CN113524933A - Green and environment-friendly printing process method - Google Patents
Green and environment-friendly printing process method Download PDFInfo
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- CN113524933A CN113524933A CN202110908319.4A CN202110908319A CN113524933A CN 113524933 A CN113524933 A CN 113524933A CN 202110908319 A CN202110908319 A CN 202110908319A CN 113524933 A CN113524933 A CN 113524933A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/10—Intaglio printing ; Gravure printing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/06—Printing inks based on fatty oils
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- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D11/104—Polyesters
- C09D11/105—Alkyd resins
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- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a green environment-friendly printing process method, which comprises the following steps: q1 determining plate making parameters; q2 platemaking; trial printing of Q3; q4 printing. The printing ink is smeared on the whole plate surface of the columnar intaglio, the redundant printing ink on the surface layer of the columnar intaglio is scraped by a doctor blade, then a printed matter is placed on the plate surface of the columnar intaglio, and then the printing ink on the columnar intaglio is printed on the printed matter by applying pressure. The print of the printed matter prepared by the process method of the invention is durable and non-adhesive.
Description
Technical Field
The invention relates to the technical field of printing, in particular to a green and environment-friendly printing process method.
Background
The printing industry is a long history and large scale system industry. Since the invention of printing technology in ancient China, the printing quantity and quality of books are continuously improved along with the improvement of the technology level. With the development of the times and the technological level, various fine novel printing technologies capable of meeting various severe requirements are required in more and more industrial and biochemical fields. Now, the printing technology is not only a traditional technology which only serves for physical books, but in modern life, whether advertisements, posters, various cultural and literature propaganda products and the like, even including products of ceramics, wood, metal and the like, become a range involved in the surface printing of objects. This therefore places not only higher demands on the printing machine, but also new standards and requirements on the conventional printing process. How to retain printed patterns and characters for a long time and improve the quality of printed matters has become one of the hot problems to be solved by the related practitioners in the industry. Therefore, the printing technology gradually deepens into various fields such as life, production and the like, and develops and grows, and now the printing industry becomes a modern industry with a large scale.
At present, the standards of consumers on living standard, quality and living development environment are continuously improved, the demand of 'green packaging materials' in the packaging market is higher and higher, namely, the environment-friendly performance is improved, and the pollution-free packaging materials which are energy-saving, low in consumption, non-toxic, pollution-free and easy to degrade are selected. Printing ink is one of the more serious contamination materials in the packaging material. Traditional printing inks contain a large amount of toxic and harmful chemicals, including heavy metals, residual solvents, organic volatiles, polycyclic aromatic hydrocarbons, and the like. Therefore, the development of new inks which are non-toxic and pollution-free and can significantly improve the printing quality of printed matters has become a problem which is widely concerned by relevant practitioners in the industry.
Patent CN102618117A provides a single-liquid environment-friendly universal composite ink and a preparation method thereof, which is composed of ester-dissolved vinyl chloride-acetate resin liquid, a dispersant, an ester solvent, rutile titanium dioxide/organic pigment, matting powder, wax powder and ester-dissolved polyurethane resin, but the printed matter obtained by printing the composite ink has poor printing quality and low glossiness of printed patterns, and printed traces are easy to have the phenomena of deterioration, cracking and the like after being stored for a long time.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a green and environment-friendly printing process method.
In order to solve the technical problems, the invention adopts the technical scheme that:
the green environment-friendly printing process method comprises the following steps:
q1 determining plate making parameters;
q2 platemaking: processing by adopting a laser engraving mode to obtain a columnar gravure;
trial printing of Q3: dipping the printing ink on the columnar intaglio, and performing test printing and drying operation on a test printed matter; judging whether the ink needs to be prepared again or the specification of the columnar intaglio is adjusted according to the obtained ink forming effect and the printing quality; if the ink forming effect and the printing quality meet the specified printing standard, batch printing can be carried out according to the current gravure specification and the ink proportion;
q4 printing: and smearing the ink on the whole plate surface of the columnar intaglio, scraping the redundant ink on the surface layer of the columnar intaglio by using a doctor blade, then placing a printed matter on the plate surface of the columnar intaglio, and then applying pressure to print the ink on the columnar intaglio onto the printed matter, thereby completing the green environment-friendly printing process.
Preferably, the green environment-friendly printing process method comprises the following steps:
q1 determines plate making parameters: adopting brick type net points, wherein the number of the net lines is 20-25/cm, and the depth of a manufactured plate is 80-100 mu m;
q2 platemaking: processing by adopting a laser engraving mode to obtain a columnar gravure;
trial printing of Q3: dipping the printing ink on the columnar intaglio, and performing test printing and drying operation on a test printed matter; judging whether the ink needs to be prepared again or the specification of the columnar intaglio is adjusted according to the obtained ink forming effect and the printing quality; if the ink forming effect and the printing quality meet the specified printing standard, batch printing can be carried out according to the current gravure specification and the ink proportion;
q4 printing: and smearing the printing ink on the whole plate surface of the columnar intaglio, scraping redundant printing ink on the surface layer of the columnar intaglio by using a doctor blade to enable the thickness of the printing ink layer of the printing ink to be 40-45 mu m, then placing a printed matter on the plate surface of the columnar intaglio, and then applying pressure to print the printing ink on the columnar intaglio onto the printed matter, thus completing the green environment-friendly printing process.
The preparation method of the ink comprises the following steps:
c1 wetting: mixing carbon black with water, heating, stirring, and simultaneously performing ultrasonic auxiliary treatment to obtain wet carbon black;
c2 pulping: mixing petroleum resin, liquid paraffin, vegetable oil and modified alkyd resin, and stirring to obtain emulsion; the vegetable oil is at least one of castor oil and cottonseed oil;
c3 reaction: mixing the wet carbon black and the slurry, adding chalk, quartz and argil, stirring, standing, and taking precipitate to obtain an intermediate product A;
c4 drying: drying the intermediate product A to obtain an intermediate product B;
c5 grinding: grinding the intermediate product B, and sieving to obtain an intermediate product C;
c6 arrangement: mixing and homogenizing the intermediate product C, liquid paraffin and an anti-drying agent to obtain an intermediate product D; the anti-drying agent is at least one of catechol and 2-methoxy-4-methylphenol;
c7 defoaming: and defoaming the intermediate product D to obtain the printing ink.
The petroleum resin has the characteristics of low acid value, good miscibility, water resistance, ethanol resistance, chemical resistance and the like, has chemical stability to acid and alkali, has the characteristics of viscosity regulation and good thermal stability, and can be used in cooperation with the modified alkyd resin prepared by the specific method of the invention to enhance the gloss, adhesion and durability of the ink, thereby obtaining a printed matter with higher printing quality. The catechol and the 2-methoxy-4-methylphenol can effectively prevent the degradation and cracking phenomenon caused by the oxidation of the ink system by oxygen in the air. The castor oil and the cottonseed oil have good wettability, low price, safety, no toxicity, wide sources and easy processing.
Preferably, the preparation method of the ink comprises the following steps:
c1 wetting: mixing carbon black with water at a bath ratio of 1kg (3-5) L, heating to 60-65 ℃, stirring at a rotating speed of 20-40rpm for 40-60min, and simultaneously performing ultrasonic auxiliary treatment with power of 300-330W and frequency of 35-37kHz to obtain wet carbon black;
c2 pulping: mixing 10-13 parts by weight of petroleum resin, 1-4 parts by weight of liquid paraffin, 13-17 parts by weight of vegetable oil and 5-8 parts by weight of modified alkyd resin, and stirring at the temperature of 105-115 ℃ and the rotating speed of 70-90rpm for 90-110min to obtain emulsion; the vegetable oil is a mixture of castor oil and cottonseed oil in a mass ratio of (4-6) to 1;
c3 reaction: mixing 33-36 parts by weight of the wet carbon black with 38-43 parts by weight of whey, adding 8-11 parts by weight of chalk, 1-3 parts by weight of quartz and 7-9 parts by weight of argil, stirring at the temperature of 55-62 ℃ and the rotation speed of 240-300rpm for 20-40min, then standing at the temperature of 12-17 ℃ for 28-35h, taking precipitate to obtain an intermediate product A;
c4 drying: drying the intermediate product A at the temperature of 110-125 ℃ and the vacuum degree of (-0.12) - (-0.1) MPa to obtain an intermediate product B;
c5 grinding: grinding the intermediate product B, and sieving the ground intermediate product B through a 2300-2500-mesh sieve to obtain an intermediate product C;
c6 arrangement: mixing the intermediate product C, the liquid paraffin and the anti-drying agent according to the mass ratio of (38-42) to (23-26) to (0.8-1.2) at 22-25 ℃, and homogenizing at the rotation speed of 12000 and 13000rpm for 2-4min to obtain an intermediate product D; the anti-drying agent is a mixture of catechol and 2-methoxy-4-methylphenol in a mass ratio of (3-5) to 1;
c7 defoaming: and (3) placing the intermediate product D in an environment with the temperature of 52-56 ℃ and the vacuum degree of 0.02-0.04MPa for defoaming for 90-110min to obtain the ink.
The preparation method of the modified alkyd resin comprises the following steps:
d1 mixing sulfonamide, cellulose and diethyl ether, then carrying out ultrasonic treatment, filtering to obtain filter residue, and drying the filter residue to obtain modified cellulose;
d2 mixing the alkyd resin, the modified cellulose, the anhydride and the anti-aging agent, blending and extruding a blank;
d3, crushing the blank and sieving to obtain the modified alkyd resin.
After being cured, the alkyd resin can show good gloss, excellent toughness and strong adhesive force, and has good wear resistance, weather resistance, insulativity and other excellent characteristics, so that the alkyd resin is modified to prepare the ink for the green environment-friendly printing process method, the ink with better gloss and stronger adhesive force is obtained, and a printed product with higher printing quality is obtained by the green environment-friendly printing process method.
However, if the alkyd resin is directly added into an ink system, the ink is easy to embrittle and crack under the stimulation of light and air humidity change during long-term storage after drying and curing due to poor compatibility between the common alkyd resin and ink raw materials, and the printing quality and the appearance of transportation, storage and use of a printed matter are extremely influenced.
Preferably, the preparation method of the modified alkyd resin comprises the following steps:
d1, mixing 3-4 parts by weight of sulfamide, 7-8 parts by weight of cellulose and 16-19 parts by weight of diethyl ether, then carrying out ultrasonic treatment for 160-37 minutes at 83-86 ℃ and with the power of 340-360W and the frequency of 35-37kHz, filtering and taking filter residue, and drying the filter residue for 8-10 hours at the temperature of 75-80 ℃ and the air pressure of 65-70kPa to obtain modified cellulose;
d2 mixing the alkyd resin, the modified cellulose, the anhydride and the anti-aging agent according to the mass ratio of (63-66): 20-23): 7-9): 1-2, then blending for 110min at the temperature of 103 ℃ and 108 ℃ and the rotating speed of 600 rpm and 800rpm, and extruding a blank with the particle size of 1-2mm through an extruder;
d3 crushing the blank, and sieving the crushed blank through a 1800-2000-mesh sieve to obtain the modified alkyd resin.
The sulfonamide is at least one of N-methyl-N-nitroso-p-toluenesulfonamide and p-aminotoluene o-sulfonanilide. Preferably, the sulfonamide is a mixture of N-methyl-N-nitroso-p-toluenesulfonamide and p-aminotoluene o-sulfonanilide in a mass ratio of (1-4) to (2-5).
The cellulose is at least one of cyanoethyl cellulose and p-aminobenzyl cellulose. Preferably, the cellulose is a mixture of cyanoethyl cellulose and p-aminobenzyl cellulose in a mass ratio of (1-5) to (1-5).
The general cellulose can further enhance the mutual infiltration degree and compatibility between the alkyd resin and various raw materials in an ink system when being grafted to the alkyd resin, but the ink on a printed matter still has the tendency of deterioration and brittle failure and the like when being stored for a long time, so the cyanoethyl cellulose containing cyanoethyl and p-aminobenzyl cellulose containing p-amino are selected as modification aids to carry out graft modification treatment on the alkyd resin.
The acid anhydride is at least one of 4,4' -oxydiphthalic anhydride and 1,4,5, 8-naphthalene tetracarboxylic anhydride. Preferably, the acid anhydride is a mixture of 4,4' -oxydiphthalic anhydride and 1,4,5, 8-naphthalene tetracarboxylic anhydride in a mass ratio of (1-3) to (1-3). More preferably, the acid anhydride is a mixture of 4,4' -oxydiphthalic anhydride and 1,4,5, 8-naphthalene tetracarboxylic anhydride in a mass ratio of 3: 2.
Modifying the two celluloses with the sulfonamides prior to the graft modification; the electronegativity of the nitroso in the N-methyl-N-nitroso-p-toluenesulfonamide and the relative orientation of the para-amino in the p-aminotoluene o-sulfonanilide enable polar groups in the two celluloses to be better contacted and entangled with alkyd resin, so that the modified alkyd resin with higher toughness and durability is obtained, and the service durability, the gloss and the adhesion of the ink are improved.
According to the invention, 4' -oxydiphthalic anhydride and 1,4,5, 8-naphthalene tetracarboxylic anhydride are used as acid anhydrides in the preparation process of the modified alkyd resin, and the polarizability of polar groups and the molecular weight of nonpolar groups in the two acid anhydrides are in a relation, so that the grafting sufficiency of the modified cellulose on the alkyd resin can be effectively enhanced when the two acid anhydrides are compounded to serve as the acid anhydrides of the modified alkyd resin, and the modified alkyd resin with higher toughness and durability is obtained, thereby improving the service durability, excellent gloss and adhesive force of the printing ink.
The anti-aging agent is at least one of coco dimethyl tertiary amine and dioctylalkyl methyl tertiary amine. Preferably, the anti-aging agent is a mixture of coco dimethyl tertiary amine and dioctyl methyl tertiary amine in a mass ratio of (7-10) to (8-12).
The two tertiary amine type anti-aging agents adopted by the invention and the modified alkyd resin are influenced by charges of polar groups of each other, so that the wettability and compatibility of the modified alkyd resin in an ink raw material system are further improved, and the gloss, the adhesive force and the durability of the ink are improved.
The ink obtained by the technical scheme of the invention meets the regulation of QB/T2024 and 2012 'gravure plastic film composite ink'.
The invention has the beneficial effects that:
1. the invention provides a green environment-friendly printing process method which comprises the steps of determining printing parameters, preparing a plate, trial printing, printing and the like, wherein a printed matter with higher printing quality is obtained by adopting the ink with higher glossiness and adhesive force prepared by the specific method, and the process method is non-toxic and pollution-free in the production process, low in cost and free of waste, and meets the theme requirements of green environment protection.
2. The ink which has higher glossiness, stronger adhesive force, oxidation resistance and long-time storage is obtained by taking carbon black, petroleum resin, liquid paraffin, vegetable oil and the modified alkyd resin prepared by the specific method of the invention as raw materials, and can be used for the green environment-friendly printing process method so as to obtain a printed matter with higher printing quality.
3. The modified alkyd resin with better glossiness, stronger mechanical toughness, more oxidation resistance and corrosion resistance is obtained by taking the alkyd resin as a matrix and taking cyanoethyl cellulose, p-aminobenzyl cellulose, 4' -oxydiphthalic anhydride, 1,4,5, 8-naphthalene tetracarboxylic anhydride, coco dimethyl tertiary amine and dioctylalkyl methyl tertiary amine as modified materials, and can be applied to printing ink to obtain the printing ink with higher printing quality.
Detailed Description
The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Introduction of some raw materials in this application:
petroleum resin, CAS: 64742-16-1, Puyang Keruid Petroleum resins GmbH, molecular weight: 2300.
alkyd resin, CAS: 63148-69-6, available from Xinran chemical Co., Ltd, Jize county, type: e51, molecular weight: 65 ten thousand.
Liquid paraffin, CAS: 8042-47-5, available from Anhui Zerise technologies, Inc., cat #: m5310, brand: Sigma-Aldrich.
Castor oil, CAS: 8001-79-4, available from Anhui Zerise technologies, Inc., cat #: l04224, brand: alfa Aesar.
Cottonseed oil, CAS: 8001-29-4, available from Anhui Zerise technologies, Inc., cat #: c725303, brand: TRC.
Carbon black, CAS: 1333-86-4, available from Anhui Zerise technologies, Inc., particle size: 800 meshes, goods number: 699632, brand: Sigma-Aldrich.
Chalk, purchased from Ling Hui mineral processing factory in Ling shou county, specification: 2000 meshes and impurity content less than or equal to 2 percent.
Quartz, CAS: 14808-60-7, available from Anhui Zerise technologies, Inc., particle size: 800 meshes, goods number: 013024, brand: alfa Aesar.
Clay, CAS: 1340-68-7, purchased from lingxin mineral processing plant, lingshou county, specifications: 2200 mesh, mohs hardness: 6, impurity content is less than or equal to 4 percent.
N-methyl-N-nitroso-p-toluenesulfonamide, CAS: 80-11-5, available from Anhui Zerise technologies, Inc., cat #: b020026-500 g.
P-aminotoluene o-sulfonanilide, CAS: 79-72-1, purchased from Ruilfeng chemical Co., Ltd, Quzhou city.
Cyanoethyl cellulose, CAS: 9004-41-5, available from Anhui Zerise technologies, Inc., cat #: 184659.
p-aminobenzyl cellulose, CAS: 9032-51-3, available from Anhui Zerise technologies, Inc., cat #: C0064.
4,4' -oxydiphthalic anhydride, CAS: 1823-59-2, available from Anhui Zerise technologies, Inc., cat #: a011185-500 g.
1,4,5, 8-naphthalenetetracarboxylic anhydride, CAS: 81-30-1, available from Anhui Zerise science, Inc., cat #: l14365, brand: alfa Aesar.
Coco dimethyl tertiary amine, CAS: 61788-93-0, available from Wuhanrong Brilliant Biotechnology Ltd.
Dioctylmethyl tertiary amine, CAS: 4455-26-9, available from Anhui Zerise technologies, Inc., cat #: m0232.
Catechol, CAS: 120-80-9, available from Anhui Zerise technologies, Inc., cat #: 135011, brand: Sigma-Aldrich.
2-methoxy-4-methylphenol, CAS: 93-51-6, available from Anhui Zerise technologies, Inc., cat #: w267112, brand: Sigma-Aldrich.
Example 1
The green environment-friendly printing process method comprises the following steps:
q1 determines plate making parameters: adopting brick type net points, wherein the number of the net lines is 22/cm, and the depth of a manufactured plate is 100 mu m;
q2 platemaking: processing by adopting a laser engraving mode to obtain a columnar gravure;
trial printing of Q3: dipping the printing ink on the columnar intaglio, and performing test printing and drying operation on a test printed matter; judging whether the ink needs to be prepared again or the specification of the columnar intaglio is adjusted according to the obtained ink forming effect and the printing quality; if the ink forming effect and the printing quality meet the specified printing standard, batch printing can be carried out according to the current gravure specification and the ink proportion;
q4 printing: and smearing the printing ink on the whole plate surface of the columnar intaglio, scraping redundant printing ink on the surface layer of the columnar intaglio by using a doctor blade to enable the thickness of the printing ink layer of the printing ink to be 45 mu m, then placing a printed matter on the plate surface of the columnar intaglio, and then applying pressure to print the printing ink on the columnar intaglio onto the printed matter, wherein the green environment-friendly printing process is finished.
The preparation method of the ink comprises the following steps:
c1 wetting: mixing carbon black with water at a bath ratio of 1kg:3L, heating to 60 deg.C, stirring at 30rpm for 50min, and performing ultrasonic auxiliary treatment with power of 300W and frequency of 35kHz to obtain wet carbon black;
c2 pulping: mixing 12 parts by weight of petroleum resin, 3 parts by weight of liquid paraffin, 15 parts by weight of vegetable oil and 7 parts by weight of modified alkyd resin, and stirring at 110 ℃ at a rotating speed of 80rpm for 100min to obtain emulsion; the vegetable oil is a mixture of castor oil and cottonseed oil in a mass ratio of 5: 1;
c3 reaction: mixing 35 parts by weight of the wetted carbon black with 40 parts by weight of whey, adding 10 parts by weight of chalk, 2 parts by weight of quartz and 8 parts by weight of argil, stirring at 60 ℃ at a rotating speed of 260rpm for 30min, subsequently standing at 15 ℃ for 30h, and taking out the precipitate to obtain an intermediate product A;
c4 drying: drying the intermediate product A under the conditions that the temperature is 120 ℃ and the vacuum degree is-0.1 MPa to obtain an intermediate product B;
c5 grinding: grinding the intermediate product B, and screening the intermediate product B through a 2500-mesh screen to obtain an intermediate product C;
c6 arrangement: mixing the intermediate product C, liquid paraffin and an anti-drying agent at a mass ratio of 40:25:1 at 25 ℃, and homogenizing at 13000rpm for 3min to obtain an intermediate product D; the anti-drying agent is a mixture of catechol and 2-methoxy-4-methylphenol in a mass ratio of 3: 1;
c7 defoaming: and (3) placing the intermediate product D in an environment with the temperature of 55 ℃ and the vacuum degree of 0.03MPa for defoaming for 100min to obtain the ink.
The preparation method of the modified alkyd resin comprises the following steps:
d1 mixing 3 parts by weight of sulfamide, 7 parts by weight of cellulose and 18 parts by weight of diethyl ether, then carrying out ultrasonic treatment for 170min at 85 ℃ and with the power of 350W and the frequency of 36kHz, filtering to obtain filter residue, and drying the filter residue for 8h at 80 ℃ and under the air pressure of 65kPa to obtain modified cellulose;
d2 mixing the alkyd resin, the modified cellulose, the acid anhydride and the anti-aging agent according to the mass ratio of 65:22:8:2, then blending for 105min at 105 ℃ at the rotating speed of 800rpm, and extruding a blank with the particle size of 1mm through an extruder;
d3 crushing the blank, and screening the crushed blank by a 2000-mesh screen to obtain the modified alkyd resin.
The sulfonamide is a mixture of N-methyl-N-nitroso-p-toluenesulfonamide and p-aminotoluene o-sulfonanilide in a mass ratio of 3: 2.
The cellulose is a mixture of cyanoethyl cellulose and p-aminobenzyl cellulose in a mass ratio of 3: 5.
The acid anhydride is a mixture of 4,4' -oxydiphthalic anhydride and 1,4,5, 8-naphthalene tetracarboxylic anhydride in a mass ratio of 3: 2.
The anti-aging agent is a mixture of coco dimethyl tertiary amine and dioctylalkyl methyl tertiary amine according to the mass ratio of 8: 9.
Example 2
Essentially the same as example 1, except that:
the preparation method of the modified alkyd resin comprises the following steps:
d1 mixing 3 parts by weight of sulfamide, 7 parts by weight of cellulose and 18 parts by weight of diethyl ether, then carrying out ultrasonic treatment for 170min at 85 ℃ and with the power of 350W and the frequency of 36kHz, filtering to obtain filter residue, and drying the filter residue for 8h at 80 ℃ and under the air pressure of 65kPa to obtain modified cellulose;
d2 mixing the alkyd resin, the modified cellulose, the acid anhydride and the anti-aging agent according to the mass ratio of 65:22:8:2, then blending for 105min at 105 ℃ at the rotating speed of 800rpm, and extruding a blank with the particle size of 1mm through an extruder;
d3 crushing the blank, and screening the crushed blank by a 2000-mesh screen to obtain the modified alkyd resin.
The sulfonamide is a mixture of N-methyl-N-nitroso-p-toluenesulfonamide and p-aminotoluene o-sulfonanilide in a mass ratio of 3: 2.
The cellulose is a mixture of cyanoethyl cellulose and p-aminobenzyl cellulose in a mass ratio of 3: 5.
The acid anhydride is 4,4' -oxydiphthalic anhydride.
The anti-aging agent is a mixture of coco dimethyl tertiary amine and dioctylalkyl methyl tertiary amine according to the mass ratio of 8: 9.
Example 3
Essentially the same as example 1, except that:
the preparation method of the modified alkyd resin comprises the following steps:
d1 mixing 3 parts by weight of sulfamide, 7 parts by weight of cellulose and 18 parts by weight of diethyl ether, then carrying out ultrasonic treatment for 170min at 85 ℃ and with the power of 350W and the frequency of 36kHz, filtering to obtain filter residue, and drying the filter residue for 8h at 80 ℃ and under the air pressure of 65kPa to obtain modified cellulose;
d2 mixing the alkyd resin, the modified cellulose, the acid anhydride and the anti-aging agent according to the mass ratio of 65:22:8:2, then blending for 105min at 105 ℃ at the rotating speed of 800rpm, and extruding a blank with the particle size of 1mm through an extruder;
d3 crushing the blank, and screening the crushed blank by a 2000-mesh screen to obtain the modified alkyd resin.
The sulfonamide is a mixture of N-methyl-N-nitroso-p-toluenesulfonamide and p-aminotoluene o-sulfonanilide in a mass ratio of 3: 2.
The cellulose is a mixture of cyanoethyl cellulose and p-aminobenzyl cellulose in a mass ratio of 3: 5.
The acid anhydride is 1,4,5, 8-naphthalene tetracarboxylic anhydride.
The anti-aging agent is a mixture of coco dimethyl tertiary amine and dioctylalkyl methyl tertiary amine according to the mass ratio of 8: 9.
Example 4
Essentially the same as example 1, except that:
the preparation method of the modified alkyd resin comprises the following steps:
d1 mixing 7 parts by weight of cellulose and 18 parts by weight of diethyl ether, then carrying out ultrasonic treatment at 85 ℃ for 170min with the power of 350W and the frequency of 36kHz, filtering to obtain filter residue, and drying the filter residue for 8h at 80 ℃ and the air pressure of 65kPa to obtain modified cellulose;
d2 mixing the alkyd resin, the modified cellulose, the acid anhydride and the anti-aging agent according to the mass ratio of 65:22:8:2, then blending for 105min at 105 ℃ at the rotating speed of 800rpm, and extruding a blank with the particle size of 1mm through an extruder;
d3 crushing the blank, and screening the crushed blank by a 2000-mesh screen to obtain the modified alkyd resin.
The cellulose is a mixture of cyanoethyl cellulose and p-aminobenzyl cellulose in a mass ratio of 3: 5.
The acid anhydride is a mixture of 4,4' -oxydiphthalic anhydride and 1,4,5, 8-naphthalene tetracarboxylic anhydride in a mass ratio of 3: 2.
The anti-aging agent is a mixture of coco dimethyl tertiary amine and dioctylalkyl methyl tertiary amine according to the mass ratio of 8: 9.
Example 5
Essentially the same as example 1, except that:
the preparation method of the modified alkyd resin comprises the following steps:
d1 mixing alkyd resin, cellulose, acid anhydride and an anti-aging agent according to the mass ratio of 65:22:8:2, then blending at 105 ℃ and the rotating speed of 800rpm for 105min, and extruding a blank with the particle size of 1mm through an extruder;
d2 crushing the blank, and screening the crushed blank by a 2000-mesh screen to obtain the modified alkyd resin.
The cellulose is a mixture of cyanoethyl cellulose and p-aminobenzyl cellulose in a mass ratio of 3: 5.
The acid anhydride is a mixture of 4,4' -oxydiphthalic anhydride and 1,4,5, 8-naphthalene tetracarboxylic anhydride in a mass ratio of 3: 2.
The anti-aging agent is a mixture of coco dimethyl tertiary amine and dioctylalkyl methyl tertiary amine according to the mass ratio of 8: 9.
Example 6
Essentially the same as example 1, except that:
the preparation method of the modified alkyd resin comprises the following steps:
d1 mixing 3 parts by weight of sulfamide, 7 parts by weight of cellulose and 18 parts by weight of diethyl ether, then carrying out ultrasonic treatment for 170min at 85 ℃ and with the power of 350W and the frequency of 36kHz, filtering to obtain filter residue, and drying the filter residue for 8h at 80 ℃ and under the air pressure of 65kPa to obtain modified cellulose;
d2 mixing the alkyd resin, the modified cellulose and the anti-aging agent according to the mass ratio of 65:22:2, then blending for 105min at 105 ℃ at the rotating speed of 800rpm, and extruding a blank with the particle size of 1mm through an extruder;
d3 crushing the blank, and screening the crushed blank by a 2000-mesh screen to obtain the modified alkyd resin.
The sulfonamide is a mixture of N-methyl-N-nitroso-p-toluenesulfonamide and p-aminotoluene o-sulfonanilide in a mass ratio of 3: 2.
The cellulose is a mixture of cyanoethyl cellulose and p-aminobenzyl cellulose in a mass ratio of 3: 5.
The anti-aging agent is a mixture of coco dimethyl tertiary amine and dioctylalkyl methyl tertiary amine according to the mass ratio of 8: 9.
Example 7
Essentially the same as example 1, except that:
the preparation method of the ink comprises the following steps:
c1 wetting: mixing carbon black with water at a bath ratio of 1kg:3L, heating to 60 deg.C, stirring at 30rpm for 50min, and performing ultrasonic auxiliary treatment with power of 300W and frequency of 35kHz to obtain wet carbon black;
c2 pulping: mixing 12 parts by weight of petroleum resin, 3 parts by weight of liquid paraffin, 15 parts by weight of vegetable oil and 7 parts by weight of alkyd resin, and stirring at 110 ℃ at a rotating speed of 80rpm for 100min to obtain emulsion; the vegetable oil is a mixture of castor oil and cottonseed oil in a mass ratio of 5: 1;
c3 reaction: mixing 35 parts by weight of the wetted carbon black with 40 parts by weight of whey, adding 10 parts by weight of chalk, 2 parts by weight of quartz and 8 parts by weight of argil, stirring at 60 ℃ at a rotating speed of 260rpm for 30min, subsequently standing at 15 ℃ for 30h, and taking out the precipitate to obtain an intermediate product A;
c4 drying: drying the intermediate product A under the conditions that the temperature is 120 ℃ and the vacuum degree is-0.1 MPa to obtain an intermediate product B;
c5 grinding: grinding the intermediate product B, and screening the intermediate product B through a 2500-mesh screen to obtain an intermediate product C;
c6 arrangement: mixing the intermediate product C, liquid paraffin and an anti-drying agent at a mass ratio of 40:25:1 at 25 ℃, and homogenizing at 13000rpm for 3min to obtain an intermediate product D; the anti-drying agent is a mixture of catechol and 2-methoxy-4-methylphenol in a mass ratio of 3: 1;
c7 defoaming: and (3) placing the intermediate product D in an environment with the temperature of 55 ℃ and the vacuum degree of 0.03MPa for defoaming for 100min to obtain the ink.
Example 8
Essentially the same as example 7, except that:
the preparation method of the ink comprises the following steps:
c1 wetting: mixing carbon black with water at a bath ratio of 1kg:3L, heating to 60 deg.C, stirring at 30rpm for 50min, and performing ultrasonic auxiliary treatment with power of 300W and frequency of 35kHz to obtain wet carbon black;
c2 pulping: mixing 12 parts by weight of petroleum resin, 3 parts by weight of liquid paraffin, 15 parts by weight of vegetable oil and 7 parts by weight of phenolic resin, and stirring at 110 ℃ at a rotating speed of 80rpm for 100min to obtain emulsion; the vegetable oil is a mixture of castor oil and cottonseed oil in a mass ratio of 5: 1;
c3 reaction: mixing 35 parts by weight of the wetted carbon black with 40 parts by weight of whey, adding 10 parts by weight of chalk, 2 parts by weight of quartz and 8 parts by weight of argil, stirring at 60 ℃ at a rotating speed of 260rpm for 30min, subsequently standing at 15 ℃ for 30h, and taking out the precipitate to obtain an intermediate product A;
c4 drying: drying the intermediate product A under the conditions that the temperature is 120 ℃ and the vacuum degree is-0.1 MPa to obtain an intermediate product B;
c5 grinding: grinding the intermediate product B, and screening the intermediate product B through a 2500-mesh screen to obtain an intermediate product C;
c6 arrangement: mixing the intermediate product C, liquid paraffin and an anti-drying agent at a mass ratio of 40:25:1 at 25 ℃, and homogenizing at 13000rpm for 3min to obtain an intermediate product D; the anti-drying agent is a mixture of catechol and 2-methoxy-4-methylphenol in a mass ratio of 3: 1;
c7 defoaming: and (3) placing the intermediate product D in an environment with the temperature of 55 ℃ and the vacuum degree of 0.03MPa for defoaming for 100min to obtain the ink.
Example 9
Essentially the same as example 1, except that:
the preparation method of the ink comprises the following steps:
c1 wetting: mixing carbon black with water at a bath ratio of 1kg:3L, heating to 60 deg.C, stirring at 30rpm for 50min, and performing ultrasonic auxiliary treatment with power of 300W and frequency of 35kHz to obtain wet carbon black;
c2 pulping: mixing 3 parts by weight of liquid paraffin, 15 parts by weight of vegetable oil and 7 parts by weight of modified alkyd resin, and stirring at 110 ℃ and the rotating speed of 80rpm for 100min to obtain emulsion; the vegetable oil is a mixture of castor oil and cottonseed oil in a mass ratio of 5: 1;
c3 reaction: mixing 35 parts by weight of the wetted carbon black with 40 parts by weight of whey, adding 10 parts by weight of chalk, 2 parts by weight of quartz and 8 parts by weight of argil, stirring at 60 ℃ at a rotating speed of 260rpm for 30min, subsequently standing at 15 ℃ for 30h, and taking out the precipitate to obtain an intermediate product A;
c4 drying: drying the intermediate product A under the conditions that the temperature is 120 ℃ and the vacuum degree is-0.1 MPa to obtain an intermediate product B;
c5 grinding: grinding the intermediate product B, and screening the intermediate product B through a 2500-mesh screen to obtain an intermediate product C;
c6 arrangement: mixing the intermediate product C, liquid paraffin and an anti-drying agent at a mass ratio of 40:25:1 at 25 ℃, and homogenizing at 13000rpm for 3min to obtain an intermediate product D; the anti-drying agent is a mixture of catechol and 2-methoxy-4-methylphenol in a mass ratio of 3: 1;
c7 defoaming: and (3) placing the intermediate product D in an environment with the temperature of 55 ℃ and the vacuum degree of 0.03MPa for defoaming for 100min to obtain the ink.
The preparation method of the modified alkyd resin comprises the following steps:
d1 mixing 3 parts by weight of sulfamide, 7 parts by weight of cellulose and 18 parts by weight of diethyl ether, then carrying out ultrasonic treatment for 170min at 85 ℃ and with the power of 350W and the frequency of 36kHz, filtering to obtain filter residue, and drying the filter residue for 8h at 80 ℃ and under the air pressure of 65kPa to obtain modified cellulose;
d2 mixing the alkyd resin, the modified cellulose, the acid anhydride and the anti-aging agent according to the mass ratio of 65:22:8:2, then blending for 105min at 105 ℃ at the rotating speed of 800rpm, and extruding a blank with the particle size of 1mm through an extruder;
d3 crushing the blank, and screening the crushed blank by a 2000-mesh screen to obtain the modified alkyd resin.
The sulfonamide is a mixture of N-methyl-N-nitroso-p-toluenesulfonamide and p-aminotoluene o-sulfonanilide in a mass ratio of 3: 2.
The cellulose is a mixture of cyanoethyl cellulose and p-aminobenzyl cellulose in a mass ratio of 3: 5.
The acid anhydride is a mixture of 4,4' -oxydiphthalic anhydride and 1,4,5, 8-naphthalene tetracarboxylic anhydride in a mass ratio of 3: 2.
The anti-aging agent is a mixture of coco dimethyl tertiary amine and dioctylalkyl methyl tertiary amine according to the mass ratio of 8: 9.
Test example 1
Ink adhesion fastness test: the fastness of adhesion of the inks obtained in the examples of the present invention was determined according to GB/T13217.7-2009 test method for liquid ink fastness. For each case, 5 samples were tested and the results averaged. The test temperature was 23 ℃ and the humidity 65%. The A disc speed was 0.8 m/s.
The test results are shown in table 1.
TABLE 1 ink adhesion fastness
Test example 2
Ink gloss testing: the gloss of the inks obtained from the examples of the present invention was measured according to GB/T13217.2-2009 "liquid ink gloss test method". For each case, 5 samples were tested and the results averaged. The test temperature was 23 ℃ and the humidity 65%.
The test results are shown in table 2.
TABLE 2 gloss of the inks
After being cured, the alkyd resin can show good gloss, excellent toughness and strong adhesive force, and has good wear resistance, weather resistance, insulativity and other excellent characteristics, so that the alkyd resin is modified to prepare the ink for the green environment-friendly printing process method, the ink with better gloss and stronger adhesive force is obtained, and a printed product with higher printing quality is obtained by the green environment-friendly printing process method. However, if the alkyd resin is directly added into an ink system, the ink is easy to embrittle and crack under the stimulation of light and air humidity change during long-term storage after drying and curing due to poor compatibility between the common alkyd resin and ink raw materials, and the printing quality and the appearance of transportation, storage and use of a printed matter are extremely influenced. The general cellulose can further enhance the mutual infiltration degree and compatibility between the alkyd resin and various raw materials in an ink system when being grafted to the alkyd resin, but the ink on a printed matter still has the tendency of deterioration and brittle failure and the like when being stored for a long time, so the cyanoethyl cellulose containing cyanoethyl and p-aminobenzyl cellulose containing p-amino are selected as modification aids to carry out graft modification treatment on the alkyd resin.
Modifying the two celluloses with the sulfonamides prior to the graft modification; the electronegativity of the nitroso in the N-methyl-N-nitroso-p-toluenesulfonamide and the relative orientation of the para-amino in the p-aminotoluene o-sulfonanilide enable polar groups in the two celluloses to be better contacted and entangled with alkyd resin, so that the modified alkyd resin with higher toughness and durability is obtained, and the service durability, the gloss and the adhesion of the ink are improved.
According to the invention, 4' -oxydiphthalic anhydride and 1,4,5, 8-naphthalene tetracarboxylic anhydride are used as acid anhydrides in the preparation process of the modified alkyd resin, and the polarizability of polar groups and the molecular weight of nonpolar groups in the two acid anhydrides are in a relation, so that the grafting sufficiency of the modified cellulose on the alkyd resin can be effectively enhanced when the two acid anhydrides are compounded to serve as the acid anhydrides of the modified alkyd resin, and the modified alkyd resin with higher toughness and durability is obtained, thereby improving the service durability, excellent gloss and adhesive force of the printing ink.
The two tertiary amine type anti-aging agents adopted by the invention and the modified alkyd resin are influenced by charges of polar groups of each other, so that the compatibility of the modified alkyd resin in an ink raw material system is further improved, and the gloss, the adhesive force and the durability of the ink are improved.
The petroleum resin has the characteristics of low acid value, good miscibility, water resistance, ethanol resistance, chemical resistance and the like, has chemical stability to acid and alkali, has the characteristics of viscosity regulation and good thermal stability, and can be used in cooperation with the modified alkyd resin prepared by the specific method of the invention to enhance the gloss, adhesion and durability of the ink, thereby obtaining a printed matter with higher printing quality.
Claims (9)
1. A preparation method of a modified alkyd resin is characterized by comprising the following steps:
d1 mixing sulfonamide, cellulose and diethyl ether, then carrying out ultrasonic treatment, filtering to obtain filter residue, and drying the filter residue to obtain modified cellulose;
d2 mixing the alkyd resin, the modified cellulose, the anhydride and the anti-aging agent, blending and extruding a blank;
d3, crushing the blank and sieving to obtain the modified alkyd resin.
2. A process for preparing a modified alkyd resin according to claim 1, wherein: the sulfonamide is at least one of N-methyl-N-nitroso-p-toluenesulfonamide and p-aminotoluene o-sulfonanilide.
3. A process for preparing a modified alkyd resin according to claim 1, wherein: the anti-aging agent is at least one of coco dimethyl tertiary amine and dioctylalkyl methyl tertiary amine.
4. A modified alkyd resin, characterized in that: obtained by a process for the preparation of a modified alkyd resin according to any of claims 1 to 3.
5. The preparation method of the ink is characterized by comprising the following steps of:
c1 wetting: mixing carbon black with water, heating, stirring, and simultaneously performing ultrasonic auxiliary treatment to obtain wet carbon black;
c2 pulping: mixing petroleum resin, liquid paraffin, vegetable oil and the modified alkyd resin of claim 4, and then stirring to obtain a milk slurry;
c3 reaction: mixing the wet carbon black and the slurry, adding chalk, quartz and argil, stirring, standing, and taking precipitate to obtain an intermediate product A;
c4 drying: drying the intermediate product A to obtain an intermediate product B;
c5 grinding: grinding the intermediate product B, and sieving to obtain an intermediate product C;
c6 arrangement: mixing and homogenizing the intermediate product C, liquid paraffin and an anti-drying agent to obtain an intermediate product D;
c7 defoaming: and defoaming the intermediate product D to obtain the printing ink.
6. The method of preparing the ink according to claim 5, wherein: the vegetable oil is at least one of castor oil and cottonseed oil.
7. The method of preparing the ink according to claim 5, wherein: the anti-drying agent is at least one of catechol and 2-methoxy-4-methylphenol.
8. An ink, characterized by: obtained by a process for the preparation of the ink according to any one of claims 5 to 7.
9. The green environment-friendly printing process method is characterized by comprising the following steps of:
q1 determining plate making parameters;
q2 platemaking: processing by adopting a laser engraving mode to obtain a columnar gravure;
trial printing of Q3: dipping the ink of claim 8 on the cylindrical intaglio plate, and performing test printing and drying operations on a test printed matter; judging whether the ink needs to be prepared again or the specification of the columnar intaglio is adjusted according to the obtained ink forming effect and the printing quality; if the ink forming effect and the printing quality meet the specified printing standard, batch printing can be carried out according to the current gravure specification and the ink proportion;
q4 printing: and smearing the ink on the whole plate surface of the columnar intaglio, scraping the redundant ink on the surface layer of the columnar intaglio by using a doctor blade, then placing a printed matter on the plate surface of the columnar intaglio, and then applying pressure to print the ink on the columnar intaglio onto the printed matter, thereby completing the green environment-friendly printing process.
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