CN1884401A - Ultraviolet light cured printing ink - Google Patents
Ultraviolet light cured printing ink Download PDFInfo
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- CN1884401A CN1884401A CN 200510027125 CN200510027125A CN1884401A CN 1884401 A CN1884401 A CN 1884401A CN 200510027125 CN200510027125 CN 200510027125 CN 200510027125 A CN200510027125 A CN 200510027125A CN 1884401 A CN1884401 A CN 1884401A
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Abstract
The invention discloses the ultra-violet light solidified printing ink. The ultra-violet light solidified printing ink hasn't volatile organic solvent, avoiding the pollution and improving the durability and flexible. The invention uses the national standard GB/T 1731-93 to test, and the baseboard uses soft PVC film. The invention uses national standard GB/T 1766-95 to test durability, and uses GB/T 1865-97 to test printing ink. The flexible is 1mm, the discoloration is 2 grade, the efflorescence is 0 grade, and the cracking is 0 grade.
Description
Technical field
The present invention relates to a kind of printing-ink, relate in particular to a kind of by ultraviolet light polymerization mode exsiccant screen printing ink.
Background technology
Ultraviolet light polymerization printing screen printing ink is that the mode by silk screen printing prints on the base material, and finishes curing reaction by the ultraviolet curing mode, forms final product.Compare with the traditional volatile dry or the printing-ink of oxidation drying, ultraviolet light cured printing ink does not contain volatile organic solvent (VOC), has therefore avoided the pollution to water and air.
UV curable ink not only has the advantage of environmental protection, and has the fast characteristics of curing speed, can increase substantially production efficiency, has adapted to the requirement of Modern High-Speed printing.
Silk screen printing is from by the sdueegee fashion of extrusion printing ink being transferred to a kind of mode of printing on the stock from the printing forme hole.Forme is constituted with softish silk screen and photosensitivity latex, and printing equipment mostly is the urethanes scraper plate.Silk screen printing not only can be used for planographic, and can be used for flexography, therefore at plastic containers, also can print above the glasswork etc.Silk screen printing is widely used in various artworks as a kind of mode of printing flexibly, pottery, fields such as woodwork, electronics, machinery.
But also there are some shortcomings in UV curable ink itself, and is relatively poor as the weather resistance of resin, also brings problems such as snappiness is relatively poor in the time of high curing rate.Patent CN1387555A discloses a kind of ultraviolet cured paint composition and has made and methods for using them, has the outward appearance and the use properties of improvement, but weather resistance is not had clear and definite improving one's methods.Patent CN1092458C discloses a kind of ultraviolet-curing paint of not flavescence, and this coating is mainly used in Lacquer finish and uses, and does not propose clear and definite solution at fading of pigment.Because printing-ink is compared with coating, painted requirement and use properties are required bigger difference, so these methods can not solve the endurance issues of ultraviolet light cured printing ink fully.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of ultraviolet light cured printing ink, to overcome the above-mentioned defective that prior art exists.
The component of ultraviolet light cured printing ink of the present invention and the degree of weight comprise:
Epoxy acrylic ester compound 5%～20%
Urethane acrylate class prepolymer 10%～40%
Pure acrylic acid ester prepolymer 2%～20%.
Light trigger 1～10%
Photosensitizers 0.25～1%
Tinting material 1～5%
Simple function and/or multifunctional acrylate functional monomer 1～30%
Uv-absorbing agent 0.5～3%
Photostabilizer 0.5～3%.
Modified additive 1～10%
Thixotropic agent 5～15nm SiO
20.5～1%
Stopper 0.1～1%.
In UV photocuring printing-ink, acrylic ester prepolymer is main moiety, and its total content is about 20%～60% of ink composite.Acrylic ester prepolymer commonly used is an epoxy acrylate.It is fast that epoxy acrylate class prepolymer has curing speed, the glossiness advantages of higher, but exist paint film flexibility poor, shortcomings such as poor durability, its content is 5%～20%.What the present invention was selected is the amine modified epoxy acrylic ester, fatty acid modified epoxy acrylate and modified bisphenol A epoxy diacrylate, preferred modified epoxy acrylic ester compounds is that the trade mark that Changxing Chemical Industry Co Ltd (Eternal) produces is 6215-100 (100% modified epoxy acrylic ester), 622A-80 (with the fatty acid modified epoxy diacrylate of 20% tripropylene glycol diacrylate dilution), 623-100 (100% modified bisphenol A epoxy diacrylate), 623A-80 (with the modified bisphenol A epoxy diacrylate of 20% tripropylene glycol diacrylate dilution), 6231A-80 (with the modified bisphenol A epoxy diacrylate of 20% tripropylene glycol diacrylate dilution), the trade mark that Ucb company produces is Ebecryl 3701 (bisphenol A epoxy acrylate of modification), Ebecryl 3702 (fatty acid modified epoxy acrylate), Ebecryl 3703 (bisphenol A epoxy acrylate of amine modification), the trade mark that Sartomer company produces is CN2100 (epoxy acrylate of amine modification), CN2101 (fatty acid modified epoxy acrylate) can select a kind of or its mixture wherein for use;
Because the weather resistance of epoxy acrylate is relatively poor, in order to improve the weather resistance of paint film, need to add all urethane acrylate class prepolymers preferably of snappiness and weather resistance, its content is 10%～40%, preferred polyurethane prepolymers is an aliphatic urethane acrylate class prepolymer, alternative this compounds comprises that the trade mark that Changxing Chemical Industry Co Ltd (Eternal) produces is 611A-85 (with the aliphatic urethane diacrylate of 15% tripropylene glycol diacrylate dilution), 611B-85 is (with 15%1, the aliphatic urethane diacrylate of 6-hexanediyl ester dilution), 6132 (based on the aliphatic urethane acrylates of polyester polyol), 6142H-80 (with the aliphatic urethane acrylate of 20% ethoxyquin Viscoat 295 dilution), the trade mark that Ucb company produces is Ebecryl 230 (a high-molecular weight aliphatic urethane diacrylate), Ebecryl 270 (aliphatic urethane diacrylate), Ebecryl 280/15IB (with the aliphatic urethane diacrylate of 15% isobornyl acrylate dilution), Ebecryl 245 (with the aliphatic urethane diacrylate of 25% tripropylene glycol diacrylate dilution), the trade mark that Sartomer company produces is CN959 (propenoic methyl carbamate), CN962 (propenoic methyl carbamate), CN965 (propenoic methyl carbamate), CN980 (propenoic methyl carbamate), BASF UA19T (with the aliphatic urethane acrylate of 35% tripropylene glycol diacrylate dilution), LR8987 is (with 30%1, the aliphatic urethane acrylate of 6-hexanediyl ester dilution), can select a kind of or its mixture wherein for use;
Angle from further raising weather resistance, ultraviolet light cured printing ink composition provided by the invention has also added the good pure acrylic acid ester prepolymer of weather resistance, the chemical name of said pure acrylic acid ester prepolymer is an acrylic ester polymer, alternative this compounds comprises that the trade mark that Changxing Chemical Industry Co Ltd produces is that (Eternal) 6530B-40 is (with 60%1, the pure acrylic resin of 6-hexanediyl ester dilution), the Ebecryl of Ucb company 745 is (with 25% tripropylene glycol diacrylate and 25%1, the pure acrylic resin of 6-hexanediyl ester dilution), Ebceryl 754 is (with 30%1, the pure acrylic resin of 6-hexanediyl ester dilution), the trade mark that fine jade color special international (Lucite International) is produced is Elvacite 4026 (multipolymer of methyl methacrylate and tripropylene glycol diacrylate), Elvacite 4036 (multipolymer of methyl methacrylate and n-BMA) can select a kind of or its mixture wherein for use;
Ultraviolet light cured printing ink provided by the invention mainly is applicable to silk screen printing, can add one or more coloured compositions according to print request.Selected coloured composition should have higher fast light rank, and its fast light rank should be more than or equal to 6.Alternative pigment comprises Pigment Yellow 73 74 (the with number pigment title of this section is international pigment index, Color Index Inernational), Pigment Yellow 73 110, pigment Yellow 12 8, pigment red 122, Pigment red 202, pigment Blue 15: 3, pigment Blue 15: 4, pigment Green 7, pigment violet 19, pigment orange 61, other pigment also comprise carbon black, titanium dioxide.Used coloured composition can be one or more of above listed raw material.
UV-light printing-ink disclosed by the invention contain simple function and (or) multifunctional acrylate functional monomer, to adjust the viscosity of printing-ink, promote the curing speed of printing-ink, selected acrylate functional monomer should have weather resistance and chemical stability preferably, simple function acrylate functional monomer is selected from isobornyl acrylate (IBOA), isobornyl methacrylate, vinylformic acid hydroxyl cyclohexyl, lauryl acrylate or lauryl methacrylate(LMA);
Multifunctional acrylate functional monomer is selected from 1,6-hexanediyl ester (HDDA), two propylene glycol diacrylates (DPGDA) that contract, tripropylene glycol diacrylate (TPGDA), ethoxyquin 1, the 6-hexanediyl ester, Viscoat 295 (TMPTA) or ethoxyquin Viscoat 295;
For ultraviolet light cured printing ink provided by the present invention can be solidified rapidly under UV-irradiation, need to add a certain amount of light bow usually and send out agent and photosensitizers.Light trigger is selected from the Darocur1173 of Ciba company (2-methyl-2-hydroxyl-1-phenyl-1-acetone), Irgacure184 (1-hydroxy-cyclohexyl phenyl ketone), Irgacure907 (2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone), Irgacure369 (2-dimethylin-1-[4-(4-morpholine) phenyl]-2-phenyl methyl-1-butanone), Iracure819 (two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide), the Lucirin TPO of BASF AG (2,4,6-trimethylbenzoyl-diphenyl phosphine oxide), Lucirin TPO-L (2,4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester), the ITX (the sec.-propyl thia is feared ketone) of first chemistry (First Chemical Corporation) etc.;
Preferred photosensitizers is 4-dimethyl ethyl aminobenzoate (EDAB).
For improving the weather resistance of printing-ink, ultraviolet light cured printing ink provided by the invention has added uv-absorbing agent and photostabilizer, and uv-absorbing agent is selected from the Tinuvin 400 (triaizine compounds) of Ciba company, Tinuvinl130 (benzotriazole cpd), photostabilizer is selected from Ciba company's T inuvin 292 (two-(1,2,2,6,6-pentamethyl--4-piperidyl)-and sebate), Tinuvin 123 is (two-(1-octyloxy-2,2,6,6-tetramethyl--4-piperidyl)-sebate).
For improving the printing performance and the storge quality of printing ink, ultraviolet light cured printing ink provided by the invention has added various modified additives, as flow agent, and defoamer and stablizer etc.Alternative defoamer comprises the high molecular polymer that contains siloxanes or do not contain siloxanes, the EFKA-2722 (is the organosilicon and the mineral oil modifier of solvent with acetate methoxyl group propyl ester/alkylbenzene) of preferred EFKA auxiliary agent company, alternative flow agent comprises the high molecular polymer that contains siloxanes or do not contain siloxanes, the EFKA-3777 (fluorine-carbon modified acrylic resin) of preferred EFKA auxiliary agent company.
Added auxiliary agent such as the thixotropic agent of regulating the ink printing performance in the ultraviolet light cured printing ink composition provided by the present invention, preferred thickening thixotropic agent is the SiO of 5～15nm
2
Also added the stopper that ink storage stability is provided in the ultraviolet light cured printing ink composition provided by the invention, stopper is selected from MEHQ, Resorcinol, compounds such as tert-butyl catechol or para benzoquinone;
Ultraviolet light cured printing ink provided by the present invention can adopt the three-roller abrasive method to produce, and the present invention does not specifically limit the mode of grinding, the addition sequence of material etc.To the ink product after grinding, its fineness should be less than 5 μ, preferably less than 3 μ.
Compare with the traditional volatile dry or the printing-ink of oxidation drying, ultraviolet light cured printing ink does not contain volatile organic solvent (VOC), has therefore avoided the pollution to water and air, has improved the weather resistance and the snappiness of printing ink simultaneously.
Adopt standard GB/T 1731-93 " the paint film flexibility assay method is to the snappiness of printing ink " to test, different is, and base plate adopts is soft pvc film.Film durability is to adopt standard GB/T 1766-95 " ranking method of paint and varnish coating aging ", GB/T 1865-97 " paint and varnish artificial weathering and man-made radiation expose (filterable xenon arc radiation) " detects printing ink of the present invention, the result shows, snappiness is lmm, 2 grades of variable colors (light discolouration), 0 grade of efflorescence (no efflorescence), ftracture 0 grade (not having cracking).
Embodiment
Embodiment 1
Ultraviolet light cured printing ink-redness
| Composition | Chemical name | Approximate quantity, weight % |
| Eternal 6215-100 | 100% modified epoxy acrylic ester | 8 |
| Eternal 611A-85 | Aliphatic urethane diacrylate with the dilution of 15% tripropylene glycol diacrylate | 38 |
| Elvacite 4026 | The multipolymer of methyl methacrylate and tripropylene glycol diacrylate | 5 |
| HDDA | 1,6 hexanediol diacrylate | 16 |
| IBOA | Isobornyl acrylate | 7 |
| TPGDA | The tripropylene glycol diacrylate | 5 |
| Irgacure 907 | 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone | 5 |
| ITX | Isopropyl thioxanthone | 2 |
| EDAB | The 4-dimethyl ethyl aminobenzoate | 1.5 |
| Pigment red 122 | 3.5 | |
| SiO 2 | SiO 2 | 1 |
| EFKA-2722 | Acetate methoxyl group propyl ester/alkylbenzene is the organosilicon and the mineral oil modifier of solvent | 0.5 |
| EFKA-3777 | Fluorine-carbon modified acrylic resin | 0.5 |
| Tinuvin 400 | Triaizine compounds | 3 |
| Tinuvin 292 | Two-(1,2,2,6,6-pentamethyl--4-piperidyl)-sebate | 3 |
| Resorcinol | Resorcinol | 1 |
| Amount to | 100 |
Embodiment 2
Ultraviolet light cured printing ink-yellow
| Composition | Chemical name | Approximate quantity, weight % |
| Ebecryl 3701 | The bisphenol A epoxy acrylate of modification | 5 |
| Ebecryl 230 | High-molecular weight aliphatic poly nitrogen ester diacrylate | 38 |
| Ebecryl 745 | With 25% tripropylene glycol diacrylate and 25%1, the pure acrylic resin of 6-hexanediyl ester dilution | 8 |
| HDDA | 1,6 hexanediol diacrylate | 13 |
| IBOA | Isobornyl acrylate | 8 |
| TPGDA | The tripropylene glycol diacrylate | 5 |
| Irgacure 907 | 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone | 5 |
| ITX | Isopropyl thioxanthone | 2 |
| EDAB | The 4-dimethyl ethyl aminobenzoate | 1.5 |
| Pigment Yellow 73 110 | 6 | |
| SiO 2 | SiO 2 | 1 |
| EFKA-2722 | Acetate methoxyl group propyl ester/alkylbenzene is the organosilicon and the mineral oil modifier of solvent | 0.5 |
| EFKA-3777 | Fluorine-carbon modified acrylic resin | 0.5 |
| Tinuvin 400 | Triaizine compounds | 3 |
| Tinuvin 292 | Two-(1,2,2,6,6-pentamethyl--4-piperidyl)-sebate | 3 |
| Resorcinol | Resorcinol | 0.5 |
| Amount to | 100 |
Embodiment 3
Ultraviolet light cured printing ink-blueness
| Composition | Chemical name | Approximate quantity, weight % |
| CN2100 | The epoxy acrylate of amine modification | 5 |
| CN962 | Propenoic methyl carbamate | 34 |
| Elvacite 4036 | The multipolymer of methyl methacrylate and n-BMA | 5 |
| HDDA | 1,6 hexanediol diacrylate | 20 |
| IBOA | Isobornyl acrylate | 8 |
| TPGDA | The tripropylene glycol diacrylate | 5 |
| Irgacure 907 | 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone | 8 |
| ITX | Isopropyl thioxanthone | 3 |
| EDAB | The 4-dimethyl ethyl aminobenzoate | 1.5 |
| Pigment Blue 15: 4 | 5 | |
| SiO 2 | SiO 2 | 1 |
| EFKA-2722 | Acetate methoxyl group propyl ester/alkylbenzene is the organosilicon and the mineral oil modifier of solvent | 0.5 |
| EFKA-3777 | Fluorine-carbon modified acrylic resin | 0.5 |
| Tinuvin 400 | Triaizine compounds | 1.5 |
| Tinuvin 292 | Two-(1,2,2,6,6-pentamethyl--4-piperidyl)-sebate | 1.5 |
| Resorcinol | Resorcinol | 0.5 |
| Amount to | 100 |
Embodiment 4
Ultraviolet light cured printing ink-black
| Composition | Chemical name | Approximate quantity, weight % |
| Eternal 623A-80 | Modified bisphenol A epoxy diacrylate with the dilution of 20% tripropylene glycol diacrylate | 7 |
| LR 8987 | With 30%1, the aliphatic urethane acrylate of 6-hexanediyl ester dilution | 31 |
| Ebecryl 754 | With 30%1, the pure acrylic resin of 6-hexanediyl ester dilution | 5 |
| HDDA | 1,6 hexanediol diacrylate | 20 |
| IBOA | Isobornyl acrylate | 8 |
| TPGDA | The tripropylene glycol diacrylate | 5 |
| Irgacure369 | 2-dimethylin-1-[4-(4-morpholine) phenyl]-2-phenyl methyl-1-butanone | 4 |
| Irgacure 907 | 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholine-1-acetone | 6 |
| ITX | The sec.-propyl thia is feared ketone | 3 |
| EDAB | The 4-dimethyl ethyl aminobenzoate | 1.5 |
| Carbon black | C | 5 |
| SiO 2 | SiO 2 | 1 |
| EFKA-2722 | Acetate methoxyl group propyl ester/alkylbenzene is the organosilicon and the mineral oil modifier of solvent | 0.5 |
| EFKA-3777 | Fluorine-carbon modified acrylic resin | 0.5 |
| Tinuvin 400 | Triaizine compounds | 1 |
| Tinuvin 292 | Two-(1,2,2,6,6-pentamethyl--4-piperidyl)-sebate | 1 |
| Resorcinol | Resorcinol | 0.5 |
| Amount to | 100 |
Embodiment 5
Ultraviolet light cured printing ink-white
| Composition | Chemical name | Approximate quantity, weight % |
| Eternal 623A-80 | Modified bisphenol A epoxy diacrylate with the dilution of 20% tripropylene glycol diacrylate | 4 |
| LR 8987 | With 30%1, the aliphatic urethane acrylate of 6-hexanediyl ester dilution | 23 |
| Ebecryl 754 | With 30%1, the pure acrylic resin of 6-hexanediyl ester dilution | 4 |
| HDDA | 1,6 hexanediol diacrylate | 10 |
| IBOA | Isobornyl acrylate | 8 |
| Lucirin TPO | 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide | 4 |
| Darocur 1173 | 2-methyl-2-hydroxyl-1-phenyl-1-acetone | 8 |
| Titanium dioxide | TiO 2 | 36 |
| EFKA-2722 | Acetate methoxyl group propyl ester/alkylbenzene is the organosilicon and the mineral oil modifier of solvent | 0.5 |
| EFKA-3777 | Fluorine-carbon modified acrylic resin | 0.5 |
| Tinuvin 400 | Triaizine compounds | 0.5 |
| Tinuvin 292 | Two-(1,2,2,6,6-pentamethyl--4-piperidyl)-sebate | 1 |
| Resorcinol | Resorcinol | 0.5 |
| Amount to | 100 |
Embodiment 6
Adopt standard GB/T 1731-93 " the paint film flexibility assay method is to the snappiness of printing ink " to test, different is, and base plate adopts is soft pvc film.Film durability is to adopt standard GB/T 1766-95 " ranking method of paint and varnish coating aging ", GB/T 1865-97 " paint and varnish artificial weathering and man-made radiation expose (filterable xenon arc radiation) " is accurate to be detected printing ink of the present invention, printing ink to embodiment 1～5 detects, and the result is as follows:
Embodiment 12345
Variable color 22221
Efflorescence 00000
Ftracture 00000
Snappiness 1111 1.5.
Claims (10)
1. a ultraviolet light cured printing ink is characterized in that, the degree of component and weight comprises:
Epoxy acrylic ester compound 5%～20%
Urethane acrylate class prepolymer 10%～40%
Pure acrylic acid ester prepolymer 2%～20%.
Light trigger 1～10%
Photosensitizers 0.25～1%
Tinting material 1～5%
Simple function and/or multifunctional acrylate functional monomer 1～30%
Uv-absorbing agent 0.5～3%
Photostabilizer 0.5～3%.
Modified additive 1～10%
Thixotropic agent 5～15nm SiO
20.5～1%
Stopper 0.1～1%.
2. ultraviolet light cured printing ink according to claim 1 is characterized in that, does not add volatile organic solvent in the component.
3. ultraviolet light cured printing ink according to claim 1, it is characterized in that, the epoxy acrylic ester compound is selected from the amine modified epoxy acrylic ester, a kind of or its mixture in fatty acid modified epoxy acrylate and the modified bisphenol A epoxy diacrylate.
4. ultraviolet light cured printing ink according to claim 1 is characterized in that, urethane acrylate class prepolymer is selected from aliphatic urethane acrylate class prepolymer.
5. ultraviolet light cured printing ink according to claim 1 is characterized in that, pure acrylic acid ester prepolymer is selected from acrylic ester polymer.
6. ultraviolet light cured printing ink according to claim 1, it is characterized in that, the selected Pigment Yellow 73 74 of tinting material, Pigment Yellow 73 110, pigment Yellow 12 8, pigment red 122, Pigment red 202, pigment Blue 15: 3, pigment Blue 15: 4, pigment Green 7, pigment violet 19, one or more in pigment orange 61, carbon black or the titanium dioxide.
7. ultraviolet light cured printing ink according to claim 1, it is characterized in that simple function acrylate functional monomer is selected from isobornyl acrylate, isobornyl methacrylate, vinylformic acid hydroxyl cyclohexyl, lauryl acrylate or lauryl methacrylate(LMA);
Multifunctional acrylate functional monomer is selected from 1,6-hexanediyl ester (HDDA), two propylene glycol diacrylates (DPGDA) that contract, tripropylene glycol diacrylate (TPGDA), ethoxyquin 1, the 6-hexanediyl ester, Viscoat 295 (TMPTA) or ethoxyquin Viscoat 295.
8. ultraviolet light cured printing ink according to claim 1, it is characterized in that, light trigger is selected from Darocurl173, Irgacure184, Irgacure907, Irgacure369, Irgacure819, Lucirin TPO, LucirinTPO-L or ITX, photosensitizers are the 4-dimethyl ethyl aminobenzoate.
9. ultraviolet light cured printing ink according to claim 1 is characterized in that uv-absorbing agent is selected from triaizine compounds or benzotriazole cpd; Photostabilizer is selected from two-(1,2,2,6,6-pentamethyl--4-piperidyl)-sebate or two-(1-octyloxy-2,2,6,6-tetramethyl--4-piperidyl)-sebate).
10. ultraviolet light cured printing ink according to claim 1, it is characterized in that, flow agent is the high molecular polymer that contains siloxanes or do not contain siloxanes, and defoamer is the high molecular polymer that contains siloxanes or do not contain siloxanes, and the thickening thixotropic agent is the SiO of 5～15nm
2, stopper is selected from MEHQ, Resorcinol, tert-butyl catechol or para benzoquinone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510027125 CN100577753C (en) | 2005-06-24 | 2005-06-24 | Ultraviolet light cured printing ink |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510027125 CN100577753C (en) | 2005-06-24 | 2005-06-24 | Ultraviolet light cured printing ink |
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| Publication Number | Publication Date |
|---|---|
| CN1884401A true CN1884401A (en) | 2006-12-27 |
| CN100577753C CN100577753C (en) | 2010-01-06 |
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| CN 200510027125 Expired - Fee Related CN100577753C (en) | 2005-06-24 | 2005-06-24 | Ultraviolet light cured printing ink |
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2005
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