CN101620380B - Resin convex mould for relief printing and method for producing organic EL elements using the same - Google Patents
Resin convex mould for relief printing and method for producing organic EL elements using the same Download PDFInfo
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- CN101620380B CN101620380B CN2009101500600A CN200910150060A CN101620380B CN 101620380 B CN101620380 B CN 101620380B CN 2009101500600 A CN2009101500600 A CN 2009101500600A CN 200910150060 A CN200910150060 A CN 200910150060A CN 101620380 B CN101620380 B CN 101620380B
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- convex mould
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- relief printing
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- 238000007639 printing Methods 0.000 title claims abstract description 72
- 239000011347 resin Substances 0.000 title claims abstract description 68
- 229920005989 resin Polymers 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 28
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- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 7
- -1 acrylic ester Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 28
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 15
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 230000008961 swelling Effects 0.000 claims description 8
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 7
- 229920005906 polyester polyol Polymers 0.000 claims description 6
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 4
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- VOFUROIFQGPCGE-UHFFFAOYSA-N nile red Chemical compound C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=O)C2=C1 VOFUROIFQGPCGE-UHFFFAOYSA-N 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
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- RXUVWJWQFPJWOV-OWOJBTEDSA-N (e)-1,2-diisocyanatoethene Chemical compound O=C=N\C=C\N=C=O RXUVWJWQFPJWOV-OWOJBTEDSA-N 0.000 description 1
- QHJXOJHVTGXCRC-UHFFFAOYSA-N 1,1-diphenylbuta-1,3-dien-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C=C)=C(C=1C=CC=CC=1)C1=CC=CC=C1 QHJXOJHVTGXCRC-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
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- QTLDSJXCGIKEJJ-UHFFFAOYSA-N 2-(ethylamino)benzonitrile Chemical compound CCNC1=CC=CC=C1C#N QTLDSJXCGIKEJJ-UHFFFAOYSA-N 0.000 description 1
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- GILMNGUTRWPWSY-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(O)COC(=O)C=C GILMNGUTRWPWSY-UHFFFAOYSA-N 0.000 description 1
- DGZIMLVEXGVYDW-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(O)COC(=O)C=C DGZIMLVEXGVYDW-UHFFFAOYSA-N 0.000 description 1
- FQMIAEWUVYWVNB-UHFFFAOYSA-N 3-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OC(C)CCOC(=O)C=C FQMIAEWUVYWVNB-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- FCMBCIBGSFJSAV-UHFFFAOYSA-N CON(C1=CC=CC=C1)OC.N=C=O Chemical class CON(C1=CC=CC=C1)OC.N=C=O FCMBCIBGSFJSAV-UHFFFAOYSA-N 0.000 description 1
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 1
- ZOMSMJKLGFBRBS-UHFFFAOYSA-N bentazone Chemical compound C1=CC=C2NS(=O)(=O)N(C(C)C)C(=O)C2=C1 ZOMSMJKLGFBRBS-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
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- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- CVKMFSAVYPAZTQ-UHFFFAOYSA-N methylhexanoic acid Natural products CCCCC(C)C(O)=O CVKMFSAVYPAZTQ-UHFFFAOYSA-N 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
- Printing Plates And Materials Therefor (AREA)
Abstract
The present invention provides a resin convex mould for relief printing with a stable dimension precision and less damage to substrates when printing even thought printing time and again, and a method for producing organic EL elements using the resin convex mould. A light-sensitive resin composition obtained by fitting a prepolymer and single-function or multi-functional monomer is used as mould material, wherein the prepolymer is prepared by adding acrylic ester into a polymerisation product of polyester polyatomic alcohol and diisocyanates.
Description
Technical field
The present invention relates to the resin convex mould for relief printing for the organic luminous layer of printing organic field luminescence (below, be called " organic EL ") element, and the method for making of using the organic EL of this relief printing plate gained.
Background technology
In recent years, as the display element in portable telephone etc., the organic EL with specialities such as slim, low power consumption, light weights just receives publicity.This organic EL consists of by form the structure of the organic luminous layer that contains organic EL luminophor between 2 relative electrodes, and makes this organic luminous layer luminous by current flowing in this organic luminous layer.
In above-mentioned organic EL luminophor, have low molecular material and macromolecular material.Usually, use low molecular material, and make its vacuum evaporation etc. form organic luminous layer at substrate, but wherein owing to the mask with fine pattern carries out patterning, if therefore substrate maximizes, then there is vacuum deposition apparatus to maximize, and the problem that significantly reduces of materials'use efficient and processing power, yield rate.Therefore, recently, in order also to tackle in batches manufacturing in the situation that substrate maximizes, attempting following method: use macromolecular material as organic EL luminophor, and with its dissolving, be dispersed in and form printing ink in the solvent, and then form organic luminous layer (for example, with reference to patent documentation 1) by print process at substrate.Yet, present, all lower as the dissolubility of the known conjugated polymer based compound of macromolecular material, therefore, in the printing ink process, must use the fragrant families such as dimethylbenzene, toluene to be used as solvent.This aromatic series series solvent part is high for the swellability of high molecular polymer, and therefore, when for example forming organic luminous layer by the hectographic printing method, there are the following problems: swelling in solvent, and cause the dimensional accuracy reduction owing to repeatedly carrying out printing treatment.
On the other hand, have with the whole bag of tricks headed by the above-mentioned hectographic printing method for print process, but because above-mentioned organic EL uses glass substrate as substrate more, therefore, use has the hectographic printing method of flexible rubber felt, and to use the toppan printing with flexible flexographic, resin plate be preferred.Yet, in the hectographic printing method, because therefore the risk that exists dimensional accuracy above-mentioned, the rubber felt to reduce more preferably adopts toppan printing.In addition, even in this toppan printing, in the situation that flexographic also has above-mentioned risk, therefore can use resin plate, wherein, mostly use commercially available solid version (for example, the product of Dong Li company manufacturing).
Patent documentation 1: TOHKEMY 2006-252787 communique
Summary of the invention
The problem that invention will solve
Yet because above-mentioned solid version is the resin relief with the solubility emulsion compositions evaporation drying gained of the water soluble polymer such as water-soluble nylon, polyvinyl alcohol (PVA) and photoresist, so it exists that hardness is high, the problem large to the damage of substrate during printing.
The present invention carries out in view of such circumstances, its purpose is, even a kind of printing treatment of repeatedly carrying out is provided, dimensional accuracy is also stable, and the resin convex mould for relief printing that when printing is little to the damage of substrate, and the method for making of using the organic EL of this relief printing plate gained.
For the method for dealing with problems
To achieve these goals, the 1st main idea of the present invention is a kind of resin convex mould for relief printing, it forms as plate material by the photosensitive polymer combination that will cooperate prepolymer and simple function or polyfunctional monomer gained, wherein said prepolymer carries out addition by the polyaddition products that makes acrylate and the pure and mild diisocyanate of polyester polyols and obtains, the 2nd main idea of the present invention is a kind of method for making of organic EL, it comprises following operation: use above-mentioned resin convex mould for relief printing, organic EL luminophor is dissolved in the printing-ink of gained is printed on the substrate in the solvent, then makes above-mentioned solvent evaporation gasification and form organic luminous layer.
The invention effect
That is to say, even the inventor etc. are in order to obtain repeatedly carrying out printing treatment, dimensional accuracy is also stable, and when printing the resin convex mould for relief printing little to substrate damage (below, referred to as " resin relief ") and carried out active research, found that, the photosensitive polymer combination that obtains acrylate and the polyaddition products of the pure and mild diisocyanate of polyester polyols being carried out the formed prepolymer of addition and simple function or polyfunctional monomer cooperate is during as plate material, can reach the initial stage purpose, and finish thus the present invention.The plate material of resin relief of the present invention is the photosensitive polymer combination with polyester pastern bone frame, therefore, plate material than aliphatics pastern bone frame, it is for aromatic series series solvent excessive swelling not, thus, even repeatedly carry out printing treatment, the dimensional accuracy of resin relief can not reduce yet, and dimensional accuracy that can stable for extended periods of time.And the hardness of resin relief is softer, and the damage to substrate during printing is little.
In addition, the method for making of organic EL of the present invention is to use above-mentioned resin relief to form organic luminous layer at substrate, therefore namely use 1 resin relief to make a plurality of organic ELs, the dimensional accuracy of the organic luminous layer of the organic EL of gained also is stable.And organic EL is little to the damage of substrate when making, and substrate can not produce damage etc.
Description of drawings
Fig. 1 is the outboard profile of an embodiment of expression resin relief of the present invention.
Fig. 2 is the amplification view of above-mentioned resin relief significant points.
Fig. 3 is the A-A sectional view of Fig. 2.
Fig. 4 is the amplification view that the above-mentioned resin relief of expression changes the significant points of example.
Fig. 5 is the B-B sectional view of Fig. 4.
Fig. 6 is the key diagram of the above-mentioned resin relief method for making of expression.
Fig. 7 is the key diagram of an embodiment of expression organic EL.
Fig. 8 is the key diagram of the method for making of the above-mentioned organic EL of expression.
Embodiment
Then, describe being used for implementing best mode of the present invention.But the present invention is not limited to these embodiments.
Fig. 1 represents an embodiment of resin relief of the present invention.In this embodiment, above-mentioned resin relief can be used for organic luminous layer 23 (with reference to Fig. 7) printing to the organic EL that consists of the organic EL color monitor of aftermentioned etc. (not shown), and, such as Fig. 2 and shown in Figure 3 as the A-A sectional view of this Fig. 2, this resin relief is formed in by substrate 1, with strip-like-shaped on the pattern printing surface of this substrate 1 and consists of with protuberances 2 with a plurality of printings that interval (pitch) parallel projections of regulation arranges.And, uses the end face of protuberance 2 to distribute in this each printing and form a plurality of microspikes (small protuberance) 3, and formation connects into the ditch section 4 of row between this each microspike 3, and printing-ink (not shown) is remained in this ditch section 4.
The JI S rubber hardness of above-mentioned resin relief and preferably has flexibility in 65～80 ° of scopes of Shore A in the scope of 60～90 ° of Shore A (shore A).If JI S rubber hardness is greater than 90 ° of Shore A, then hardness is excessive, has the risk that substrate is produced damage, if less than 60 ° of Shore A, then hardness is excessively soft, and printing-ink oozes out when having printing, produces dropping liquid, and can't obtain the risk of harsh image.
In addition, above-mentioned resin relief can use aqueous cleaning to develop, and when resin relief described later was made, uncured portion was washed with aqueous cleanings such as washings.
In addition, above-mentioned resin relief is in methyl phenyl ethers anisole, cyclohexyl benzene or tetralin or their mixed solvent as the aromatic series series solvent that dissolves, disperses organic EL luminophor, be continuous impregnating in the time of 24 hours under 20～25 ℃ the environment in room temperature, have weight rate before and after the dipping and be the swelling ratio in 0.2～15% scope.Like this, above-mentioned resin relief can swelling to the aromatic series series solvent.Therefore, using by the dissolving of aromatic series series solvent, when disperseing the printing-ink of organic EL luminophor gained, because above-mentioned resin relief can swelling, even therefore repeatedly carry out printing treatment, the dimensional accuracy of resin relief can not reduce yet, and dimensional accuracy that can stable for extended periods of time.
Above-mentioned weight rate preferably sets in 1～10% scope.If above-mentioned weight rate surpasses 10%, then owing to repeatedly carrying out the risk that there is the dimensional accuracy reduction of resin relief in printing treatment.In addition, above-mentioned weight rate is more low more preferred, if be about 1%, does not then almost observe the reduction of above-mentioned dimensional accuracy, but considers common access times, as long as in 5～7% scope, does not just have the risk that above-mentioned dimensional accuracy reduces.In addition, at the mixed solvent that uses methyl phenyl ethers anisole, cyclohexyl benzene or tetralin during as the aromatic series series solvent, it cooperates ratio can Set arbitrarily.In addition, when carrying out the mensuration of above-mentioned weight rate, using thickness is the material that the resin relief of 0.13～0.30cm is cut into 2cm * 3cm size.
In addition, above-mentioned resin relief has preferably that length growth rate when cutting off is 15～200%, pulling strengrth is under 2～100MPa, and maximum stretching force is the resin properties of 30～200N.If surpass this scope, then rubber hardness rises, and has produced the defective that as mentioned above substrate is produced damage, and if be lower than this scope, then rubber hardness reduces, and has the above-mentioned problem that produces dropping liquid when printing.
For example, when carrying out the wire printing, the shape of above-mentioned microspike 3 is preferably circular cone shape or cylindric (being circular cone shape in Fig. 2 and Fig. 3), and considers the height H of microspike 3 from the better viewpoint of transfer printing
1Preferably in the scope of 1～500 μ m, the diameter D of end face
1Preferably in the scope of 5～500 μ m, the interval W between the adjacent microspike 3
1Preferably in the scope of 5～500 μ m.
In addition, also can replace above-mentioned microspike 3, such as Fig. 4 and shown in Figure 5 as the B-B sectional view of this Fig. 4, at the end face formation strip jog of printing with protuberance 2,, a plurality of strip raised lines 5 that wherein said strip jog is arranged by the spaced and parallel with regulation, the strip chase (strip recess) that forms between adjacent 2 strip raised lines 56 consist of.The cross sectional shape of above-mentioned strip raised line 5 is preferably platform shape or rectangular-shaped (being the platform shape in Fig. 4 and Fig. 5), and considers the height H of strip raised line 5 from the better viewpoint of transfer printing
2Preferably in the scope of 1～500 μ m, the width D of end face
2Preferably in the scope of 5～500 μ m, the furrow width of strip chase 6 (recess width) W
2Preferably in the scope of 5～500 μ m.In addition, when the organic luminous layer 23 with organic EL is applied in the lighting use etc. of non-display device purposes, can uses and not carry out above-mentioned linear pattern and the galley of full pattern (BETA pattern) by whole monochrome.
This resin relief cooperates the photosensitive polymer combination of gained to make as plate material with prepolymer and simple function or polyfunctional monomer, and wherein said prepolymer carries out addition by the polyaddition products that makes acrylate and the pure and mild diisocyanate of polyester polyols and obtains.
Above-mentioned polyester polyol carries out polycondensation and polyester copolymer of obtaining etc. such as the dicarboxylic acid that can enumerate formations such as making saturated fatty acid, unsaturated fatty acid, aromatic acid and polyvalent alcohol.
Herein, polyvalent alcohol refers to have the alcohol of 2 above hydroxyls in 1 molecule, specifically, can enumerate ethylene glycol, propylene glycol, diethylene glycol etc., and can be used singly or in combination.
In addition, as above-mentioned diisocyanate, for example can use aliphatics, alicyclic, aromatic diisocyanate, for example can list 2, the 4-toluene diisocyanate, 2, the 6-toluene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, 4,4,-dicyclohexyl methyl hydride diisocyanate, dimethoxyaniline isocyanates (dianisidineisocyanate), 3,3 '-dimethylbenzene-4,4 '-diisocyanate, the P-xylene diisocyanate, 1,3-cyclohexane dimethyl isocyanates, 1,5-naphthalene diisocyanate, trans-vinylene diisocyanate, 2,6-diisocyanate methylhexanoic acid ester, diphenyl ether-4,4 '-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc.As this method that makes the pure and mild diisocyanate of polyester polyols carry out addition polymerization, can use in the past known method.
As the aforesaid propylene acid esters, such as enumerating (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, polyethyleneglycol (methyl) acrylate etc.
Acrylate is for the addition of above-mentioned prepolymer, such as being undertaken by known graft polymerization method (graft polymerization) etc. in the past.Herein, acrylate is for proportional usually being set as with respect to 1 mole of prepolymer of adding of prepolymer, and acrylate is in 0.5～5.0 mole the scope.If adding of acrylate is proportional above above-mentioned scope, then produce the defective of the rubber hardness rising of resin relief, and if less than this scope, the problem that can't form resin relief is arranged then.
As above-mentioned simple function or multifunctional single polymers, can enumerate with 1,3-butanediol diacrylate or 1,4-butanediol diacrylate, 1,6-hexanediyl ester, diethylene glycol diacrylate, neopentylglycol diacrylate, polyethyleneglycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol acrylate, 2-EHA, acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate, acrylic acid 2-hydroxyl-3-phenoxy group propyl ester are main various monomers.
The prepolymer that makes acrylate and above-mentioned polyaddition products carry out addition and obtain and the mixing ratio of simple function or polyfunctional monomer can cooperate arbitrarily according to the target conditions that realizes regulation hardness and flexibility, swelling ratio.In addition, in these prepolymers, monomer mixture, with respect to the range fit Photoepolymerizationinitiater initiater of potpourri with 0.001～10 % by weight.
Above-mentioned photosensitive polymer combination can be liquid, solid shape or powder shaped, when it is solid shape or powder shaped, makes in use liquid.
Use this plate material, for example the above-mentioned resin relief of manufacturing as described below.That is to say, at first, prepare negative film 11 shown in Figure 6.Should negative film 11 in the zone corresponding to above-mentioned resin relief, in circular hole 11a, formed the part corresponding with the microspike 3 of this relief printing plate, and the inboard of this circular hole 11a is transparent, part in addition is black.Then, this negative film 11 is laminated on the surface of glass substrate 12 of downside, then photosensitive polymer combination aqueous, that have polyester pastern bone frame is coated on the surface of this negative film 11, and makes it reach certain thickness.In Fig. 6, represent this coating layer with symbol 13, in this coating layer 13, represent uncured predetermined portions described later with symbol 13a, represent the predetermined portions that solidifies with oblique line part S.Then, transparent basement membrane (not shown) is laminated on the surface of above-mentioned coating layer 13, and the glass substrate 14 of upside is laminated on the surface of this basement membrane.
Then, as shown in Figure 6, use lamp 15, across light such as the glass substrate 14 of upside and basement membrane irradiation ultraviolet radiations, and across light such as the glass substrate 12 of downside, negative film 11 irradiation ultraviolet radiations.Thus, the light of injecting above the layer that forms from above-mentioned photosensitive polymer combination 13 whole and solidify from the part (the oblique line part S of Fig. 6) that the light that the circular hole 11a of negative film 11 injects reaches.At this moment, the degree of depth that reaches of light is regulated by the irradiation light intensity.Then, remove glass plate 12,14 up and down, negative film 11, and use developer solution to wash, remove because the black part of negative film 11 and light does not reach thereby uncured part (uncured portion).Then, after drying cured portion, the light (post-exposure) such as formation side irradiation ultraviolet radiation by at microspike 3 solidify fine rule etc. exactly.Can make resin relief shown in Figure 1 like this.
In this above-mentioned embodiment, because above-mentioned plate material is the photosensitive polymer combination with the high polyester pastern bone frame of polarity, the resin relief that therefore uses above-mentioned plate material made is for aromatic series series solvent swelling hardly.Therefore, even repeatedly carry out printing treatment, the dimensional accuracy of above-mentioned resin relief can not reduce yet, and dimensional accuracy that can stable for extended periods of time.The hardness of above-mentioned resin relief is softer in addition, and the substrate that is printed body for when printing is not damaged almost.
Fig. 7 represents to use an embodiment of the organic EL that above-mentioned resin relief makes.In this embodiment, above-mentioned organic EL is by consisting of at transparent or semitransparent anode 22, organic luminous layer 23 and the negative electrode 24 of the surface of glass substrate 21 formation.This element by with above-mentioned the two poles of the earth 22,24 between the voltage supplied with of the power supply 25 that is connected, and on the organic luminous layer 23 that is formed between the two poles of the earth 22,24 current flowing, and luminous thus.Then, this EL light shows by glass substrate 21.In addition, organic luminous layer 23 has redness (R), green (G), blue (B) 3 kinds, and organic luminous layer 23 of all kinds forms strip, and the spaced and parallel setting to stipulate, and repetition is red, green, blue order is configured.And when the printing of the organic luminous layer 23 of 1 look, use 1 resin relief, and can use the resin relief corresponding to organic luminous layer 23 quantity.
Above-mentioned organic EL is following manufacturing for example.That is to say, at first, form anode 22 on the surface of glass substrate 21.In this operation, by vacuum vapour deposition, sputtering method etc. the transparent conductivity materials such as tin indium oxide (ITO), zinc oxide aluminum are coated on the surface of glass substrate 21 to form transparent anode 22, the gold that perhaps evaporation is thinner, platinum are to form translucent anode 22.
Then, use above-mentioned resin relief, and on above-mentioned anode 22, form successively positive hole transfer layer and organic luminous layer 23 by the toppan printing of routine.In the formation operation of this organic luminous layer 23, at first prepare to make organic EL luminophor dissolving, the redness that is dispersed in gained in the aromatic series series solvent, green, blue 3 kinds of printing-inks.Prepare in addition the printing machine that possesses print roller 31, anilox roll (anilox roll) 32, print station 33, ink feeder 34, scrapes the scraper 35 of residue printing-ink on the anilox roll 32 shown in Figure 8.Then, above-mentioned resin relief is installed on the print roller 31, and the glass substrate 21 that will be formed with above-mentioned anode 22 (not shown) is placed on the print station 33.Then, the printing-ink that will have certain color (for example red) is supplied to anilox roll 32 by printing feedway 34, and makes print roller 31 and anilox roll 32 rotations.At this moment, above-mentioned printing-ink is maintained in the ditch section 4 of printing with protuberance 2 end faces of above-mentioned resin relief.Then, come mobile printing platform 33 with the rotary synchronous of print roller 31, the printing-ink that will have certain color is printed on the anode 22 on glass substrate 21 surfaces, and then heating makes the aromatic series series solvent evaporation gasification in the printing-ink, forms organic luminous layer 23.For other 2 kinds of colors, carry out equally respectively this printing, and form the organic luminous layer 23 of 3 looks at assigned position.
Then, form negative electrode 24 at above-mentioned organic luminous layer 23.This negative electrode 24 is made of metallic element simple substance such as Li, Na, Mg, La, Ce, Ca.In the formation operation of this negative electrode 24, use electrical resistance heating, under the vacuum tightness of regulation, Yi Bian use quartzy resonant mode film thickness gauge to monitor, Yi Bian by each vapor deposition source above-mentioned each metallic element monomer is total to evaporation on organic luminous layer 23.Then, above-mentioned the two poles of the earth 22,24 are connected with power supply 25.Produce so above-mentioned organic EL.
According to this method for making, namely use 1 resin relief to make a plurality of organic ELs, the dimensional accuracy of the organic luminous layer 23 of the organic EL of gained also is stable.And organic EL is little to the damage of substrate when making, and glass substrate 21 can not produce damage etc.
The viscosity of above-mentioned organic EL luminophor and can be used low molecular material or macromolecular material in 2～100mPas scope.As low molecular material, such as enumerating triphenylbut diene, cumarin, Nile red (nile red), oxadiazole derivative etc.In addition; as macromolecular material; for example can enumerate poly-(2-Oxy-1 in the last of the ten Heavenly stems; the 4-phenylene) (DO-PPP); poly-[2-(2 '-ethylhexyl oxygen base)-5-methoxyl-1; the 4-phenylacetylene] (MEH-PPV); poly-[5-methoxyl-(sulfonylation 2-propoxyl group)-1; the 4-phenylacetylene] (MP S-PPV); poly-[2; two (the hexyl Oxy-1s of 5-; the 4-phenylene)-(1-cyano group ethenylidene)] (CN-PPV); it is poly-that [2-(2;-ethylhexyl oxygen base)-5-methoxyl-Isosorbide-5-Nitrae-phenylene-(1-cyano group ethenylidene)] (MEH-CN-PPV); poly-(dioctyl fluorene) etc.In addition, as wherein used solvent, such as enumerating cyclohexyl benzene, trichloro-benzenes, methyl phenyl ethers anisole, dimethylbenzene, ethylamino benzonitrile acid esters, cyclohexyl pyrrolidone, butyl cellosolve, dichloro-benzenes, toluene etc., they can use separately or mix more than 2 kinds and use.Mixing ratio during mixing decides according to organic luminous layer 23.
Embodiment
Then, embodiment is described.
The resin relief of set-up dirgram 1～structure shown in Figure 3.The JIS rubber hardness of this resin relief is 85 ° of Shore A, is 23 ℃ of lower continuous impregnatings in the time of 24 hours in methyl phenyl ethers anisole, in room temperature, and this resin relief weight rate is 5%.This resin relief uses the plate material shown in the following table 1, and makes with the method identical with the method for making of above-mentioned resin relief, and the gross thickness of version is 1.3mm, and substrate thickness is 0.7mm.
Table 1
| The gross thickness (mm) of version | Rubber hardness (°) | Weight rate (%) | Pulling strengrth (MPa) | Length growth rate during cut-out (%) | |
| Materials A | 1.30 | 88 | 1.5 | 2.4 | 20 |
| Material B | 1.30 | 84 | 3.1 | 3.6 | 30 |
| Material C | 1.30 | 90 | 4.2 | 2.4 | 25 |
(annotating 1) rubber hardness is according to JIS K6253 " the hardness test method of rubber ", and the use dumbbell shape is measured for No. 3.
Length growth rate when (annotating 2) pulling strengrth and cut-out is measured according to JIS K6251 " stretching test method of rubber ".
(annotate 3) weight rate is according under 23～25 ℃ room temperature environment, measure the weight before and after the test film continuous impregnating of 1.3mm * 20mm * 30mm 24 hours.
As printing machine, prepare machine shown in Figure 8 (the adagio printing machine that MTTEC Co., Ltd. make, FC33S).Its printing condition is: being 3.5～6.5mm with the crack width adjustment between resin relief and the anilox roll, be 7.5～12.5mm with the crack width adjustment between resin relief and the glass substrate, and print speed printing speed is adjusted into 20m/ minute.
As doubtful printing ink, use methyl phenyl ethers anisole, tetralin are mixed with 1 to 1, and make 0.2～1.5 % by weight Polyvinyl carbazole (Northeast chemical company makes, and molecular weight is 90000) be dissolved in the material that wherein obtains.This doubtful printing ink is carried by the dry air of 0.01～0.1MPa, and is adjusted into and only has 0.5～5 milliliter 40 seconds and be supplied on the anilox roll.
Version cylinder at printing machine is installed above-mentioned resin relief, and under above-mentioned printing condition, print speed printing speed, drive this printing machine, doubtful ink printing be used for is being consisted of the glass substrate of organic EL, then, make methyl phenyl ethers anisole, tetralin evaporation gasification and remove at the hot plate that is heated to 60～90 ℃, and only separate out effective constituent, form organic luminous layer.
Use this organic luminous layer of interference of light measurement microscope, it is 400～700 that the result detects
Thickness.In addition, make UV-lamp near the film surface, confirmed that doubtful printing ink is luminous, and be coated with organic EL luminophor.
Claims (5)
1. the method for making of an organic EL is characterized in that, this method for making possesses following operation:
Prepare the operation of resin convex mould for relief printing, the photosensitive polymer combination of this resin convex mould for relief printing by will cooperating prepolymer and simple function or polyfunctional acrylic ester monomer gained is as plate material, and wherein said prepolymer carries out addition by the polyaddition products that makes acrylate and the pure and mild diisocyanate of polyester polyols and obtains; With,
Use the ditch section of protuberance end face in the printing of described resin convex mould for relief printing, maintenance is dissolved in organic EL luminophor the printing-ink of gained in the aromatic series series solvent, this printing-ink is printed on the substrate that the surface is formed with anode, then makes described aromatic series series solvent evaporation gasification and form the operation of organic luminous layer.
2. the method for making of organic EL according to claim 1, the hardness of described resin convex mould for relief printing is set in the JIS durometer in the scope of 60～90 ° of Shore A, and described plate material can use aqueous cleaning to develop.
3. the method for making of organic EL according to claim 1 and 2, described resin convex mould for relief printing is in methyl phenyl ethers anisole, cyclohexyl benzene or tetralin or their mixed solvent as the aromatic series series solvent that dissolves, disperses described organic EL luminophor, be continuous impregnating in the time of 24 hours under 20～25 ℃ the environment in room temperature, have weight rate before and after the dipping and be the swelling ratio in 0.2～15% scope.
4. the method for making of organic EL according to claim 1 and 2, described resin convex mould for relief printing have that length growth rate when cutting off is 15～200%, pulling strengrth is under 2～100MPa, and maximum stretching force is the resin properties of 30～200N.
5. the method for making of organic EL according to claim 1 and 2, described resin convex mould for relief printing has the printing protuberance of pattern printing surface, and to have formed in its surface the recess width that is used for keeping printing-ink be that strip recess or the protuberance diameter of 10～500 μ m is the small protuberance of 10～500 μ m.
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| JP2008170638 | 2008-06-30 | ||
| JP2008170638A JP4607212B2 (en) | 2008-06-30 | 2008-06-30 | Manufacturing method of organic EL element |
| JP2008-170638 | 2008-06-30 |
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| JP (1) | JP4607212B2 (en) |
| KR (1) | KR101627857B1 (en) |
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| CN107160878A (en) * | 2017-07-24 | 2017-09-15 | 东莞市陆陆兴工业自动化科技有限公司 | A kind of cutting die with printing functionality |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3948665A (en) * | 1973-01-05 | 1976-04-06 | Basf Aktiengesellschaft | Laminates for the manufacture of flexographic printing plates comprising photocrosslinkable reaction product of saturated polyester glycol, diisocyanate, and diol |
| US5688633A (en) * | 1994-12-13 | 1997-11-18 | Macdermid Imaging Technology, Inc. | Soft relief photopolymer printing plates for flexographic printing |
| CN1519797A (en) * | 2003-02-05 | 2004-08-11 | 株式会社小村技术 | Relief for forming layer |
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| JP2004252093A (en) * | 2003-02-19 | 2004-09-09 | Asahi Kasei Chemicals Corp | Method of manufacturing liquid photosensitive resin letterpress printing plate |
| JP2004322329A (en) * | 2003-04-21 | 2004-11-18 | Sumitomo Rubber Ind Ltd | Printing plate for flexography, method for producing it and method for producing organic el element comprising process for forming organic light emitting layer using it |
| JP5158925B2 (en) * | 2006-07-11 | 2013-03-06 | 旭化成イーマテリアルズ株式会社 | Manufacturing method of printing substrate |
| JP2008140579A (en) * | 2006-11-30 | 2008-06-19 | Toppan Printing Co Ltd | Organic el element and its manufacturing method, and letterpress |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3948665A (en) * | 1973-01-05 | 1976-04-06 | Basf Aktiengesellschaft | Laminates for the manufacture of flexographic printing plates comprising photocrosslinkable reaction product of saturated polyester glycol, diisocyanate, and diol |
| US5688633A (en) * | 1994-12-13 | 1997-11-18 | Macdermid Imaging Technology, Inc. | Soft relief photopolymer printing plates for flexographic printing |
| CN1519797A (en) * | 2003-02-05 | 2004-08-11 | 株式会社小村技术 | Relief for forming layer |
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| JP2010010065A (en) | 2010-01-14 |
| HK1139747A1 (en) | 2010-09-24 |
| TWI448821B (en) | 2014-08-11 |
| CN101620380A (en) | 2010-01-06 |
| JP4607212B2 (en) | 2011-01-05 |
| KR101627857B1 (en) | 2016-06-07 |
| TW201015227A (en) | 2010-04-16 |
| KR20100003212A (en) | 2010-01-07 |
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