CA2175588A1 - Transfer printing medium - Google Patents
Transfer printing mediumInfo
- Publication number
- CA2175588A1 CA2175588A1 CA002175588A CA2175588A CA2175588A1 CA 2175588 A1 CA2175588 A1 CA 2175588A1 CA 002175588 A CA002175588 A CA 002175588A CA 2175588 A CA2175588 A CA 2175588A CA 2175588 A1 CA2175588 A1 CA 2175588A1
- Authority
- CA
- Canada
- Prior art keywords
- ink
- curable
- prepolymer
- transfer printing
- printing medium
- 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.)
- Abandoned
Links
- 238000010023 transfer printing Methods 0.000 title claims abstract description 26
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 25
- 239000003086 colorant Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000012719 thermal polymerization Methods 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- 239000000976 ink Substances 0.000 description 62
- 239000003999 initiator Substances 0.000 description 30
- -1 polyethylene Polymers 0.000 description 20
- 239000010410 layer Substances 0.000 description 17
- 239000006185 dispersion Substances 0.000 description 13
- 239000004615 ingredient Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000000975 dye Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 230000000977 initiatory effect Effects 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 240000007930 Oxalis acetosella Species 0.000 description 4
- 235000008098 Oxalis acetosella Nutrition 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229960000834 vinyl ether Drugs 0.000 description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000005410 aryl sulfonium group Chemical group 0.000 description 3
- 229910003460 diamond Inorganic materials 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 3
- DLYDGDHLODCOQF-UHFFFAOYSA-N 1-ethenoxyethenylcyclohexane Chemical compound C=COC(=C)C1CCCCC1 DLYDGDHLODCOQF-UHFFFAOYSA-N 0.000 description 2
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 125000005409 triarylsulfonium group Chemical group 0.000 description 2
- KNXVOGGZOFOROK-UHFFFAOYSA-N trimagnesium;dioxido(oxo)silane;hydroxy-oxido-oxosilane Chemical compound [Mg+2].[Mg+2].[Mg+2].O[Si]([O-])=O.O[Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O KNXVOGGZOFOROK-UHFFFAOYSA-N 0.000 description 2
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- CZAVRNDQSIORTH-UHFFFAOYSA-N 1-ethenoxy-2,2-bis(ethenoxymethyl)butane Chemical compound C=COCC(CC)(COC=C)COC=C CZAVRNDQSIORTH-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- YOTSWLOWHSUGIM-UHFFFAOYSA-N 1-ethenoxy-4-[2-(4-ethenoxyphenyl)propan-2-yl]benzene Chemical compound C=1C=C(OC=C)C=CC=1C(C)(C)C1=CC=C(OC=C)C=C1 YOTSWLOWHSUGIM-UHFFFAOYSA-N 0.000 description 1
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- 101150034533 ATIC gene Proteins 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000212977 Andira Species 0.000 description 1
- XUKUURHRXDUEBC-KAYWLYCHSA-N Atorvastatin Chemical compound C=1C=CC=CC=1C1=C(C=2C=CC(F)=CC=2)N(CC[C@@H](O)C[C@@H](O)CC(O)=O)C(C(C)C)=C1C(=O)NC1=CC=CC=C1 XUKUURHRXDUEBC-KAYWLYCHSA-N 0.000 description 1
- 241000984642 Cura Species 0.000 description 1
- LKPVGEQCXYXTIH-UHFFFAOYSA-N O=P(=O)C1=CC=NN=N1 Chemical compound O=P(=O)C1=CC=NN=N1 LKPVGEQCXYXTIH-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 108091000041 Phosphoenolpyruvate Carboxylase Proteins 0.000 description 1
- 229920002560 Polyethylene Glycol 3000 Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000007869 azo polymerization initiator Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- NONJJLVGHLVQQM-JHXYUMNGSA-N phenethicillin Chemical compound N([C@@H]1C(N2[C@H](C(C)(C)S[C@@H]21)C(O)=O)=O)C(=O)C(C)OC1=CC=CC=C1 NONJJLVGHLVQQM-JHXYUMNGSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
-
- 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
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/38207—Contact thermal transfer or sublimation processes characterised by aspects not provided for in groups B41M5/385 - B41M5/395
-
- 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
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
-
- 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
- B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat
-
- 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
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
- B41M5/465—Infrared radiation-absorbing materials, e.g. dyes, metals, silicates, C black
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Thermal Sciences (AREA)
- Toxicology (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Printing Plates And Materials Therefor (AREA)
- Laminated Bodies (AREA)
- Paper (AREA)
- Polymerisation Methods In General (AREA)
Abstract
A transfer printing medium that includes a carrier to which is applied a curable laser-tranisferrable ink having one or more layers. The transfer medium is capable of converting laser energy to hoat. The ink includes: (a) at least one colorrant; (b) at least one polymerization initiator; and (c) at least one curable prepolymer.
Description
~ Wo ss/13195 2 1 7 5 ~ 8 8 PCT/US94/1134S
'I'RAN.CF~R ~KTl~L I Nr. M~nIl~N
Background of the Invention This invention relates to laser-induced transfer 5 printing.
In laser-induced transfer printing, irradiation of an ink-bearing carrier with laser light causes the ink to transfer from the carrier to a 6urface, e.g., the surface of a microelectronic device, audio cassette, computer 10 A;~'Ptte, or syringe body. By r-nir~ ting the 8C:~nn~n~
parameters of the laser beam, the ink can be deposited in a ~L~yL ' pattern.
~c of the Invention In a first a6pect, the invention features a 15 transfer printing medium that includes a carrier to which is applied a curable laser-transferrable ink having one or more layers. The transfer medium is capable of converting laser energy to heat. The ink inrlll~3D~ (a) at least one colorant; (b) at least one polymerization 20 initiator; and (c) at least one curable prepolymer. By "colorant" it is meant any additive that imparts color to the ink, ;nf~ ;n~ the colors white and black. Colorants include both dyes and pigments, as well as met~ l l; 70d coatings. By "prepolymer" it i8 meant any species 25 capable of being polymerized following either thermal or pl~o~o~ ...ir~l initiation to form a polymer.
In preferred ~ s, the ink transfers to a surface of interest and cures in one step upon application of laser energy. In one preferred 30: ' ; , at least one of the polymerization initiators is a thermal polymerization initiator and at least one of the prepolymers is th~rr- 1 1 y curable . In another preferred ~ L, at least one of the polymerization initiators is a photoinitiator and at least one of the 35 prepolymers is photochemically curable.
Wo95/l3l9s PCTIUS94/11345 2175~88 One example of a preferred prepolymer i8 an epoxy-functinn~ Dd prepolymer. A second example i5 an epoxy-fl1nr~ inn~l; 7Dd prepolymer, ;n^~ with a vinyl ether-fllnn~ inr~li7D~ prepolymer. A third example i8 an epoxy-S funct; nn51 l; 7e~ prepolymer , - i nD-l with an acrylate-functinnAl;~ed prepolymer. A fourth example lnr-lll~C the acrylate-functinnAl; ~tl prepolymers themselves. A fifth example i5 a blocked isocyanate-function~l; 7Dd prepolymer and a sixth example is a blend of a vinyl ether-10 functionalized prepolymer and a maleate- or r~ n;dD-funct; nn~ ed prepolymer.
At least one of the ink layers may be a curable size coat that includes a polymerization initiator and a curable prepolymer. The size coat is used in combination 15 with a color coat layer. In one preferred ~n~horli L, the color coat is non-curable and; nrlll~ C a colorant and a thermoplastic film-forming resin. In another preferred , the color coat is curable and includQs a colorant, a polymerization initiator, and a curable 20 prepolymer. In the case of curable color coats used with curable size coats, the poly![~erization initiators and prepolymers f ound in the respective layers may be the same as, or different from, each other.
In a second aspect, the invention f eatures a 25 laser-induced transfer printing method using the above-described transfer printing medium. The method ;n~ Dc the steps of irradiating the particular transfer printing medium with laser light of a predet~rm;nDd wavelength to transfer the ink from the carrier to a surface of 30 interest, and curing the ink to adhere thQ ink to the 6urface of interest. The transfer and cure of the ink may be effected in a single step through irradiation with said laser light. Cure may also be e~fected in a 6eparate step subsequent to transfer.
~ Wo 95113195 217 ~ 5 8 8 PCTNS94111345 , The invention provides transfer printing media featuring curable inks that adhere well to the surface on which they are deposited following la6er irradiation.
The inks transfer cleanly from the supporting carrier and 5 cure rapidly; in some cases, transfer and cure are effected in a single step. It is not n--r~ to add a separate self-oxidizing material such as nitrore~ l nce in order to effect transfer. In addition, the ability to use nu.. cu~able layers (e.g., non-curable color coats) in l0 combination with curable layers (e.g., curable size coats~ expands the types of materials that can be used for the inks, enabling the properties of the inks to be adjusted as needed for a particular application.
Other f eatures and advantages of the invention 15 will be ay~a~e-lL from the following description of the preferred ~mhQ~i- Ls thereof, and from the claims.
DescriPtion of the Preferred E'---i- c The invention features a transfer printing medium capable of converting laser energy to heat in which a 20 curable laser-transferrable ink having one or more layers i5 deposited on a carrier. The carrier must have sufficiently low surface energy to permit transfer of the ink. It also must not melt or otherwise deform upon laser irradiation. Examples of suitable carriers include 25 flexible plastic films such as polyethylene, polypropylene, and polyester.
The transfer medium is capable of converting laser energy to heat to promote transfer of the ink from the carrier to the surface of interest. To this end, one or 30 more thermal convertors are incul~vLated into the carrier, the ink, or both. The thermal convertors may be separate additives or may be part of the prepolymer.
In the case of separately added Cv~ Lu1 2~
inrll-~l~cl in the ink, the amount of convertor ranges from 35 about o . 25 to about 30% by weight (ba23ed upon the total ~ro 9S/13195 ; PCr/US94/1134~ ~
'I'RAN.CF~R ~KTl~L I Nr. M~nIl~N
Background of the Invention This invention relates to laser-induced transfer 5 printing.
In laser-induced transfer printing, irradiation of an ink-bearing carrier with laser light causes the ink to transfer from the carrier to a 6urface, e.g., the surface of a microelectronic device, audio cassette, computer 10 A;~'Ptte, or syringe body. By r-nir~ ting the 8C:~nn~n~
parameters of the laser beam, the ink can be deposited in a ~L~yL ' pattern.
~c of the Invention In a first a6pect, the invention features a 15 transfer printing medium that includes a carrier to which is applied a curable laser-transferrable ink having one or more layers. The transfer medium is capable of converting laser energy to heat. The ink inrlll~3D~ (a) at least one colorant; (b) at least one polymerization 20 initiator; and (c) at least one curable prepolymer. By "colorant" it is meant any additive that imparts color to the ink, ;nf~ ;n~ the colors white and black. Colorants include both dyes and pigments, as well as met~ l l; 70d coatings. By "prepolymer" it i8 meant any species 25 capable of being polymerized following either thermal or pl~o~o~ ...ir~l initiation to form a polymer.
In preferred ~ s, the ink transfers to a surface of interest and cures in one step upon application of laser energy. In one preferred 30: ' ; , at least one of the polymerization initiators is a thermal polymerization initiator and at least one of the prepolymers is th~rr- 1 1 y curable . In another preferred ~ L, at least one of the polymerization initiators is a photoinitiator and at least one of the 35 prepolymers is photochemically curable.
Wo95/l3l9s PCTIUS94/11345 2175~88 One example of a preferred prepolymer i8 an epoxy-functinn~ Dd prepolymer. A second example i5 an epoxy-fl1nr~ inn~l; 7Dd prepolymer, ;n^~ with a vinyl ether-fllnn~ inr~li7D~ prepolymer. A third example i8 an epoxy-S funct; nn51 l; 7e~ prepolymer , - i nD-l with an acrylate-functinnAl;~ed prepolymer. A fourth example lnr-lll~C the acrylate-functinnAl; ~tl prepolymers themselves. A fifth example i5 a blocked isocyanate-function~l; 7Dd prepolymer and a sixth example is a blend of a vinyl ether-10 functionalized prepolymer and a maleate- or r~ n;dD-funct; nn~ ed prepolymer.
At least one of the ink layers may be a curable size coat that includes a polymerization initiator and a curable prepolymer. The size coat is used in combination 15 with a color coat layer. In one preferred ~n~horli L, the color coat is non-curable and; nrlll~ C a colorant and a thermoplastic film-forming resin. In another preferred , the color coat is curable and includQs a colorant, a polymerization initiator, and a curable 20 prepolymer. In the case of curable color coats used with curable size coats, the poly![~erization initiators and prepolymers f ound in the respective layers may be the same as, or different from, each other.
In a second aspect, the invention f eatures a 25 laser-induced transfer printing method using the above-described transfer printing medium. The method ;n~ Dc the steps of irradiating the particular transfer printing medium with laser light of a predet~rm;nDd wavelength to transfer the ink from the carrier to a surface of 30 interest, and curing the ink to adhere thQ ink to the 6urface of interest. The transfer and cure of the ink may be effected in a single step through irradiation with said laser light. Cure may also be e~fected in a 6eparate step subsequent to transfer.
~ Wo 95113195 217 ~ 5 8 8 PCTNS94111345 , The invention provides transfer printing media featuring curable inks that adhere well to the surface on which they are deposited following la6er irradiation.
The inks transfer cleanly from the supporting carrier and 5 cure rapidly; in some cases, transfer and cure are effected in a single step. It is not n--r~ to add a separate self-oxidizing material such as nitrore~ l nce in order to effect transfer. In addition, the ability to use nu.. cu~able layers (e.g., non-curable color coats) in l0 combination with curable layers (e.g., curable size coats~ expands the types of materials that can be used for the inks, enabling the properties of the inks to be adjusted as needed for a particular application.
Other f eatures and advantages of the invention 15 will be ay~a~e-lL from the following description of the preferred ~mhQ~i- Ls thereof, and from the claims.
DescriPtion of the Preferred E'---i- c The invention features a transfer printing medium capable of converting laser energy to heat in which a 20 curable laser-transferrable ink having one or more layers i5 deposited on a carrier. The carrier must have sufficiently low surface energy to permit transfer of the ink. It also must not melt or otherwise deform upon laser irradiation. Examples of suitable carriers include 25 flexible plastic films such as polyethylene, polypropylene, and polyester.
The transfer medium is capable of converting laser energy to heat to promote transfer of the ink from the carrier to the surface of interest. To this end, one or 30 more thermal convertors are incul~vLated into the carrier, the ink, or both. The thermal convertors may be separate additives or may be part of the prepolymer.
In the case of separately added Cv~ Lu1 2~
inrll-~l~cl in the ink, the amount of convertor ranges from 35 about o . 25 to about 30% by weight (ba23ed upon the total ~ro 9S/13195 ; PCr/US94/1134~ ~
2~
solids content of the ink) . The particular C~IIV~L L~. is selected based upon the particular laser energy used f or irradiation. In the case of Co2 lasers, the preferred convertors are carbon black, polyethylene glycol te.g., 5 PEG 3000 commercially available from Union Carbide), talc (e.g~, Nytal 400 commercially available from R.T.
Vanderbilt), and PPZ, a phosphotriazine ~ ._i~lly available from Idemitsu Petrorh~ cAl s Co. Ltd; PPZ may also function as a prepolymer. In the case of Nd:YAG
10 lasers, the preferred convertors are IR99, IRA 980, and IRl65, all of which are proprietary dyes ~:ially available from Glendale Protective Technologies, IR dye 14, 617 (a proprietary dye commercially available from Eastman Kodak), and Pro~et gooNP (a proprietary dye 15 _ ~ially available from ICI). In the case of diode lasers, the preferred convertors are IR dye 14,617 and IRA 980.
The inks may have one or more layers, with particular ingredients (e.g., prepolymer, polymerization 20 initiator, etc. ) being present in any of the layers. One example of ink is a one layer ink (referred to here as a "one-pass" coating) having a curable color coat that ;nrl-lrloc, in a single layer, a curable prepolymer, a polymerization initiator, and a colorant. Another 25 example i8 a two layer ink (referred to here as a "two-pass" coa'cing) having a color coat (which may be curable or n~ uL~lble) in combination with an overlying curable size coat that includes a curable prepolymer and a polymerization initiator.
Because the inks are curable, ;~rlhoc; nn upon transfer to a surface of interest is; ~ved. The &lvc...Lc.ge of the size coat (which is transferred with the color coat upon laser irradiation) is that A~ho~cion is further o~h:-nrod, thereby making it rOcc; hlo to use even 35 a non-curable color coat.
~ ~VO 95113195 2 1 7 ~ ~ 8 8 Pcrluss4lll34s The inks contain one or more curable prepolymers, with the total amount of curable prepolymer ranging from 25 to 95~ by weight (based upon the total solids content of the ink). Curable prepolymers useful in the invention 5 have two or more functional groups available for croEG~ ;nkin~ (which occurs either simult InPollGly with transfer upon application of laser radiation or following laser irradiation in a separate thermal or photo~-cure step).
One class of suLtable curable prepolymers i nrlll~Dc epoYy-functio"~li70d prepolymers such as hiGrhPnol A
diglycidyl ether (commercially available from Shell Oil under the designation Epon 1001) and epoxy-function~l i 7Pd novolac resins (e.g., Epon 164 ~ . ially available 15 from Shell Oil). Lower molecular Pr.,Y;.lPc such as UVR6110 (a liquid ~iipp~y;rle commercially available from Union Carbide) may be added as well.
A second class of suitable curable prepolymers 1PG these epoxy-funct~ 70d prepolymers in 20 combination with one or more vinyl ether-functionalized prepolymers which co-cure with the epoxy-function~ sd prepolymers. Examples of suitable vinyl ether-functionalized prepolymers include bisphenol A-divinyl ether adduct; 2,4-toluene diisocyanate/l,y-l-."cy~-.Lyl vinyl 25 ether adduct; cyclohexyl divinyl ether ~;ially available from GAF or ISI Products; vinyl ethyl ether, vinyl isobutyl ether, vinyl octadecyl ether, polyethylene glycol divinyl ether, polytetrahydrofuran/350/divinyl ether, and trimethylol propane trivinyl ether, all of 30 which are commercially available from BASF; Rapi/cure divinyl ether/3, Rapi/cure cyclohexyl vinyl ether, Rapi/cure PEPC, and Rapi/cure hydroxy butyl vinyl ether, all of which are commercially available from ISP; and V~Pct~ ~- 2010, 2031, 2032, 4010, 4020, and 4030, all of 35 which are commercially available from Allied-Signal.
~IVO 95/131sS PCT/US94/11345 2175~
A third class of suitable cura41e prepolymers ~nr1~ Pc the above-described epoxy-functit~n~l ;7ed prepolymers in combination with one or more acrylate-fl~n~ nAl; 7ed prepolymers~ 1P~: of acrylate-5 fllnt~tioni~li7Pcl prepolymers include RDX 29522 and Ebecryl639 tboth of which are commercially available from Radcure); Sartomer 351 (commercially available from Sartomer); and NR440 (commercially available from Zeneca Re6ins) .
A fourth class of s~;t~l~1e curable prepolymers inrl-lrlPq the acrylate-funct;nn~l;rPd prepolymers themselves without the epoxy-f-~nrt; r~nA l; ~qd prepolymers .
A fifth class of suitable curable prepolymers ; nr~ blocked isocyanate-functionalized prepolymers .
15 Exa_ples include B1299 (commercially available from Ku18) and BL4165A (commercially available from Miles).
A sixth class of suitable curable prepolymers includes the above-described vinyl ether-functi~-n~1;7~
prepolymers in combination with maleate- or r-lP;mltlP-20 func~ n~l; 7P(~ prepolymers. Examples of maleate-functi~n~ prepolymers include 89-8902 (- ~lally available ~rom Cargil Products); and Astrocure 78HV and A:~Ll~-,uLe: 78LV (both of which are ~- ~ially availa~le from Zircon). Examples of r-lP;m;~p-functio~ zed 25 prepolyners include BMI/S/M/20/TDA (~ ~;lally ~vailable from Mitsui Toatsu Ohpm;c~l, Inc.
one or more non-curable layers may be used in combination with one or more curable layers. For example, a nu-. _uLable color coat may be ~ ' lned with an 30 overlying curable size coat. Suitable ~ uLable re8ins are ~h ~ tic film-forming resins. Examples include acrylic resins such as Rhoplex B85 (an acrylic dispersion commercially available ~rom Rohm & Kaas) and Amsco 3011 (an acrylic dispersion available from Rohm & Kaas);
35 urethane resins such as QW-16 (a urethane dispersion ~ WO 95/13195 2 1 7 5 ~ ~ 8 PCr/US94111345 useful as a film-former that i5 commercially available from K.J. Quinn); phenoxy resins such as PKHW 35 (~ ~;ially available from Union Carbide); and combinations thereof. The amount of nol- _uL~.ble 5 prepolymer in the ink ranges from about 15 to about 35 by weight (based upon the total solids content o~ the ink ) .
The inks also contain a polymerization initiator in an amount ranging from about 0.1 to 596 by weight 10 (based upon the total solids content of the ink). The initiator (which typically is a free radical or cationic initiator) may be a photochemical initiator or a thermal initiator; in some cases, the same initiator can act as both a thermal and a photo~h-~mic~l initiator. In the 15 case of multi-layer inks containing multiple curable layers, layers containing photochemical initiators may be ;nc~cl with layers ccntaining thermal initiators. In addition, some initiators may be used in conjunction with accelerators such as benzpinacole, copper II salts (e.g., 20 copper benzoate), and hFYArh ~nylethane.
In the case of thermal initiators, the initiator must exhibit good stability at ambient t~ c~Lu.~ to prevent ~L~ Lule curing of the prepolymer. In addition, the initiation temperature must be within the range 25 achievable by laser irradiation. Examples of suitable thermal initiators for cationic initiation include aryl ~ulfonium salts (e.g., the salts described in W090/11303, hereby incu.y~. lLed by reference); aryl ~ ni~lm salts (e.g., UVE 9310 and U 479, both of which are ~ .:ially 30 available from General Electric); and i.lm salts (e.g., FC520, commercially available from 3M). Examples of suitable thermal initiators for free radical initiation include the class of compounds leading to peroxy radicals, e.g., hydroperoxides, peLc,..y~Lers, and 35 peroxyketals; representative ~ __ '~ are commercially Wo 95113195 PCTiUS94/11345 ~ 1 7~
~vailable from Elf-Atochem. Also suitable for free radical initiation are azo polymerization initiators .;ially available from Wako.
In the case of photnl h-mi~l initiators, the 5 initiator must also exhibit good stability st ambient t~ ~LUL.~ to prevent pr ~ur~: curing of the prepolymer. In addition, it must exhibit absorption maxima ln regions of the ele.:~L, -_ Atic :jUe~ -Lu.,.
different from the regions in which the colorant e~chibits 10 absorption maxima. Examples of suitable photn~ hAm;cAl initiators for cationic initiation include aryl sulfonium salts (e.g., WI 6974 commercially available from Union Carbide) and aryl iodonium salts (e.g., UVE 9310 and U
479, both of which are commercially available from 15 General Electric). Another example of a suitable initiator for cationic initiation i8 hydroxy naphthyl imide sulfonate ester. Examples of suitable photoAh-m~AAl initiators for ~ree radical initiation include CPTX and ITX (both ~ ~ially available from 20 Ciba-Geigy), each of which is ~i nAfl with methyl diethanolamine (commercially available from Aldrich lA-h_mi~AAl CO~; lucerin TP0 ( ~.lally available from BASF) ' ;n_,fl, with methyl fl;~fhAnnlamine; Darcure 4265 (commercially available from Ciba Geigy), and Irgacure 25 369 '-;ne~fl, with ITX.
The ink contains one or more colorants, which may be dyes, ri~_ ~L, or me~;~ll;7-d coatings (e.g., an Al1~m~n~79d coating). In the case of dyes and pigments, the colorant is present in an amount ranging from a~out 30 35 to 65~ by weight (based upon the total solids content of the ink). The particular colorant is chosen based upon the color desired on the final printed surfacQ.
Examples of suitable colorants include pigments such as talc, Tio2 (white), phthalogreen (GT-674-D), chrome green 35 oxide (6099), ultramarine blue (R5-9), black oxide (BR-~VO 95113195 2 1 7 5 S 8 8 PCrlUS94/11345 , , ' . . 1 ,. ,..
_ g _ 5099D), Kroma red (7097), and rl~vclp~:LIIl yellow (HR-70), and dyes such as dynonicidine (2915) and Dianell orange, as well as the aforementioned - ~ 11 i 7arl coatings.
In the case of inks containing photocurable 5 prepolymers, a 6ensitizer may be added in an amount ranging from about 0 . 5 to 8% by weight (based upon the total solids content of the ink) to extend the irradiating wavelength for photoinitiation into the visible region. Such sensitizers are useful, for 10 example, where the formulation contains large amounts of Tio2 pigment which absorbs light below 400 nm and thus competes with the initiator. Examples of suitable sensitizers, all of which are commercially available from Aldrich Chemical Co., include perylene, rubrene, 15 phenothiazine, anthracene derivatives, and thioxanthones, as well as lucerin TPO (commercially available from BASF) .
Other ingredients which may be added to the inks to improve the coatability, printability, print 20 performance, and durability of the inks include various ~iurfactants, dispersing agents, and polymer dispersions.
The amount of each ingredient is selected based upon the desired properties. Examples of suitable surfactants (which may be anionic, cationic, or nnn;oni~-) include 25 Triton X-100 (an aryl ethoxylate _ ~:ially available from Rohm & E~aas) and Fc 430 (a fluoroaliphatic polymeric ester available from 3M). Examples of suitable dispersing agents include polyacrylate salts such as Daxad 30, a 30% aqueous solution of polyso~ rylate 30 commercially available from W. R. Grace . r la~: of suitable dispersions include Shamrock 375 and Aquacer 355, both of which are polyethylene wax dispersions commercially available from Diamond Shamrock.
The transf er medium according to the invention is 35 yL~=~a~ d by combining the ink ingredients in an aqueous Wo 95/~3195 PCr/USs4/11345 217SS~3 ~
or organic solvent (with aqueous solvents being preferred), and then applying the resulting composition to the carrier. If a size coat is used, it is applied on top of the color coat. To facilitate coating, the total 5 sollds content of the ink is adjusted to be between lO
and 50% by weight of the ink. The coated carrier is then irradiated with laser light le.g., as described in the commonly ~e~cl~n~ et al. application, U.S.
Serial No. 08/_, filed CU1IUUL1e~ 1Y with this 10 application and hereby in~uL~uuLated by reference) to transfer the ink from the carrier to a desired surface, e.g., the surface of a semiconductor device. Suitable lasers include Cû2 lasers (irradiation wavelength equals 10.6ILm), Nd:YAG lasers (irradiation wavelength equals 15 1.06~m), and diode lasers (irradiation wavelength equals, e.g., 0 . 9~m) . The particular irradiation wavelength, power, ~nd time of application parameters are selected to ensure clean transfer.
In the case of some inks, laser irradiation both 20 transfers and cures the ink simultaneously. With other inks, a separate thermal or photo~-h~ c~l cure is effected following transfer. The cure conditions are selected based upon the particular prepolymers and initiators used in the f ormulation .
The invention will now be further described by way of the following examples.
r le l This example describes the ~)L ~ar,ltion of a transfer medium having one-pass, thermally curable, 3 0 ca~ i ~n i C:~ 1 1 y initiated, ink .
The following ingredients were combined to form a lase~ sferrable ink (all amounts in weight percent):
Tio2 55 . 0 Ri ~rh~nnl A-DVE adduct 13 . 0 21~5588 ~ WO95/13195 PcrluS94111345 ", . t ., 352011 24.8 PEG 30002 5 . 0 Aryl sulfonium salt3 2 . 0 Triton X-1004 0 . 2 5 1 Agueous dispersion of hi ~rh~ l A-epichl~L~ ydLin adduct formerly available from Rhone-Poulenc.
2 pOlyethylene glycol (Mn = 3000) ~ially available from Union Carbide.
3 Aryl sulfonium salt thermal initiator of the type 10 described in W090/11303.
solids content of the ink) . The particular C~IIV~L L~. is selected based upon the particular laser energy used f or irradiation. In the case of Co2 lasers, the preferred convertors are carbon black, polyethylene glycol te.g., 5 PEG 3000 commercially available from Union Carbide), talc (e.g~, Nytal 400 commercially available from R.T.
Vanderbilt), and PPZ, a phosphotriazine ~ ._i~lly available from Idemitsu Petrorh~ cAl s Co. Ltd; PPZ may also function as a prepolymer. In the case of Nd:YAG
10 lasers, the preferred convertors are IR99, IRA 980, and IRl65, all of which are proprietary dyes ~:ially available from Glendale Protective Technologies, IR dye 14, 617 (a proprietary dye commercially available from Eastman Kodak), and Pro~et gooNP (a proprietary dye 15 _ ~ially available from ICI). In the case of diode lasers, the preferred convertors are IR dye 14,617 and IRA 980.
The inks may have one or more layers, with particular ingredients (e.g., prepolymer, polymerization 20 initiator, etc. ) being present in any of the layers. One example of ink is a one layer ink (referred to here as a "one-pass" coating) having a curable color coat that ;nrl-lrloc, in a single layer, a curable prepolymer, a polymerization initiator, and a colorant. Another 25 example i8 a two layer ink (referred to here as a "two-pass" coa'cing) having a color coat (which may be curable or n~ uL~lble) in combination with an overlying curable size coat that includes a curable prepolymer and a polymerization initiator.
Because the inks are curable, ;~rlhoc; nn upon transfer to a surface of interest is; ~ved. The &lvc...Lc.ge of the size coat (which is transferred with the color coat upon laser irradiation) is that A~ho~cion is further o~h:-nrod, thereby making it rOcc; hlo to use even 35 a non-curable color coat.
~ ~VO 95113195 2 1 7 ~ ~ 8 8 Pcrluss4lll34s The inks contain one or more curable prepolymers, with the total amount of curable prepolymer ranging from 25 to 95~ by weight (based upon the total solids content of the ink). Curable prepolymers useful in the invention 5 have two or more functional groups available for croEG~ ;nkin~ (which occurs either simult InPollGly with transfer upon application of laser radiation or following laser irradiation in a separate thermal or photo~-cure step).
One class of suLtable curable prepolymers i nrlll~Dc epoYy-functio"~li70d prepolymers such as hiGrhPnol A
diglycidyl ether (commercially available from Shell Oil under the designation Epon 1001) and epoxy-function~l i 7Pd novolac resins (e.g., Epon 164 ~ . ially available 15 from Shell Oil). Lower molecular Pr.,Y;.lPc such as UVR6110 (a liquid ~iipp~y;rle commercially available from Union Carbide) may be added as well.
A second class of suitable curable prepolymers 1PG these epoxy-funct~ 70d prepolymers in 20 combination with one or more vinyl ether-functionalized prepolymers which co-cure with the epoxy-function~ sd prepolymers. Examples of suitable vinyl ether-functionalized prepolymers include bisphenol A-divinyl ether adduct; 2,4-toluene diisocyanate/l,y-l-."cy~-.Lyl vinyl 25 ether adduct; cyclohexyl divinyl ether ~;ially available from GAF or ISI Products; vinyl ethyl ether, vinyl isobutyl ether, vinyl octadecyl ether, polyethylene glycol divinyl ether, polytetrahydrofuran/350/divinyl ether, and trimethylol propane trivinyl ether, all of 30 which are commercially available from BASF; Rapi/cure divinyl ether/3, Rapi/cure cyclohexyl vinyl ether, Rapi/cure PEPC, and Rapi/cure hydroxy butyl vinyl ether, all of which are commercially available from ISP; and V~Pct~ ~- 2010, 2031, 2032, 4010, 4020, and 4030, all of 35 which are commercially available from Allied-Signal.
~IVO 95/131sS PCT/US94/11345 2175~
A third class of suitable cura41e prepolymers ~nr1~ Pc the above-described epoxy-functit~n~l ;7ed prepolymers in combination with one or more acrylate-fl~n~ nAl; 7ed prepolymers~ 1P~: of acrylate-5 fllnt~tioni~li7Pcl prepolymers include RDX 29522 and Ebecryl639 tboth of which are commercially available from Radcure); Sartomer 351 (commercially available from Sartomer); and NR440 (commercially available from Zeneca Re6ins) .
A fourth class of s~;t~l~1e curable prepolymers inrl-lrlPq the acrylate-funct;nn~l;rPd prepolymers themselves without the epoxy-f-~nrt; r~nA l; ~qd prepolymers .
A fifth class of suitable curable prepolymers ; nr~ blocked isocyanate-functionalized prepolymers .
15 Exa_ples include B1299 (commercially available from Ku18) and BL4165A (commercially available from Miles).
A sixth class of suitable curable prepolymers includes the above-described vinyl ether-functi~-n~1;7~
prepolymers in combination with maleate- or r-lP;mltlP-20 func~ n~l; 7P(~ prepolymers. Examples of maleate-functi~n~ prepolymers include 89-8902 (- ~lally available ~rom Cargil Products); and Astrocure 78HV and A:~Ll~-,uLe: 78LV (both of which are ~- ~ially availa~le from Zircon). Examples of r-lP;m;~p-functio~ zed 25 prepolyners include BMI/S/M/20/TDA (~ ~;lally ~vailable from Mitsui Toatsu Ohpm;c~l, Inc.
one or more non-curable layers may be used in combination with one or more curable layers. For example, a nu-. _uLable color coat may be ~ ' lned with an 30 overlying curable size coat. Suitable ~ uLable re8ins are ~h ~ tic film-forming resins. Examples include acrylic resins such as Rhoplex B85 (an acrylic dispersion commercially available ~rom Rohm & Kaas) and Amsco 3011 (an acrylic dispersion available from Rohm & Kaas);
35 urethane resins such as QW-16 (a urethane dispersion ~ WO 95/13195 2 1 7 5 ~ ~ 8 PCr/US94111345 useful as a film-former that i5 commercially available from K.J. Quinn); phenoxy resins such as PKHW 35 (~ ~;ially available from Union Carbide); and combinations thereof. The amount of nol- _uL~.ble 5 prepolymer in the ink ranges from about 15 to about 35 by weight (based upon the total solids content o~ the ink ) .
The inks also contain a polymerization initiator in an amount ranging from about 0.1 to 596 by weight 10 (based upon the total solids content of the ink). The initiator (which typically is a free radical or cationic initiator) may be a photochemical initiator or a thermal initiator; in some cases, the same initiator can act as both a thermal and a photo~h-~mic~l initiator. In the 15 case of multi-layer inks containing multiple curable layers, layers containing photochemical initiators may be ;nc~cl with layers ccntaining thermal initiators. In addition, some initiators may be used in conjunction with accelerators such as benzpinacole, copper II salts (e.g., 20 copper benzoate), and hFYArh ~nylethane.
In the case of thermal initiators, the initiator must exhibit good stability at ambient t~ c~Lu.~ to prevent ~L~ Lule curing of the prepolymer. In addition, the initiation temperature must be within the range 25 achievable by laser irradiation. Examples of suitable thermal initiators for cationic initiation include aryl ~ulfonium salts (e.g., the salts described in W090/11303, hereby incu.y~. lLed by reference); aryl ~ ni~lm salts (e.g., UVE 9310 and U 479, both of which are ~ .:ially 30 available from General Electric); and i.lm salts (e.g., FC520, commercially available from 3M). Examples of suitable thermal initiators for free radical initiation include the class of compounds leading to peroxy radicals, e.g., hydroperoxides, peLc,..y~Lers, and 35 peroxyketals; representative ~ __ '~ are commercially Wo 95113195 PCTiUS94/11345 ~ 1 7~
~vailable from Elf-Atochem. Also suitable for free radical initiation are azo polymerization initiators .;ially available from Wako.
In the case of photnl h-mi~l initiators, the 5 initiator must also exhibit good stability st ambient t~ ~LUL.~ to prevent pr ~ur~: curing of the prepolymer. In addition, it must exhibit absorption maxima ln regions of the ele.:~L, -_ Atic :jUe~ -Lu.,.
different from the regions in which the colorant e~chibits 10 absorption maxima. Examples of suitable photn~ hAm;cAl initiators for cationic initiation include aryl sulfonium salts (e.g., WI 6974 commercially available from Union Carbide) and aryl iodonium salts (e.g., UVE 9310 and U
479, both of which are commercially available from 15 General Electric). Another example of a suitable initiator for cationic initiation i8 hydroxy naphthyl imide sulfonate ester. Examples of suitable photoAh-m~AAl initiators for ~ree radical initiation include CPTX and ITX (both ~ ~ially available from 20 Ciba-Geigy), each of which is ~i nAfl with methyl diethanolamine (commercially available from Aldrich lA-h_mi~AAl CO~; lucerin TP0 ( ~.lally available from BASF) ' ;n_,fl, with methyl fl;~fhAnnlamine; Darcure 4265 (commercially available from Ciba Geigy), and Irgacure 25 369 '-;ne~fl, with ITX.
The ink contains one or more colorants, which may be dyes, ri~_ ~L, or me~;~ll;7-d coatings (e.g., an Al1~m~n~79d coating). In the case of dyes and pigments, the colorant is present in an amount ranging from a~out 30 35 to 65~ by weight (based upon the total solids content of the ink). The particular colorant is chosen based upon the color desired on the final printed surfacQ.
Examples of suitable colorants include pigments such as talc, Tio2 (white), phthalogreen (GT-674-D), chrome green 35 oxide (6099), ultramarine blue (R5-9), black oxide (BR-~VO 95113195 2 1 7 5 S 8 8 PCrlUS94/11345 , , ' . . 1 ,. ,..
_ g _ 5099D), Kroma red (7097), and rl~vclp~:LIIl yellow (HR-70), and dyes such as dynonicidine (2915) and Dianell orange, as well as the aforementioned - ~ 11 i 7arl coatings.
In the case of inks containing photocurable 5 prepolymers, a 6ensitizer may be added in an amount ranging from about 0 . 5 to 8% by weight (based upon the total solids content of the ink) to extend the irradiating wavelength for photoinitiation into the visible region. Such sensitizers are useful, for 10 example, where the formulation contains large amounts of Tio2 pigment which absorbs light below 400 nm and thus competes with the initiator. Examples of suitable sensitizers, all of which are commercially available from Aldrich Chemical Co., include perylene, rubrene, 15 phenothiazine, anthracene derivatives, and thioxanthones, as well as lucerin TPO (commercially available from BASF) .
Other ingredients which may be added to the inks to improve the coatability, printability, print 20 performance, and durability of the inks include various ~iurfactants, dispersing agents, and polymer dispersions.
The amount of each ingredient is selected based upon the desired properties. Examples of suitable surfactants (which may be anionic, cationic, or nnn;oni~-) include 25 Triton X-100 (an aryl ethoxylate _ ~:ially available from Rohm & E~aas) and Fc 430 (a fluoroaliphatic polymeric ester available from 3M). Examples of suitable dispersing agents include polyacrylate salts such as Daxad 30, a 30% aqueous solution of polyso~ rylate 30 commercially available from W. R. Grace . r la~: of suitable dispersions include Shamrock 375 and Aquacer 355, both of which are polyethylene wax dispersions commercially available from Diamond Shamrock.
The transf er medium according to the invention is 35 yL~=~a~ d by combining the ink ingredients in an aqueous Wo 95/~3195 PCr/USs4/11345 217SS~3 ~
or organic solvent (with aqueous solvents being preferred), and then applying the resulting composition to the carrier. If a size coat is used, it is applied on top of the color coat. To facilitate coating, the total 5 sollds content of the ink is adjusted to be between lO
and 50% by weight of the ink. The coated carrier is then irradiated with laser light le.g., as described in the commonly ~e~cl~n~ et al. application, U.S.
Serial No. 08/_, filed CU1IUUL1e~ 1Y with this 10 application and hereby in~uL~uuLated by reference) to transfer the ink from the carrier to a desired surface, e.g., the surface of a semiconductor device. Suitable lasers include Cû2 lasers (irradiation wavelength equals 10.6ILm), Nd:YAG lasers (irradiation wavelength equals 15 1.06~m), and diode lasers (irradiation wavelength equals, e.g., 0 . 9~m) . The particular irradiation wavelength, power, ~nd time of application parameters are selected to ensure clean transfer.
In the case of some inks, laser irradiation both 20 transfers and cures the ink simultaneously. With other inks, a separate thermal or photo~-h~ c~l cure is effected following transfer. The cure conditions are selected based upon the particular prepolymers and initiators used in the f ormulation .
The invention will now be further described by way of the following examples.
r le l This example describes the ~)L ~ar,ltion of a transfer medium having one-pass, thermally curable, 3 0 ca~ i ~n i C:~ 1 1 y initiated, ink .
The following ingredients were combined to form a lase~ sferrable ink (all amounts in weight percent):
Tio2 55 . 0 Ri ~rh~nnl A-DVE adduct 13 . 0 21~5588 ~ WO95/13195 PcrluS94111345 ", . t ., 352011 24.8 PEG 30002 5 . 0 Aryl sulfonium salt3 2 . 0 Triton X-1004 0 . 2 5 1 Agueous dispersion of hi ~rh~ l A-epichl~L~ ydLin adduct formerly available from Rhone-Poulenc.
2 pOlyethylene glycol (Mn = 3000) ~ially available from Union Carbide.
3 Aryl sulfonium salt thermal initiator of the type 10 described in W090/11303.
4 Surfactant ~ lally available from Rohm & Haas.
Water was added to adjust the total solids content to 3596 by weight, after which the resulting ink was coated onto a 1. 2 mil thick polypropylene carrier f ilm 15 using a #15 mayer rod. The coated surface of the film was then placed in intimate contact with the surface of a molded s~ n~ otor device. Next, a C02 laser was directed through the uncoated side of the carrier film to transfer the ink to the surface of the semiconductor 20 device. The laser dwelled on each addressed piYel for 16 ~sec. The power output of the laser at the point of contact with the coated film was 14 . 5 W. The device bearing the transferred image was then placed in a forced hot air oven for 30 min. at 175C to cure the ink. After 25 curing, the transferred image was found to be resistant to L,c:at L with 1,1,1-trichloroethane (3 min. soak, 10 brush strokes, cycled 3 times).
r le 2 This example describes the ~L-:paLe.tion of a 30 transfer medium having a two-pass, cat;-~n;~lly initiated ink in which both the color coat and the size coat are pho~o~-hF~n; c~ l 1 y curable .
The following ingredients were inod to form a photochemically curable color coat (all amounts in weight 35 percent):
Water was added to adjust the total solids content to 3596 by weight, after which the resulting ink was coated onto a 1. 2 mil thick polypropylene carrier f ilm 15 using a #15 mayer rod. The coated surface of the film was then placed in intimate contact with the surface of a molded s~ n~ otor device. Next, a C02 laser was directed through the uncoated side of the carrier film to transfer the ink to the surface of the semiconductor 20 device. The laser dwelled on each addressed piYel for 16 ~sec. The power output of the laser at the point of contact with the coated film was 14 . 5 W. The device bearing the transferred image was then placed in a forced hot air oven for 30 min. at 175C to cure the ink. After 25 curing, the transferred image was found to be resistant to L,c:at L with 1,1,1-trichloroethane (3 min. soak, 10 brush strokes, cycled 3 times).
r le 2 This example describes the ~L-:paLe.tion of a 30 transfer medium having a two-pass, cat;-~n;~lly initiated ink in which both the color coat and the size coat are pho~o~-hF~n; c~ l 1 y curable .
The following ingredients were inod to form a photochemically curable color coat (all amounts in weight 35 percent):
5 ' PCr~S94111345 ~
21~ S
TiO2 55 . 0 2, 4-toluene diisocyanate/HBVE adductl 35 . 8 QW-16 (urethane dispersion) 2 2 . 0 ppz3 5 . 0 5Triton X-1004 0 . 2 WI 69745 2.0 l Hydroxy butyl divinyl ether adduct.
2 Pre-made urethane dispersion commercially available from X.J. Quinn.
10 3 Commercially available from Idemitsu P~LLV~ CO.
Ltd .
4 Surfactant commercially available from Rohm & Naas.
5 Triaryl sulfonium salt-based initiator commercially available from Union Carbide.
Water was added to adjust the total solids content to 35% by weight, after which the resulting color coat was applied to a l . 2 mil thick polypropylene carrier f ilm using a ~13 mayer rod.
The following ingredients were combined to form a 20 photn~h~ l ly curable size coat (all amounts in wlaight percent):
EPON l00ll 89. l WI 6ll02 5. 45 FC-4303 2 . 47 WI 69744 1.68 Perylene5 o . 3 ppz6 l . 0 1 R~ ~:phPnrll A diglycidyl ether commercially available from Shell Oil Co.
30 2 Liquid ~ier~Yicl~ commercially available from Union Carbide .
3 Fluoroaliphatic polymeric ester surfactant commercially available from 3~ Co.
4 Triaryl sulfonium salt-based initiator commercially 35 available from Union Carbide.
I wo 95/13195 217 5 5 8 8 PCT/US94/113J5 5 Photosensitizer commercially available from Aldrich rh~.m; ~ 1 CO .
21~ S
TiO2 55 . 0 2, 4-toluene diisocyanate/HBVE adductl 35 . 8 QW-16 (urethane dispersion) 2 2 . 0 ppz3 5 . 0 5Triton X-1004 0 . 2 WI 69745 2.0 l Hydroxy butyl divinyl ether adduct.
2 Pre-made urethane dispersion commercially available from X.J. Quinn.
10 3 Commercially available from Idemitsu P~LLV~ CO.
Ltd .
4 Surfactant commercially available from Rohm & Naas.
5 Triaryl sulfonium salt-based initiator commercially available from Union Carbide.
Water was added to adjust the total solids content to 35% by weight, after which the resulting color coat was applied to a l . 2 mil thick polypropylene carrier f ilm using a ~13 mayer rod.
The following ingredients were combined to form a 20 photn~h~ l ly curable size coat (all amounts in wlaight percent):
EPON l00ll 89. l WI 6ll02 5. 45 FC-4303 2 . 47 WI 69744 1.68 Perylene5 o . 3 ppz6 l . 0 1 R~ ~:phPnrll A diglycidyl ether commercially available from Shell Oil Co.
30 2 Liquid ~ier~Yicl~ commercially available from Union Carbide .
3 Fluoroaliphatic polymeric ester surfactant commercially available from 3~ Co.
4 Triaryl sulfonium salt-based initiator commercially 35 available from Union Carbide.
I wo 95/13195 217 5 5 8 8 PCT/US94/113J5 5 Photosensitizer commercially available from Aldrich rh~.m; ~ 1 CO .
6 C ;ially available from Idemitsu Pt:L-U- 1 ;c~ Co.
Ltd .
Methyl ethyl ketone was added to adjust the total solids content of the 6ize coat to 2596 by weight, after which the resulting size coat was applied on top of the color coat using a #5 mayer rod.
The coated surface of the film was then placed in lO intimate contact with the surface of a molded semicon~ t tor device. Next, a C02 laser was directed through the uncoated side of the carrier film to transfer the ink (color coat plus size coat) to the surface of the semicnn~ rtor device. The laser dwelled on each 15 all.~ssed pixel for 20 ~sec. The power output of the laser at the point of contact with the coated film was 14 . 5 W. The device bearing the transferred image was then cured (5 min. at a 150C preheat, followed by a 3.6 gec ~O~UL~ to W radiation). The resulting cured 20 printed image was found to be resistant to ~.~a, with l, l, l-trichloroethane (3 min. soak, lO brush strokes, cycled 3 times ) .
r le 3 This example describes the yL~ Lion of a 25 transfer medium having a wu ~ass, cat;nn;n~lly curable ink in which the color coat is non-cura~le and the size coat is thc.rr- 11 y curable .
The following ingredients were ;n~d to form a non ~_u--ble color coat (all amounts in weight percent):
Water 54. 0 Daxad 30l 0 5 Tio2 38 . 4 Triton X-lOo2 o . 5 CUULu~k 3753 6.2 Rhoplex B854 l . 4 WOss/l3lss v PCT/US94/113~5 2175~8~
Amsco 30115 7.7 1 Polyacrylate dispersing agent ~ ially available f rom W . R . Grace .
2 Surfactant commercially available from Rohm & Haas.
5 3 Polyethylene wax dispersion commercially available from Diamond Shamrock.
4 Acrylic dispersion commercially available from Rohm &
Haas .
5 Acrylic dispersion ~ .;ially available from Rohm &
l0 Haas.
Enough ammonium hydroxide was added to adjust the pH to 8.5, after which the resulting color coat was applied to a 1.2 mil thick polypropylene carrier film at a coat weight of 69 mg/m2.
The following ingredients were ;nPd to form a photonhP~ Al ly curable size coat (all amounts in weight percent):
EPON l00ll 88 . 2 WR 6llo2 ll . 6 20FC-4303 3.0 W 4794 l. 6 IR 995 0 . 5 Benzpinacole6 o . 47 1 R; ~rhPnnl A diglycidyl ether cially available 25 from Shell Oil Co.
2 Liguid ~i;Prn~ P commercially available from Union Carbide .
3 Fluoroaliphatic polymeric ester surfactant ~;iall available from 3N co~
30 4 Io~nn;l-~ salt thermal initiator commercially available from General Electric .
5 Dye ~ ~ially available from Glendale Protective ~echnologies .
6 Accelerator commercially available from Aldrich 35 ~'hP~n;cAl Co.
~ ~0 95/13195 2 1 7 ~ ~ 8 8 PCr/US94/11345 ~ ~"f ~
Methyl ethyl ketone was added to adjust the total solids content of the size coat to 259~ by weight, after which the resulting size coat was applied on top of the color coat using a ~5 mayer rod.
The coated surface of the film was then placed in intimate contact with the surface of a molded 8~micon~ tor device. Next, a Nd:YAG laser was directed through the uncoated side of the carrier ~ilm to transfer the ink (color coat plu5 size coat) to the surface of the 10 s~i cnn~ tor device. The laser dwelled on each ~ dLe~ed pixel for 18 ~Lsec. The power output of the laser at the point of contact with the coated f ilm was 4.5 W. The device bearing the transferred image was then cured (4 min. at 175C). The resulting cured printed 15 image was found to be resistant to LLe:al L with 1,1,1-trichloroethane (3 min. soak, 10 brush strokes, cycled 3 times) .
r le 4 This example describes the ~r~paL~tion of a 20 transfer medium having a one-pass, fhF-~-lly curable, ca~inniAlly initiated ink in which transfer and cure takes place in a single step upon laser irradiation.
The following ingredients were _ 'in~ld to form a laser-transferrable ink (all amounts in weight percent):
Talcl 30.0 UVE 93102 7.0 Copper benzoate3 0.14 Epon 1644 51. 43 CHVE54 11. 43 30 1 Nytal 400 commercially available from R.T. Vanderbilt.
2 Photo and thermal initiator _ ~cially available rrom General Electric.
3 ~-c~] ~ator commercially available from Aldrich 'h ~-m i A 1 Co .
35 4 Epoxy novolac resin having an epoxy equivalent of 200-240 commercially available from Shell Oil.
WO 95~13195 PCrlUS94/11345 21~ ~588 5 Cyclohexyl divinyl ether commercially available from GAF or ISI Products.
Methyl ethyl ketone was added to adjust the total 801ids content to 50% by weight, after which the 5 resulting ink was coated onto a 1. 2 mil thick polypropylene carrier film using a ~10 mayer rod. The coated surface of the film was then placed in intimate contact with a glass slide. Next, a C02 laser was directed through the uncoated side of the carrier ~ilm to 10 trnnsfer the ink to the surface of the glass slide. The laser dwelled on each addressed pixel for 80 ~sec. After addressing, the transferred coating was removQd form the glass slide and analyzed by differential S~Anninq calorimetry. There was no evidence of residual heat of 15 reaction, indicating that the tranar~aLLt:d coating had cured during the transfer step.
r le 5 This example describes the ~ ~a~a~ion of a transf er medium having a two-pass, f ree radical-initiated 20 ink in which both the color coat and the ~iize coat are pho~Ir h.o~; CAl ly curable.
The following ingredients were combined to form a photochemically curable color coat (all amounts in weight percent):
25Tio2 65 . 0 Aquacer 3551 11. 0 NR 4402 18.8 ppz3 3 . 0 Triton X-1004 0 . 2 30Daracure 42655 2 . 0 1 Polyethylene wax dispersion commercially available from Diamond Shamrock.
2 Acrylate-funct;~nAl; ~ed prepolymer ~:iall available from Zeneca Resins.
35 3 Commercially available from Idemitsu P~l,L~ 1R CO.
Ltd .
~ WO95113195 ~17~588 PCT/US9~11rl45 ~
4 Surfactant _ . lally available from Rohm & Haas.
5 photnrhPm~r~l free radical initiator ~;ially available from Ciba Geigy.
Water was added to adjust the total solids content 5 to 4096 by weight, after which the resulting color coat was applied to a 1.2 mil thick polypropylene carrier film using a J~13 mayer rod.
The following ingredients were ~ined to form a photorhPm;r~lly curable size coat (all amounts in weight 10 percent):
NR 4401 78 . 0 Ebecryl 6392 20 . 0 Daracure 42653 2. 0 1 Acrylate-f-lnrtinn~l ized prepolymer ~ ially 15 available from Zeneca Resins.
2 Acrylate-functinn;~li7Pcl prepolymer commercially available from Radcure.
3 Photorhpmi r;~-l free radical initiator commercially available from Ciba Geigy.
Water was added to adjust the total solids content of the size coat to 40% by weight, after which the resulting size coat was applied on top of the color coat using a ~5 mayer rod.
The coated surface of the film was then placed in 25 intimate contact with the surface of a molded 8Pm i rnn~ rtor device . Next, a CO2 laser was directed through the uncoated side of the carrier film to transfer the ink (color coat plus size coat) to the surface of the Somi rnn-ll-rtnr device. The laser dwelled on each 30 add~ asOed pixel for 20 ~sec. The power output of the laser at the point of contact with the coated f ilm was 14 . 5 W. The device bearing the transferred image was then cured (5 min. at a 100C preheat, followed-by passage through a W fusion oven equipped with an H bulb 35 at a speed of 100 in. /min. ) . The resulting cured printed W095113195 , PCrlUS94111345 21~55~
image was found to be re6istant to treatment with 1,1,1-trichloroethane (3 min. soak, lo brush strokes, cycled 3 times ) .
other ~mho~l;~ Ls are within the following claims.
What is claimed is:
Ltd .
Methyl ethyl ketone was added to adjust the total solids content of the 6ize coat to 2596 by weight, after which the resulting size coat was applied on top of the color coat using a #5 mayer rod.
The coated surface of the film was then placed in lO intimate contact with the surface of a molded semicon~ t tor device. Next, a C02 laser was directed through the uncoated side of the carrier film to transfer the ink (color coat plus size coat) to the surface of the semicnn~ rtor device. The laser dwelled on each 15 all.~ssed pixel for 20 ~sec. The power output of the laser at the point of contact with the coated film was 14 . 5 W. The device bearing the transferred image was then cured (5 min. at a 150C preheat, followed by a 3.6 gec ~O~UL~ to W radiation). The resulting cured 20 printed image was found to be resistant to ~.~a, with l, l, l-trichloroethane (3 min. soak, lO brush strokes, cycled 3 times ) .
r le 3 This example describes the yL~ Lion of a 25 transfer medium having a wu ~ass, cat;nn;n~lly curable ink in which the color coat is non-cura~le and the size coat is thc.rr- 11 y curable .
The following ingredients were ;n~d to form a non ~_u--ble color coat (all amounts in weight percent):
Water 54. 0 Daxad 30l 0 5 Tio2 38 . 4 Triton X-lOo2 o . 5 CUULu~k 3753 6.2 Rhoplex B854 l . 4 WOss/l3lss v PCT/US94/113~5 2175~8~
Amsco 30115 7.7 1 Polyacrylate dispersing agent ~ ially available f rom W . R . Grace .
2 Surfactant commercially available from Rohm & Haas.
5 3 Polyethylene wax dispersion commercially available from Diamond Shamrock.
4 Acrylic dispersion commercially available from Rohm &
Haas .
5 Acrylic dispersion ~ .;ially available from Rohm &
l0 Haas.
Enough ammonium hydroxide was added to adjust the pH to 8.5, after which the resulting color coat was applied to a 1.2 mil thick polypropylene carrier film at a coat weight of 69 mg/m2.
The following ingredients were ;nPd to form a photonhP~ Al ly curable size coat (all amounts in weight percent):
EPON l00ll 88 . 2 WR 6llo2 ll . 6 20FC-4303 3.0 W 4794 l. 6 IR 995 0 . 5 Benzpinacole6 o . 47 1 R; ~rhPnnl A diglycidyl ether cially available 25 from Shell Oil Co.
2 Liguid ~i;Prn~ P commercially available from Union Carbide .
3 Fluoroaliphatic polymeric ester surfactant ~;iall available from 3N co~
30 4 Io~nn;l-~ salt thermal initiator commercially available from General Electric .
5 Dye ~ ~ially available from Glendale Protective ~echnologies .
6 Accelerator commercially available from Aldrich 35 ~'hP~n;cAl Co.
~ ~0 95/13195 2 1 7 ~ ~ 8 8 PCr/US94/11345 ~ ~"f ~
Methyl ethyl ketone was added to adjust the total solids content of the size coat to 259~ by weight, after which the resulting size coat was applied on top of the color coat using a ~5 mayer rod.
The coated surface of the film was then placed in intimate contact with the surface of a molded 8~micon~ tor device. Next, a Nd:YAG laser was directed through the uncoated side of the carrier ~ilm to transfer the ink (color coat plu5 size coat) to the surface of the 10 s~i cnn~ tor device. The laser dwelled on each ~ dLe~ed pixel for 18 ~Lsec. The power output of the laser at the point of contact with the coated f ilm was 4.5 W. The device bearing the transferred image was then cured (4 min. at 175C). The resulting cured printed 15 image was found to be resistant to LLe:al L with 1,1,1-trichloroethane (3 min. soak, 10 brush strokes, cycled 3 times) .
r le 4 This example describes the ~r~paL~tion of a 20 transfer medium having a one-pass, fhF-~-lly curable, ca~inniAlly initiated ink in which transfer and cure takes place in a single step upon laser irradiation.
The following ingredients were _ 'in~ld to form a laser-transferrable ink (all amounts in weight percent):
Talcl 30.0 UVE 93102 7.0 Copper benzoate3 0.14 Epon 1644 51. 43 CHVE54 11. 43 30 1 Nytal 400 commercially available from R.T. Vanderbilt.
2 Photo and thermal initiator _ ~cially available rrom General Electric.
3 ~-c~] ~ator commercially available from Aldrich 'h ~-m i A 1 Co .
35 4 Epoxy novolac resin having an epoxy equivalent of 200-240 commercially available from Shell Oil.
WO 95~13195 PCrlUS94/11345 21~ ~588 5 Cyclohexyl divinyl ether commercially available from GAF or ISI Products.
Methyl ethyl ketone was added to adjust the total 801ids content to 50% by weight, after which the 5 resulting ink was coated onto a 1. 2 mil thick polypropylene carrier film using a ~10 mayer rod. The coated surface of the film was then placed in intimate contact with a glass slide. Next, a C02 laser was directed through the uncoated side of the carrier ~ilm to 10 trnnsfer the ink to the surface of the glass slide. The laser dwelled on each addressed pixel for 80 ~sec. After addressing, the transferred coating was removQd form the glass slide and analyzed by differential S~Anninq calorimetry. There was no evidence of residual heat of 15 reaction, indicating that the tranar~aLLt:d coating had cured during the transfer step.
r le 5 This example describes the ~ ~a~a~ion of a transf er medium having a two-pass, f ree radical-initiated 20 ink in which both the color coat and the ~iize coat are pho~Ir h.o~; CAl ly curable.
The following ingredients were combined to form a photochemically curable color coat (all amounts in weight percent):
25Tio2 65 . 0 Aquacer 3551 11. 0 NR 4402 18.8 ppz3 3 . 0 Triton X-1004 0 . 2 30Daracure 42655 2 . 0 1 Polyethylene wax dispersion commercially available from Diamond Shamrock.
2 Acrylate-funct;~nAl; ~ed prepolymer ~:iall available from Zeneca Resins.
35 3 Commercially available from Idemitsu P~l,L~ 1R CO.
Ltd .
~ WO95113195 ~17~588 PCT/US9~11rl45 ~
4 Surfactant _ . lally available from Rohm & Haas.
5 photnrhPm~r~l free radical initiator ~;ially available from Ciba Geigy.
Water was added to adjust the total solids content 5 to 4096 by weight, after which the resulting color coat was applied to a 1.2 mil thick polypropylene carrier film using a J~13 mayer rod.
The following ingredients were ~ined to form a photorhPm;r~lly curable size coat (all amounts in weight 10 percent):
NR 4401 78 . 0 Ebecryl 6392 20 . 0 Daracure 42653 2. 0 1 Acrylate-f-lnrtinn~l ized prepolymer ~ ially 15 available from Zeneca Resins.
2 Acrylate-functinn;~li7Pcl prepolymer commercially available from Radcure.
3 Photorhpmi r;~-l free radical initiator commercially available from Ciba Geigy.
Water was added to adjust the total solids content of the size coat to 40% by weight, after which the resulting size coat was applied on top of the color coat using a ~5 mayer rod.
The coated surface of the film was then placed in 25 intimate contact with the surface of a molded 8Pm i rnn~ rtor device . Next, a CO2 laser was directed through the uncoated side of the carrier film to transfer the ink (color coat plus size coat) to the surface of the Somi rnn-ll-rtnr device. The laser dwelled on each 30 add~ asOed pixel for 20 ~sec. The power output of the laser at the point of contact with the coated f ilm was 14 . 5 W. The device bearing the transferred image was then cured (5 min. at a 100C preheat, followed-by passage through a W fusion oven equipped with an H bulb 35 at a speed of 100 in. /min. ) . The resulting cured printed W095113195 , PCrlUS94111345 21~55~
image was found to be re6istant to treatment with 1,1,1-trichloroethane (3 min. soak, lo brush strokes, cycled 3 times ) .
other ~mho~l;~ Ls are within the following claims.
What is claimed is:
Claims (23)
1. A transfer printing medium comprising a carrier to which is applied a curable laser-transferrable ink having one or more layers, said ink comprising (a) at least one colorant;
(b) at least one polymerization initiator; and (c) at least one curable prepolymer, said transfer medium being capable of converting laser energy to heat.
(b) at least one polymerization initiator; and (c) at least one curable prepolymer, said transfer medium being capable of converting laser energy to heat.
2. The transfer printing medium of claim 1 wherein said ink transfers to a surface of interest and cures in one step upon application of laser energy.
3. The transfer printing medium of claim 1 wherein at least one of said polymerization initiators comprises a thermal polymerization initiator and at least one of said prepolymers is thermally curable.
4. The transfer printing medium of claim 1 wherein at least one of said polymerization initiators comprises a photoinitiator and at least one of said prepolymers is photochemically curable.
5. The transfer printing medium of claim 1 wherein at least one of said prepolymers comprises an epoxy-functionalized prepolymer.
6. The transfer printing medium of claim 5 wherein said prepolymer further comprises a vinyl ether-functionalized prepolymer.
7. The transfer printing medium of claim 5 wherein said prepolymer further comprises an acrylate-functionalized prepolymer.
8. The transfer printing medium of claim 1 wherein at least one of said prepolymers comprises an acrylate-functionalized prepolymer.
9. The transfer printing medium of claim 1 wherein at least one of said prepolymers comprises a blocked isocyanate-functionalized prepolymer.
10. The transfer printing medium of claim 1 wherein at least one of said prepolymers comprises a blend of a vinyl ether-functionalized prepolymer and a maleate- or maleimide-functionalized prepolymer.
11. The transfer printing medium of claim 1 wherein at least one of the layers of said ink is a curable size coat comprising a polymerization initiator and a curable prepolymer.
12. The transfer printing medium of claim 1 wherein at least one of the layers of said ink is a curable size coat comprising a polymerization initiator and a curable prepolymer and at least one of the layers of said ink is a non-curable color coat comprising a colorant and a thermoplastic film-forming resin.
13. The transfer printing medium of claim 1 wherein at least one of the layers of said ink is a curable size coat comprising a polymerization initiator and a curable prepolymer and at least one of the layers of said ink is a curable color coat comprising a colorant, a polymerization initiator, and a curable prepolymer.
14. A laser-induced transfer printing method comprising the steps of (a) providing a transfer printing medium capable of converting laser energy to heat comprising a carrier to which is applied a curable laser-transferrable ink having one or more layers, said ink comprising (i) at least one colorant;
(ii) at least one polymerization initiator; and (iii) at least one curable prepolymer;
(b) irradiating said medium with laser light of a predetermined wavelength to transfer said ink to a surface of interest; and (c) curing said ink to adhere said ink to the surface of interest.
(ii) at least one polymerization initiator; and (iii) at least one curable prepolymer;
(b) irradiating said medium with laser light of a predetermined wavelength to transfer said ink to a surface of interest; and (c) curing said ink to adhere said ink to the surface of interest.
15. The method of claim 14 wherein the transfer and cure of said ink are effected in a single step through irradiation with said laser light.
16. The method of claim 14 wherein at least one of said polymerization initiators comprises a thermal polymerization initiator and at least one of said prepolymers is thermally curable.
17. The method of claim 14 wherein at least one of said polymerization initiators comprises a photoinitiator and at least one of said prepolymers is photochemically curable.
18. The method of claim 14 wherein at least one of the layers of said ink is a curable size coat comprising a polymerization initiator and a curable prepolymer.
19. The method of claim 14 wherein at least one of the layers of said ink is a curable size coat comprising a polymerization initiator and a curable prepolymer and at least one of the layers of said ink is a non-curable color coat comprising a colorant and a thermoplastic film-forming resin.
20. The method of claim 14 wherein at least one of the layers of said ink is a curable size coat comprising a polymerization initiator and a curable prepolymer and at least one of the layers of said ink is a curable color coat comprising a colorant, a polymerization initiator, and a curable prepolymer.
21. The method of claim 14 wherein said the transfer and cure of said ink are effected in a single step through irradiation with said laser light.
22. The method of claim 14 wherein the transfer and cure of said ink are effected in separate steps.
23. A laser-induced transfer printing method comprising the steps of (a) providing a transfer printing medium capable of converting laser energy to heat comprising a carrier to which is applied a curable laser-transferrable ink;
and (b) irradiating said medium with laser light of a predetermined wavelength, whereupon said laser light transfers said ink to a surface of interest and cures said ink to adhere said ink to the surface of interest.
and (b) irradiating said medium with laser light of a predetermined wavelength, whereupon said laser light transfers said ink to a surface of interest and cures said ink to adhere said ink to the surface of interest.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14928593A | 1993-11-09 | 1993-11-09 | |
| US08/149,285 | 1993-11-09 | ||
| PCT/US1994/011345 WO1995013195A1 (en) | 1993-11-09 | 1994-10-06 | Transfer printing medium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2175588A1 true CA2175588A1 (en) | 1995-05-18 |
Family
ID=22529568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002175588A Abandoned CA2175588A1 (en) | 1993-11-09 | 1994-10-06 | Transfer printing medium |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0728073B1 (en) |
| JP (1) | JPH07232480A (en) |
| KR (1) | KR100322459B1 (en) |
| AT (1) | ATE179125T1 (en) |
| CA (1) | CA2175588A1 (en) |
| DE (1) | DE69418056T2 (en) |
| WO (1) | WO1995013195A1 (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5757313A (en) * | 1993-11-09 | 1998-05-26 | Markem Corporation | Lacer-induced transfer printing medium and method |
| US6037968A (en) * | 1993-11-09 | 2000-03-14 | Markem Corporation | Scanned marking of workpieces |
| WO1996024495A1 (en) * | 1995-02-10 | 1996-08-15 | Klaus Kall | Method of coating a transparent carrier plate and coated carrier plate produced according to this method |
| GB9617416D0 (en) * | 1996-08-20 | 1996-10-02 | Minnesota Mining & Mfg | Thermal bleaching of infrared dyes |
| US5695907A (en) * | 1996-03-14 | 1997-12-09 | Minnesota Mining And Manufacturing Company | Laser addressable thermal transfer imaging element and method |
| US5747217A (en) * | 1996-04-03 | 1998-05-05 | Minnesota Mining And Manufacturing Company | Laser-induced mass transfer imaging materials and methods utilizing colorless sublimable compounds |
| US7534543B2 (en) | 1996-04-15 | 2009-05-19 | 3M Innovative Properties Company | Texture control of thin film layers prepared via laser induced thermal imaging |
| US5725989A (en) | 1996-04-15 | 1998-03-10 | Chang; Jeffrey C. | Laser addressable thermal transfer imaging element with an interlayer |
| US5998085A (en) * | 1996-07-23 | 1999-12-07 | 3M Innovative Properties | Process for preparing high resolution emissive arrays and corresponding articles |
| US6075223A (en) | 1997-09-08 | 2000-06-13 | Thermark, Llc | High contrast surface marking |
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| US6238847B1 (en) | 1997-10-16 | 2001-05-29 | Dmc Degussa Metals Catalysts Cerdec Ag | Laser marking method and apparatus |
| JPH11180099A (en) | 1997-12-18 | 1999-07-06 | Matsushita Electric Ind Co Ltd | Method for marking and resin molding with mark |
| AU2514800A (en) * | 1999-01-27 | 2000-08-18 | United States Of America As Represented By The Secretary Of The Navy, The | Matrix assisted pulsed laser evaporation direct write |
| US6177151B1 (en) * | 1999-01-27 | 2001-01-23 | The United States Of America As Represented By The Secretary Of The Navy | Matrix assisted pulsed laser evaporation direct write |
| WO2000078554A1 (en) | 1999-06-22 | 2000-12-28 | Omg Ag & Co. Kg | Laser marking compositions and method |
| US6228543B1 (en) | 1999-09-09 | 2001-05-08 | 3M Innovative Properties Company | Thermal transfer with a plasticizer-containing transfer layer |
| US6503316B1 (en) | 2000-09-22 | 2003-01-07 | Dmc2 Degussa Metals Catalysts Cerdec Ag | Bismuth-containing laser markable compositions and methods of making and using same |
| US6730376B2 (en) * | 2001-02-09 | 2004-05-04 | 3M Innovative Properties Company | Thermally transferable compositions and methods |
| US7238396B2 (en) | 2002-08-02 | 2007-07-03 | Rieck Albert S | Methods for vitrescent marking |
| US7678526B2 (en) | 2005-10-07 | 2010-03-16 | 3M Innovative Properties Company | Radiation curable thermal transfer elements |
| US7396631B2 (en) | 2005-10-07 | 2008-07-08 | 3M Innovative Properties Company | Radiation curable thermal transfer elements |
| EP1954505A1 (en) | 2005-11-22 | 2008-08-13 | Merck Patent GmbH | Process for a thermal transfer of a liquid crystal film using a transfer element |
| DE102005057474A1 (en) * | 2005-11-30 | 2007-05-31 | Merck Patent Gmbh | Method for flexible and individual marking of products, documents of value and security documents, involves introduction of security features into layer system |
| US9744559B2 (en) | 2014-05-27 | 2017-08-29 | Paul W Harrison | High contrast surface marking using nanoparticle materials |
| DE102018111132A1 (en) | 2018-05-09 | 2019-11-14 | Lpkf Laser & Electronics Aktiengesellschaft | Use of a component in a composition, composition for laser transfer printing and laser transfer printing method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4812354A (en) * | 1986-05-14 | 1989-03-14 | Mitsubishi Paper Mills, Ltd. | Color image recording material |
| JPH03244588A (en) * | 1990-02-22 | 1991-10-31 | Canon Inc | Transfer recording medium |
-
1994
- 1994-10-06 AT AT94930625T patent/ATE179125T1/en not_active IP Right Cessation
- 1994-10-06 KR KR1019960702442A patent/KR100322459B1/en not_active IP Right Cessation
- 1994-10-06 CA CA002175588A patent/CA2175588A1/en not_active Abandoned
- 1994-10-06 EP EP94930625A patent/EP0728073B1/en not_active Expired - Lifetime
- 1994-10-06 WO PCT/US1994/011345 patent/WO1995013195A1/en active IP Right Grant
- 1994-10-06 DE DE69418056T patent/DE69418056T2/en not_active Expired - Fee Related
- 1994-11-08 JP JP6273758A patent/JPH07232480A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0728073B1 (en) | 1999-04-21 |
| EP0728073A1 (en) | 1996-08-28 |
| JPH07232480A (en) | 1995-09-05 |
| DE69418056T2 (en) | 1999-11-11 |
| KR960705689A (en) | 1996-11-08 |
| WO1995013195A1 (en) | 1995-05-18 |
| DE69418056D1 (en) | 1999-05-27 |
| ATE179125T1 (en) | 1999-05-15 |
| KR100322459B1 (en) | 2002-10-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |