CN114953802B - Treatment-free CTP plate with wear-resistant protective layer - Google Patents
Treatment-free CTP plate with wear-resistant protective layer Download PDFInfo
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- CN114953802B CN114953802B CN202210530543.9A CN202210530543A CN114953802B CN 114953802 B CN114953802 B CN 114953802B CN 202210530543 A CN202210530543 A CN 202210530543A CN 114953802 B CN114953802 B CN 114953802B
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- protective layer
- wear
- water
- resistant protective
- polyvinyl alcohol
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- 239000011241 protective layer Substances 0.000 title claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 26
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 23
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- FLISWPFVWWWNNP-BQYQJAHWSA-N dihydro-3-(1-octenyl)-2,5-furandione Chemical compound CCCCCC\C=C\C1CC(=O)OC1=O FLISWPFVWWWNNP-BQYQJAHWSA-N 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 230000000844 anti-bacterial effect Effects 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 17
- 239000004593 Epoxy Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 150000008064 anhydrides Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 108010010803 Gelatin Proteins 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 229920000159 gelatin Polymers 0.000 claims description 11
- 239000008273 gelatin Substances 0.000 claims description 11
- 235000019322 gelatine Nutrition 0.000 claims description 11
- 235000011852 gelatine desserts Nutrition 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- JZNOXYXRJDVNOM-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,6,6,6-tridecafluoro-5-iodohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(I)C(F)(F)F JZNOXYXRJDVNOM-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000007792 addition Methods 0.000 claims description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000007853 buffer solution Substances 0.000 claims description 3
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- SWAOGFOBFBPBRS-UHFFFAOYSA-N 1-(diethylamino)ethanol;hydrochloride Chemical compound [Cl-].CC[NH+](CC)C(C)O SWAOGFOBFBPBRS-UHFFFAOYSA-N 0.000 claims 3
- 238000005299 abrasion Methods 0.000 claims 3
- 230000001105 regulatory effect Effects 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 125000003158 alcohol group Chemical group 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000002955 isolation Methods 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- -1 quaternary ammonium salt cation Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000012856 weighed raw material Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000003860 storage Methods 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
- B41N3/00—Preparing for use and conserving printing surfaces
- B41N3/03—Chemical or electrical pretreatment
-
- 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
- C09D129/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Plant Pathology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a no-treatment CTP plate with a wear-resistant protective layer, which belongs to the technical field of printing and comprises an aluminum plate base support, a photosensitive layer and a wear-resistant protective layer which are distributed from bottom to top; the protective layer of CTP is water-based coating, usually selects polyvinyl alcohol as main material, and polyvinyl alcohol has good hydrophilicity, and is easy to absorb moisture, and can have the following effects on the performance of the plate: so that the oxygen barrier property of the protective layer is reduced, thereby reducing the sensitivity, and the scratch resistance of the protective layer is reduced or the lining paper is adhered; according to the invention, the polyvinyl alcohol is treated, and the octenyl succinic anhydride reacts with hydroxyl in the polyvinyl alcohol structure, so that a hydrophobic hydrocarbon long chain is introduced into the polyvinyl alcohol structure, so that the water-soluble polymer is improved, the water-soluble polymer has good fluidity and dispersibility compared with single hydrophilic polyvinyl alcohol, the film forming effect of the water-based coating is improved, and the oxygen isolation performance of the water-based coating is enhanced.
Description
Technical Field
The invention belongs to the technical field of printing, and particularly relates to a no-treatment CTP plate with a wear-resistant protective layer.
Background
In photopolymerization systems, high sensitivity is essential. And oxygen in the air can obviously reduce the sensitivity of the plate. Oxygen in the air has two effects on the photoinitiation system, and on one hand, the excited state of the photoinitiation can be promoted to be extinguished: on the other hand, the generated free radicals can be promoted to be extinguished. Therefore, a protective layer is coated on the photosensitive layer of the lithographic printing plate to isolate oxygen, thereby improving the sensitivity of the printing plate.
Because the sensitivity and stability of the plate are basically contradictory, the protective layer of the CTP plate is a water-based coating, and the CTP plate is easy to absorb moisture, and can have the following effects on the performance of the plate: the oxygen-insulating property of the protective layer is reduced, so that the sensitivity is reduced, the scratch resistance of the protective layer is reduced or the lining paper is adhered, the defect of an image-text area is easily generated after exposure, moisture enters the photosensitive coating through the protective layer, and strong hydrogen bonding action with resin, oligomer or monomer rich in hydroxyl and carboxyl occurs, and the crystallization phenomenon of small molecular substances is seriously caused, so that the stability of the plate is affected.
Improper application of the protective paste can also cause the plate to become soiled. If the glue solution with too low concentration is used in the glue coating process, the coating amount of the protective glue is insufficient, the effect of protecting the printing plate cannot be really achieved, and the non-image part is subjected to oxidation reaction, or the water loss of the printing plate mesh layer is excessive, the water retention property is poor, and the printing plate is dirty. Such as uneven coating of the protective paste or obvious paste paths, can cause the plate to become dirty.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the invention provides a no-treatment CTP plate with a wear-resistant protective layer.
The aim of the invention can be achieved by the following technical scheme:
a kind of disposable CTP edition with wear-resisting protective layer, including aluminum edition base support, photosensitive layer, wear-resisting protective layer that distributes from bottom to top;
the wear-resistant protective layer comprises water-soluble polymers, antibacterial components, auxiliary agents and solvents;
the water-soluble polymer is prepared by the following steps:
mixing polyvinyl alcohol and deionized water, adding sodium hydroxide at 35-40deg.C, adjusting pH to about 9, maintaining the temperature unchanged, adding anhydride solution, stirring for 3-4 hr, and adjusting pH to about 6 with hydrochloric acid to obtain water-soluble polymer.
Further, the solvent is one or more of deionized water, ethanol and methanol, which are mixed according to any proportion.
Further, the photosensitive layer is coated with a resin containing a photosensitive composition.
The resin containing the photosensitive composition comprises film forming resin, unsaturated monomer, prepolymer, initiating system and other auxiliary agents.
Further, the weight of the coating layer after the wear-resistant protective layer is dried is 1-5g/m 2 。
Further, the wear-resistant protective layer comprises the following raw materials in percentage by weight: 20-30% of water-soluble polymer, 1-2% of antibacterial component, 0.5-0.8% of auxiliary agent and the balance of solvent.
Further, the auxiliary agent is one of amide, cyclohexanediol and sorbitol.
Further, the anhydride solution is octenyl succinic anhydride and isopropanol in an amount of 1g:10mL of the mixture.
Further, the dosage ratio of polyvinyl alcohol, deionized water and anhydride solution was 1g:10mL:10mL. The polymerization degree of the polyvinyl alcohol ranges from 300 to 2400.
Further, the antibacterial component is prepared by the steps of:
mixing N, N-diethyl ethanol thiolate and tertiary butanol, adding sodium hydroxide aqueous solution, stirring at 20 ℃ for 20min, adding perfluorobutyl ethyl iodide, heating to 80 ℃, stirring for 12h, then spin-evaporating to remove the solvent, extracting with aqueous solution for 3 times, washing with saturated saline water for 3 times, spin-drying to obtain fluorine-containing monomer; the molar ratio of N, N-diethyl-ethanol thiolate to perfluorobutyl ethyl iodide is 1:1, a step of; the molar ratio of the amount of sodium hydroxide in the aqueous sodium hydroxide solution to the amount of N, N-diethylthiolate is 2.1:1, a step of;
under the protection of nitrogen, mixing fluorine-containing monomers and methanol, heating to 40 ℃, dropwise adding epichlorohydrin, keeping the temperature unchanged after the addition, continuously stirring for 2 hours, cooling to room temperature, removing the solvent by rotary evaporation, washing with anhydrous diethyl ether, and drying in vacuum after the washing is finished to obtain epoxy quaternary ammonium salt; the mass ratio of the fluorine-containing monomer to the epoxy chloropropane is 3:1.
mixing gelatin and a buffer solution with a pH value of 10, stirring for 1h at 50 ℃, adding epoxy quaternary ammonium salt, keeping the temperature unchanged, continuously stirring for 6h, freeze-drying at low temperature, removing excessive epoxy quaternary ammonium salt by using methanol, finally washing by using deionized water, removing the methanol, and freeze-drying to obtain the antibacterial component.
The preparation of the antibacterial component takes gelatin as a carrier, the gelatin has abundant hydroxyl, amino and other active groups in the structure, after the gelatin is subjected to chemical modification by utilizing epoxy quaternary ammonium salt, quaternary ammonium salt cation antibacterial groups are introduced into the structure of the gelatin, and when the gelatin is used as raw materials in the antibacterial component and the wear-resistant protective layer for mixing, the mixing effect of each substance is good, hydrogen bonds are formed among molecules, an interactive network structure is formed, the protection effect on a photosensitive layer is improved, and the antibacterial component has better wear resistance compared with a linear high polymer material.
The quaternary ammonium salt has an antibacterial effect, the gelatin is used as a carrier, after the antibacterial component is added, the mixing effect is good, the fluorocarbon long chain is introduced into the structure of the epoxy quaternary ammonium salt, and the epoxy quaternary ammonium salt can be enriched on the surface of the epoxy quaternary ammonium salt after the wear-resistant protective layer is formed, so that the oxygen isolation capability is further improved, and meanwhile, the epoxy quaternary ammonium salt has a promoting effect on preventing moisture from passing through.
Further, the dosage mass ratio of the gelatin to the epoxy quaternary ammonium salt is 8:1.
the invention has the beneficial effects that:
the protective layer of CTP is water-based coating, usually selects polyvinyl alcohol as main material, and polyvinyl alcohol has good hydrophilicity, and is easy to absorb moisture, and can have the following effects on the performance of the plate: so that the oxygen barrier property of the protective layer is reduced, thereby reducing the sensitivity, and the scratch resistance of the protective layer is reduced or the lining paper is adhered; according to the invention, the polyvinyl alcohol is treated, and the octenyl succinic anhydride reacts with hydroxyl in the polyvinyl alcohol structure, so that a hydrophobic hydrocarbon long chain is introduced into the polyvinyl alcohol structure, so that the water-soluble polymer is improved, the water-soluble polymer has good fluidity and dispersibility compared with single hydrophilic polyvinyl alcohol, the film forming effect of the water-based coating is improved, and the oxygen isolation performance of the water-based coating is enhanced.
The raw materials used in the protective layer are environment-friendly, have no pungent smell, have good film forming property and smoothness, and have good protective effect on the plate.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. 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.
The aluminum plate is degreased, decontaminated, chemically etched and the like by adopting a conventional support treatment method, and resin containing photosensitive composition is coated on the surface of the treated aluminum plate base support.
A kind of disposable CTP edition with wear-resisting protective layer, including aluminum edition base support, photosensitive layer, wear-resisting protective layer that distributes from bottom to top;
the wear-resistant protective layer comprises water-soluble polymers, antibacterial components, auxiliary agents and solvents;
the photosensitive layer is formed by coating a resin containing a photosensitive composition.
The resin containing the photosensitive composition comprises film forming resin, unsaturated monomer, prepolymer, initiating system and other auxiliary agents. 1.8 parts of polyurethane acrylic ester, 1.8 parts of acrylic ester oligomer, 1.5 parts of diethylene glycol diacrylate, 0.2 part of sensitizer, 0.2 part of photopolymerization initiator (CIBA, titanocene compound), 50.02 parts of cyanine dye cyanine, 40 parts of methyl ethyl ketone and 40 parts of ethylene glycol monoethyl ether are mixed to prepare resin of photosensitive composition, and then the resin is coated to prepare a photosensitive layer, wherein the coating weight is 2g/m 2 。
Example 1
Preparing an antibacterial component:
mixing N, N-diethyl ethanol thiolate and tertiary butanol, adding sodium hydroxide aqueous solution, stirring at 20 ℃ for 20min, adding perfluorobutyl ethyl iodide, heating to 80 ℃, stirring for 12h, then spin-evaporating to remove the solvent, extracting with aqueous solution for 3 times, washing with saturated saline water for 3 times, spin-drying to obtain fluorine-containing monomer; the molar ratio of N, N-diethyl-ethanol thiolate to perfluorobutyl ethyl iodide is 1:1, a step of; the molar ratio of the amount of sodium hydroxide in the aqueous sodium hydroxide solution to the amount of N, N-diethylthiolate is 2.1:1, a step of;
under the protection of nitrogen, mixing fluorine-containing monomers and methanol, heating to 40 ℃, dropwise adding epichlorohydrin, keeping the temperature unchanged after the addition, continuously stirring for 2 hours, cooling to room temperature, removing the solvent by rotary evaporation, washing with anhydrous diethyl ether, and drying in vacuum after the washing is finished to obtain epoxy quaternary ammonium salt; the mass ratio of the fluorine-containing monomer to the epoxy chloropropane is 3:1.
mixing gelatin and a buffer solution with a pH value of 10, stirring for 1h at 50 ℃, adding epoxy quaternary ammonium salt, keeping the temperature unchanged, continuously stirring for 6h, freeze-drying at low temperature, removing excessive epoxy quaternary ammonium salt by using methanol, finally washing by using deionized water, removing the methanol, and freeze-drying to obtain the antibacterial component. The dosage mass ratio of the gelatin to the epoxy quaternary ammonium salt is 8:1.
example 2
A kind of disposable CTP edition with wear-resisting protective layer, including aluminum edition base support, photosensitive layer, wear-resisting protective layer that distributes from bottom to top;
the wear-resistant protective layer comprises a water-soluble polymer, the antibacterial component prepared in the example 1, an auxiliary agent and a solvent; the water-soluble polymer is prepared by the following steps:
mixing polyvinyl alcohol and deionized water, adding sodium hydroxide at 35 ℃, adjusting the pH value to about 9, keeping the temperature unchanged, adding an anhydride solution, continuously stirring for 3 hours, and adjusting the pH value to about 6 by using hydrochloric acid after stirring is finished to obtain the water-soluble polymer. Anhydride solution octenyl succinic anhydride and isopropanol 1g:10mL of the mixture. The dosage ratio of polyvinyl alcohol, deionized water and anhydride solution is 1g:10mL:10mL.
The auxiliary agent is amide; the solvent is deionized water.
Weighing the following raw materials in percentage by weight: 20% of water-soluble polymer, 2% of antibacterial component, 0.8% of auxiliary agent and the balance of solvent; mixing the weighed raw materials, coating, and drying the wear-resistant protective layer to obtain a coating weight of 5g/m 2 。
Example 3
A kind of disposable CTP edition with wear-resisting protective layer, including aluminum edition base support, photosensitive layer, wear-resisting protective layer that distributes from bottom to top;
the wear-resistant protective layer comprises a water-soluble polymer, the antibacterial component prepared in the example 1, an auxiliary agent and a solvent; the water-soluble polymer is prepared by the following steps:
mixing polyvinyl alcohol and deionized water, adding sodium hydroxide at 38 ℃, adjusting the pH value to about 9, keeping the temperature unchanged, adding an anhydride solution, continuously stirring for 4 hours, and adjusting the pH value to about 6 by using hydrochloric acid after stirring is finished to obtain the water-soluble polymer. Anhydride solution octenyl succinic anhydride and isopropanol 1g:10mL of the mixture. The dosage ratio of polyvinyl alcohol, deionized water and anhydride solution is 1g:10mL:10mL.
The auxiliary agent is cyclohexanediol; the solvent is deionized water and ethanol which are mixed in equal volume.
Weighing the following raw materials in percentage by weight: 25% of water-soluble polymer, 2% of antibacterial component, 0.8% of auxiliary agent and the balance of solvent; mixing the weighed raw materials, coating, and drying the wear-resistant protective layer to obtain a coating weight of 3g/m 2 。
Example 4
A kind of disposable CTP edition with wear-resisting protective layer, including aluminum edition base support, photosensitive layer, wear-resisting protective layer that distributes from bottom to top;
the wear-resistant protective layer comprises a water-soluble polymer, the antibacterial component prepared in the example 1, an auxiliary agent and a solvent; the water-soluble polymer is prepared by the following steps:
mixing polyvinyl alcohol and deionized water, adding sodium hydroxide at 40 ℃, adjusting the pH value to about 9, keeping the temperature unchanged, adding an anhydride solution, continuously stirring for 4 hours, and adjusting the pH value to about 6 by using hydrochloric acid after stirring is finished to obtain the water-soluble polymer. Anhydride solution octenyl succinic anhydride and isopropanol 1g:10mL of the mixture. The dosage ratio of polyvinyl alcohol, deionized water and anhydride solution is 1g:10mL:10mL.
The auxiliary agent is sorbitol; the solvent is deionized water and methanol.
Weighing the following raw materials in percentage by weight: 30% of water-soluble polymer, 1% of antibacterial component, 0.8% of auxiliary agent and the balance of solvent; mixing the weighed raw materials, coating, and drying the wear-resistant protective layer to obtain a coating weight of 1g/m 2 。
Comparative example 1
Compared with example 3, the antibacterial component in the wear-resistant protective layer is divided into the epoxy quaternary ammonium salt prepared in example 1, and the rest raw materials and the preparation process are kept unchanged.
Comparative example 2
Compared with the example 3, the water-soluble polymer in the wear-resistant protective layer is changed into polyvinyl alcohol, and the rest raw materials and the preparation process are kept unchanged.
The samples prepared in examples 2-4 and comparative examples 1-2 were tested and the test results are shown in Table 1 below: the antibacterial rate is detected by using GB/T2591-2003; the test strain was Staphylococcus aureus at 37.+ -. 1 ℃ for 24 hours.
Heating and humidifying the prepared sample in a wet and hot aging box at 50 ℃ and 80 percent: placing the sample plate in a damp-heat aging box for three days, making a plate on a plate making machine, and then developing and processing; the sensitivity was tested.
Firstly, measuring the density of the plate, then setting a control group, wherein the control group is to place the wear-resistant protective layer in a constant-temperature water bath at 35 ℃ for 5 days, then making a plate, and comparing the change of the density of the plate before and after constant-temperature rest; the smaller the difference, the more stable.
TABLE 1
| Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| Antibacterial rate/% | 99.1 | 99.2 | 99.1 | 99.1 | 99.1 |
| Sensitivity of sensitivity | 80 | 82 | 81 | 70 | 64 |
| Stability of | 0.1 | 0.1 | 0.1 | 0.3 | 0.4 |
As can be seen from Table 1 above, the samples prepared according to the present invention have good storage stability and still maintain good sensitivity after high humidity and heat aging.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (7)
1. A kind of disposable CTP edition with wear-resisting protective layer, including aluminum edition base support, photosensitive layer, wear-resisting protective layer that distributes from bottom to top; the wear-resistant protective layer is characterized by comprising a water-soluble polymer, an antibacterial component, an auxiliary agent and a solvent;
the water-soluble polymer is prepared by the following steps:
mixing polyvinyl alcohol and deionized water, adding sodium hydroxide at 35-40 ℃ to regulate the pH, keeping the temperature unchanged, adding an anhydride solution, continuously stirring for 3-4 hours, and regulating the pH by using hydrochloric acid after stirring to obtain a water-soluble polymer;
the antibacterial component is prepared by the following steps:
mixing N, N-diethylaminoethanol hydrochloride and tertiary butanol, adding sodium hydroxide aqueous solution, stirring at 20 ℃ for 20min, adding perfluorobutyl ethyl iodide, heating to 80 ℃, and stirring for 12h to obtain a fluorine-containing monomer; the molar ratio of N, N-diethylaminoethanol hydrochloride to perfluorobutyl ethyl iodide is 1:1, a step of; the molar ratio of the amount of sodium hydroxide in the aqueous sodium hydroxide solution to the amount of N, N-diethylaminoethanol hydrochloride is 2.1:1, a step of;
under the protection of nitrogen, mixing fluorine-containing monomers and methanol, heating to 40 ℃, dropwise adding epichlorohydrin, keeping the temperature unchanged after the addition, and continuously stirring for 2 hours to obtain epoxy quaternary ammonium salt; the mass ratio of the fluorine-containing monomer to the epoxy chloropropane is 3:1, a step of;
mixing gelatin and buffer solution with pH value of 10, stirring at 50deg.C for 1 hr, adding epoxy quaternary ammonium salt, maintaining temperature, and stirring for 6 hr to obtain antibacterial component.
2. The CTP plate having the abrasion resistant protective layer according to claim 1, wherein the solvent is one or more of deionized water, ethanol and methanol mixed in an arbitrary ratio.
3. The CTP plate having the abrasion resistant protective layer according to claim 1, wherein said photosensitive layer is coated with a resin containing a photosensitive composition.
4. The no-treatment CTP plate having a wear-resistant protective layer according to claim 1, wherein the wear-resistant protective layer has a coating weight of 1 to 5g/m after drying 2 。
5. The no-process CTP plate having a wear-resistant protective layer according to claim 1, wherein said wear-resistant protective layer comprises the following raw materials in weight percent: 20-30% of water-soluble polymer, 1-2% of antibacterial component, 0.5-0.8% of auxiliary agent and the balance of solvent.
6. The no-process CTP plate having an abrasion resistant protective layer according to claim 1, wherein the auxiliary agent is one of amide, cyclohexanediol and sorbitol.
7. The CTP plate having a wear resistant protective layer according to claim 1, wherein the anhydride solution is octenyl succinic anhydride and isopropyl alcohol in an amount of 1g:10mL of the mixture.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012089072A1 (en) * | 2010-12-30 | 2012-07-05 | 乐凯华光印刷科技有限公司 | Infrared sensitive and chemical treatment free photosensitive composition and lithographic plate fabricated by using same |
| CN109814337A (en) * | 2019-01-25 | 2019-05-28 | 安徽强邦印刷材料有限公司 | A kind of directly upper machine of double coatings exempts from processing CTP editions |
| CN113512358A (en) * | 2021-05-27 | 2021-10-19 | 安徽强邦新材料股份有限公司 | Treatment-free printing plate environment-friendly coating and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012089072A1 (en) * | 2010-12-30 | 2012-07-05 | 乐凯华光印刷科技有限公司 | Infrared sensitive and chemical treatment free photosensitive composition and lithographic plate fabricated by using same |
| CN109814337A (en) * | 2019-01-25 | 2019-05-28 | 安徽强邦印刷材料有限公司 | A kind of directly upper machine of double coatings exempts from processing CTP editions |
| CN113512358A (en) * | 2021-05-27 | 2021-10-19 | 安徽强邦新材料股份有限公司 | Treatment-free printing plate environment-friendly coating and preparation method thereof |
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