CN114506164B - Plate material, printing plate, preparation method of printing plate and printing method - Google Patents
Plate material, printing plate, preparation method of printing plate and printing method Download PDFInfo
- Publication number
- CN114506164B CN114506164B CN202111619650.0A CN202111619650A CN114506164B CN 114506164 B CN114506164 B CN 114506164B CN 202111619650 A CN202111619650 A CN 202111619650A CN 114506164 B CN114506164 B CN 114506164B
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- polymer layer
- printing
- plate
- printing plate
- polymethyl methacrylate
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- 238000007639 printing Methods 0.000 title claims abstract description 151
- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 108
- 229920001577 copolymer Polymers 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 12
- YIVVDEYNVAZRBI-UHFFFAOYSA-N C(C=C)(=O)NC(C)C.[N] Chemical compound C(C=C)(=O)NC(C)C.[N] YIVVDEYNVAZRBI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010410 layer Substances 0.000 claims description 119
- 229920001400 block copolymer Polymers 0.000 claims description 42
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 36
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 36
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 35
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 35
- 229920002530 polyetherether ketone Polymers 0.000 claims description 35
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- -1 polytetrafluoroethylene Polymers 0.000 claims description 25
- 239000011557 critical solution Substances 0.000 claims description 21
- 238000001125 extrusion Methods 0.000 claims description 16
- 238000004090 dissolution Methods 0.000 claims description 11
- 239000003292 glue Substances 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 8
- 239000012790 adhesive layer Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 229910000838 Al alloy Inorganic materials 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052804 chromium Inorganic materials 0.000 abstract description 9
- 239000011651 chromium Substances 0.000 abstract description 9
- 238000010147 laser engraving Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- B41N1/04—Printing plates or foils; Materials therefor metallic
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Printing Plates And Materials Therefor (AREA)
Abstract
The invention belongs to the field of printing plate manufacturing, and particularly relates to a plate, a printing plate, a preparation method of the printing plate and a printing method. The plate provided by the invention comprises a substrate, and a bonding layer, a first polymer layer and a second polymer layer which are sequentially laminated on the substrate; the first polymer layer is made of polymethyl methacrylate-poly nitrogen isopropyl acrylamide segmented copolymer, the number average molecular weight of the segmented copolymer is 36000-56000, the dispersity index PDI is 1.10-1.50, and the poly nitrogen isopropyl acrylamide accounts for 0.45-0.70% of the segmented copolymer by volume; the material used for the second polymer layer is a hydrophobic and oleophobic material. The plate provided by the invention does not contain chromium, can be directly used for printing paper money after the expression of the groove structure image-text is finished through laser engraving, does not need to wipe the plate in the printing process, has no loss of ink, can reduce the use amount of the ink, and improves the printing amount.
Description
Technical Field
The invention belongs to the field of printing plate manufacturing, and particularly relates to a plate, a printing plate, a preparation method of the printing plate and a printing method.
Background
In the printing industry, the traditional water gel printing plate is manufactured by electroplating a chromium layer on a metal surface layer with specific specification sand, and the printing plate making process for finishing fine pictures and texts comprises the steps of cleaning, coating and rubberizing, plate burning and developing, plate drawing and positioning, post exposure, corrosion, glue removal and the like. The printing principle is that a hydrophilic layer of a chromium layer is utilized to form a 'water film', ink is not adhered, an image-text formed by corroding the chromium layer is a hydrophobic and oleophilic area, the ink is absorbed, then a printer is used for printing, and in the printing process, once printing, a plate wiping operation is needed to be carried out so as to remove the polluted 'water film'.
The prior printing plate material mainly has the following defects:
Firstly, a chromium layer needs to be plated on the surface of a substrate, and a chromium simple substance and ions thereof are toxic substances, so that harmful substances such as waste water, waste gas, waste residue and the like are easy to generate in the manufacturing process of the chromium layer, and the ecological environment is directly influenced; secondly, organic glue, corrosive acid, hazardous chemicals such as ultraviolet light and the like and harmful radiation are used in the plate making process, so that the environment-friendly production is not facilitated; thirdly, the plate making process has more steps, mass defects are easy to accumulate, and the plate is wasted; fourthly, the plate wiping operation is easy to damage the plate material, so that the printing quantity is reduced, and the wiped ink cannot be reused, so that waste is caused.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a printing plate, a preparation method thereof and a printing method.
The invention provides a plate material, which comprises a substrate, and a bonding layer, a first polymer layer and a second polymer layer which are sequentially laminated on the substrate;
the first polymer layer is made of polymethyl methacrylate-poly nitrogen isopropyl acrylamide segmented copolymer, the number average molecular weight of the segmented copolymer is 36000-56000, the dispersity index PDI is 1.10-1.50, and the poly nitrogen isopropyl acrylamide accounts for 0.45-0.70% of the segmented copolymer by volume;
the material used for the second polymer layer is a hydrophobic and oleophobic material.
The low critical solution temperature T of the polymethyl methacrylate-poly nitrogen isopropyl acrylamide segmented copolymer is 29-30 ℃;
When the use temperature of the plate is lower than the low critical dissolution temperature T of the block copolymer, the contact angle alpha of the block copolymer to water is more than 0 degrees and less than 40 degrees, and the contact angle alpha to oil is more than 110 degrees;
when the plate use temperature is higher than the low critical dissolution temperature T of the block copolymer, the contact angle alpha of the block copolymer to water is more than 140 degrees, and the contact angle alpha to oil is 0 degrees < alpha < 30 degrees.
Preferably, the material used for the second polymer layer is a coextrudate of polymethyl methacrylate, polytetrafluoroethylene and polyetheretherketone.
Preferably, the polymethyl methacrylate accounts for 10-30% of the mass of the coextrudate, the polytetrafluoroethylene accounts for 40-70% of the mass of the coextrudate, and the polyether-ether-ketone accounts for 20-30% of the mass of the coextrudate.
Preferably, the mass ratio of polymethyl methacrylate, polytetrafluoroethylene and polyether ether ketone in the coextrudate of polymethyl methacrylate, polytetrafluoroethylene and polyether ether ketone is 1:3:1.
Preferably, the material used for the bonding layer is glue; the substrate is made of one of nickel, nickel alloy, iron, copper alloy, aluminum alloy and stainless steel.
The invention also provides a preparation method of the printing plate, which comprises the following steps: and sequentially coating a bonding layer, a first polymer layer and a second polymer layer on the substrate to obtain the printing plate.
The invention also provides a printing plate which is obtained by etching the printing plate or the printing plate prepared by the method.
Preferably, the printing plate includes a substrate, and a bonding layer, a first polymer layer, and a second polymer layer sequentially laminated on the substrate;
a plurality of grooves are formed in one side, far away from the first polymer layer, of the second polymer layer so as to form an image-text structure;
The depth H1 of the groove is smaller than the total thickness H of the first polymer layer and the second polymer layer and not smaller than the thickness H2 of the second polymer layer.
Preferably, the depth H1 of the groove is smaller than the total thickness H of the first polymer layer and the second polymer layer and larger than the thickness H2 of the second polymer layer.
Preferably, the depth h1 of the groove is 0.01 mm < h1 < 0.2 mm.
The invention also provides a preparation method of the printing plate, which comprises the following steps: and etching a plurality of grooves on the surface of the printing plate or the printing plate prepared by the method, wherein the grooves form a required image-text structure, and the printing plate is obtained.
The invention also provides a printing method, which is characterized in that the printing plate or the printing plate prepared by the method is used for printing, the printing temperature is higher than the low critical solution temperature T of the block copolymer, the printing plate stained with the ink is placed in an environment lower than the low critical solution temperature T of the block copolymer after the printing is finished, the printing plate is placed in a static state, residual ink in a groove of the printing plate is automatically separated out, then the printing plate is washed by water, and the printing process is finished after the printing plate is dried.
The technical scheme of the invention has the following advantages:
The plate provided by the invention comprises a substrate, and a bonding layer, a first polymer layer and a second polymer layer which are sequentially laminated on the substrate; the first polymer layer is made of polymethyl methacrylate-poly nitrogen isopropyl acrylamide segmented copolymer, the number average molecular weight of the segmented copolymer is 36000-56000, the dispersity index PDI is 1.10-1.50, and the poly nitrogen isopropyl acrylamide accounts for 0.45-0.70% of the segmented copolymer by volume; the material used for the second polymer layer is a hydrophobic and oleophobic material.
The invention utilizes polymethyl methacrylate-poly nitrogen isopropyl acrylamide segmented copolymer, the number average molecular weight of the segmented copolymer is 36000-56000, the dispersivity index PDI is 1.10-1.50, the poly nitrogen isopropyl acrylamide accounts for 0.45-0.70% of the volume percentage of the segmented copolymer, the segmented copolymer is used as a first polymer layer of a printing plate material, the segmented copolymer is characterized by being hydrophilic and oleophobic when the segmented copolymer is lower than a low critical solution temperature, and is hydrophobic and oleophilic when the segmented copolymer is higher than the low critical solution temperature, meanwhile, a hydrophobic oleophobic material is used as a second polymer layer, when the segmented copolymer is used as a printing plate material, a corresponding groove structure is only needed to be etched on the second polymer layer according to a required image-text structure, the depth of the groove structure is ensured to be smaller than the total thickness of the first polymer layer and the second polymer layer, the bottom of the groove is the polymethyl methacrylate-poly nitrogen isopropyl acrylamide segmented copolymer material, the printing temperature is only required to be ensured to be higher than the low critical solution temperature of the segmented copolymer in the printing process, the hydrophobic and oleophobic material is formed by the groove, the hydrophobic and oleophobic material is required to be automatically transferred to the low critical solution temperature, the image-text structure is only to be placed on a low-soluble region of the printing plate material, and the printing plate can be automatically removed from the printing plate structure, and the printing plate is only required to be placed on a non-clean water region.
The plate provided by the invention does not contain chromium, does not depend on a layout to form a water film, has a temperature response characteristic according to the wettability of the segmented copolymer, realizes the oleophobicity of the image and text of the groove structure by means of temperature adjustment, does not use organic glue, corrosive acid and other chemicals when the image and text are expressed, can be directly used for printing paper money after the image and text of the groove structure are expressed by laser engraving, replaces a multi-step preparation process, avoids defect accumulation, and enhances the image and text reduction authenticity of a printing stock. Meanwhile, the pattern-text area of the plate groove structure provided by the invention has low critical solution temperature, and wettability is hydrophobic and oleophilic when the temperature is higher than the low critical solution temperature of the block copolymer, for example, t is more than or equal to 40 ℃ and less than or equal to 60 ℃, so that the adhesion and transfer of the printing ink can be completed, and the non-pattern-text area is hydrophobic and oleophobic and is not stained with the printing ink, and the plate is not required to be wiped; when the temperature is lower than the low critical dissolution temperature of the block copolymer, such as that t is more than or equal to 10 ℃ and less than or equal to 25 ℃, the wettability of the pattern area of the groove structure is hydrophilic and oleophobic, and after printing is finished, the printing ink in the pattern area is automatically separated out, so that the self-cleaning of the plate can be finished, the plate is not required to be wiped in the printing process, the loss of the printing ink is avoided, the using amount of the printing ink can be reduced by 20%, and the printing amount of the printing ink is improved by about 6% compared with that of the traditional plate.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic view of a plate structure according to the present invention;
FIG. 2 is a schematic view of a printing plate according to the present invention;
FIG. 3 is a schematic illustration of a printing plate of the present invention as it is being printed;
FIG. 4 is a schematic view of a printing plate of the present invention after printing is completed;
Reference numerals:
1-a substrate; 2-a bonding layer; 3-a first polymer layer; 4-a second polymer layer; 5-grooves; 6-ink.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
As shown in fig. 1, the plate provided by the invention comprises a substrate 1, and a bonding layer 2, a first polymer layer 3 and a second polymer layer 4 which are sequentially laminated on the substrate 1;
the first polymer layer 3 is made of polymethyl methacrylate-poly nitrogen isopropyl acrylamide segmented copolymer, the number average molecular weight of the segmented copolymer is 36000-56000, the dispersity index PDI is 1.10-1.50, and the poly nitrogen isopropyl acrylamide accounts for 0.45-0.70% of the segmented copolymer by volume;
the material used for the second polymer layer 4 is a hydrophobic and oleophobic material.
The invention utilizes polymethyl methacrylate-poly nitrogen isopropyl acrylamide segmented copolymer (PMMA-PNIPAM), the number average molecular weight of the segmented copolymer is 36000-56000, the dispersivity index PDI is 1.10-1.50, the poly nitrogen isopropyl acrylamide accounts for 0.45-0.70 percent of the volume of the segmented copolymer, the segmented copolymer is used as a first polymer layer 3 of a plate material, and the molecular chain of the poly nitrogen isopropyl acrylamide (PNIPAM) has hydrophilic amide groups and hydrophobic isopropyl groups, so that the obtained polymethyl methacrylate-poly nitrogen isopropyl acrylamide segmented copolymer after copolymerization crosslinking has Low Critical Solution Temperature (LCST), at the temperature lower than the LCST, the PNIPAM volume in the segmented copolymer suddenly relaxes, the amide groups occupy the surface, and the material is hydrophilic and oleophobic; at temperatures above LCST, PNIPAM volume in the block copolymer suddenly shrinks, isopropyl groups occupy the surface, at this time the material is rendered hydrophobic and oleophilic, therefore, the block copolymer is rendered hydrophilic and oleophobic at temperatures below the low critical solution temperature, at temperatures above the low critical solution temperature, while the hydrophobic and oleophobic material is used as the second polymer layer 4, when the printing plate material is used, the corresponding groove 5 structure is only needed to be etched on the second polymer layer 4 according to the needed image-text structure, the depth of the groove 5 structure is ensured to be smaller than the total thickness of the first polymer layer 3 and the second polymer layer 4, and not smaller than the thickness of the second polymer layer 4, at this time, the bottom of the groove 5 is made of polymethyl methacrylate-polyazido isopropyl acrylamide block copolymer material, only the printing temperature is ensured to be higher than the low critical solution temperature of the block copolymer, the image-text structure region formed by the groove 5 is oleophilic to adhere to the printing ink 6, when the printing plate material is used as the printing plate material, the non-text structure region (the groove 5 structure) on the surface of the second polymer layer 4 is only needed to be etched on the second polymer layer 4, the non-image-text structure is used as the hydrophobic and oleophobic material is only needed to be removed when the printing plate structure is needed to be dried, and finally the printing plate region is only is needed to be dried, and the image-text region is only is removed.
The plate provided by the invention does not contain chromium, does not use organic glue, corrosive acid and other chemicals when the image and text are expressed, can be directly used for printing paper money after the image and text expression of the groove 5 structure is completed by laser engraving, replaces a multi-step preparation process, avoids defect accumulation, and enhances the image and text reduction authenticity of a printing stock. Meanwhile, the pattern-text area of the plate groove 5 structure provided by the invention has low critical solution temperature, and wettability is hydrophobic and oleophilic when the temperature is higher than the low critical solution temperature of the block copolymer, for example, t is more than or equal to 40 ℃ and less than or equal to 60 ℃, so that the attachment and transfer of the printing ink 6 can be completed, and the non-pattern-text area is hydrophobic and oleophobic, is not stained with the printing ink 6, and does not need to be wiped; when the temperature is lower than the low critical dissolution temperature of the block copolymer, such as that t is more than or equal to 10 ℃ and less than or equal to 25 ℃, the wettability of the image-text area of the groove 5 structure is hydrophilic and oleophobic, and after printing is finished, the ink 6 in the image-text area is automatically separated out, so that the self-cleaning of the plate can be finished, the plate is not required to be rubbed in the printing process, the loss of the ink 6 is avoided, the consumption of the ink 6 can be reduced by 20%, and the printing quantity of the plate is improved by about 6% compared with that of the traditional plate.
The polymethyl methacrylate-poly nitrogen isopropyl acrylamide segmented copolymer is an existing segmented copolymer and can be prepared through commercial or existing synthetic methods. The polymethyl methacrylate-poly nitrogen isopropyl acrylamide segmented copolymer is synthesized by adopting an ATRP (atom transfer radical polymerization) method. Optionally, the synthesis of the polymethyl methacrylate-poly nitrogen isopropyl acrylamide block copolymer comprises the following steps:
1) Bipyridine (1.2 mmol), cuCl (0.5 mmol), alpha-bromopropionic acid ethyl ester (0.5 mmol), methyl methacrylate (50 mmol) are sequentially added into a 100ml three-necked flask at room temperature, stirring is carried out to fully mix, nitrogen is continuously introduced for 30min, sealing is carried out, reflux reaction is carried out in an oil bath at 105 ℃ for a preset time, the three-necked flask is taken out, natural cooling is carried out, tetrahydrofuran is taken as a solvent, anhydrous methanol is taken as a precipitant to purify a polymer, vacuum drying is carried out until the weight is constant, and calculation is carried out; the number average molecular weight of the prepared macromolecular prepolymer initiator PMMA-Br is Mn=26000, and the dispersity (PDI) is 1.24.
2) To a 100ml three-necked flask, a prepolymer PMMA-Br (0.25 mmol), cuCl (0.25 mmol), pentamethyldimethylene triamine (0.5 mmol), azoisopropylacrylamide (26.7 mmol) and N, N-dimethylformamide were sequentially added at room temperature, and the mixture was stirred to be sufficiently mixed to make it appear brownish red, and continuously introduced with nitrogen for 30min, and then the mixture was sealed, reacted in an oil bath at 105℃for a predetermined time, and then the three-necked flask was taken out, naturally cooled, and the polymer was dissolved in tetrahydrofuran, and was subjected to secondary precipitation in petroleum ether through an alumina column, and dried to constant weight to obtain a polymethyl methacrylate-polyazaisopropyl acrylamide block copolymer (PMMA-PNIPAM).
The number average molecular weight of the block copolymer is 36000-56000, the dispersity index PDI is 1.10-1.50, and the volume percentage of the poly-nitrogen isopropyl acrylamide to the block copolymer is 0.45-0.70%; the low critical dissolution temperature T of the block copolymer is 29-30 ℃; when the use temperature of the plate is lower than the low critical dissolution temperature T of the block copolymer, the contact angle alpha of the block copolymer to water is more than 0 degrees and less than 40 degrees, and the contact angle alpha to oil is more than 110 degrees; when the plate use temperature is higher than the low critical dissolution temperature T of the block copolymer, the contact angle alpha of the block copolymer to water is more than 140 degrees, and the contact angle alpha to oil is 0 degrees < alpha < 30 degrees.
The kind of the hydrophobic and oleophobic material used for the second polymer layer 4 is not particularly limited in the present invention, and preferably, the material used for the second polymer layer 4 is a co-extrusion of polymethyl methacrylate (PMMA), polytetrafluoroethylene (PTFE) and Polyetheretherketone (PEEK). The polymethyl methacrylate (PMMA), polytetrafluoroethylene (PTFE) and polyether ether ketone (PEEK) materials are all known materials and can be prepared by means of commercial or existing synthetic methods. Optionally, the PMMA has a number average molecular weight ranging from 900000 to 1600000, PTFE has a number average molecular weight ranging from 10000 to 30000, and PEEK has a number average molecular weight ranging from 8000 to 12800. The co-extrusion of polymethyl methacrylate (PMMA), polytetrafluoroethylene (PTFE) and polyether ether ketone (PEEK) can be prepared by the prior known method, specifically, polymethyl methacrylate (PMMA), polytetrafluoroethylene (PTFE) and polyether ether ketone (PEEK) can be melted respectively, then three substances are fused, finally extrusion molding is carried out, the technological parameters can be determined according to the melting temperature of the respective substances, and the technical barrier does not exist. Optionally, the co-extrusion process is: polymethyl methacrylate (PMMA), polytetrafluoroethylene (PTFE) and polyether ether ketone (PEEK) are respectively formed into melt in three extruders, and then the melt is converged and co-extruded into a composite machine head to form a composite polymer.
According to the invention, polymethyl methacrylate (PMMA), polytetrafluoroethylene (PTFE) and polyether ether ketone (PEEK) in the coextrusion of polymethyl methacrylate (PMMA), polytetrafluoroethylene (PTFE) and polyether ether ketone (PEEK) can influence the hydrophobicity, oleophobicity, friction coefficient and wear resistance of the second polymer layer 4, wherein the polymethyl methacrylate in the coextrusion of polymethyl methacrylate (PMMA), polytetrafluoroethylene (PTFE) and polyether ether ketone accounts for 10% -30% of the mass of the coextrusion, the polytetrafluoroethylene accounts for 40% -70% of the mass of the coextrusion, the polyether ether ketone accounts for 20% -30% of the mass of the coextrusion, the more preferable mass ratio of polymethyl methacrylate, polytetrafluoroethylene and polyether ether ketone in the coextrusion of polymethyl methacrylate, polytetrafluoroethylene and polyether ether ketone is 1:3:1, the second polymer layer 4 formed by the coextrusion of polymethyl methacrylate (PMMA), polytetrafluoroethylene (PTFE) and polyether ether ketone (PEEK) obtained under the ratio is subjected to polishing, the contact angle is 5754 DEG, the water contact angle is more than or less than 25mm, the water contact angle is more than or equal to 5mm, the water contact angle is more than or less than 25mm, the water contact angle is more than or equal to 20.0.0 mm, and the water contact angle is more than or less than 25mm is measured within a range of 570.0.0.0.5, and the water contact angle is less than or equal to the water contact angle is less than the water, and is measured.
The invention does not limit the kind of material used for the adhesive layer 2, and the material used is optionally glue, and optionally methacrylate structural glue.
The material type of the substrate 1 is not particularly limited, and the material used for the substrate 1 may be selected from one of nickel, nickel alloy, iron, copper alloy, aluminum alloy, and stainless steel.
The thickness of the substrate 1, the adhesive layer 2, the first polymer layer 3 and the second polymer layer 4 is not particularly limited, and can be adjusted according to actual requirements. Optionally, the thickness of the substrate 1 is 0.30-0.55 mm, the thickness of the adhesive layer 2 is 0.001-0.050 mm, the thickness of the first polymer layer 3 is 0.10-0.25 mm, and the thickness of the second polymer layer 4 is 0.010-0.015 mm.
The invention also provides a preparation method of the printing plate, which comprises the following steps: and coating a bonding layer 2, a first polymer layer 3 and a second polymer layer 4 on the substrate 1 in sequence to obtain the printing plate.
The invention also provides a printing plate which is obtained by etching the printing plate or the printing plate prepared by the method. Alternatively, the etching may employ laser engraving.
In an alternative embodiment, as shown in fig. 2, the printing plate includes a substrate 1 and an adhesive layer 2, a first polymer layer 3 and a second polymer layer 4 sequentially laminated on the substrate 1;
a plurality of grooves 5 are formed in one side, far away from the first polymer layer 3, of the second polymer layer 4 so as to form an image-text structure;
the depth H1 of the grooves 5 is smaller than the total thickness H of the first polymer layer 3 and the second polymer layer 4 and not smaller than the thickness H2 of the second polymer layer 4.
The materials and composition of the substrate 1, the adhesive layer 2, the first polymer layer 3 and the second polymer layer 4 are as described above.
In an alternative embodiment, the depth H1 of the recess 5 is smaller than the total thickness H of the first polymer layer 3 and the second polymer layer 4 and larger than the thickness H2 of the second polymer layer 4. The depth of the groove 5 can effectively ensure that the bottom of the groove 5 is made of polymethyl methacrylate-poly nitrogen isopropyl acrylamide segmented copolymer material.
In an alternative embodiment, the depth h1 of the groove 5 is 0.01 mm < h1 < 0.2 mm.
The invention also provides a preparation method of the printing plate, which comprises the following steps: and etching a plurality of grooves 5 on the surface of the printing plate or the printing plate prepared by the method, wherein the grooves 5 form a required image-text structure, and thus the printing plate is obtained.
The invention also provides a printing method, as shown in fig. 3 and 4, wherein the printing temperature is higher than the low critical solution temperature T of the block copolymer, the printing plate stained with the ink 6 is placed in an environment lower than the low critical solution temperature T of the block copolymer after the printing is finished, the residual ink 6 in the printing plate groove 5 is automatically separated out, then the printing plate is washed by water, and the printing process is finished after drying.
Optionally, when the printing temperature is more than or equal to 40 ℃ and less than or equal to 60 ℃, the printing temperature is higher than the Low Critical Solution Temperature (LCST) of the PMMA-PNIPAM block copolymer, the image-text area formed by the groove 5 structure is hydrophobic and oleophilic, the attachment and transfer of the ink 6 are completed, and the non-image-text structural area (the area outside the groove 5 structure) on the surface of the second polymer layer 4 is hydrophobic and oleophobic, and is not stained with the ink 6;
when the temperature is more than or equal to 10 ℃ and less than or equal to 25 ℃ after printing is finished, the temperature is lower than the Low Critical Solution Temperature (LCST) of the PMMA-PNIPAM block copolymer, the image-text area formed by the groove 5 structure is hydrophilic and oleophobic, and the printing ink 6 in the lines of the image-text area is automatically separated out, so that the self-cleaning characteristic is realized. The plate prepared by the method is non-disposable, the wettability of the PMMA-PNIPAM block copolymer is correspondingly changed during the reciprocating transformation at the temperature lower than and higher than the LCST, the wettability transformation and the reversible characteristics of the temperature response are provided, and the plate can be repeatedly used on and off a printer under the condition of conforming to the printing performance.
The following describes the technical scheme of the invention by specific embodiments:
Example 1
The present embodiment provides a plate, a printing plate and a printing method, as shown in fig. 1 to 4, the plate includes a substrate 1, and a bonding layer 2, a first polymer layer 3 and a second polymer layer 4 sequentially laminated on the substrate 1;
the first polymer layer 3 is made of polymethyl methacrylate-poly nitrogen isopropyl acrylamide segmented copolymer, the number average molecular weight of the segmented copolymer is 36000-56000, the dispersity index PDI is 1.10-1.50, and the poly nitrogen isopropyl acrylamide accounts for 0.45-0.70% of the segmented copolymer by volume;
The material used for the second polymer layer 4 is a co-extrusion of polymethyl methacrylate, polytetrafluoroethylene and polyetheretherketone.
The printing plate comprises the printing plate material and further comprises a plurality of grooves 5 formed in one side, away from the first polymer layer 3, of the second polymer layer 4 so as to form an image-text structure;
the depth H1 of the grooves 5 is smaller than the total thickness H of the first polymer layer 3 and the second polymer layer 4 and not smaller than the thickness H2 of the second polymer layer 4.
The preparation method of the plate material and the printing plate comprises the following steps:
1) Taking a metal copper plate with the thickness of 0.4 mm, the width of 900 mm and the length of 900 mm as a substrate 1, and coating glue with the thickness of 0.008 mm on the substrate 1 to form a bonding layer 2;
2) Coating a polymethyl methacrylate-poly (azoisopropyl acrylamide) (PMMA-PNIPAM) block copolymer with a thickness of 0.2 mm on the adhesive layer 2 to form a first polymer layer 3, wherein the number average molecular weight mn=39800 of the block copolymer has a polymer dispersibility index pdi=1.37, the poly (azoisopropyl acrylamide) accounts for 0.54% of the volume of the block copolymer, at this time, the low critical dissolution temperature of the polymethyl methacrylate-poly (azoisopropyl acrylamide) block copolymer is 30 ℃, and the water contact angle of the block copolymer is < 10 ° and the oil contact angle is > 140 ° when the temperature is measured to be < 30 ℃; at a temperature of > 30 ℃, the contact angle of the block copolymer to water is > 160 DEG, and the contact angle to oil is < 20 DEG;
3) Spraying a co-extrusion of polymethyl methacrylate, polytetrafluoroethylene and polyether ether ketone with the thickness of 0.01 mm on the surface of the first polymer layer 3 to form a second polymer layer 4, wherein the mass ratio of polymethyl methacrylate (PMMA), polytetrafluoroethylene (PTFE) and polyether ether ketone (PEEK) in the co-extrusion is 1:3:1 (the polymethyl methacrylate accounts for 20% of the mass of the co-extrusion, the polytetrafluoroethylene accounts for 60% of the mass of the co-extrusion, the polyether ether ketone accounts for 20% of the mass of the co-extrusion), the friction coefficient of the second polymer layer 4 is 0.08 after grinding and polishing, the roughness Rz is 0.4um, the contact angle to water is 150 DEG at the temperature of 25 ℃, and the contact angle to oil is 130 DEG, and the thickness tolerance in the area of a plate 54×54 mm 2 is less than or equal to +/-6 um, so that the plate is obtained;
4) Etching a plurality of grooves 5 on the surface of the second polymer layer 4 of the printing plate by using a laser, wherein the grooves 5 form a required image-text structure to finish image-text expression for printing, the depth of the grooves 5 is more than 0.01 mm and less than 1mm and less than 0.2 mm, and the bottom of the grooves 5 is made of polymethyl methacrylate-poly-nitrogen isopropyl acrylamide block copolymer material to obtain the printing plate;
At this time, when the printing plate is used at a temperature range of less than 30 ℃, the wettability of the image-text structural area formed by the grooves 5 is hydrophilic and oleophobic, and when the printing plate is used at a temperature range of more than 30 ℃, the wettability of the image-text structural area formed by the grooves 5 is oleophilic and hydrophobic.
The embodiment also provides a printing method, which comprises the following steps:
Fixing the prepared printing plate on a printing machine for printing, wherein the printing temperature is 55 ℃, the non-image-text structural area (the area except the groove 5 structure) on the surface of the second polymer layer 4 of the printing plate is oleophobic and not stained with ink 6, and the image-text structural area formed by the groove 5 is oleophilicly adhered with the ink 6 and transferred to a printing stock to finish printing; after the printing is finished, the printing plate is placed in an environment of 25 ℃, residual ink 6 in the image-text structural area is automatically separated out, the printing plate is washed by purified water, the residual ink 6 in the image-text structural area is removed, and the printing plate is dried for reuse.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (13)
1. The printing plate is characterized by comprising a substrate, and a bonding layer, a first polymer layer and a second polymer layer which are sequentially laminated on the substrate;
the first polymer layer is made of polymethyl methacrylate-poly nitrogen isopropyl acrylamide segmented copolymer, the number average molecular weight of the segmented copolymer is 36000-56000, the dispersity index PDI is 1.10-1.50, and the poly nitrogen isopropyl acrylamide accounts for 0.45-0.70% of the segmented copolymer by volume;
The material used for the second polymer layer is a hydrophobic and oleophobic material;
a plurality of grooves are formed in one side, far away from the first polymer layer, of the second polymer layer so as to form an image-text structure;
The depth H1 of the groove is smaller than the total thickness H of the first polymer layer and the second polymer layer and not smaller than the thickness H2 of the second polymer layer.
2. The plate according to claim 1, wherein the polymethyl methacrylate-polyazitaneisopropyl acrylamide block copolymer has a low critical dissolution temperature T of 29 ℃ to 30 ℃;
When the use temperature of the plate is lower than the low critical dissolution temperature T of the block copolymer, the contact angle alpha of the block copolymer to water is more than 0 degrees and less than 40 degrees, and the contact angle alpha to oil is more than 110 degrees;
when the plate use temperature is higher than the low critical dissolution temperature T of the block copolymer, the contact angle alpha of the block copolymer to water is more than 140 degrees, and the contact angle alpha to oil is 0 degrees < alpha < 30 degrees.
3. A plate according to claim 1 or 2, wherein the material used for the second polymer layer is a co-extrusion of polymethyl methacrylate, polytetrafluoroethylene and polyetheretherketone.
4. A plate according to claim 3, wherein the co-extrusion of polymethyl methacrylate, polytetrafluoroethylene and polyetheretherketone comprises 10-30% of the mass of the co-extrusion, polytetrafluoroethylene comprises 40-70% of the mass of the co-extrusion and polyetheretherketone comprises 20-30% of the mass of the co-extrusion.
5. The plate of claim 4, wherein the mass ratio of polymethyl methacrylate, polytetrafluoroethylene and polyetheretherketone in the co-extrusion of polymethyl methacrylate, polytetrafluoroethylene and polyetheretherketone is 1:3:1.
6. A plate according to claim 1 or 2, wherein the material used for the adhesive layer is glue; the substrate is made of one of nickel, nickel alloy, iron, copper alloy, aluminum alloy and stainless steel.
7. A method of producing a plate as claimed in any one of claims 1 to 6, comprising the steps of: and sequentially coating a bonding layer, a first polymer layer and a second polymer layer on the substrate to obtain the printing plate.
8. A printing plate, characterized in that it is obtained by etching a plate material according to any one of claims 1-6 or a plate material prepared by a method according to claim 7.
9. The printing plate according to claim 8, wherein the printing plate comprises a substrate and a tie layer, a first polymer layer and a second polymer layer sequentially laminated on the substrate;
a plurality of grooves are formed in one side, far away from the first polymer layer, of the second polymer layer so as to form an image-text structure;
The depth H1 of the groove is smaller than the total thickness H of the first polymer layer and the second polymer layer and not smaller than the thickness H2 of the second polymer layer.
10. The printing plate of claim 9 wherein the depth H1 of the grooves is less than the total thickness H of the first polymer layer and the second polymer layer and greater than the thickness H2 of the second polymer layer.
11. The printing plate according to claim 10, wherein the depth h1 of the grooves is 0.01 mm < h1 < 0.2 mm.
12. A method of producing a printing plate according to any one of claims 8 to 11, comprising the steps of: etching a plurality of grooves on the surface of the printing plate prepared by the method of any one of claims 1-6 or claim 7, wherein the grooves form a required image-text structure, and thus the printing plate is obtained.
13. A printing method, characterized in that printing is performed by using the printing plate according to any one of claims 8 to 11 or the printing plate prepared by the method according to claim 12, wherein the printing temperature is higher than the low critical solution temperature T of the block copolymer, the printing plate stained with ink is placed in an environment lower than the low critical solution temperature T of the block copolymer after printing is finished, the ink remained in the grooves of the printing plate is automatically separated out, then the printing plate is washed with water, and the printing process is completed after drying.
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| CN105818562B (en) * | 2015-01-05 | 2018-06-15 | 中国科学院化学研究所 | A kind of plate used for water color ink and preparation method thereof |
| CN109826015B (en) * | 2019-01-30 | 2021-03-26 | 广西大学 | A temperature-sensitive/pH dual-responsive smart nanofiber material and its preparation method and application |
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