent imaging, e.g. corona treatment, simultaneous coating, pre-treatments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the invention relates to a process for the production of strongly adherent coatings on inorganic or organic substrates, wherein a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, one or more photoinitiators are applied to the inorganic or organic substrate by spraying processes, and the substrate so precoated with photoinitiator is provided with a final coating.
  • adhesion properties of coatings e.g. finishes, paints, printing inks or adhesives
  • inorganic or organic substrates especially on non-polar substrates such as polyethylene, polypropylene or fluorine-containing polyolefins
  • primers special priming coatings
  • a further possibility lies in exposing the substrates to be coated to a plasma treatment or corona treatment and then coating them, it being possible for a grafting process with e.g. acrylate monomers to be carried out between those two operations (J. Polym. Sci., Part A: Polym. Chem.31, 1307-1314 (1993)).
  • WO 99/06204 describes a corona treatment unit that enables the corona-treated substrate to be sprayed with an aerosol.
  • a corona treatment unit that enables the corona-treated substrate to be sprayed with an aerosol.
  • an information brochure (Nanotec S.r.1) produced by Nanotec S.r.l, a corresponding apparatus is described specifically for the treatment of web-shaped materials.
  • coatings of photocurable compositions having especially good adherence can be obtained by applying to a substrate to be coated, after it has been subjected to a plasma treatment (low pressure and/or normal pressure plasmas), corona treatment or flame treatment, a reactive substance, e.g. a photoinitiator, in the form of a nano- layer by means of aerosol spray coating, and optionally drying and irradiating the substrate so treated.
  • a plasma treatment low pressure and/or normal pressure plasmas
  • corona treatment or flame treatment e.g. a reactive substance, e.g. a photoinitiator, in the form of a nano- layer by means of aerosol spray coating, and optionally drying and irradiating the substrate so treated.
  • the substrates so pretreated are provided with a coating and cured.
  • the resulting coatings exhibit surprisingly good adhesion which does not undergo any appreciable deterioration even after several days' storage or exposure to sunlight.
  • the invention therefore relates to a process for the production of a strongly adherent coating on an inorganic or organic substrate, wherein a) a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, b) one or more chemically active substances or a solution, suspension or emulsion of one or more chemically active substances or mixtures of chemically active substances with monomers or/and oligomers containing at least one ethylenically unsaturated group are applied to the inorganic or organic substrate, and c) those afore-mentioned substances are optionally dried using suitable methods and are irradiated with electromagnetic waves, wherein the application of the solution, suspension or emulsion in process step b) is carried out in the form of an aerosol by means of a nano-spraying process.
  • the process is simple to carry out and allows a high throughput per unit of time since laborious application steps or slow crosslinking reactions are not required.
  • the process is especially well suited to workpieces that are composed of different plastics and/or metals or types of glass and that, without pretreatment, would therefore exhibit different degrees of adhesion on the different components, or that, in the case of a conventional primer treatment, exhibit different affinities for the primer.
  • reactive substance in the sense of this Application there come into consideration: b1) liquid photoinitiators or a solution, suspension or emulsion of one or more photoinitiators or mixtures of photoinitiators with monomers or/and oligomers containing at least one ethylenically unsaturated group, or b2) at least one radical-forming initiator and at least one UV-absorber containing at least one ethylenically unsaturated group and/or at least one monomeric or oligomeric ethylenically unsaturated compound in the form of solutions, suspensions or emulsions, or b3) liquid electron or H donors or a solution, suspension or emulsion of one or more electron or H donors or mixtures of electron or H donors with monomers or/and oligomers containing at least one ethylenically unsaturated group, or b4) 1.
  • At least one activatable initiator or 2 at least one activatable initiator and at least one ethylenically unsaturated compound in the form of solutions, suspensions or emulsions, wherein at least one function-controlling group which results in the attainment of desired surface properties of the treated substrate is incorporated in the activatable initiator and/or the ethylenically unsaturated compound, or b5) 1. at least one activatable initiator or 2.
  • the solution, emulsion or suspension may also contain further additives, for example light stabilisers, antistatics, flow improvers, dispersants and adhesion promoters.
  • a fixing step for the reactive substance e.g. the photoinitiator, is carried out by exposure with UV ⁇ /IS light.
  • drying includes both variants, both the removal of the solvent and the fixing of the reactive substance, e.g. the photoinitiator.
  • step c) of the above-described processes the drying, that is to say the removal of the solvent, is optional. That step can be omitted, for example, when no solvent was used, for example when a liquid photoinitiator, or a liquid reactive substance, was used.
  • the fixing in step c) of the process by irradiation with electromagnetic waves, especially UV7VIS radiation, must be carried out. Suitable apparatus for drying and irradiation is described hereinbelow.
  • the invention relates also to a process for the production of strongly adherent coatings on an inorganic or organic substrate, wherein a) a low-temperature plasma treatment, a corona discharge treatment or a flame treatment is carried out on the inorganic or organic substrate, b) one or more chemically active substances or a solution, suspension or emulsion of one or more chemically active substances or mixtures of chemically active substances with monomers or/and oligomers containing at least one ethylenically unsaturated group are applied to the inorganic or organic substrate, and c) those afore-mentioned substances are optionally dried using suitable methods and are irradiated with electromagnetic waves, wherein the application of the solution, suspension or emulsion in process step b) is carried out in the form of an aerosol by means of a nano-spraying process, and d) the substrate so pre-coated with a specific nano-layer is provided with a further coating.
  • a characteristic feature of the process according to the invention is application of the primer layer containing the reactive substance, e.g. the photoinitiator, in the form of an aerosol.
  • the layer thickness of which is in the nanometre range of approximately 5-500 nm, e.g.5-100 nm, preferably 5-50 nm, e.g.5-10 nm.
  • nano-layers are advantageous economically, since material consumption will be low.
  • the nano-layers in question are regularly arranged layers, producing an especially homogeneous surface.
  • aerosol containing the active substance e.g. the photoinitiator, according to process step b) is performed by means of spray devices that are known in the art and which, for example, are commercially available.
  • spray devices that are known in the art and which, for example, are commercially available.
  • Such devices are described, for example, by G. Bolte and S. Kluth in coatings 2/98, 38-40; G. Bolte in Flexo+Tief-Druck 2-2003, 8-12; WO 99/06204 and in an information brochure (Nanotec S.r.1) produced by Nanotec S.r.l.
  • liquid droplets containing solvent/water/chemically active material
  • carrier gases e.g. air, nitrogen, CO 2
  • the concentration of the chemically active substance, e.g. the photoinitiator, in that aerosol is typically ⁇ 20 % in solution, being approximately from 0.01 to 20 %, preferably from 0.1 to 20 %.
  • concentration of the chemically active substance, e.g. the photoinitiator in that aerosol is typically ⁇ 20 % in solution, being approximately from 0.01 to 20 %, preferably from 0.1 to 20 %.
  • layer thicknesses of the chemically active substance, e.g. the photoinitiator in the nanometre range are obtained.
  • parameters such as droplet formation, droplet concentration and surface tension of the aerosol droplets have to be adjusted accordingly. Spray devices equipped to do so are, as already mentioned above, known in the prior art and are also commercially available.
  • the electrical energy can be coupled in by inductive or capacitive means. It may be direct current or alternating current; the frequency of the alternating current may range from a few kHz up into the MHz range. A power supply in the microwave range (GHz) is also possible.
  • GHz microwave range
  • primary plasma gases it is possible to use, for example, He, argon, xenon, N 2 , O 2 , H 2) steam or air.
  • the process according to the invention is not sensitive per se in respect of the coupling-in of the electrical energy.
  • the process can be carried out batchwise, for example in a rotating drum, or continuously in the case of films, fibres or woven fabrics. Such methods are known and are described in the prior art.
  • the process is preferably carried out under corona discharge conditions.
  • Corona discharges are produced under normal pressure conditions, the ionised gas used being most frequently air.
  • other gases and mixtures are also possible, as described, for example, in COATING Vol. 2001, No. 12, 426, (2001).
  • the advantage of air as ionisation gas in corona discharges is that the operation can be carried out in an apparatus open to the outside and, for example, a film can be drawn through continuously between the discharge electrodes.
  • Such process arrangements are known and are described, for example, in J. Adhesion Sci. Technol. Vol 7, No. 10, 1105, (1993).
  • Three-dimensional workpieces can be treated with a free plasma jet, the contours being followed with the assistance of robots.
  • the spray device for applying the aerosol can also be present e.g. in the corona discharge station itself.
  • the flame treatment of substrates is known to the person skilled in the art.
  • Corresponding industrial apparatus for example for the flame treatment of films, is commercially available.
  • a film is conveyed on a cooled cylindrical roller past the flame-treatment apparatus, which consists of a chain of burners arranged in parallel, usually along the entire length of the cylindrical roller. Details can be found in the brochures of the manufacturers of flame-treatment apparatus (e.g. esse Cl, flame treaters, Italy).
  • the parameters to be chosen are governed by the particular substrate to be treated. For example, the flame temperatures, the flame intensity, the dwell times, the distance between substrate and burner, the nature of the combustion gas, air pressure, humidity, are matched to the substrate in question.
  • As flame gases it is possible to use, for example, methane, propane, butane or a mixture of 70 % butane and 30 % propane.
  • Process step b) that is to say the application of the reactive substance in the form of an aerosol, is carried out, for example, in the same apparatus as that in which the corona treatment was carried out (see, for example, the apparatus described in WO 99/06204).
  • the pretreatment a) is carried out, the treated substrate is removed from the apparatus used, and then step b) is performed in a different apparatus, the substrate is removed and then drying and exposure is optionally carried out according to step c).
  • the inorganic or organic substrate to be treated can be in any solid form.
  • the substrate is preferably in the form of a woven fabric, a fibre, a film or a three-dimensional workpiece.
  • the substrate may be, for example, a thermoplastic, elastomeric, inherently crosslinked or cross- linked polymer, a metal oxide, a ceramic material, glass, a metal, leather or a textile.
  • the pretreatment of the substrate in the form of plasma-, corona- or flame-treatment can, for example, also be carried out immediately after the extrusion of a fibre or film, and also directly after film-drawing.
  • the inorganic or organic substrate is preferably a thermoplastic, elastomeric, inherently crosslinked or crosslinked polymer, a metal oxide, a ceramic material, a type of glass or a metal, especially a thermoplastic, elastomeric, inherently crosslinked or crosslinked polymer.
  • thermoplastic, elastomeric, inherently crosslinked or crosslinked polymers examples include thermoplastic, elastomeric, inherently crosslinked or crosslinked polymers.
  • Polymers of mono- and di-olefins for example polypropylene, polyisobutylene, poly- butene-1, poly-4-methylpentene-1 , polyisoprene or polybutadiene and also polymerisation products of cycloolefins, for example of cyclopentene or norbornene; and also polyethylene (which may optionally be crosslinked), for example high density polyethylene (HDPE), high density polyethylene of high molecular weight (HDPE-HMW), high density polyethylene of ultra-high molecular weight (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE), (VLDPE) and
  • HDPE high density polyethylene
  • HDPE-HMW high density polyethylene of high molecular weight
  • HDPE-UHMW high density polyethylene of ultra-high molecular weight
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • Polyolefins that is to say polymers of mono-olefins, as mentioned by way of example in the preceding paragraph, especially polyethylene and polypropylene, can be prepared by various processes, especially by the following methods: a) by free radical polymerisation (usually at high pressure and high temperature); b) by means of a catalyst, the catalyst usually containing one or more metals of group IVb, Vb, Vlb or VIM. Those metals generally have one or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls, which may be either ⁇ - or ⁇ - coordinated.
  • ligands such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls, which may be either ⁇ - or ⁇ - coordinated.
  • Such metal complexes may be free or fixed to carriers, for example to activated magnesium chloride, titanium(lll) chloride, aluminium oxide or silicon oxide.
  • Such catalysts may be soluble or insoluble in the polymerisation medium.
  • the catalysts can be active as such in the polymerisation or further activators may be used, for example metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxanes, the metals being elements of group(s) la, lla and/or Ilia.
  • the activators may have been modified, for example, with further ester, ether, amine or silyl ether groups.
  • Such catalyst systems are usually referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or Single Site Catalysts (SSC).
  • Copolymers of mono- and di-olefins with one another or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/butene-1 copolymers, propylene/isobutylene copolymers, ethylene/butene-1 copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/- alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and copolymers thereof with carbon monoxide, or ethylene/acrylic acid copolymers and salts thereof (ionomers), and
  • Hydrocarbon resins for example C 5 -C 9
  • hydrogenated modifications thereof for example tackifier resins
  • Polystyrene poly(p-methylstyrene), poly(oc-methylstyrene).
  • Copolymers of styrene or -methylstyrene with dienes or acrylic derivatives for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/buta- diene/alkyl acrylate and methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; high-impact-strength mixtures consisting of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and also block copolymers of styrene, for example styrene/butadiene/styrene, styrene/- isoprene/styrene, styrene/ethylene-butylene/s
  • Graft copolymers of styrene or ⁇ -methylstyrene for example styrene on polybutadi- ene, styrene on polybutadiene/styrene or polybutadiene/acrylonitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleic acid imide on polybutadiene; styrene and maleic acid imide on polybutadiene, styrene and maleic acid imide on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and
  • Halogen-containing polymers for example polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene/isoprene (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and co-polymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, poly- vinylidene fluoride; and copolymers thereof, such as vinyl chloride/vinyl idene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate.
  • halogen-containing polymers for example polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene/isoprene (halobutyl rubber), chlorinated or chlorosul
  • Polymers derived from ⁇ , ⁇ -unsaturated acids and derivatives thereof such as poly- acrylates and polymethacrylates, or polymethyl methacrylates, polyacrylamides and poly- acrylonitriles impact-resistant-modified with butyl acrylate.
  • Copolymers of the monomers mentioned under 9) with one another or with other unsaturated monomers for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate copolymers, acrylonitrile/vinyl halide copolymers or aery lo n itrile/al yl methacrylate/butadiene terpolymers.
  • Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate or maleate, poly- vinylbutyral, polyallyl phthalate, polyallylmelamine; and the copolymers thereof with olefins mentioned in Point 1.
  • cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
  • Polyacetals such as polyoxymethylene, and also those polyoxymethylenes which contain comonomers, for example ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides derived from m-xylene, diamine and adipic acid; polyamides prepared from hexamethylene- diamine and iso- and/or tere-phthalic acid and optionally an elastomer as modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide.
  • Polyureas Polyureas, polyimides, polyamide imides, polyether imides, polyester imides, poly- hydantoins and polybenzimidazoles.
  • Polyesters derived from dicarboxylic acids and dialcohols and/or from hydroxycarbox- ylic acids or the corresponding lactones such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates, and also block polyether esters derived from polyethers with hydroxyl terminal groups; and also polyesters modified with polycarbonates or MBS. 19. Polycarbonates and polyester carbonates.
  • Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, and also vinyl compounds as crosslinking agents, and also the halogen-containing, difficultly combustible modifications thereof.
  • Crosslinkable acrylic resins derived from substituted acrylic esters, e.g. from epoxy acrylates, urethane acrylates or polyester acrylates.
  • Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of bisphenol-A diglycidyl ethers, bisphenol-F diglycidyl ethers, that are crosslinked using customary hardeners, e.g. anhydrides or amines with or without accelerators.
  • Natural polymers such as cellulose, natural rubber, gelatin, or polymer-homologously chemically modified derivatives thereof, such as cellulose acetates, propionates and butyr- ates, and the cellulose ethers, such as methyl cellulose; and also colophonium resins and derivatives.
  • Mixtures (polyblends) of the afore-mentioned polymers for example PP/EPDM, poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic RUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
  • the substrate can, for example, be one as used in the commercial printing sector, for bed intaglio printing, bed offset printing or continuous printing, posters, calendars, forms, labels, packaging films, tapes, credit cards, furniture profiles, etc..
  • the substrate is not confined to use in the non-nutrition sector.
  • the substrate may also be, for example, a material for use in the field of nutrition, e.g. as packaging for foodstuffs; cosmetics, medicaments, efc..
  • substrates have been pretreated according to processes of the invention it is also possible, for example, for substrates that usually have poor compatibility with one another to be adhesively bonded to one another or laminated.
  • paper should also be understood as being an inherently crosslinked polymer, especially in the form of card(board), which can additionally be coated with e.g. Teflon®.
  • substrates are, for example, commercially available.
  • thermoplastic, crosslinked or inherently crosslinked plastics is preferably a polyolefin, polyamide, polyacrylate, polycarbonate, polystyrene or an acrylic/melamine, alkyd or poly- urethane surface-coating.
  • Polycarbonate, polyethylene and polypropylene are especially preferred.
  • the plastics may be, for example, in the form of films, injection-moulded articles, extruded workpieces, fibres, felts or woven fabrics.
  • inorganic substrates there come into consideration especially glass, ceramic materials, metal oxides and metals. They may be silicates and semi-metal or metal oxide glasses which are in the form of layers or in the form of powders preferably having average particle diameters of from 10 nm to 2000 ⁇ m. The particles may be dense or porous. Examples of oxides and silicates are SiO 2] TiO 2 , ZrO 2 , MgO, NiO, W0 3 , AI 2 O 3 , La 2 O 3 , silica gels, clays and zeolites. Preferred inorganic' substrates, in addition to metals, are silica gels, aluminium oxide, titanium oxide and glass and mixtures thereof.
  • metal substrates there come into consideration especially Fe, Al, Ti, Ni, Mo, Cr and steel alloys.
  • metal substrates are aluminium, chromium, steel and vanadium, which are used, for example, for the manufacture of high-quality mirrors, such as, for example, telescope mirrors or vehicle headlamp mirrors. Aluminium is especially preferred.
  • liquid photoinitiators or a solution, suspension or emulsion of one or more photoinitiators or mixtures of photoinitiators with monomers or/and oligomers containing at least one ethylenically unsaturated group are used as chemically active substance b1 ).
  • any compounds and mixtures that form one or more free radicals when irradiated with electromagnetic waves are suitable for use in the process according to the invention as photoinitiators in process step b1 ).
  • These include initiator systems consisting of a plurality of initiators and systems that function independently of one another or synergistically.
  • initiator systems consisting of a plurality of initiators and systems that function independently of one another or synergistically.
  • sensitisers for example acridines, xanthenes, thiazenes, coumarins, thioxanthones, triazines and dyes.
  • photoinitiators for Free Radical and Cationic Polymerisation 2nd Edition John Wiley & Son Ltd.
  • the photoinitiator suitable for the process according to the invention in step b) may be either an initiator having an unsaturated group or an initiator not having such a group.
  • Such compounds and derivatives are derived, for example, from the following classes of compounds: benzoins, benzil ketals, acetophenones, hydroxyalkylphenones, arninoalkyl- phenones, acylphosphine oxides, acylphosphine sulfides, acyloxyiminoketones, alkylamino- substituted ketones, such as Michler's ketone, peroxy compounds, dinitrile compounds, halogenated acetophenones, phenylglyoxalates,-dimeric phenylglyoxalates, benzophenones, oximes and oxime esters, thioxanthones, coumarins, ferrocenes, titanocenes, onium salts, sulfonium salts, iodonium salts, diazonium salts, borates, triazines, bisimidazoles, poly- silanes and dye
  • the photoinitiator is a compound of formula I or la
  • (IN) is a photoinitiator basic structure
  • A is a spacer group or a single bond
  • (RG) is hydrogen or at least one functional ethylenically unsaturated group
  • RG' is a single bond or a divalent radical containing at least one functional ethylenically unsaturated group, or is a trivalent radical.
  • (IN) is a photoinitiator basic structure of formula (II) or (III)
  • Ri is a group (A), (B), (C) or (III) -fo ⁇ yay-OR,, (C); n is a number from 0 to 6;
  • R 2 is hydrogen, d-C ⁇ 2 alkyl .
  • halogen the group (RG)-A- or, when R-, is a group (A), two radicals R 2 in the ortho-position with respect to the carbonyl group may together also be -S- o II or — c — ;
  • R_ ⁇ independently of each other are C ⁇ -C 6 al_kyl, C ⁇ -C 6 alkanoyl, phenyl or benzoyl, each of the radicals phenyl and benzyl being unsubstituted or substituted by halogen,
  • R 5 is hydrogen, halogen, C C 12 alkyl or C C ⁇ 2 alkoxy or the group (RG)-A-;
  • R 6 is OR 9 or N(R 9 ) 2 or is — ⁇ / , — N H , — N N-R 10 , - N o or SO 2 R 9 ;
  • R 7 and R 8 independently of each other are hydrogen, CrC- ⁇ alkyl, C 2 -C ⁇ alkenyl, C1-C12- alkoxy, phenyl or benzyl or R 7 and R 8 together are C 2 -C 6 alkylene;
  • R 9 is hydrogen, CrC 6 alkyl or CrC 6 alkanoyl;
  • R 10 is hydrogen, or phenyl;
  • R11 is C C 4 alkyl or >
  • X1 is oxygen or sulfur.
  • (IN) is, for example, a group
  • a in the compounds of formula I or la is, for example, a single bond or a spacer group
  • X, Y and Z independently of one another are a single bond, -O-, -S- ,-N(R 10 )-, -(CO)-,
  • Ai and A 2 independently of each other are, for example, CrC 4 alkylene, C 3 -C 12 cycloalkylene, phenylene, phenylene-CrC 4 alkylene or CrC a!kylene-phenylene-C ⁇ -C alkylene.
  • a, b, c and d independently of one another are the numbers 0 to 4.
  • RG is a single bond, ,c-Si- or — c— c — , especially H c-sf- or and R a , R b and R 0 independently of one another are hydrogen or C C 6 alkyl, especially hydrogen or methyl.
  • compounds containing unsaturated groups can be prepared by reacting 4-[2- hydroxyethoxy)-benzoyl]-1-hydroxy-1 -methyl-ethane (Irgacure ® 2959, Ciba Specialty Chemicals) with isocyanates containing acryloyl or methacryloyl groups or with other compounds containing acryloyl or methacryloyl groups, see e.g. US 4922004.
  • unsaturated photoinitiators are, for example, 4-(13-acryloyl- I ⁇ .IO.IS-pentaoxatridecy -benzophenone (Uvecryl P36 from UCB), 4-benzoyl-N,N-di- methyl-N-[2-(1-oxo-2-propenyl)oxy]ethylphenylmethanaminium chloride (Quantacure ABQ from Great Lakes), and, for example, some copolymerisable unsaturated tertiary amines (Uvecryl P101, Uvecryl P104, Uvecryl P105, Uvecryl P115 from UCB Radcure Specialties) or copolymerisable aminoacrylates (Photomer 4116 and Photomer 4182 from Ackros; Laromer LR8812 from BASF; CN381 and CN386 from Cray Valley).
  • Unsaturated acetophenone and benzophenone derivatives are described, for example, in US 3214492, US 3429852, US 3622848 and US 4304895, for
  • US 4672079 discloses inter alia the preparation of 2-hydroxy-2-methyl(4-vinylpropiophe- none), 2-hydroxy-2-methyl-p-(1-methylvinyl)propiophenone, p-vinylbenzoylcyclohexanol, p-
  • reaction products described in JP Kokai Hei 2-2&2307, of 4-[2-hydroxy- ethoxy)-benzoyl]-1-hydroxy-1 -methyl-ethane (Irgacure ® 2959, Ciba Specialty Chemicals) and isocyanates containing acryloyl or methacryloyl groups, for example
  • Photoinitiators not having an unsaturated group are known to the person skilled in the art and are commercially available in a considerable diversity and number. In principle, all photoinitiators that after plasma treatment, corona treatment or flame treatment adhere to the surface of the particular substrate treated are suitable in the process.
  • C C ⁇ 2 Alkyl is linear or branched and is, for example, CrC 8 -, CrC 6 - or C C -alkyl.
  • Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl-pentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl or dodecyl, especially, for example, methyl or butyl.
  • CrCeAlkyl and C C 4 alkyl are also linear or branched and have, for example, the meanings given above up to the corresponding number of carbon atoms.
  • Ci-CeAlkyl substituents for benzoyl or phenyl are especially C r C alkyl, for example methyl or butyl.
  • Halogen is fluorine, chlorine, bromine or iodine, especially chlorine or bromine, preferably chlorine.
  • C ⁇ -C 6 alkanoyl is linear or branched and is, for example, C ⁇ -C alkanoyl. Examples are formyl, acetyl, propionyl, butanoyl, isobutanoyl, pentanoyl and hexanoyl, preferably acetyl.
  • CrC- ⁇ kanoyl has the meanings given above up to the corresponding number of carbon atoms.
  • CrC ⁇ 2 Alkoxy is a linear or branched radical and is, for example, CrC 8 -, C ⁇ -C 6 - or C ⁇ -C 4 - alkoxy. Examples are methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobut- oxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, 2,4,4-trimethylpentyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy, decyloxy and dodecyloxy, especially methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, preferably methoxy.
  • CrC ⁇ Alkoxy, CrC 6 - alkoxy and C C alkoxy are also linear or branched and have, for example, the meanings given above up to the corresponding
  • Ci-C ⁇ Alkylthio is a linear or branched radical and is, for example, C C 4 alkylthio. Examples are methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert- butylthio, pentylthio and hexylthio, especially methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert-butylthio, preferably methylthio.
  • d-C-jAlkylthio is also linear or branched and has, for example, the meanings given above up to the corresponding number of carbon atoms.
  • Phenyl or benzoyl radicals substituted by halogen, CrC 6 alkyl, C C 6 alkylthio or C C 6 alkoxy are, for example, mono- to penta-substituted, for example mono-, di- or tri-substituted, especially di- or tri-substituted, on the phenyl ring.
  • Preference is given, for example, to 2,4,6- trimethylbenzoyl, 2,6-dichlorobenzoyl, 2,6-dimethylbenzoyl and 2,6-dimethoxybenzoyl.
  • d-C.AIkylene and C 2 -C 6 alkylene are linear or branched alkylene, for example C 2 -C alkylene, e.g. methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert- butylene, pentylene or hexylene.
  • C C 4 alkylene e.g.
  • ethylene or butyl- ene — CH-CH 2 - , — CH-(CH 2 ) 2 - , — CH-(CH 2 ) 3 - or -C(CH 3 ) 2 -CH 2 - , and methylene CH g CH g CH g and ethylene.
  • Phenylene-CrC alkylene is phenylene that is substituted by C C alkylene at one position of the aromatic ring, whereas C ⁇ -C alkylene-phenylene-C C alkylene is phenylene that is substituted by C ⁇ -C 4 alkylene at two positions of the phenylene ring.
  • the alkylene radicals are in each case linear or branched and have, for example, the meanings given above up to the corresponding number of carbon atoms. Examples are ,
  • the alkylene groups may, however, also be situated at other positions of the phenylene ring, for example also in the 1,3-position.
  • Cycloalkylene is, for example, C3-C12- or C 3 -C 8 -cycloalkylene, for example cyclopropylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclododecylene, especially cyclopentylene and cyclohexylene, preferably cyclohexylene.
  • C 3 -C ⁇ 2 Cycloalkylene also denotes, however, a
  • C 2 -C ⁇ 2 Alkenyl radicals may be mono- or poly-unsaturated and linear or branched and are, for example, C -C 8 -, C -C 6 - or C 2 -C -alkenyl. Examples are allyl, methallyl, 1,1-dimethylallyl, 1- butenyl, 2-butenyl, 1,3-pentadienyl, 1-hexenyl, 1-octenyl, decenyl or dodecenyl, especially allyl.
  • R 7 and R 8 together are d-C ⁇ alkylene, they form together with the carbon atom to which they are bonded a C 3 -C 7 cycloalkyl ring.
  • C 3 -C 7 Cycloalkyl is, for example, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, especially cyclopentyl and cyclohexyl, preferably cyclo- hexyl.
  • Suitable monomers or/and oligomers that comprise at least one ethylenically unsaturated group and which may be present in the solution, emulsion or suspension according to b1) are, for example, those described below in the case of d1).
  • UV absorbers suitable as reactive substance b2) include compounds from the following classes: hydroxyphenyl-benzotriazoles, hydroxyphenyl-benzophenones, oxalic acid amides, triazines, oxalanilides, cyanoacrylates, salicylic acids and hydroxyphenylpyrimidines. Also especially suitable are UV absorbers comprising an ethylenically unsaturated group. As ethylenically unsaturated groups there come into consideration especially those which can be polymerised by free radical polymerisation; in addition to vinyl and vinylidene groups there are to be mentioned especially acrylate, methacrylate, allyl ether, styryl ether and vinyl ether groups.
  • R15 to R17 independently of one another may be H, linear or branched alkyl groups, substituted or unsubstituted aryl groups, or ethylenically unsaturated groups bonded directly or via spacer groups;
  • Ri5 and R ⁇ 6 independently of one another may be H, linear or branched alkyl groups, or substituted or unsubstituted aryl groups. Special preference is given to the following compounds:
  • -CH 2 CH(OH)CH 2 OCOC(CH 3 ) CH 2 .
  • -CH 2 CH CH 2 .
  • R ⁇ 5 is H, d-C 12 alkyl, C 6 -C 10 aryl and R i6 is H, halogen, C C ⁇ 2 alkyl or C 6 -C ⁇ 0 aryl;
  • the following compounds are also preferred: -cyano- ⁇ , ⁇ -diphenylacrylic acid ethyl ester or isooctyl ester, -methoxycarbonylcinnamic acid methyl ester, ⁇ -cyano- ⁇ -methyl-p-methoxy- cinnamic acid methyl ester or butyl ester, -methoxycarbonyl-p-methoxycinnamic acid methyl ester, N-( ⁇ -methoxycarbonyl- ⁇ -cyanovinyl)-2-methyl-indoline, N-(phthalimidomethyl)acryl- amide, vinylphenyl acetate, 9-vinylanthracene, phenyJmethacrylate, 2-phenylethyl acrylate, 2- phenylethylmethacrylate, 4-(2-acryloxyethoxy)-2-hydroxybenzophenone, 3-allyl-4-hydroxy- acetophenone.
  • synergists UV absorbers combined with other substances
  • Such synergists can also be used within the context of the invention.
  • synergists are light stabilisers, free radical scavengers, peroxide decomposers etc.
  • Examples of synergists are compounds from the following classes: sterically hindered amines, amino ethers (>NOR-compounds), benzoxazines and/or thioethers.
  • a number of compounds may be mentioned as examples: bis(2 J 2,6,6-tetramethylpiperidyl) sebacate, bis(2,2,6,6-tetramethylpiperidyl) succinate, bis(1 ,2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di-tert-butyl-4- hydroxybenzylmalonic acid bis(1 ,2,2,6,6-pentamethylpiperidyl) ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N'-bis(2,2,6 J 6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert- octylamino-2,6-dichloro-1,3,5-s-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetra
  • Suitable free-radical-forming initiators according to b2) are, for example, those mentioned in b1), both those compounds having an ethylenically unsaturated group and those not having that group.
  • Suitable monomeric or oligomeric ethylenically unsaturated compounds that may be present in the solution, emulsion or suspension according to b2) are, for example, those described hereinbelow in d1).
  • Suitable electron or H donors b3) are, for example, primary, secondary or tertiary amines, thiols or thioethers or mixtures thereof.
  • all amines, thiols and thioethers that comprise at least one ethylenically unsaturated group are suitable for use in the process according to the invention.
  • the amines may also be oligomeric amines. Special preference is given to compounds of formulae Xa, Xb, Xc, Xd and Xe.
  • R 23 is d-Cisalkyl, phenyl, phenyl-d-C 3 alkyl or a group
  • q is a number from 0 to 3;
  • R 24 is C ⁇ -C ⁇ 8 alkyl, phenyl or phenyl-d-C 3 alkyl;
  • ⁇ 5 is a direct bond, a group -(CH 2 ) P - or a branched C 3 -C ⁇ 8 alkylene group; and
  • p is a number from 1 to 12.
  • R 2 ⁇ and R 22 are d-C alkyl or form together with the nitrogen atom to which they are bonded a morpholine radical.
  • R 23 is d-C alkyl or benzyl.
  • R 2 is preferably d-C 4 alkyl and p is preferably from 1 to 4.
  • R 21 and R 22 together with the nitrogen atom form a 5- or 6-membered cycloaliphatic ring which may, in addition, be interrupted by a nitrogen or oxygen atom, that ring may, for example, be cyclopentyl, cyclohexyl, pyrrolidine, morpholine, pyrazoline, pyrazolidone, imidazoline, imidazolidine, oxazolidine, oxazolidinone, piperidine, piperazine or piperazinone.
  • the majority of the compounds of formulae Xa to Xe are known and are commercially available or can be prepared by analogous processes. Vinyl ethers or styrenes containing amine or thio groups are also suitable compounds.
  • dimethyl-bis(methylthio)methylene malonate N-vinylpyrrolidone and N,N- diethyl-2-ethylvinyl ether.
  • Suitable amines that can also be used in the context of the present invention are furthermore provided by a number of manufacturers under their trade names. Examples are mentioned below.
  • the following groups are to be understood as being a function-controlling group in accordance with the chemically active substances used in b4) of the process according to the invention: i) a hydrophilic or hydrophobic group for controlling hydrophilicity/hydrophobicity, ii) an acid, neutral or basic functional group for controlling acid/base properties, iii) a functional group having a high or low incremental refraction, for controlling refractive index, iv) a functional group having an effect on the growth of cells and/or organisms, for controlling biological properties, v) a functional group having an effect on combustibility, for controlling flame resistance properties, and/or vi) a functional group having an effect on electrical conductivity, for controlling antistatic properties.
  • hydrophilic group a polar group, such as an alcohol, ether, acid, ester, aldehyde, keto, sugar, phenol, urethane, acrylate, vinyl ether, epoxy, amide, acetal, ketal, anhydride, quatemised amino, imide, carbonate or nitro group, a salt of an acid, or a (poly)glycol unit.
  • a polar group such as an alcohol, ether, acid, ester, aldehyde, keto, sugar, phenol, urethane, acrylate, vinyl ether, epoxy, amide, acetal, ketal, anhydride, quatemised amino, imide, carbonate or nitro group, a salt of an acid, or a (poly)glycol unit.
  • a carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid, phenol, amino acid or amino, pyridine, pyrimidine, piperidine, pyrrole or imidazole group is especially advantageous to use allylamine, 2-aminoethyl methacrylate, 4-vinylpyridine, vinylpyrrolidone, vinyl imidazole, morpholinoethyl acrylate, acrylic acid, 2-propene-1-sulfonic acid, sorbic acid, cinnamic acid or maleic acid.
  • a benzyl group, a partially or completely halogenated benzyl group, or a partially or completely halogenated alkane, alkene or alkyne group is preferably used, benzyl acrylate, 1H,1H,7H-dodecafluoroheptyl methacrylate, 1H,1H-heptafluorobutyl acrylate and trifluoroethyl acrylate having been found especially advantageous.
  • a group that controls biological properties it is possible to use a group having antifouling properties, such as copper(ll) methacrylate, dibutyltin maleate, tin(ll) methacrylate or zinc dimethacrylate.
  • Another possibility for controlling the biological properties is to use a group that promotes growth of biological systems.
  • Succinimide, glucoside and sugar groups have been found especially advantageous for that purpose, especially good results being obtained with N- acyloxysuccinimide or 2-methacryloxyethylglucoside.
  • a group that controls flame resistance properties a completely or partially chlorinated or brominated alkane or nitrogen- or phosphorus-containing group is used.
  • phenyltribromomethylsulphone 2,2,2-trichloro-1-[4-(1,1-dimethylethyl)phenyl]- ethanone, tribromoneopentyl methacrylate, bis(2-methacryloxyethyl) phosphate or monoacryloxyethyl phosphate.
  • the antistatic properties can also be controlled by selecting a suitable functional group.
  • Functional groups that are especially suitable for the purpose are tertiary amino, ethoxylated amino, alkanol amide, glycerol stearate, sorbitan or sulfonate groups, such as especially 2- diisopropylaminoethyl methacrylate, 3-dimethylaminoneopentyl acrylate or oleylbis(2-hydr- oxyethyl)amine, stearyl acrylate and/or vinyl stearate.
  • An activatable initiator incorporating at least one group that interacts with a subsequently applied coating to impart adhesion or reacts with groups contained therein in accordance with the chemically active substances used in b5) of the process according to the invention is to be understood as being, for example, a compound which is capable of specifically introducing chemical functionalities to produce the reactive groups.
  • Suitable activatable initiators are all compounds or mixtures of compounds that produce one or more free radicals (including in the form of intermediates) when heated and/or when irradiated with electromagnetic waves. These include, in addition to compounds or combinations that are usually thermally activated, such as, for example, peroxides and hydroperoxides (also in combination with accelerators, such as amines and/or cobalt salts) and amino ethers (NOR compounds), photochemically activatable compounds (e.g. benzoins) or combinations of chromophores with coinitiators (e.g. benzophenone and tert-amines) or mixtures thereof. It is also possible to use sensitizers with coinitiators (e.g.
  • thioxanthones with tert-amines or chromophores (e.g. thioxanthones with amino ketones).
  • Redox systems such as a combination of H 2 O 2 with iron(ll) salts, can also be used. It is also possible to use electron-transfer pairs, such as dyes and borates and/or amines.
  • a compound or a combination of compounds from the following classes: peroxides, peroxodicarbonates, persulfates, benzopinacols, dibenzyls, disulfides, azo compounds, redox systems, benzoins, benzil ketals, acetophenones, hydroxyalkylpheno ⁇ es, aminoalkylphenones, acylphosphine oxides, acylphosphine sulfides, acyloxyiminoketones, halogenated acetophenones, phenyl glyoxalates, benzophenones, oximes and oxime esters, thioxanthones, camphorquinones, ferrocenes, titanocenes, sulfonium salts, iodonium salts, diazonium salts, onium salts, bora- alkyls, borates, triazines, bisimid
  • Preferred compounds are. dibenzoyl peroxide, benzoyl peroxide, dicumyl peroxide, cumyl hydroperoxide, diisopropyl peroxidicarbonate, methyl ethyl ketone peroxide, bis(4-tert-butyl- cyclohexyl) peroxidicarbonate, ammonium peroxomonosulfate, ammonium peroxodisulfate, dipotassium persulfate, disodium persulfate, N.N-azobisisobutyronitrile, 2,2'-azobis(2,4- dimethylpentanenitrile).
  • the irradiation in step c) is preferably carried out using radiation sources described hereinafter (in d1)).
  • the radiation dose used in step c) is, for example, from 1 to 100O mJ/cm 2 , such as approximately 1-800 mJ/cm 2 , or, for example, 1-500 mJ/cm 2 , for example from 5 to 300 mJ/cm 2 , preferably from 10 to 200 mJ/cm 2 .
  • the irradiation and, where appropriate, previous drying can be carried out, for example, in air or under inert gas conditions.
  • Nitrogen for example, comes into consideration as inert gas in this context, but other inert gases, such as, for example, CO 2 or argon, helium etc. or mixtures thereof are also suitable.
  • Suitable systems and corresponding apparatus are familiar to the person skilled in the art and, for example, are also commercially available.
  • the workpiece can be stored or further processed directly, and a further coating d) can be applied.
  • a further coating d) can be applied.
  • the latter step comprises, for example, the following: either d1), preferably, a radiation-curable coating containing ethylenically unsaturated bonds is applied by known techniques, or d2) a coating that dries/cures by different means, for example a printing ink or a surface coating, is applied.
  • Coating can be carried out, for example, by pouring, immersion, spraying, brush application, knife application, roller application or spin-coating.
  • the further layer d) may, however, also be, for example, d3) a metal layer.
  • the further coating d) is d1) a composition comprising at least one ethylenically unsaturated monomer or oligomer, which is cured by UV/NIS radiation or an electron beam; or d2) a printing ink or surface coating, or d3) a metal layer.
  • the unsaturated compounds of the radiation-curable composition d1) may contain one or more ethylenically unsaturated double bonds. They may be lower molecular weight (monomeric) or higher molecular weight (oligomeric). Examples of monomers having a double bond are alkyl and hydroxyalkyl acrylates and methacrylates, e.g. methyl, ethyl, butyl, 2-ethylhexyl and 2-hydroxyethyl acrylate, isobomyl acrylate and methyl and ethyl methacrylate. Silicone acrylates are also of interest.
  • acrylonitrile acrylamide, methacrylamide, ⁇ -substituted (meth)acrylamides
  • vinyl esters such as vinyl acetate, vinyl ethers, such as isobutyl vinyl ether, styrene, alkyl- and halo-styrenes, ⁇ -vinylpyrrolidone, vinyl chloride and vinylidene chloride.
  • Examples of monomers having more than one double bond are ethylene glycol diacrylate, 1,6-hexanediol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropyl- ene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate and bis- phenol-A diacrylate, 4,4'-bis(2-acryloyloxyethoxy)diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, vinyl acrylate, divinylben- zene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, tris(hydr- oxyethyl) isocyanurate triacrylate (Sartomer 368; from Cray Valley) and tris(2-acryloylethyl
  • acrylic esters of alkoxylated polyols for example glycerol ethoxylate triacrylate, glycerol propoxylate triacrylate, trimethylolpropaneethoxylate triacrylate, trimethylolpropanepropoxylate triacrylate, pentaerythritol ethoxylate tetraacrylate, pentaerythritol propoxylate triacrylate, pentaerythritol propoxylate tetraacrylate, neopentyl glycol ethoxylate diacrylate or neopentyl glycol propoxylate diacrylate to be used in radiation- curable systems.
  • the degree of alkoxylation of the polyols used may vary.
  • oligomeric polyunsaturated compounds examples include acrylated epoxy resins, acrylated or vinyl-ether- or epoxy-group-containing polyesters, polyurethanes and polyethers.
  • unsaturated oligomers are unsaturated polyester resins, which are usually produced from maleic acid, phthalic acid and one or more diols and have molecular weights of about from 500 to 3000.
  • vinyl ether monomers and oligomers and also maleate-terminated oligomers having polyester, polyurethane, polyether, polyvinyl ether and epoxide main chains.
  • esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides and polymers having ethylenically unsaturated groups in the chain or in side groups, e.g. unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and iso- prene copolymers, polymers and copolymers having (meth)acrylic groups in side chains, and also mixtures of one or more such polymers.
  • unsaturated polyesters, polyamides and polyurethanes and copolymers thereof alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and iso- prene copolymers, polymers and copolymers having (meth)acrylic groups in side chains, and also mixtures of one or more such polymers.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid and unsaturated fatty acids such as linolenic acid or oleic acid.
  • Acrylic and methacrylic acid are preferred.
  • Suitable polyols are aromatic and especially aliphatic and cycloaliphatic polyols.
  • aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di(4-hydroxyphenyl)propane, and novolaks and resols.
  • polyepoxides are those based on the said polyols, especially the aromatic polyols and epichlorohydrin.
  • Also suitable as polyols are polymers and copolymers that contain hydroxyl groups in the polymer chain or in side groups, e.g. polyvinyl alcohol and copolymers thereof or polymethacrylic acid hydroxyalkyl esters or copolymers thereof.
  • polyols are oligoesters having hydroxyl terminal groups.
  • aliphatic and cycloaliphatic polyols include alkylenediols having preferably from 2 to 12 carbon atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4- butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols having molecular weights of preferably from 200 to 1500, 1,3- cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris( ⁇ -hydroxyethyl)amine, trimethylolethane, trimethylolpropane, pentaerythrito
  • the polyols may have been partially or completely esterified by one or by different unsaturated carboxylic acid(s), it being possible for the free hyd roxyl groups in partial esters to have been modified, for example etherified, or esterified by other carboxylic acids.
  • esters are: trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacryl- ate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pen-taacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipenta
  • polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1 ,4-butylenediamine, 1,5-pentylenediamine, 1,6- hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diarnino-cyclohexane, isophor- onediamine, phenylenediamine, bisphenylenediamine, di- ⁇ -aminoethyl ether, diethylenetri- amine, triethylenetetramine and di( ⁇ -aminoethoxy)- and di( ⁇ -aminopropoxy)-ethane.
  • polyamines are polymers and copolymers which may have additional amino groups in the side chain and oligoamides having amino terminal groups.
  • unsaturated amides are: methylene bisacrylamide, 1 ,6-hexamethylene bisacrylamide, diethylenetriamine trismethacrylamide, bis(methacrylamidopropoxy)ethane, ⁇ -methacryl- amidoethyl methacrylate and N-[( ⁇ -hydroxyethoxy)ethyl]-acrylamide.
  • Suitable unsaturated polyesters and polyamides are derived, for example, from maleic acid and diols or diamines.
  • the maleic acid may have been partially replaced by other dicarboxylic acids. They may be used together with ethylenically unsaturated comonomers, e.g. styrene.
  • the polyesters and polyamides may also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, especially from those having longer chains of e.g. from 6 to 20 carbon atoms.
  • Examples of polyurethanes are those composed of saturated diisocyanates and unsaturated diols or unsaturated diisocyanates and saturated diols.
  • Suitable comonomers include, for example, olefins, such as ethylene, propene, butene, hexene, (meth)acrylates, acrylonitrile, styrene and vinyl chloride. Polymers having (meth)acrylate groups in the side chain are likewise known.
  • Examples are reaction products of novolak-based epoxy resins with (meth)acrylic acid; homo- or co-polymers of vinyl alcohol or hydroxyalkyl derivatives thereof that have been esterified with (meth)acrylic acid; and homo- and co-polymers of (meth)acrylates that have been esterified with hydroxyalkyl (meth)acrylates.
  • (meth)acrylate includes both the acrylate and the methacrylate.
  • An acrylate or methacrylate compound is especially used as the mono- or poly-ethylenically unsaturated compound.
  • the composition comprises at least one further photoinitiator or coinitiator for curing with UVVIS radiation.
  • the invention also relates, therefore, to a process wherein, in process step d1), a photo- polymerisable composition comprising at least one ethylenically unsaturated monomer or/and oligomer and at least one photoinitiator and/or coinitiator is applied to the pretreated substrate and cured by means of UV/VIS radiation.
  • UV/VIS radiation is to be understood as being electromagnetic radiation in a wavelength range of from 150 nm to 800 nm. Preference is given to the range from 200 nm to 500 nm. Suitable radiation sources are known to the person skilled in the art and are commercially available.
  • the light-sensitivity of the compositions according to process step d1) generally ranges from about 150 nm to about 600 nm (UV region).
  • a large number of the most varied kinds of light source may be used.
  • Both point sources and planiform radiators (lamp arrays) are suitable. Examples are: carbon arc lamps, xenon arc lamps, medium-pressure, super-high-pressure, high-pressure and low-pressure mercury radiators doped, where appropriate, with metal halides (metal halide lamps), microwave-excited metal vapour lamps, excimer lamps, super- actinic fluorescent tubes, fluorescent lamps, argon incandescent lamps, flash lamps, photographic floodlight lamps, light-emitting diodes (LED), electron beams and X-rays.
  • metal halides metal halide lamps
  • microwave-excited metal vapour lamps excimer lamps
  • super- actinic fluorescent tubes fluorescent lamps
  • argon incandescent lamps argon incandescent lamps
  • flash lamps photographic floodlight lamps
  • the distance between the lamp and the substrate to be exposed may vary according to the intended use and the type and strength of the lamp and may be, for example, from 2 cm to 150 cm. Also suitable are laser light sources, for example excimer lasers, such as Krypton-F lasers for irradiation at 248 nm. Lasers in the visible range may also be used. Using that method, it is possible to produce printed circuits in the electronics industry, lithographic offset printing plates or intaglio printing plates, and photographic image recording materials.
  • suitable radiation sources relates both to the irradiation step c) (fixing of the photoinitiator) in the process according to the invention and to the procedure of process step d1) (curing of the photocurable composition).
  • Curing of the composition applied in process step d1) or d2) may, in addition, also be carried out using daylight or daylight-equivalent light sources.
  • the dose of radiation used in process step c) is, for example, from 1 to 1000 mJ/cm 2 , such as 1-800 mJ/cm 2 , or, for example, 1-500 mJ/cm 2 , e.g. from 5 to 300 mJ/cm 2 , preferably from 10 to 200 mJ/cm 2 .
  • Photoinitiators that do not have unsaturated groups are preferably used in those compositions.
  • benzophenones benzophenone derivatives, acetophenone, acetophenone derivatives, such as, for example, ⁇ -hydroxycycloalkyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propanone or 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl- propionyl)-benzyl]-phenyl ⁇ -2-methyl-propan-1-one, dialkoxyacetophenone, -hydroxy- or ⁇ -aminoacetophenone, such as e.g.
  • sensitisers which shift or broaden the spectral sensitivity and thus bring about an acceleration of the photopolymerisation.
  • They are especially aromatic carbonyl compounds, for example benzophenone, thioxanthone, especially isopropyl thioxanthone, anthraquinone and 3-acylcoumarin derivatives, terphenyls, styryl ketones, and also 3-(aroylmethylene)-thiazolines, camphorquinone, and also eosine, rhodamine and erythrosine dyes.
  • Amines for example, can also be regarded as photosensitisers when the photoinitiator layer grafted on according to the invention consists of a benzophenone or benzophenone derivative.
  • the radiation-curable composition may comprise further additives, especially light stabilisers.
  • additional additives are governed by the intended use of the coating in question and will be familiar to the person skilled in the art.
  • compositions may also be pigmented when suitable photoinitiators are chosen, it being possible for coloured pigments and white pigments to be used.
  • the photocurable compositions (process step d1)) can be applied in layer thicknesses of from about 0.1 ⁇ m to about 1000 ⁇ m, preferably from about 1 ⁇ m to 100 ⁇ m. In the range of low layer thicknesses of ⁇ 50 ⁇ m, pigmented compositions, for example, are also referred to as printing inks.
  • UV absorbers e.g. those of the hydroxyphenyl- benzotriazole, hydroxyphenylbenzophenone, oxalic acid amide or hydroxyphenyl-s-triazine type.
  • Such compounds can be used singly or in the form of mixtures, with or without the use of sterically hindered amines (HALS).
  • HALS sterically hindered amines
  • other stabilisers such as phosphites or phosphonites, for example, are also suitable.
  • additives that are customary in the art, e.g. antistatics, flow improvers and adhesion promoters.
  • compositions applied in process step d), for example d1) or d2) are, for example, pigmented or non-pigmented surface coatings, inks, ink-jet inks; printing inks, for example screen printing inks, offset printing inks, flexographic printing inks; or overprint varnishes; or primers; or printing plates, offset printing plates; powder coatings, adhesives or repair coatings, repair varnishes or repair putty compositions.
  • compositions used in process step d1) need not necessarily comprise a photoinitiator - for example they may be customary electron-beam-curable compositions (without photoinitiator) known to the person skilled in the art.
  • the substrates pretreated in accordance with the process of the invention may be coated with conventional photocurable compositions and cured by UV/VIS radiation or an electron beam in a further step d1) or, alternatively, d2) provided with a conventional coating that is dried, for example, in air or thermally. Drying may also be effected, for example, by absorption, e.g. penetration into the substrate.
  • the coating used in process step d2) is preferably a printing ink.
  • a printing ink is, for example, a liquid or paste-form dispersion that comprises colorants (pigments or dyes), binders and also optionally solvents and/or optionally water and additives.
  • the binder and, if applicable, the additives are generally dissolved in a solvent.
  • Customary viscosities in the Brookfield viscometer are, for example, from 20 to 5000 mPa-s, for example from 20 to 1000 mPa-s, for liquid printing inks.
  • the values range, for example, from 1 to 100 Pa s, preferably from 5 to 50 Pa-s.
  • the person skilled in the art will be familiar with the ingredients and compositions of printing inks.
  • Suitable pigments like the printing ink formulations customary in the art, are generally known and widely described.
  • Printing inks comprise pigments advantageously in a concentration of, for example, from 0.01 to 40 % by weight, preferably from 1 to 25 % by weight, especially from 5 to 10 % by weight, based on the total weight of the printing ink.
  • the printing inks can be used, for example, for intaglio printing, flexographic printing, screen printing, offset printing, lithography or continuous or dropwise ink-jet printing on material pretreated in accordance with the process of the invention using generally known formulations, for example in publishing, packaging or shipping, in logistics, in advertising, in security printing or in the field of office equipment.
  • Suitable printing inks are both solvent-based printing inks and water-based printing inks.
  • printing inks based on aqueous acrylates are to be understood as including polymers or copolymers that are obtained by polymerisation of at
  • Suitable organic solvents are water-miscible solvents customarily used by the person skilled in the art, for example alcohols, such as methanol, ethanol and isomers of propanol, butanol and pentanol, ethylene glycol and ethers thereof, such as ethylene glycol methyl ether and ethylene glycol ethyl ether, and ketones, such as acetone, ethyl methyl ketone or cyclo, for example isopropanol. Water and alcohols are preferred.
  • Suitable printing inks comprise, for example, as binder primarily an acrylate polymer or copolymer and the solvent is selected, for example, from the group consisting of water, d-C 5 alcohols, ethylene glycol, 2-(d-C 5 alkoxy)-ethanol, acetone, methyl ethyl ketone and any mixtures thereof.
  • the printing inks may, where appropriate, also comprise customary additives known to the person skilled in the art in customary concentrations.
  • a printing ink is usually prepared by dilution of a printing ink concentrate and can then be used in accordance with methods known perse.
  • the printing inks may, for example, also comprise alkyd systems that dry oxidatively.
  • the printing inks are dried in a known manner customary in the art, optionally with heating of the coating.
  • a suitable aqueous printing ink composition comprises, for example, a pigment or a combination of pigments, a dispersant and a binder.
  • Dispersants that come into consideration include, for example, customary dispersants, such as water-soluble dispersants based on one or more arylsulfonic acid/formaldehyde condensation products or on one or more water-soluble oxalkylated phenols, non-ionic dispersants or polymeric acids.
  • customary dispersants such as water-soluble dispersants based on one or more arylsulfonic acid/formaldehyde condensation products or on one or more water-soluble oxalkylated phenols, non-ionic dispersants or polymeric acids.
  • arylsulfonic acid/formaldehyde condensation products are obtainable, for example, by sulfonation of aromatic compounds, such as naphthalene itself or naphthalene-containing mixtures, and subsequent condensation of the resulting arylsulfonic acids with formaldehyde.
  • aromatic compounds such as naphthalene itself or naphthalene-containing mixtures
  • Suitable oxalkylated phenols are likewise known and are described, for example, in US 4218218 and DE 19727767.
  • Suitable non-ionic dispersants are, for example, alkylene oxide adducts, polymerisation products of vinylpyrrolidone, vinyl acetate or vinyl alcohol and co- or ter-polymers of vinyl pyrrolidone with vinyl acetate and/or vinyl alcohol. It is also possible, for example, to use polymeric acids which act both as dispersants and as binders.
  • binder components examples include acrylate-group- containing, vinyl-group-containing and/or epoxy-group-containing monomers, prepolymers and polymers and mixtures thereof. Further examples are melamine acrylates and silicone acrylates.
  • the acrylate compounds may also be non-ionically modified (e.g. provided with amino groups) or ionically modified (e.g. provided with acid groups or ammonium groups) and used in the form of aqueous dispersions or emulsions (e.g. EP 704469, EP 12339).
  • the solventless acrylate polymers can be mixed with so-called reactive diluents, for example vinyl-group-containing monomers.
  • the printing ink compositions may also comprise as additional component, for example, an agent having a water-retaining action (humectant), e.g. polyhydric alcohols, polyalkylene glycols, which renders the compositions especially suitable for ink-jet printing.
  • an agent having a water-retaining action e.g. polyhydric alcohols, polyalkylene glycols, which renders the compositions especially suitable for ink-jet printing.
  • the printing inks may comprise further auxiliaries, such as are customary especially for (aqueous) ink-jet inks and in the printing and coating industries, for example preservatives (such as glutardialdehyde and/or tetramethylolacetyleneurea, anti-oxidants, degassers/defoamers, viscosity regulators, flow improvers, anti-settling agents, gloss improvers, lubricants, adhesion promoters, anti-skin agents, matting agents, emulsifiers, stabilisers, hydrophobic agents, light stabilisers, handle improvers and antistatics.
  • preservatives such as glutardialdehyde and/or tetramethylolacetyleneurea, anti-oxidants, degassers/defoamers, viscosity regulators, flow improvers, anti-settling agents, gloss improvers, lubricants, adhesion promoters, anti-skin agents, matting agents, e
  • Printing inks suitable in process step d2) also include, for example, those comprising a dye
  • Such printing inks may comprise organic solvents, e.g. water-miscible organic solvents, for example d-C alcohols, amides, ketones or ketone alcohols, ethers, nitrogen-containing heterocyclic compounds, polyalkylene glycols, C -C 6 alkylene glycols and thioglycols, further polyols, e.g.
  • glycerol and d-dalkyl ethers of polyhydric alcohols usually in an amount of from 2 to 30 % by weight, based on the total weight of the printing ink.
  • the printing inks may also, for example, comprise solubilisers, e.g. ⁇ -caprolactam.
  • the printing inks may, inter alia for the purpose of adjusting the viscosity, comprise thickeners of natural or synthetic origin. Examples of thickeners include commercially available alginate thickeners, starch ethers or locust bean flour ethers.
  • the printing inks comprise such thickeners e.g. in an amount of from 0.01 to 2 % by weight, based on the total weight of the printing ink.
  • the printing inks may comprise buffer substances, for example borax, borates, phosphates, polyphosphates or citrates, in amounts of e.g. from 0.1 to 3 % by weight, in order to establish a pH value of e.g. from 4 to 9, especially from 5 to 8.5.
  • buffer substances for example borax, borates, phosphates, polyphosphates or citrates
  • surfactants or humectants include commercially available anionic and non-ionic surfactants.
  • Humectants that come into consideration include, for example, urea or a mixture of sodium lactate (advantageously in the form of a 50 to 60 % aqueous solution) and glycerol and/or propylene glycol in amounts of e.g. from 0.1 to 30 % by weight, especially from 2 to 30 % by weight, in the printing inks.
  • the printing inks may also comprise customary additives, for example foam- reducing agents or especially substances that inhibit the growth of fungi and/or bacteria.
  • additives are usually used in amounts of from 0.01 to 1 % by weight, based on the total weight of the printing ink.
  • the printing inks may also be prepared in customary manner by mixing the individual components together, for example in the desired amount of water.
  • the viscosity or other physical properties of the printing ink especially those properties which influence the affinity of the printing ink for the substrate in question, to be adapted accordingly.
  • the printing inks are also suitable, for example, for use in recording systems of the kind in which a printing ink is expressed from a small opening in the form of droplets which are directed towards a substrate on which an image is formed.
  • Suitable substrates are, for example, textile fibre materials, paper, plastics or aluminium foils pretreated by the process according to the invention.
  • Suitable recording systems are e.g. commercially available ink-jet printers.
  • the coating d3) which can be applied to the substrate pretreated in accordance with steps a)-c) there come into consideration, for example, metals, semi-metals or metal oxides deposited from the gas phase.
  • irradiation using electromagnetic waves is carried out, either while the metal, semi-metal or metal oxide is being deposited from the gas phase or after that process.
  • suitable metals, semi-metals and metal oxides that can be applied to the substrate pretreated in accordance with the process of the invention steps a)-c) are zinc, copper, nickel, gold, silver, platinum, palladium, chromium, molybdenum, aluminium, iron, titanium. Preference is given to gold, silver, chromium, molybdenum, aluminium and copper, especially aluminium and copper. Also of interest are, for example, semi-metals and metal oxides such as aluminium oxide, chromium oxide, iron oxide, copper oxide and silicon oxide. Gold, silver, chromium, molybdenum, aluminium and copper are preferred.
  • the metals, semi-metals or metal oxides are vaporised and are deposited under vacuum conditions on the substrate provided with the photoinitiator layer. This deposition may, as already mentioned, be carried out while performing irradiation with electromagnetic radiation. Alternatively, it is possible to carry out irradiation after the deposition of the metal.
  • the temperatures for the deposition step depend upon the metal used and are, for example, especially in a range of from 300 to 2000°C, preferably in the range of from 800 to 1800°C.
  • the UV radiation during the deposition step may, for example, be produced by an anodic arc whereas, for UV irradiation after the deposition, the lamps described hereinbefore are suitable.
  • the metal-coated substrates may be used, for example, as diffusion-inhibiting layers or as electromagnetic shields or they are used as decorative elements, for decorative foils, or for foils used for packaging, e.g. for food packaging.
  • the process according to the invention can be carried out within a wide pressure range, the discharge characteristics shifting as the pressure increases from a pure low-temperature plasma towards a corona discharge and finally changing into a pure corona discharge at an atmospheric pressure of about 1000-1100 mbar.
  • the process is preferably carried out at a process pressure of from 10 "6 mbar up to atmospheric pressure (1013 mbar), especially in the range of from 10 " to 10 "2 mbar as a plasma process and at atmospheric pressure as a corona process.
  • the flame treatment is usually carried out at atmospheric pressure.
  • the process is preferably carried out using as the carrier gas an inert gas or a mixture of an inert gas with a reactive gas.
  • air, CO 2 , nitrogen and/or noble gases are preferably used as the gas.
  • the photoinitiator layer deposited preferably has a thickness ranging, for example, from a monomolecular layer up to 100 nm, e.g. from 5 to 100 nm, or from 5 to 50 nm, e.g. 5-10 nm, preferably from 5 nm to 100 nm.
  • the plasma treatment or corona treatment of the inorganic or organic substrate a) preferably takes place for from 1 ms to 300 s, especially from 10 ms to 200 s.
  • process step b) it is advantageous to apply the photoinitiator as quickly as possible after the plasma-, corona- or flame-pretreatment, but for many purposes it may also be acceptable to carry out reaction step b) after a time delay. It is preferable, however, to carry out process step b) immediately after process step a) or within 24 hours after process step a). Also of interest is a process wherein process step c) is carried out immediately after process step b) or within 24 hours after process step b).
  • the pretreated and photoinitiator-coated substrate can be subjected to process step d) immediately after coating and drying in accordance with process steps a), b) and c) or it can be stored in the pretreated form.
  • the chemically active substance for example the photoinitiator in the case of b1), or where applicable the mixture of a plurality of chemically active substances (photoinitiators) and/or coinitiators, is applied to the corona-, plasma- or flame-pretreated substrate, for example, in pure form, that is to say without further additives, when the substances concerned are liquid, or alternatively is applied in combination with a monomer or oligomer, or dissolved in a solvent.
  • the initiator, or the initiator mixture can also, for example, be dispersed, suspended or emulsified in water, a dispersant being added as necessary.
  • Suitable dispersants e.g. any surface-active compounds, preferably anionic and non-ionic surfactants, and also polymeric dispersants, are usually known to the person skilled in the art and are described, for example, in US 4965294 and US 5168087.
  • Suitable solvents are in principle any substances in which component b), e.g. the photoinitiator or the photoinitiators, can be converted into a state suitable for application, whether in the form of a solution or in the form of a suspension or emulsion.
  • Suitable solvents are, for example, alcohols, such as ethanol, propanol, isopropanol, butanol, ethylene glycol etc., ketones, such as acetone; methyl ethyl ketone, acetonitrile, aromatic hydrocarbons, such as toluene and xylene, esters and aldehydes, such as ethyl acetate, ethyl formate, aliphatic hydrocarbons, e.g. petroleum ether, pentane, hexane, cyclohexane, halogenated hydrocarbons, such as dichloromethane or chloroform, or alternatively oils, natural oils, castor oil, vegetable oil etc., and also synthetic oils.
  • alcohols, water and esters are preferred.
  • Suitable monomers and oligomers are, for example, those described above in connection with the photocurable composition.
  • process step b1) is a process wherein the photoinitiators or mixtures thereof with monomers or oligomers in combination with one or more liquids (such as solvents or water) are used in the form of solutions, suspensions and emulsions.
  • liquids such as solvents or water
  • process step b1) it is therefore possible in process step b1) to apply to the pretreated substrate, for example, 0.1-15 %, e.g. 0.1-5 %, of a photoinitiator having an unsaturated group or, for example, 0.1-15 %, e.g. 0.1-5 %, of a photoinitiator, for example not having an unsaturated group, and, for example, 0.5-10 % of a monomer, such as an acrylate, methacrylate, vinyl ether etc..
  • step b) for example the photoinitiators, mixtures thereof with one another or with monomers or oligomers, is carried out, as described above, by spraying in the form of an aerosol.
  • the photoinitiators for example the photoinitiators, mixtures thereof with one another or with monomers or oligomers
  • step b) the application of the substances in step b), for example the photoinitiators, mixtures thereof with one another or with monomers or oligomers.
  • the chemically active substances e.g. the photoinitiators
  • the chemically active substances are applied as mixtures with monomers or/and solvents or/and water in the form of liquids, solutions, emulsions or suspensions, they are used, for example, in concentrations of up to 20 %, e.g. from 0.01 to 20 %, or 0.01-10 %, e.g.0.1-20 %, or 0.5-10 %, based on the solution being applied.
  • the liquids comprising the photoinitiator may, in addition, contain e.g. further substances, such as defoamers, emulsifiers, surfactants, antifouling agents, wetting agents and other additives customarily used in the industry, especially the coating and paint industries.
  • further substances such as defoamers, emulsifiers, surfactants, antifouling agents, wetting agents and other additives customarily used in the industry, especially the coating and paint industries.
  • drying coatings are known and they can all be used in the claimed process.
  • the irradiation of the coating in order to fix the photoinitiator in process step c) (and also to cure the formulation in process step d), especially d1)) can be carried out, as already mentioned above, using any sources that emit electromagnetic waves of wavelengths that can be absorbed by the photoinitiators used.
  • sources are generally radiation sources that emit radiation in the range from 200 nm to 700 nm.
  • electron beams is also a possibility.
  • lasers and LEDs Light Emitting Diodes.
  • the whole area of the coating or parts thereof may be irradiated. Partial irradiation is of advantage when only certain regions are to be rendered adherent. Suitable radiation sources are, for example, those already described above.
  • the drying and/or irradiation can be carried out under air or under inert gas.
  • Nitrogen gas comes into consideration as inert gas, but other inert gases, such as CO 2 or argon, helium etc. or mixtures thereof, can also be used. Suitable systems and apparatus are known to the person skilled in the art and are commercially available.
  • the invention further relates to the use of photoinitiators and photoinitiator systems in the process according to the invention.
  • the invention also relates to strongly adherent coatings obtainable in accordance with the process described above.
  • Strongly adherent coatings of that kind are important not only as protective layers or coverings, which may additionally be pigmented, but also for image-forming coatings, for example in resist and printing plate technology.
  • the irradiation can be effected through a mask or by writing using moving laser beams (Laser Direct Imaging - LDI). Such partial irradiation can be followed by a development or washing step in which portions of the applied coating are removed by means of solvents and/or water or mechanically.
  • the image-forming step can be carried out either in process step c) or in process step d).
  • the image-forming step may be a crosslinking reaction or alternatively a reaction in which the solubility of the formulation is altered.
  • the invention therefore relates also to a process wherein portions of the photoinitiators, or mixtures thereof with monomers and/or oligomers, applied in process step b) that have not been crosslinked after irradiation in process step c) are removed by treatment with a solvent and/or water and/or mechanically, and to a process wherein after irradiation in process step d1) portions of the coating are removed by treatment with a solvent and/or water and/or mechanically.
  • image-forming processes it is possible for image-forming processes to be used either in one of the two process steps c) and d1) or in both of steps c) and d1) in succession.
  • a biaxially oriented polypropylene film (thickness 15 ⁇ m, Trespaphan) is corona-treated in air four times using a ceramic electrode (manual corona station type CEE 42-0-1 MD, width 330 mm, produced by SOFTAL) placed at a distance of approx. 1-2 mm, at an output of 600 W and at a treatment rate of 10 cm/s.
  • a ceramic electrode manufactured corona station type CEE 42-0-1 MD, width 330 mm, produced by SOFTAL
  • a 1 % ethanolic solution of photoinitiator A is applied to the treated side of the film using a spray device in the form of an aerosol. After drying, the film is irradiated using a UV processor (Fusion Systems) with a microwave-excited mercury lamp with an output of 120 W/cm at a belt speed of 30 m/min .
  • a UV processor Fusion Systems
  • a microwave-excited mercury lamp with an output of 120 W/cm at a belt speed of 30 m/min .
  • a radiation-curable printing ink composition of the following composition is applied to the substrate pretreated in that manner: 18.3 parts Ebecryl 1608 (bisphenol A epoxy acrylate, dissolved in 20 % OTA 480, an oligomeric triacrylate, UCB) 18.3 parts Ebecryl 657 (polyester tetraacrylate, UCB), 20.0 parts Ebecryl 220 (hexa-functional aromatic urethane acrylate, UCB), 20.9 parts Ebecryl 150 (bisphenol A derivative diacrylate oligomer, UCB), 22.5 parts Irgalit blue GLO (copper phthalocvanin ( ⁇ ).
  • Ebecryl 1608 bisphenol A epoxy acrylate, dissolved in 20 % OTA 480, an oligomeric triacrylate, UCB
  • Ebecryl 657 polyyester tetraacrylate, UCB
  • Ebecryl 220 hexa-functional aromatic urethane acrylate, UCB
  • Ciba Specialty Chemicals 100.0 3 % 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone (IRGACURETM 369, Ciba Specialty Chemicals) are incorporated into that formulation.
  • a plasma treatment is carried out in a plasma reactor at 13.56 MHz and at a variable output of from 10 to 100 W.
  • a polyethylene film (PE film) is exposed to an argon/oxygen plasma
  • the sample After drying, the sample is irradiated with an 80 W/cm mercury lamp at a belt speed of
  • a copper layer is deposited, in the same reactor, using an anodic arc process (VALICO process) under a pressure of 2x10 "4 mbar.
  • VALICO process an anodic arc process
  • the crucible temperature is 1500-1600°C. In approx. 1 minute, a layer of 1 ⁇ m thickness has been deposited.
  • the copper layer cannot be detached by an adhesive tape.

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Abstract

La présente invention concerne un procédé de production de couches adhérant fortement sur un substrat organique ou inorganique, avec exécution d'un traitement au plasma basse température, un traitement à décharge corona, ou un traitement à la flamme, sur le substrat organique ou inorganique, une ou plusieurs substances chimiquement actives ou une solution, suspension ou émulsion d'une ou de plusieurs substances chimiquement actives ou des mélanges de substances chimiquement actives avec des monomères et/ou oligomères contenant au moins un groupe éthyléniquement insaturé sont appliqués en aérosol sur le substrat organique ou inorganique, et les substances précédemment mentionnées sont éventuellement séchées au moyen de procédés appropriés, puis sont irradié avec des ondes électromagnétiques, et le substrat ainsi pré-enduit d'une nano-couche est pourvu d'une autre couche.
PCT/EP2005/050994 2004-03-15 2005-03-07 Procede de production de couches adherant fortement Ceased WO2005089957A1 (fr)

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EP04101043.0 2004-03-15
EP04101043 2004-03-15

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WO2005089957A1 true WO2005089957A1 (fr) 2005-09-29

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EP1914279A3 (fr) * 2006-10-19 2008-05-07 Seiko Epson Corporation Ensemble de photo à composition d'encre durcissable, et procédé d'enregistrement et enregistrements utilisant l'ensemble de composition d'encre
GB2447107A (en) * 2006-12-12 2008-09-03 Ford Global Tech Llc Decorating a plastic component by plasma treatment and coating with curable resin
EP1978038A1 (fr) * 2007-04-02 2008-10-08 Vlaamse Instelling Voor Technologisch Onderzoek (Vito) Procédé pour la fabrication d'un revêtement à l'aide de la technologie de plasma à pression atmosphérique
US7744984B2 (en) 2006-06-28 2010-06-29 Ford Global Technologies, Llc Method of treating substrates for bonding
US7981219B2 (en) 2006-12-12 2011-07-19 Ford Global Technologies, Llc System for plasma treating a plastic component
US8048530B2 (en) 2005-09-21 2011-11-01 Ford Global Technologies, Llc Method of coating a substrate for adhesive bonding
WO2012084811A1 (fr) * 2010-12-20 2012-06-28 Agfa Graphics Nv Fluide approprié au jet et durcissable pour la fabrication d'une matrice d'impression flexographique
WO2013062081A1 (fr) * 2011-10-27 2013-05-02 富士フイルム株式会社 Procédé pour la fabrication de produit durci, et produit durci
EP2589438A1 (fr) 2011-11-07 2013-05-08 Vlaamse Instelling voor Technologisch Onderzoek (VITO) Procédé d'activation de surface par plasma et objet obtenu par ledit procédé
US8480799B2 (en) 2007-09-18 2013-07-09 Seiko Epson Corporation Inkjet-recording non-aqueous ink composition, inkjet recording method, and recorded matter
US8518169B2 (en) 2007-01-29 2013-08-27 Seiko Epson Corporation Ink set, ink container, inkjet recording method, recording device, and recorded matter
US8523343B2 (en) 2010-01-28 2013-09-03 Seiko Epson Corporation Aqueous ink composition, ink jet recording method, and recorded matter
US8530538B2 (en) 2005-03-29 2013-09-10 Seiko Epson Corporation Ink composition
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US8673994B2 (en) 2006-11-30 2014-03-18 Seiko Epson Corporation Ink composition, two-pack curing ink composition set, and recording method and recorded matter using these
US8894197B2 (en) 2007-03-01 2014-11-25 Seiko Epson Corporation Ink set, ink-jet recording method, and recorded material
CN104259073A (zh) * 2014-08-25 2015-01-07 宁波净源膜科技有限公司 一种超疏油疏水涂层及其加工方法
US9034427B2 (en) 2008-02-29 2015-05-19 Seiko Epson Corporation Method of forming opaque layer, recording process, ink set, ink cartridge, and recording apparatus
GB2527763A (en) * 2014-06-30 2016-01-06 Innovia Films Ltd Process
GB2527764A (en) * 2014-06-30 2016-01-06 Innovia Films Ltd Process
US9309341B2 (en) 2010-12-20 2016-04-12 Agfa Graphics Nv Curable jettable fluid for making a flexographic printing master
IT201800004997A1 (it) * 2018-05-02 2019-11-02 Impianto e metodo per effettuare rivestimenti di nanomateriali su superfici di oggetti, in particolare impianti di illuminazione
CN114478436A (zh) * 2022-03-14 2022-05-13 浙江扬帆新材料股份有限公司 一种含有可聚合的衣康酸基团改性的α-氨基酮类光引发剂及其制备方法和用途

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US8530538B2 (en) 2005-03-29 2013-09-10 Seiko Epson Corporation Ink composition
US8048530B2 (en) 2005-09-21 2011-11-01 Ford Global Technologies, Llc Method of coating a substrate for adhesive bonding
WO2007041133A3 (fr) * 2005-10-03 2007-07-12 Randall T Lake Composition de revetement durcissant a l'exposition aux rayonnements, et procede correspondant
US7744984B2 (en) 2006-06-28 2010-06-29 Ford Global Technologies, Llc Method of treating substrates for bonding
US7790245B2 (en) 2006-10-19 2010-09-07 Seiko Epson Corporation Photo curable ink composition set, and recording method and recordings employing ink composition set
EP1914279A3 (fr) * 2006-10-19 2008-05-07 Seiko Epson Corporation Ensemble de photo à composition d'encre durcissable, et procédé d'enregistrement et enregistrements utilisant l'ensemble de composition d'encre
US8673994B2 (en) 2006-11-30 2014-03-18 Seiko Epson Corporation Ink composition, two-pack curing ink composition set, and recording method and recorded matter using these
US9790386B2 (en) 2006-11-30 2017-10-17 Seiko Epson Corporation Ink composition, two-pack curing ink composition set, and recording method and recorded matter using these
US9169410B2 (en) 2006-11-30 2015-10-27 Seiko Epson Corporation Ink composition, two-pack curing ink composition set, and recording method and recorded matter using these
GB2447107A (en) * 2006-12-12 2008-09-03 Ford Global Tech Llc Decorating a plastic component by plasma treatment and coating with curable resin
GB2447107B (en) * 2006-12-12 2011-06-15 Ford Global Tech Llc A method for decorating a plastic component with a coating
US7981219B2 (en) 2006-12-12 2011-07-19 Ford Global Technologies, Llc System for plasma treating a plastic component
US8518169B2 (en) 2007-01-29 2013-08-27 Seiko Epson Corporation Ink set, ink container, inkjet recording method, recording device, and recorded matter
US8894197B2 (en) 2007-03-01 2014-11-25 Seiko Epson Corporation Ink set, ink-jet recording method, and recorded material
US9616675B2 (en) 2007-03-01 2017-04-11 Seiko Epson Corporation Ink set, ink-jet recording method, and recorded material
US20100028561A1 (en) * 2007-04-02 2010-02-04 Vlaamese Instelling Voor Technologisch Onderzoek N .V. (VITO) Method for producing a coating by atmospheric pressure plasma technology
WO2008119823A1 (fr) * 2007-04-02 2008-10-09 Vlaamse Instelling Voor Technologisch Onderzoek (Vito) Procédé de formation d'un revêtement par technologie plasma à pression atmosphérique
EP1978038A1 (fr) * 2007-04-02 2008-10-08 Vlaamse Instelling Voor Technologisch Onderzoek (Vito) Procédé pour la fabrication d'un revêtement à l'aide de la technologie de plasma à pression atmosphérique
US8480799B2 (en) 2007-09-18 2013-07-09 Seiko Epson Corporation Inkjet-recording non-aqueous ink composition, inkjet recording method, and recorded matter
US8663751B2 (en) 2007-09-19 2014-03-04 Vlaamse Instelling Voor Technologisch Onderzoek N.V. (Vito) Method for stable hydrophilicity enhancement of a substrate by atmospheric pressure plasma disposition
US9034427B2 (en) 2008-02-29 2015-05-19 Seiko Epson Corporation Method of forming opaque layer, recording process, ink set, ink cartridge, and recording apparatus
US8523343B2 (en) 2010-01-28 2013-09-03 Seiko Epson Corporation Aqueous ink composition, ink jet recording method, and recorded matter
US8614264B2 (en) 2010-01-28 2013-12-24 Seiko Epson Corporation Aqueous ink composition, ink jet recording method and recorded material
US9309341B2 (en) 2010-12-20 2016-04-12 Agfa Graphics Nv Curable jettable fluid for making a flexographic printing master
WO2012084811A1 (fr) * 2010-12-20 2012-06-28 Agfa Graphics Nv Fluide approprié au jet et durcissable pour la fabrication d'une matrice d'impression flexographique
JP2013091741A (ja) * 2011-10-27 2013-05-16 Fujifilm Corp 硬化物の製造方法および硬化物
WO2013062081A1 (fr) * 2011-10-27 2013-05-02 富士フイルム株式会社 Procédé pour la fabrication de produit durci, et produit durci
US8962099B2 (en) * 2011-11-07 2015-02-24 Vlaamse Instelling Voor Technologisch Onderzoek (Vito) Plasma surface activation method and resulting object
US20130112347A1 (en) * 2011-11-07 2013-05-09 Vlaamse Instelling Voor Technologisch Onderzoek (Vito) Plasma surface activation method and resulting object
EP2589438A1 (fr) 2011-11-07 2013-05-08 Vlaamse Instelling voor Technologisch Onderzoek (VITO) Procédé d'activation de surface par plasma et objet obtenu par ledit procédé
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CN114478436A (zh) * 2022-03-14 2022-05-13 浙江扬帆新材料股份有限公司 一种含有可聚合的衣康酸基团改性的α-氨基酮类光引发剂及其制备方法和用途
CN114478436B (zh) * 2022-03-14 2024-04-30 浙江扬帆新材料股份有限公司 一种含有可聚合的衣康酸基团改性的α-氨基酮类光引发剂及其制备方法和用途

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