EP0202803A2 - Aushärten mit Laser von Beschichtungen und Tinten - Google Patents
Aushärten mit Laser von Beschichtungen und Tinten Download PDFInfo
- Publication number
- EP0202803A2 EP0202803A2 EP86303326A EP86303326A EP0202803A2 EP 0202803 A2 EP0202803 A2 EP 0202803A2 EP 86303326 A EP86303326 A EP 86303326A EP 86303326 A EP86303326 A EP 86303326A EP 0202803 A2 EP0202803 A2 EP 0202803A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- cure
- photoinitiator
- curing
- single pulse
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 128
- 239000000976 ink Substances 0.000 title description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 37
- 230000000694 effects Effects 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000000049 pigment Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 9
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 claims description 8
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 6
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 claims description 5
- -1 acyl phosphene Chemical compound 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 206010034962 Photopsia Diseases 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- ZBVQEUUTPTVMHY-UHFFFAOYSA-N phenyl-(2-phenylphenyl)methanone Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 ZBVQEUUTPTVMHY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000065 phosphene Inorganic materials 0.000 claims description 2
- WSDQIHATCCOMLH-UHFFFAOYSA-N phenyl n-(3,5-dichlorophenyl)carbamate Chemical compound ClC1=CC(Cl)=CC(NC(=O)OC=2C=CC=CC=2)=C1 WSDQIHATCCOMLH-UHFFFAOYSA-N 0.000 claims 1
- 230000001795 light effect Effects 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 24
- 239000000975 dye Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 10
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 9
- 238000005286 illumination Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000011087 paperboard Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 2
- JDFDJNNXQVYWMX-UHFFFAOYSA-N 4-[2-(dimethylamino)ethyl]benzoic acid Chemical compound CN(C)CCC1=CC=C(C(O)=O)C=C1 JDFDJNNXQVYWMX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical class NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 239000000852 hydrogen donor Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- SUAYFRHPQLERMW-UHFFFAOYSA-N 2-methyl-1,2-diphenylpropan-1-one Chemical compound C=1C=CC=CC=1C(C)(C)C(=O)C1=CC=CC=C1 SUAYFRHPQLERMW-UHFFFAOYSA-N 0.000 description 1
- SGSKTOKJZHJRCN-UHFFFAOYSA-N 4-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(Cl)=CC=C2 SGSKTOKJZHJRCN-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VVBLNCFGVYUYGU-UHFFFAOYSA-N Michlers ketone Natural products C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- VZTQQYMRXDUHDO-UHFFFAOYSA-N [2-hydroxy-3-[4-[2-[4-(2-hydroxy-3-prop-2-enoyloxypropoxy)phenyl]propan-2-yl]phenoxy]propyl] prop-2-enoate Chemical compound C=1C=C(OCC(O)COC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCC(O)COC(=O)C=C)C=C1 VZTQQYMRXDUHDO-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QDHUQRBYCVAWEN-UHFFFAOYSA-N amino prop-2-enoate Chemical class NOC(=O)C=C QDHUQRBYCVAWEN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- 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
- 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
Definitions
- Ultraviolet coatings are typically composed of a liquid or solid polymer and/or oligomer and/or a monomer, and a photoinitiator.
- a hydrogen donor such as amines or thiols and their analogues including polymeric analogues are optionally included with the photoinitiator to increase production of radicals used to start the polymer chains.
- a photoinitiator molecule When a photoinitiator molecule absorbs a photon of light it can form a radical that combines with a monomer or polymer to start the growth of Long chain polymers thereby effecting a cure of the coating or ink.
- Typical ultraviolet lamp based systems require a fluence of one Joule per square centimetre or greater to ensure cured coatings or films of practical thickness. While the expenditure of such energies leads to practical curing speeds, major advantages are to be gained if the fluence can be reduced so as to allow curing of more film with the same light energy resulting in increased output. Freedom to select the one best wavelength and wavelength bandwidth is also advantageous. Further, when making a thick coating, the surface often cures before the body of the coating, leading to a wrinkling of that coating and poor surface adhesion.
- ovens are used to remove solvents and thus dry and/or polymerise conventional solvent or aqueous based coatings. Such ovens occupy considerable space and require relatively large amounts of energy to maintain their temperature as well as the provision of ventilation for the removal of solvent fumes. The desirability of a more even cure rate through the depth of the coating is readily apparent as are the benefits to be gained by reduced fluence to effect photo-polymerization.
- UV lamps are used for clear coatings and inks, but ozone, heat removal and non-useful wavelengths of light can reduce their effectiveness. So little light from these lamps can penetrate a typical thick pigmented coating that they are not used commercially to any significant extent for this purpose.
- the present invention consists in a method of curing a coating comprising applying said coating to a surface, said coating comprising a liquid or solid polymer and/or oligomer, and/or a monomer and at least one photoinitiator, and irradiating said coating with ultraviolet laser light of at least one predetermined wavelength, wherein the at least one predetermined wavelength is selected so as to be preferentially absorbed by the at least one photoinitiator rather than the other components of the coating.
- the coating is in the form of a pigmented coating or ink
- the coating further comprises a pigment and the at least one predetermined wavelength of said laser light is selected so as to be minimally absorbed by the pigment.
- a particularly preferred method in accordance with the invention provides that the laser light is applied to the coating by being pulsed.
- at least 25 pulses of the laser light are required to effect a cure.
- at least 50 pulses are required to effect a cure.
- the single pulse fluence of the applied laser light is kept low and preferably4 3mJ/cm 2 .
- the total energy to effect a cure is very significantly reduced where the single pulse fluence is reduced and the total number of pulses applied to the coating or ink is increased while operating, at a predetermined pulse repetition rate.
- pigmented coatings are of a thickness ⁇ 0.5 microns; clear coatings have a thickness ⁇ 2 microns; and printing inks have a thickness ⁇ 20 microns.
- the laser source may be placed remote from the coating location since its light output is easily transmitted long distances. Techniques for expanding the beam and making it sufficiently uniform are readily apparent.
- the present invention has been employed in the curing of commercial quality coatings of 20 microns and larger thicknesses with 50% of rutile Ti0 2 by weight.
- laser light is used to achieve a through cure of the coating by penetrating the coating at a wavelength of minimum absorption due to the pigment.
- a photoinitiator is used that absorbs light at this wavelength and whose concentration may be adjusted for maximum energy efficiency.
- a nitrogen atmosphere is used to counteract oxygen inhibition during the curing process and very short pulses of light, typically of the order of 20-40 nonoseconds, are employed to initiate polymer growth in a particular area of the coating.
- very short pulses of light typically of the order of 20-40 nonoseconds
- the use of consecutive pulses of short duration promotes the cure to completion in combination with low fluence of light.
- Typical UV laser curable coatings suitable for use in the present invention may be composed of but not limited to the following materials:-1.
- Reactive Oligomer (s) A low molecular weight polymer (typically greater than 500 in weight average molecular weight) with one or more reactive functionalities to include unsaturated reaction sites, such as but not limited to acrylates or acrylamides or polyester, polyether, alkyd, cellulosics, acrylic, epoxy, silicone polyester, urethanes or any combination thereof.
- a polyene/polythiol type system, or a system such as a cationic initiated type may also be employed.
- Anionic initiated types may also be employed.
- a typical photoinitiator system could preferably include two of the following family groups, as follows:
- Typical UV curable coatings for use in the present invention may typically be composed of the materials recited above for clear coating but together with coloured pigments such as Ti0 2 .
- the photoinitiator for titanium dioxide pigment systems typically being CTX/MDEOA, DETX/MDEOA, ITX/MDEOA, and RTX/MDEOA.
- MDEOA may be replaced by Ethyl-p-dimethylaminobenzoate, EPB, and also p-dimethylaminoethylbenzoate.
- DETX analogues and Acyl Phosphine oxide and analogues, related polymers and amines and aminobenzoates.
- the photoinitiator concentration may be adjusted to minimise the laser energy per sq. cm at a given concentration of pigment which is required to completely cure the coating.
- Lasers employed in the practice of the invention may typically have a band width of around 5 nanometers or less centred at the processing wavelength. There is a narrow optimum in wavelength for each combination of pigment and photoinitiator. Doubling the wavelength spread or shifting the wavelength 5 nanometres either side of optimum will increase the energy requirement.
- acylphosphine oxide as the photoinitiator is particularly advantageous and its use results in a hard, well cured coating with good and pure white colour.
- Wavelengths of UV laser between 400 and 450 nm have been successfully employed as rutile Ti0 2 does not absorb as strongly in that range.
- other pigments with absorption at shorter wavelengths in the UV region of the spectrum or thinner coatings, such as inks, will require less energy/cm 2 to cure.
- photoinitiators are preferred where they absorb at those wavelengths where the pigments used have least absorption.
- Lasers which are typically suited in the operation of the present invention are rare gas halide (excimer) lasers which have achieved marked improvements in reliability and average power since their development in 1976.
- Lasers of interest include such as are referenced in "Solvent Dependent Characteristics of XeCl Pumped UV Dye Lasers" by Cassard, Corkum and Alcock, Appl. Phys. 25,17-22 (1981).
- the basic principle of laser curing of coatings and inks in accordance with the invention relies on the fact that laser light is substantially monochromatic, so that all the light can be employed to perform useful work.
- the photoinitiator is chosen to have its maximum activity at the laser wavelength.
- Fig. 1 the absorption curve of the photoinitiator trigonal 12 is plotted, with the line showing 100% of the laser light at 308 nm.
- the mercury lamps that are currently used for curing clear coatings have many lines, only a few of which do useful work. For instance, in Fig. 1, emissions of wavelengths above 350 nm are poorly absorbed by the photoinitiator, and emissions below 270 nm do not penetrate the bulk of the coating. The remaining emissions around 300 nm comprise only 10% of the lamp's output light in the UV region.
- Fig. 2 demonstrates that very thick (50 - 150 microns) clear coatings may be cured by the laser method. Total laser energy required to cure reaches an optimum for a given concentration of the photoinitiator, DETX.
- coatings were illuminated by an expanded laser beam in a nitrogen atmosphere until an excellent (commercially acceptable) cure was obtained.
- the graph of Fig. 3 shows that a lower fluence (a more expanded laser beam) leads to a lower energy requirement for cure.
- the lowest fluence allowable is given by the largest practical area of illumination. This in turn determines the lowest possible total fluence and hence the fastest "belt speed" at which material may be cured.
- the slope of these data is well explained by the theory of radical recombination.
- Fig. 5 demonstrates that ultraviolet curing of coatings containing Ti0 2 (i.e. opaque paints) must be done at longer wavelength than the absorption edge of Ti0 2 (shown here at 400 to 410 nm). At shorter wavelength, the light is all absorbed before reaching the bottom of the coating.
- the theoretical curing speed can be considered to be proportional to the intensity of light reaching the bottom of the coating.
- the experimental curve of Fig. 6 for the energy to cure vs. wavelength shows a very sharp optimum for the photoinitiator DETX.
- the illuminating wavelength should preferably be 422 + 5 nm.
- the dye Popop can be made to lase at many wavelengths (see Fig. 8), including the optimum ones for D ETX and acylphosphine oxide (APO) pigmented coatings with Ti0 2 .
- Fig. 9 demonstrates that the dye laser method is able to cure thick (up to 60 microns) pigmented coatings, with different loadings of Ti0 2 .
- the optimum photoinitiator e.g., acylphosphine oxide, concentration changes with illumination intensity as shown in the plot of Fig. 12. Fortunately, low fluence is associated with both faster cure speeds and lower photoinitiator concentration, which means lower costs.
- Inks employed in these examples carry the trade name "Viodri” as marketed by Coates Brothers Australia Pty. Ltd., their exact composition is unknown.
- Coates literature says they contain polyfunctional acrylate esters and photoinitiators such as benzophenone.
- Clear varnishes in these examples consisted of epoxy acrylate and HDDA (hexanedioldiacrylate) in a 60/40 ratio.
- a photoinitiator at a .5-3% level, along with an amine (N-methyldiethanol amine) in the same concentration as the photoinitiator.
- Coatings were spread onto paperboard with a wire-wound bar for less than 50 micron thickness, or between layers of tape for the 150 micron thickness. Coatings were cured under a nitrogen atmosphere with low fluence illumination directly from an excimer laser operating at 308 nm (Lambda Physik EMG 203) or 351 nm (Lambda Physik 150 ETS).
- a scratch test was used to determine a successful cure, and the minimum total energy to cure was noted.
- Photoinitiator - acylphosphine oxide at concentration 3% Thickness - 60 microns. Pigment loading - 32% Ti0 2 by weight.
- a typical mix of ingredients for a clear coating in accordance with the invention comprises the following by weight: 56.4% epoxy acrylate oligomer (51-650 of A.C. Hatrick Chemicals Pty. Limited (A.C.H.)); 37.6% H.D.O.D.A. hexane diol diacrylate (A.C.H.); 3% Trigonal 12 phenyl benzophenone (AKZO Chemicals); and 3% MDEOA methyl diethanol amine (Union Carbide) .
- This mixture was applied wet to a thickness of 7 m by draw down bars and was cured under a nitrogen blanket with a single pulse fluence of 0.0065 millijoules/cm 2 .
- the total energy required to cure was 0.9 mJ/cm 2 and the state of cure was assessed by measuring hardness of the coating via a scratch test.
- the substrate to which the coating was applied was high quality low porosity white paper.
- the wet sample coating having dimensions of 10cm x 5cm was irradiated by a laser beam of dimensions l5cm x 15cm.
- the results of this static test when extrapolated to a dynamic environment equate to a belt travelling at 667 metres/min, the belt being 1 metre wide and the illuminated area being 1 x 3m 2 .
- This example also concerns a clear coating formed from the following ingredients in percentages of the total mixture by weight: 56.4% Celrad 3700 epoxy acrylate oligomer (Celanese Corporation); 37.6% HDODA (A.C.H.); 3% Trigonal 12 (AKZO Chemicals); and 3% MDEOA (Union Carbide).
- the wet coating was applied to a thickness of 5 ⁇ m with a draw down bar and the same substrate was employed as for Example I but the single pulse fluence applied was 0.00015 millijoules/cm 2 and the total energy to cure was 0.29 mJ/cm 2 .
- the equivalent belt speed in this case is 2069 m/min for the same area of illumination as in Example I.
- a pigmented coating was produced by curing a mixture of the following ingredients combined in weight percentages as follows: 61% of a 60/40 mixture of epoxy acrylate oligomer (ACH 51-650) and H.D.O.D.A. (A.C.H.); 32% TiO 2 RHD 2 (I.C.I); 3% Trigcnal 12; and 4% acyl phosphene oxide (BASF).
- the equivalent belt speed in this case using an illuminated area of 1 x 3m 2 is 50 m/min.
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Electromagnetism (AREA)
- Mechanical Engineering (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU541/85 | 1985-05-14 | ||
AUPH054185 | 1985-05-14 | ||
AU56822/86A AU581981B2 (en) | 1985-05-14 | 1986-05-14 | Laser curing of coatings and inks |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0202803A2 true EP0202803A2 (de) | 1986-11-26 |
EP0202803A3 EP0202803A3 (de) | 1987-06-03 |
Family
ID=25631457
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86303326A Withdrawn EP0202803A3 (de) | 1985-05-14 | 1986-05-01 | Aushärten mit Laser von Beschichtungen und Tinten |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0202803A3 (de) |
AU (1) | AU581981B2 (de) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0353583A2 (de) * | 1988-08-05 | 1990-02-07 | Siemens Aktiengesellschaft | Verfahren zur Erzeugung dünner Schichten auf Siliconbasis |
EP0402546A2 (de) * | 1989-06-14 | 1990-12-19 | Poly-Flex Circuits, Inc. | Gedruckte Schaltungsplatte |
EP0426904A1 (de) * | 1989-11-06 | 1991-05-15 | Dunfries Investments Limited | Verfahren zum Aufbringen einer Beschichtung auf eine Unterlage |
EP0440178A1 (de) * | 1990-01-31 | 1991-08-07 | Herberts Gesellschaft mit beschränkter Haftung | Verfahren zum Beschichten von Substraten mit durch UV-Strahlung härtbaren Überzugsmitteln |
EP0447169A1 (de) * | 1990-03-13 | 1991-09-18 | BAUSCH & LOMB INCORPORATED | Laser-Aushärten von Kontaktlinsen |
DE4230149A1 (de) * | 1992-09-09 | 1994-03-17 | Heraeus Noblelight Gmbh | Verfahren zur Herstellung von oxydischen Schutzschichten |
DE19649301A1 (de) * | 1996-11-28 | 1998-06-04 | Orga Kartensysteme Gmbh | Verfahren zum Aufbringen von Markierungen, Beschriftungen und/oder Strukturierungen auf die Oberfläche einer Ausweiskarte o. dgl. |
WO1999026728A2 (de) * | 1997-11-20 | 1999-06-03 | E.I. Du Pont De Nemours And Company, Inc. | Verfahren zur mehrschichtigen lackierung von substraten |
WO1999026732A1 (de) * | 1997-11-20 | 1999-06-03 | E.I. Du Pont De Nemours And Company, Inc. | Verfahren zur mehrschichtigen lackierung von substraten |
WO1999026733A1 (de) * | 1997-11-20 | 1999-06-03 | E.I. Du Pont De Nemours And Company, Inc. | Verfahren zur mehrschichtigen lackierung von substraten |
US6078713A (en) * | 1998-06-08 | 2000-06-20 | Uv Technology, Inc. | Beam delivery system for curing of photo initiated inks |
WO2000050245A1 (en) * | 1999-02-25 | 2000-08-31 | Kimberly-Clark Worldwide, Inc. | Printing apparatus |
WO2000061301A1 (en) * | 1999-04-09 | 2000-10-19 | Tec-Masters, Inc. | Encoding symbologies and graphics on nonporous materials |
WO2001098223A1 (en) * | 2000-06-16 | 2001-12-27 | Alcatel | Uv-cure of coatings for an optical fiber with a laser |
US7022382B1 (en) * | 2000-06-16 | 2006-04-04 | Alcatel | UV-cure of coatings for an optical fiber with a laser |
US7522281B2 (en) * | 2004-12-20 | 2009-04-21 | Heidelberger Druckmaschinen Ag | Apparatus and method for detecting moisture in a printing plate exposer |
WO2020234576A1 (en) * | 2019-05-17 | 2020-11-26 | The University Of Birmingham | Tunable materials |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6524379B2 (en) | 1997-08-15 | 2003-02-25 | Kimberly-Clark Worldwide, Inc. | Colorants, colorant stabilizers, ink compositions, and improved methods of making the same |
AU2853000A (en) | 1999-01-19 | 2000-08-01 | Kimberly-Clark Worldwide, Inc. | Novel colorants, colorant stabilizers, ink compositions, and improved methods ofmaking the same |
US6368395B1 (en) | 1999-05-24 | 2002-04-09 | Kimberly-Clark Worldwide, Inc. | Subphthalocyanine colorants, ink compositions, and method of making the same |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2447790A1 (de) * | 1974-10-07 | 1976-04-08 | Scm Corp | Ultraviolett- und laserhaertung polymerisierbarer bindemittel |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3847771A (en) * | 1973-03-30 | 1974-11-12 | Scm Corp | Uv and laser curing of pigmented polymerizable binders |
-
1986
- 1986-05-01 EP EP86303326A patent/EP0202803A3/de not_active Withdrawn
- 1986-05-14 AU AU56822/86A patent/AU581981B2/en not_active Ceased
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2447790A1 (de) * | 1974-10-07 | 1976-04-08 | Scm Corp | Ultraviolett- und laserhaertung polymerisierbarer bindemittel |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0353583A3 (en) * | 1988-08-05 | 1990-03-07 | Siemens Aktiengesellschaft | Method for making thin silicone coatings |
US4983419A (en) * | 1988-08-05 | 1991-01-08 | Siemens Aktiengesellschaft | Method for generating thin layers on a silicone base |
EP0353583A2 (de) * | 1988-08-05 | 1990-02-07 | Siemens Aktiengesellschaft | Verfahren zur Erzeugung dünner Schichten auf Siliconbasis |
EP0402546A3 (de) * | 1989-06-14 | 1991-12-18 | Poly-Flex Circuits, Inc. | Gedruckte Schaltungsplatte |
EP0402546A2 (de) * | 1989-06-14 | 1990-12-19 | Poly-Flex Circuits, Inc. | Gedruckte Schaltungsplatte |
EP0426904A1 (de) * | 1989-11-06 | 1991-05-15 | Dunfries Investments Limited | Verfahren zum Aufbringen einer Beschichtung auf eine Unterlage |
EP0440178A1 (de) * | 1990-01-31 | 1991-08-07 | Herberts Gesellschaft mit beschränkter Haftung | Verfahren zum Beschichten von Substraten mit durch UV-Strahlung härtbaren Überzugsmitteln |
EP0447169A1 (de) * | 1990-03-13 | 1991-09-18 | BAUSCH & LOMB INCORPORATED | Laser-Aushärten von Kontaktlinsen |
US5154861A (en) * | 1990-03-13 | 1992-10-13 | Bausch & Lomb Incorporated | Laser curing of contact lens |
DE4230149A1 (de) * | 1992-09-09 | 1994-03-17 | Heraeus Noblelight Gmbh | Verfahren zur Herstellung von oxydischen Schutzschichten |
DE19649301A1 (de) * | 1996-11-28 | 1998-06-04 | Orga Kartensysteme Gmbh | Verfahren zum Aufbringen von Markierungen, Beschriftungen und/oder Strukturierungen auf die Oberfläche einer Ausweiskarte o. dgl. |
DE19649301C2 (de) * | 1996-11-28 | 1998-12-10 | Orga Kartensysteme Gmbh | Verfahren zum Aufbringen von Markierungen, Beschriftungen und Strukturierungen auf die Oberfläche einer Ausweiskarte oder einer anderen Karte |
US6165696A (en) * | 1996-11-28 | 2000-12-26 | Orga Kartensysteme Gmbh | Process for applying marks letterings and structures on the surface of an identity card or a different card |
WO1999026728A2 (de) * | 1997-11-20 | 1999-06-03 | E.I. Du Pont De Nemours And Company, Inc. | Verfahren zur mehrschichtigen lackierung von substraten |
WO1999026733A1 (de) * | 1997-11-20 | 1999-06-03 | E.I. Du Pont De Nemours And Company, Inc. | Verfahren zur mehrschichtigen lackierung von substraten |
WO1999026728A3 (de) * | 1997-11-20 | 1999-07-15 | Herberts & Co Gmbh | Verfahren zur mehrschichtigen lackierung von substraten |
WO1999026732A1 (de) * | 1997-11-20 | 1999-06-03 | E.I. Du Pont De Nemours And Company, Inc. | Verfahren zur mehrschichtigen lackierung von substraten |
US6078713A (en) * | 1998-06-08 | 2000-06-20 | Uv Technology, Inc. | Beam delivery system for curing of photo initiated inks |
WO2000050245A1 (en) * | 1999-02-25 | 2000-08-31 | Kimberly-Clark Worldwide, Inc. | Printing apparatus |
WO2000061301A1 (en) * | 1999-04-09 | 2000-10-19 | Tec-Masters, Inc. | Encoding symbologies and graphics on nonporous materials |
WO2001098223A1 (en) * | 2000-06-16 | 2001-12-27 | Alcatel | Uv-cure of coatings for an optical fiber with a laser |
US7022382B1 (en) * | 2000-06-16 | 2006-04-04 | Alcatel | UV-cure of coatings for an optical fiber with a laser |
US7522281B2 (en) * | 2004-12-20 | 2009-04-21 | Heidelberger Druckmaschinen Ag | Apparatus and method for detecting moisture in a printing plate exposer |
WO2020234576A1 (en) * | 2019-05-17 | 2020-11-26 | The University Of Birmingham | Tunable materials |
Also Published As
Publication number | Publication date |
---|---|
EP0202803A3 (de) | 1987-06-03 |
AU5682286A (en) | 1986-11-20 |
AU581981B2 (en) | 1989-03-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0202803A2 (de) | Aushärten mit Laser von Beschichtungen und Tinten | |
EP1448729B1 (de) | Tintenstrahldrucktinte mit einem geringen gehalt an photoinitiator und verfahren und gerät zur härtung derselben | |
CN100443308C (zh) | 固化 | |
US7278728B2 (en) | Ink-jet printing system | |
KR100645387B1 (ko) | 광경화성 잉크 젯 잉크 조성물 | |
US5747115A (en) | UV-curable and non-volatile pigmented coatings | |
DE19957900A1 (de) | Lichthärtung von strahlungshärtbaren Massen unter Schutzgas | |
GB2388609A (en) | Radiation curable ink and preparation method and image forming method using the same | |
EP1572467B1 (de) | Aushärtung | |
EP1586459B1 (de) | Anordnung und Verfahren zum Tintenstrahldruck | |
NO861861L (no) | Fremgangsmaate ved laserherding av belegg og fargestoff. | |
EP1000125B1 (de) | Verfahren zur beschichtung eines substrates | |
US6078713A (en) | Beam delivery system for curing of photo initiated inks | |
JP3141790B2 (ja) | 活性エネルギー線照射方法および活性エネルギー線照射物 | |
EP2810783B1 (de) | Tintenstrahldruckverfahren | |
EP3517582B1 (de) | Strahlungshärtbare tintenstrahltintenzusammensetzung | |
JPH06157962A (ja) | インキ、特にオフセット印刷用のuv−硬化性の印刷インキ、ならびにそのインキ乾燥のための装置および方法。 | |
Stowe | High-power UV lamps for industrial UV curing applications | |
Stowe | Key Factors of UV Curing of Ink Jet Printing | |
GB2071121A (en) | Method and apparatus for producing a surface covering having reduced surface gloss and surface covering produced thereby |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): BE DE FR GB IT NL SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): BE DE FR GB IT NL SE |
|
17P | Request for examination filed |
Effective date: 19871105 |
|
17Q | First examination report despatched |
Effective date: 19890526 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
18W | Application withdrawn |
Withdrawal date: 19900602 |
|
R18W | Application withdrawn (corrected) |
Effective date: 19900602 |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: PAUL, GEORGE LANGE Inventor name: SUPUROVIC, DARKO Inventor name: MAYRICK, ROBERT GEORGE Inventor name: REID, GAVIN PIERCE Inventor name: KLICK, DAVID I. Inventor name: AKERMAN, ALFRED M. Inventor name: TSUDA, HARUKI |