CN1777658A - Jet ink composition for low surface energy substrates - Google Patents
Jet ink composition for low surface energy substrates Download PDFInfo
- Publication number
- CN1777658A CN1777658A CN 200480008789 CN200480008789A CN1777658A CN 1777658 A CN1777658 A CN 1777658A CN 200480008789 CN200480008789 CN 200480008789 CN 200480008789 A CN200480008789 A CN 200480008789A CN 1777658 A CN1777658 A CN 1777658A
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- China
- Prior art keywords
- weight
- inkjet compositions
- resin
- composition
- rosin
- Prior art date
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- Granted
Links
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- 239000011347 resin Substances 0.000 claims abstract description 58
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 39
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 39
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000007639 printing Methods 0.000 claims abstract description 27
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- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 239000000020 Nitrocellulose Substances 0.000 claims abstract description 10
- 229920001220 nitrocellulos Polymers 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 27
- 239000000049 pigment Substances 0.000 claims description 19
- 239000004840 adhesive resin Substances 0.000 claims description 18
- 229920006223 adhesive resin Polymers 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- -1 glycerol ester Chemical class 0.000 claims description 16
- 239000000975 dye Substances 0.000 claims description 15
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
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- 150000002148 esters Chemical class 0.000 claims description 6
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
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- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 abstract description 8
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- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 3
- QPQKUYVSJWQSDY-UHFFFAOYSA-N 4-phenyldiazenylaniline Chemical compound C1=CC(N)=CC=C1N=NC1=CC=CC=C1 QPQKUYVSJWQSDY-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- 239000011707 mineral Substances 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229920001342 Bakelite® Polymers 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 239000004637 bakelite Substances 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LLNAMUJRIZIXHF-CLFYSBASSA-N (z)-2-methyl-3-phenylprop-2-en-1-ol Chemical compound OCC(/C)=C\C1=CC=CC=C1 LLNAMUJRIZIXHF-CLFYSBASSA-N 0.000 description 1
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- TVBNRFCUTVWHQB-UHFFFAOYSA-N 1-anilino-4-(methylamino)anthracene-9,10-dione Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(NC)=CC=C1NC1=CC=CC=C1 TVBNRFCUTVWHQB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- IAFBRPFISOTXSO-UHFFFAOYSA-N 2-[[2-chloro-4-[3-chloro-4-[[1-(2,4-dimethylanilino)-1,3-dioxobutan-2-yl]diazenyl]phenyl]phenyl]diazenyl]-n-(2,4-dimethylphenyl)-3-oxobutanamide Chemical compound C=1C=C(C)C=C(C)C=1NC(=O)C(C(=O)C)N=NC(C(=C1)Cl)=CC=C1C(C=C1Cl)=CC=C1N=NC(C(C)=O)C(=O)NC1=CC=C(C)C=C1C IAFBRPFISOTXSO-UHFFFAOYSA-N 0.000 description 1
- GBPWTMZRCAESKB-UHFFFAOYSA-N 2-amino-n,n-dipropylacetamide;hydrochloride Chemical compound Cl.CCCN(CCC)C(=O)CN GBPWTMZRCAESKB-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- MAZRKDBLFYSUFV-UHFFFAOYSA-N 3-[(1-anilino-1,3-dioxobutan-2-yl)diazenyl]-2-hydroxy-5-nitrobenzenesulfonic acid chromium Chemical compound CC(=O)C(C(=O)NC1=CC=CC=C1)N=NC2=C(C(=CC(=C2)[N+](=O)[O-])S(=O)(=O)O)O.[Cr] MAZRKDBLFYSUFV-UHFFFAOYSA-N 0.000 description 1
- BPTKLSBRRJFNHJ-UHFFFAOYSA-N 4-phenyldiazenylbenzene-1,3-diol Chemical compound OC1=CC(O)=CC=C1N=NC1=CC=CC=C1 BPTKLSBRRJFNHJ-UHFFFAOYSA-N 0.000 description 1
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- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 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
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- YARNEMCKJLFQHG-UHFFFAOYSA-N prop-1-ene;styrene Chemical compound CC=C.C=CC1=CC=CC=C1 YARNEMCKJLFQHG-UHFFFAOYSA-N 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 239000001047 purple dye Substances 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- TVRGPOFMYCMNRB-UHFFFAOYSA-N quinizarine green ss Chemical compound C1=CC(C)=CC=C1NC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1NC1=CC=C(C)C=C1 TVRGPOFMYCMNRB-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Disclosed are jet ink compositions suitable for printing on substrates such as plastics and oil contaminated metals messages having excellent adhesion, for example, scratch resistance. The jet ink composition comprises one or more organic solvents, a rosin resin, and a colorant, and optionally a co-binder resin, e.g., a vinyl resin. Preferably, the jet ink composition is free or substantially free of a cellulose nitrate resin and/or a slow evaporating solvent. The present invention further provides a method for printing scrathc resistant messages on a low surface energy substrate comprising projecting a stream of droplets of the jet ink composition to the substrate, controlling the direction of the stream so that the droplets are caused to form the desired printed messages, and allowing the messages to dry.
Description
Technical field
[0001] the present invention relates to be suitable for printing to have the ink jet ink composition that improves tack and resistance to marring information.Usually on low surface energy substrates, on the metal substrate of low surface energy plastic bottom material and oil pollution during printing information, the present invention is particularly advantageous especially.The invention still further relates to a kind of printing and have the method for improving tack and the such information of scratch resistance.
Background technology
[0002] ink jet printing is a kind of technology of knowing, and when adopting this technology print, printing equipment does not contact with the base material of deposition Printing Marks.In brief, the technology that ink jet printing relates to is that ink droplets stream is ejected on the surface, and the control of its stream of liquid droplets direction reached makes its ink droplet form desirable printed images on that surface.This not contact print technology is suitable for symbol is coated on the ground of for example glass, metal or plastic containers and packing material and so on particularly well.
[0003] in following publication, can see the comment of relevant ink jet printing many aspects: people such as Kuhn, " American of science " (Scientific American), April,, 162-178 page or leaf in 1979; Keeling, " physical technology " (Phys.Technol.), 12 (5), 196-303 (1981).Various ink-jet apparatus have been described: 3 060 429,3 298 030,3 373 437,3 416 153 and 3 673 601 in the United States Patent (USP) below.
[0004] generally speaking, ink jet ink composition should satisfy some service requirements when ink jet printing is operated.These requirements relate to viscosity, resistivity, solubleness, the consistency of component, and the wettability of ground.In addition, this ink should be to do and anti-plastifying soon, rub resistance, easily, do not stop up yet, and make just its machine parts of possibility rapid cleaning of a little effort by ink nozzle.In addition, printed information and ground should have enough tacks.
[0005] plastic bottom material, particularly polyolefine usually are used for packing.For example, oriented polypropylene (OPP) film is widely used as wrapping material, the housing material of picture cigarette pack and packing case carton, because their energy heat seals, and has good barrier performance, the freshness and the water content that keep connection with wrapping of piece, however also there are some problems in these grounds and other low surface energy substrates aspect the quality of printing information and the intensity.If the tack of information and ground is bad, sometimes when normal processing even use medium relatively power just can wipe these information or scrape and wipe.In order to alleviate this problem, sometimes plastic bottom material is carried out surface preparation, for example oxidation, carona handle or Cement Composite Treated by Plasma, or prime.But some pre-treatment increase the cost of packing material production method undisputedly like this.
[0006] in addition, the OPP film usually contains slip additive, conveniently to take off sealing member or suitable frictional coefficient is provided.These additives mainly are the fatty acid amides of migration, and they haze film surface, and smooth performance also is provided.It is believed that these additives are passed and aspect the reduction in time in ink adhesivity, and tack all is the factor that works because of the aging different aspects that change of film.Like this existence of some additives make on the low surface energy film ink adhesivity in addition have more challenge.
[0007] once did some trials, for example used some acrylamide or chloro acrylic resin, provided the composition for ink that improves printing information and low surface energy plastic bottom material tack, for example referring to US 5 430 093 and 5 500 251.But other approach also needs.
[0008] foregoing shows, also need be at frosting, particularly low-yield surface is for example on the polyolefin surfaces, printing generally has the information of wear resistance or scratch resistance, the composition for ink that has the information of anti-fingernail scratch or the frictional property of anti-the nail especially.
[0009] the invention provides a kind of like this composition.By the specification sheets of the present invention that provides here, advantage of the present invention and other inventive features will become apparent.
Summary of the invention
[0010] the present invention can satisfy above-mentioned requirements to a large extent, the invention provides a kind of inkjet compositions, and it is suitable for for example printing the information with wear resistance and scratch resistance on plastics and so on ground.This inkjet compositions contains one or more organic solvents, rosin resin and tinting material, and randomly helps tackiness agent (cobinder) resin, for example Vinylite.Preferably, this inkjet compositions does not have or does not have basically nitrocellulose resin and/or slow-evaporating solvent.
[0011] the present invention also provides a kind of method with wear resistance or scratch resistance information of printing on ground, this method comprises this inkjet compositions stream of liquid droplets is ejected on the ground, the control of this stream of liquid droplets direction reached make its drop form needed printing information, allow its information drying again.
[0012] description by the specific embodiment of the invention is done here, aforementioned advantages of the present invention and other inventive features will become apparent.
Embodiment
[0013] the invention provides a kind of inkjet compositions, it is suitable at ground, for example prints the information with wear resistance or scratch resistance on the low surface energy plastics, and said composition contains one or more organic solvents, tinting material and rosin resin.This composition for ink can also contain one or more components, for example helps adhesive resin, softening agent, wetting agent, defoamer and conductive agent.
[0014] the present invention is based on this discovery that the inkjet compositions that contains rosin resin has performance unique, beyond expectation.Be printed on ground, low-yield especially ground, for example information on the polyolefine and this ground have splendid tack.These information show that scratch resistance is improved.Another advantage of composition for ink of the present invention is to print the information with wear resistance on low-yield surface, also is like this when even not using adhesion promoter or surface treatment.Although do not need, can expect that surface treatment or adhesion promoter can even improve tack more.
[0015] in an embodiment, the invention provides a kind of inkjet compositions, it contains one or more organic solvents, rosin resin, helps adhesive resin and tinting material, and wherein this inkjet compositions does not have or do not have basically nitrocellulose resin.In another embodiment, the invention provides a kind of inkjet compositions, it contains one or more organic solvents, rosin resin, Vinylite and tinting material.In another embodiment, the invention provides a kind of inkjet compositions, it contains one or more organic solvents, rosin resin and tinting material, and wherein this inkjet compositions does not have or do not have basically nitrocellulose resin and slow-evaporating solvent.
[0016] inkjet compositions of the present invention can be continuously or in drops is used for the printing press of needs.When being used for continuous ink jet printing, they have (1) at the about 1.6-10.0 centipoise of 25 ℃ viscosity; (2) resistivity 50-2000ohm-cm; And the about 1100-1700 meter per second of (3) velocity of sound.
[0017] inkjet compositions of the present invention contains at least a organic solvent.Can use 2,3,4 or the ORGANIC SOLVENT MIXTURES more than 4 kind.Can use any suitable solvent, and in a preferred embodiment, this solvent has rosin resin and/or helps the enough solubleness of adhesive resin (helping adhesive resin if use), and in a preferred embodiment, the enough solubleness that this solvent has rosin resin and helps adhesive resin.This organic solvent preferably also has sufficient volatility or velocity of evaporation, to reach printing information suitable (for example short) time of drying.The organic solvent example comprises alcohol, ketone, ester, ether, acid amides and combination thereof, preferably ketone, more preferably lower ketones.The special example of an organic solvent is a methylethylketone.If water is arranged, then preferably water-content is kept very low, for example the weight in solvent mixture is lower than 5%, more preferably is lower than 2%, also more preferably is lower than 1%.
[0018] content of this organic solvent or solvent mixture can be suitable, for example in the weight about at the most 90% of this inkjet compositions.In an embodiment, the content of organic solvent or solvent mixture can be about 30 weight % of this inkjet compositions to about 90 weight %, preferably about 50 weight % are to about 80 weight %.In another embodiment, the content of organic solvent or solvent mixture can be about 70 weight % of this inkjet compositions to about 90 weight %, preferably about 75 weight % to 85 weight %.
[0019] according to some embodiment of the present invention, this inkjet compositions does not have or does not have basically slow-evaporating solvent, for example with respect to the velocity of evaporation 1.0 of n-butyl acetate, below the velocity of evaporation of slow-evaporating solvent about 0.5 or 0.5, below preferably about 0.3 or 0.3, below more preferably about 0.2 or 0.2.For example referring to US 6 444 019, the 5th hurdle, 2-26 is capable.If slow-evaporating solvent is arranged, preferably its amount seldom, for example its amount is about 5 weight % or lower of this inkjet compositions, more preferably about 3 weight % or lower, even more preferably about 1 weight % or lower.
[0020] inkjet compositions of the present invention contains rosin resin.Can use any suitable rosin resin.This rosin resin can be natural resin or modified resin.Modified rosin base resin for example comprises stable rosin resin, polymerized rosin base resin and esterified rosin base resin.Can use monovalent alcohol, for example as methyl alcohol, ethanol, propyl alcohol etc., multivalence alcohol, for example ethylene glycol, propylene glycol, glycerol, tetramethylolmethane etc. carry out esterification.Rosin resin also can for example carry out modification by the maleic anhydride addition reaction by addition reaction, or carries out modification by hydrogenation or dehydrogenation reaction, makes rosin resin become more stable, and is for example more stable to oxidizing reaction.In a preferred embodiment, this rosin resin is the staybelite base resin of glycerin modification.In an embodiment, this rosin resin has low acid number, and for example about 20 or lower, as about 10 or lower, preferably about 8 or lower.The staybelite base examples of resins of glycerin modification is the STAYBELITE that obtains from Hercules Inc
_Ester 10, and its acid number is 8.
[0021] rosin resin of appropriate amount can be arranged, for example in some embodiment, its amount is that about 20 weight % of this inkjet compositions are to about 40 weight %, preferably about 25 weight % are to about 35 weight %, and at some in other the embodiment, its amount be about 5 weight % of this inkjet compositions to about 20 weight %, preferably about 7 weight % are to about 15 weight %.In some embodiments of pigment were for example arranged, the amount of rosin resin also can be that about 1 weight % is to about 5 weight %.
[0022] do not wish to be subjected to any theory or machine-processed constraint, can think when in printing information, rosin resin being arranged that it works the solid solvent effect of making slip additive, and slip additive hazes substrate surface.When rosin resin absorbed (or dissolving) slip additive in the printed images, this additive was not stayed between ground and the printing information at the interface.The absorption of this additive or dissolving can prevent the tack variation between printing information and ground.It is believed that this phenomenon can be the reason that causes tack to be improved.This ink jet ink composition can also be penetrated in some pollutent on ground, for example is penetrated in the oily pollutent on metal tin part (for example lid), for ground provides good tack.
[0023] in some embodiments, inkjet compositions of the present invention can contain one or more and helps adhesive resin.Can use any suitable adhesive resin that helps.Help the example of adhesive resin to comprise Vinylite, acrylic resin, styrene-propene acid resin, silicone resin, polyester, polymeric amide, Polyvinylpyrolidone (PVP), urethane resin, Resins, epoxy, Synolac, hydrocarbon resin, Nitrocellulose (or nitrocellulose), celluosic resin, cellulose acetate, ketone resin and air aldehyde resin.In some embodiment, it is preferred that high-molecular weight helps adhesive resin, for example molecular weight about 10000 or the higher adhesive resin that helps.Helping the special example of adhesive resin is BAKELITE
TMVMCH resin (UnionCarbide), it is vinylchlorid, vinyl acetate between to for plastic and maleic acid terpolymer (86: 13: 1), its number-average molecular weight is about 21000.
[0024] adhesive resin that helps of appropriate amount can be arranged, preferably, its amount is lower than rosin resin.For example, about 1 weight % that this amount that helps adhesive resin can be this inkjet compositions is to about 20 weight %, and preferably about 2 weight % are to about 10 weight %, and more preferably about 3 weight % are to about 5 weight %.
[0025] inkjet compositions of some embodiments of the present invention does not have or does not have basically Nitro cellulose resin.If any, the amount of Nitro cellulose resin seldom, for example its amount is about 5 weight % or lower, more preferably about 3 weight % or lower, even more preferably about 1 weight % or lower.
[0026] inkjet compositions of the present invention contains tinting material, and it can be dyestuff, pigment etc. and combination thereof.Preferably, this tinting material is a dyestuff.In the present invention, can use any dyestuff that can be dissolved in this composition for ink.The dyestuff example that is applicable to composition for ink of the present invention includes, without being limited to yellow dyes, for example C.I. solvent yellow 19 (C.I.13900A), C.I. solvent yellow 21 (C.I.18690), C.I. solvent yellow 61, C.I. solvent yellow 80 etc., orange dye, for example C.I. solvent orange 1 (C.I.11920), C.I. orange 37, C.I. orange 40 etc.; Orchil, for example C.I. solvent red 8, C.I. solvent red 81, C.I. solvent red 82, C.I. solvent red 84, C.I. solvent red 100 etc.; Purple dye, for example C.I. solvent purple 8, C.I. solvent violet 21 etc.; Blue dyes, for example C.I. solvent blue 2, C.I. solvent blue 19 1, C.I. solvent blue 25, C.I. solvent blue 36, C.I. solvent blue 55 etc.; Green colouring material, for example C.I. solvent green 3 etc.; The brown dyestuff, for example the C.I. solvent is brown etc.; Black dyes, for example C.I. solvent black 3, C.I. solvent black 5, C.I. solvent black 7, C.I. solvent black 22, C.I. solvent black 27, C.I. solvent black 29 etc.The special example of dyestuff is a C.I. solvent black 29, and it can obtain with Valifast Black 3810 (Orient Chemical) or Orasol Black RLI (Ciba) from the market.
[0027] in some embodiment of the present invention, pigment can be preferred; If the ground of for example planning to use is dark, opaque pigment can provide better contrast.Organic and mineral dye both is fit to.Suitable opaque mineral dye example comprises titanium dioxide (anatase octahedrite and rutile), pucherite, zinc oxide, zinc sulphide and lithopone.Suitable opaque pigment dyestuff example comprises pigment yellow 13 9, pigment orange 16, pigment orange 34, pigment orange 61, pigment orange 62, pigment orange 64, Pigment red 254, Pigment red 255, bistre 5 etc.Other example of pigment dyestuff is a carbon black.Carbon black comprises thermally oxidized black, furnace black and dim.Other suitable organic and mineral dye example comprises that metallized azo is red, for example red 49: 1 (barium salt), red 49: 2 (calcium salt), red 63: 1 (calcium salt), toluidine red, naphthol red, Pyrazalones, rhodamine; Quinacridone, for example red B, red Y, pinkish red B, magenta and purple, phthalocyanine blue, phthalocyanine green, carbazole Huang, single aryl Huang, diarylide yellow, chrome yellow, red shallow lake C; You are dark red for lithol, and for example calcium and barium salt, lithol rubine, Bon are purplish red, perylene pigment; Red 2B pigment, contains iron mica, spathic iron ore, pyrite, iron oxide yellow, red iron oxide, Prussian blue, orange 36, diaryl orange, dianisidine orange, tolyl orange and dinitro aniline orange at, lead chromate, lead silico-chromate, zinc-chrome yellow, baryta yellow, strontium yellow, titanium nickel yellow, limonite, rhombohedral iron ore, magnetite orange comprising calcium, barium and magnesium salts, chrome yellow, chrome orange, molybdenum.Other suitable pigment example comprises the color lake, for example the color lake that is generated by matching stain and basic metal or alkaline-earth metal.
[0028] in this composition for ink tinting material can be arranged, its amount is to reach contrast gradient and the readable needed any amount of wishing.The amount of tinting material preferably in the weight of this inkjet compositions about 1% to about 18%, more preferably be in the weight of this inkjet compositions about 2% to about 15%.
[0029] inkjet compositions of the specific embodiment of the invention can also contain softening agent.It is believed that this softening agent can improve ink film forming flexibility when dry on ground.Improving flexibility has to a certain extent and helps improve wear resistance.Can use in industrial known any suitable manufacturing methods.For example referring to US 5 594 044, this patent walks to the 7th hurdle the 6th row and discloses the softening agent that is suitable for inkjet compositions on the 6th hurdle the 36th, here its disclosure is referenced by reference.The preferred plasticizer that is used for composition for ink of the present invention is SANTICIZERTM160, and it is neighbour-phthalic acid butyl benzyl ester, can obtain from Monsanto Co.
[0030] softening agent of any appropriate amount can be arranged.For example in this inkjet compositions, the amount of softening agent can be the about 5 weight % up to this composition for ink, preferably its amount be about 0.5 weight % of this composition for ink to about 3 weight %, more preferably about 0.5% to about 2 weight %.
[0031] inkjet compositions of some embodiments of the present invention can also contain the wetting agent of for example controlling the ink droplets size.Can any suitable wetting agent.A wetting agent example is a tensio-active agent.Tensio-active agent can be negatively charged ion, positively charged ion, nonionic or amphoteric tensio-active agent.From New York, Ta Lidun, Witco Corp., the SILWET that OSI Specialties Group obtains
TML-7622 is a silicone base wetting agent, is a preferred wetting agent example.As for other wetting agent, for example can be referring to US 5 594 044, the 5th hurdle 43-64 page or leaf is referenced by reference its disclosure here.
[0032] amount of wetting agent can be in the about at the most 1 weight % of the weight of this inkjet compositions, preferably about 0.1% to about 1% in this inkjet compositions.
[0033] inkjet compositions of some embodiments of the present invention can contain defoamer.This defoamer has reduced the foaming trend of this inkjet compositions.Suitable defoamer example is USA, the BYK of BYK-Chemie
TM065.Can use the defoamer of any appropriate amount, for example in the weight about at the most 1% of this inkjet compositions.
[0034] this inkjet compositions also can contain other additive of knowing usually in the ink for ink-jet print printing technology, for example regulates the additive of viscosity, resistivity and velocity of evaporation.One or more wetting Agent for Printing Inkss can be arranged.
[0035] this inkjet compositions also can contain one or more conductive agents.When if conductive agent is arranged, then their amount is at most about 2.0 weight % of this composition for ink typically.Suitable conductive agent example comprises trifluoromethayl sulfonic acid lithium, right-the toluenesulphonic acids tetraethyl ammonium, tetrabutyl phosphonium bromide phosphorus, 4-propyl bromide, tetrabutylammonium chloride, tetrabutyl ammonium nitrate, hexafluorophosphate.In the presence of solvent that ink uses, some dyestuffs (for example soluble dye) can provide sufficient electric conductivity, therefore can use conductive agent.If use pigment then may need conductive agent.
[0036] the invention provides some embodiments of inkjet compositions, wherein the amount of one or more organic solvents is that about 50 weight % of said composition are to about 80 weight %, the amount of rosin resin be about 20 weight % of said composition to about 40 weight %, and the amount of tinting material is that about 5 weight % of said composition are to about 10 weight %.This inkjet compositions can also contain wetting agent, and its amount is that about 0.1 weight % of said composition is to about 1 weight %.
[0037] the present invention also provides some embodiments of inkjet compositions, wherein the amount of one or more organic solvents is that about 70 weight % of said composition are to about 90 weight %, the amount of rosin resin is that about 1 weight % of said composition is to about 20 weight %, the amount that helps adhesive resin is that about 2 weight % of said composition are to about 10 weight %, preferably about 2 weight % are to about 6 weight %, and the amount of tinting material is that about 2 weight % of said composition are to about 15 weight %.This inkjet compositions can also contain wetting agent, its amount be about 0.1 weight % of said composition to about 1 weight %, softening agent, its amount is about 0.1 weight % to 2 weight % of said composition, and/or defoamer, its amount is that 0.5 weight % of said composition is to about 1.5 weight %.
[0038] the present invention also provides a kind of method that is printed with sticking power information on low surface energy substrates, this method comprises any above-mentioned inkjet compositions stream of liquid droplets is ejected on this ground, the control of the direction of its stream of liquid droplets reached make its drop form desirable printing information, and allow its information drying.According to the present invention, can print any suitable ground with low surface energy.The advantage of composition for ink of the present invention is to print the ground that contains the additive that hazes, and gained information has resistance to wearing of improvement and scratch resistance.
[0039] example of suitable ground comprises plastics and the metal or the pollution metal that are coated with unction or lubricant.Examples of plastics comprises polyolefine, for example polyethylene and polypropylene, preferably polypropylene; And halogenated polyolefin, for example polyvinyl chloride (PVC).These plastics can be orientation or non-orientation.If these plastics are orientated, then they can be single shafts to orientation, biax orientation and combination, preferably biax orientation.A kind of special example of suitable ground is the polypropylene (BOPP) of biax orientation, the Wrapping films that for example most of cigarette packs and packing case carton use.Expect for example haloolefin and the homopolymer of alkene and the ground of multipolymer,, also be suitable for using inkjet compositions of the present invention to print as polyvinylidene difluoride (PVDF), PTFE, polychlorotrifluoroethylene, copolymer from vinyl chloride and vinylidene chloride.In some embodiments, the surface energy of ground is about 40 dynes per centimeter or lower.
[0040] the following examples will further specify the present invention, therefore in no case should explain it is to limit its protection domain.
Embodiment
[0041] these embodiment explanations are according to the inkjet compositions (table 1) of some embodiment preparation of the present invention.These embodiment also illustrate some performances (table 2-5) of inkjet compositions of the present invention.The inkjet compositions of embodiment 1-4 is printed on the BOPP film sample, and by using light pressure scratch 10 times, the anti-nail scratch of measuring printed codes changed with the time after printing, and write down the degree of removing coding.Comparative example 1-4 is commercially available inkjet compositions.2-4 is shown in the results are shown in of anti-nail scratch test.Because the BOPP sample arrives the breadboard asynchronism(-nization) of applicant, so these samples are difficult to wear out.Therefore, sample No.1 arrives the earliest, and it is slower that sample No.2 and 4 arrives, and sample No.3,5 and 6 arrives in succession.The scratch resistance grading: 1-does not have any variation; 2-removes a little; 3-partly removes; The 4-major part is removed; And 5-removes fully.
[0042] tests at the anti-nail frictional property of coding that is difficult on the printed lid, and list the hard nail friction number of removing coding at table 5.
Table 1 inkjet compositions embodiment
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| MEK (solvent) STAYBELITE Ester 10 (rosin resin) BAKELITE VMCH (vinylite) SANTICIZER 160 (plasticizer) ORASOL BLACK RLI (dyestuff) SLLWET L-7622 (wetting agent) BYK 065 (defoamer) amounts to | 83.2 8.0 3.3 1.0 4.0 0.5 100％ | 80.7 10.0 3.3 1.0 4.5 0.5 100％ | 76.6 12.0 5.0 5.0 0.5 0.9 100％ | 61.5 30.0 8.0 0.5 100％ |
The anti-nail scratch that table 2. printing is back 72 hours
| Sample number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | The comparative example 1 | The comparative example 2 | The comparative example 3 | The comparative example 4 |
| 1 2 3 4 5 6 | 2 1 2 1 1 1 | 1 1 2 1 1 1 | 1 1 1 1 1 1 | 2 1 2 2 1 1 | 4 4 3 4 4 3 | 5 5 4 4 4 4 | 5 5 5 5 5 5 | 5 5 4 4 5 5 |
The anti-nail scratch that table 3. printing is back 24 hours
| Sample number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | The comparative example 1 | The comparative example 2 | The comparative example 3 | The comparative example 4 |
| 1 2 3 4 5 6 | 2 1 1 1 1 1 | 1 1 1 1 1 1 | 1 1 1 1 1 1 | 2 1 2 2 2 1 | 3 3 3 3 3 3 | 4 4 3 4 3 3 | 5 4 5 5 5 5 | 4 3 3 4 4 4 |
The anti-nail scratch that table 4. printing is back 1 hour
| Sample number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | The comparative example 1 | The comparative example 2 | The comparative example 3 | The comparative example 4 |
| 1 2 3 4 5 6 | 2 1 2 1 1 1 | 2 1 1 1 1 1 | 1 1 1 1 1 1 | 1 1 2 2 2 1 | 3 3 2 3 2 3 | 3 2 2 2 3 2 | 5 4 4 5 5 5 | 4 3 3 3 3 3 |
The anti-nail frictional property of encoding on table 5. cover
| Printed back 1 hour | Embodiment 1 | The comparative example 1 | The comparative example 2 | The comparative example 4 |
| Cover | 10+ | 2-3 | 3-4 | 4-5 |
[0043] above-mentioned data show that inkjet compositions of the present invention and low surface energy substrates have splendid tack (anti-nail scratch and anti-nail frictional property).Inkjet compositions of the present invention is particularly advantageous for the use of low surface energy substrates, and inkjet compositions of the present invention also should have the tack and the scratch resistance of improvement on the high surface energy ground.
[0044] all reference of enumerating here, comprising publication, patent application and patent, all be referenced by reference equally, all point out to be referenced by reference separately and specially as every part of reference, and propose in full with it here.
[0045] in describing context of the present invention, use term " a kind of " and " be somebody's turn to do " and similar indication (especially below in claims) all be interpreted as comprising single plural number both, unless point out in addition here or obviously and the context conflict.Term " comprises ", " having ", " comprising " and " containing " all be interpreted as open-ended term (promptly meaning " including, without being limited to "), unless otherwise noted.Here the scope of the value of listing is only attempted as mentioning the simple expression method of each monodrome that drops on this scope individually, unless point out in addition, and quotes each monodrome in this specification sheets here, as being to list its separately here.All methods described herein can be carried out according to any suitable order, unless point out in addition here or obvious and context conflict.Any and all embodiment adopt, or the representative language that provides here (as " for example ") only attempts the present invention is described better, and do not limit the scope of the invention, unless claimed in addition.Do not have any term in this manual and should be interpreted as showing that to implementing the present invention be substantial any non-claimed element.
[0046] described preferred embodiment of the present invention here, implemented known best mode when of the present invention comprising the inventor.Those skilled in the art's those preferred embodiment changes after reading above-mentioned specification sheets will become apparent.The inventor expects that those skilled in the art can utilize such change in due course, and the inventor attempts to adopt the mode except that special description here to implement the present invention.Therefore, present invention includes all changes and use the equivalent that in claims, illustrates that law allows.In addition, any combination of above-mentioned element is all comprised by the present invention in all possible change, unless point out in addition here or conflict with context significantly in addition.
Claims (22)
1. inkjet compositions, it contains one or more organic solvents, a kind of rosin resin, a kind of adhesive resin and a kind of tinting material of helping, and wherein this inkjet compositions does not have or does not have basically nitrocellulose resin.
2. inkjet compositions, it contains one or more organic solvents, a kind of rosin resin, a kind of Vinylite and a kind of tinting material.
3. inkjet compositions, it contains one or more organic solvents, a kind of rosin resin and a kind of tinting material, and wherein this inkjet compositions does not have or does not have basically nitrocellulose resin and slow-evaporating solvent.
4. according to the described inkjet compositions of each claim among the claim 1-3, wherein said composition has (1) at the about 1.6-10.0 centipoise of 25 ℃ viscosity; (2) the about 50-2000ohm-cm of resistivity; And the about 1100-1700 meter per second of (3) velocity of sound.
5. according to the described inkjet compositions of each claim among the claim 1-4, wherein said one or more organic solvents are selected from alcohol, ketone, ester, ether, acid amides and combination thereof.
6. inkjet compositions according to claim 5, one of wherein said ketone is methylethylketone.
7. according to the described inkjet compositions of each claim among the claim 1-6, wherein said rosin resin is a rosin ester resin.
8. inkjet compositions according to claim 7, wherein rosin ester resin is the hydrogenated wood rosin glycerol ester resin.
9. inkjet compositions according to claim 8, wherein the hydrogenated wood rosin glycerol ester resin is the hydrogenated wood rosin glycerol ester resin of glycerol modification.
10. inkjet compositions according to claim 3, it also contains and helps adhesive resin.
11. inkjet compositions according to claim 10, wherein helping adhesive resin is Vinylite.
12. according to the described inkjet compositions of each claim in the aforesaid right requirement, wherein tinting material is dyestuff, pigment, color lake and combination thereof.
13. according to the described inkjet compositions of each claim in the aforesaid right requirement, it also contains one or more following substances: softening agent, wetting agent and defoamer.
14. inkjet compositions according to claim 1, wherein the content of one or more organic solvents is that about 70 weight % of said composition are to about 90 weight %, the content of rosin resin is that about 1 weight % of said composition is to about 20 weight %, the content that helps adhesive resin be about 2 weight % of said composition to about 10 weight %, and the content of tinting material is that about 2 weight % of said composition are to about 15 weight %.
15. inkjet compositions according to claim 3, wherein the content of one or more organic solvents is that about 50 weight % of said composition are to about 80 weight %, the content of rosin resin be about 20 weight % of said composition to about 40 weight %, and the content of tinting material is that about 5 weight % of said composition are to about 10 weight %.
16. according to claim 14 or 15 described inkjet compositions, it also contains one or more following substances: wetting agent, its amount are that about 0.1 weight % of said composition is to about 1 weight %; Softening agent, its amount are that about 0.1 weight % of said composition is to about 2 weight %; And defoamer, its amount is that about 0.5 weight % of said composition is to about 1.5 weight %.
17. method of on low surface energy substrates, printing information with tack, this method comprises being ejected into described ground according to the described inkjet compositions stream of liquid droplets of each claim in the aforesaid right requirement, the direction of controlling this stream of liquid droplets makes its drop form needed printing information, allows its information drying again.
18. described method according to claim 17, wherein low surface energy substrates is plastics.
19. method according to claim 18, wherein these plastics are polyolefine or halogenated polyolefin.
20. method according to claim 19, wherein this polyolefine is a polypropylene.
21. method according to claim 20, wherein this polypropylene is single-or two-axial orientation polypropylene.
22. method according to claim 17, wherein low surface energy substrates is the metal of oil-pollution.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US44654303P | 2003-02-12 | 2003-02-12 | |
| US60/446,543 | 2003-02-12 | ||
| US10/775,979 | 2004-02-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1777658A true CN1777658A (en) | 2006-05-24 |
| CN100387663C CN100387663C (en) | 2008-05-14 |
Family
ID=36766640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200480008789XA Expired - Lifetime CN100387663C (en) | 2003-02-12 | 2004-02-11 | Jet ink composition for low surface energy substrates |
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| Country | Link |
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| CN (1) | CN100387663C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574153A (en) * | 2009-09-30 | 2012-07-11 | 录象射流技术公司 | Thermal ink jet ink composition |
| CN101541893B (en) * | 2006-09-15 | 2012-08-29 | 录象射流技术公司 | Solvent-based ink composition |
| CN102792129A (en) * | 2010-02-18 | 2012-11-21 | 录象射流技术公司 | Wetness indicating ink compositions |
| CN103298894A (en) * | 2010-11-12 | 2013-09-11 | 录象射流技术公司 | Method of printing on a film substrate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5941370A (en) * | 1982-08-04 | 1984-03-07 | Hitachi Ltd | White ink composition for ink jet recording |
| JPS6092370A (en) * | 1983-10-27 | 1985-05-23 | Tokyo Ohka Kogyo Co Ltd | Ink composition for ink jet recording |
| US5800601A (en) * | 1995-11-06 | 1998-09-01 | Videojet Systems International, Inc. | Food grade jet inks |
| US6726756B1 (en) * | 2000-05-26 | 2004-04-27 | Videojet Technologies Inc. | Continuous ink jet printing ink composition |
-
2004
- 2004-02-11 CN CNB200480008789XA patent/CN100387663C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101541893B (en) * | 2006-09-15 | 2012-08-29 | 录象射流技术公司 | Solvent-based ink composition |
| CN102574153A (en) * | 2009-09-30 | 2012-07-11 | 录象射流技术公司 | Thermal ink jet ink composition |
| US8920552B2 (en) | 2009-09-30 | 2014-12-30 | Videojet Technologies Inc. | Thermal ink jet ink composition |
| CN102574153B (en) * | 2009-09-30 | 2015-02-18 | 录象射流技术公司 | Thermal ink jet ink composition |
| CN102792129A (en) * | 2010-02-18 | 2012-11-21 | 录象射流技术公司 | Wetness indicating ink compositions |
| CN103298894A (en) * | 2010-11-12 | 2013-09-11 | 录象射流技术公司 | Method of printing on a film substrate |
| CN103298894B (en) * | 2010-11-12 | 2016-05-18 | 录象射流技术公司 | The method of printing in film substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100387663C (en) | 2008-05-14 |
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