CN113652117A - Environment-friendly ink and application thereof in printing process - Google Patents
Environment-friendly ink and application thereof in printing process Download PDFInfo
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- CN113652117A CN113652117A CN202111042001.9A CN202111042001A CN113652117A CN 113652117 A CN113652117 A CN 113652117A CN 202111042001 A CN202111042001 A CN 202111042001A CN 113652117 A CN113652117 A CN 113652117A
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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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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
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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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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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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- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses an environment-friendly ink and application thereof in a printing process method. The environment-friendly ink comprises carbon black, petroleum resin, liquid paraffin, vegetable oil, alkyd resin and functionalized hydrogen-terminated silicone oil. The glossiness, the adhesive force, the stability and the hardness of the environment-friendly ink can be obviously improved, so that the environment-friendly ink can be stored for a long time; the environment-friendly ink provided by the invention has the advantages of no solvent volatilization in the film forming process, high environment-friendly degree, small influence on human bodies and environment, and capability of being used in a printing process to obtain a printed matter with higher printing quality. 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 environment-friendly ink and application thereof in a printing process method.
Background
Ink is an important material for printing, and is used for expressing patterns and characters on a printing material through printing or inkjet. 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
In view of the above-mentioned drawbacks of the prior art, the present invention provides an environmentally friendly ink and its use in a printing process.
A printing process comprising the steps of: 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 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 to enable the thickness of the ink layer of the 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 ink on the columnar intaglio onto the printed matter, wherein the 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 (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 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.
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'.
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 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 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.
Further, the 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 environment-friendly ink on the cylindrical intaglio, and performing test printing and drying operation on a test printed matter; judging whether the environment-friendly ink needs to be prepared again or the specification of the columnar gravure needs to be adjusted according to the obtained environment-friendly ink forming effect and the printing quality; if the environment-friendly 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 environment-friendly ink proportion;
q4 printing: and smearing the environment-friendly ink on the whole plate surface of the columnar intaglio, scraping the redundant environment-friendly ink on the surface layer of the columnar intaglio by using a doctor blade to enable the thickness of the ink layer of the environment-friendly 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 environment-friendly ink on the columnar intaglio onto the printed matter, wherein the printing process is finished.
Further, the preparation method of the environment-friendly 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, 3-8 parts by weight of hydrogen-terminated silicone 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 milk; 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 environment-friendly ink.
Further preferably, the preparation method of the environment-friendly 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, 3-8 parts by weight of functionalized hydrogen-terminated silicone oil and 5-8 parts by weight of modified alkyd resin, and then 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 environment-friendly ink.
The preparation method of the functionalized hydrogen-terminated silicone oil comprises the following steps: mixing tripropylene glycol dipropionate, hydrogen-terminated silicone oil, trifluoropropyltrimethoxysilane, isopropanol solution of chloroplatinic acid and tert-butyl catechol, heating to 125 ℃ at the temperature of 100 ℃ and reacting for 12-20H at the rotating speed of 500-700r/min, removing volatile matters by reduced pressure distillation after the reaction is finished, and drying to obtain modified hydrogen-terminated silicone oil, wherein the mass ratio of the tripropylene glycol dipropionate, the hydrogen-terminated silicone oil, the trifluoropropyltrimethoxysilane, the isopropanol solution of the chloroplatinic acid to the tert-butyl catechol is (0.8-2): (0.5-1.5): (0.1-0.5): (15-20): (0.1-0.5), and the isopropanol solution of the chloroplatinic acid is prepared by adding 1g of H2 Cl 6-6H 2Pt 2O into 35mL of isopropanol and uniformly mixing; uniformly mixing modified hydrogen-terminated silicone oil, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and dibutyltin maleate, heating to 80-100 ℃, reacting at the rotating speed of 500-700r/min for 10-15h, centrifuging, taking precipitate, and drying to obtain the functionalized hydrogen-terminated silicone oil, wherein the mass ratio of the modified hydrogen-terminated silicone oil, the 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and the dibutyltin maleate is 1 (3-6) to (0.5-2).
The modified hydrogen-terminated silicone oil is prepared by adopting tripropylene glycol dipropyl isopropyl ester, hydrogen-terminated silicone oil and trifluoropropyl trimethoxy silane, and the modified hydrogen-terminated silicone oil is further modified by adopting 2- (3, 4-epoxycyclohexyl) ethyltrimethoxy silane to prepare functionalized hydrogen-terminated silicone oil, wherein the functionalized hydrogen-terminated silicone oil has more reactive active sites, and is introduced into the ink, so that the wear resistance, stability and hardness of the ink are obviously improved, and the bonding strength is improved; the compatibility of the functionalized hydrogen-terminated silicone oil with petroleum resin and modified alkyd resin is improved.
The invention has the beneficial effects that:
the invention discloses an environment-friendly ink and application thereof in a printing process method, wherein carbon black, petroleum resin, liquid paraffin, vegetable oil and alkyd resin are used as raw materials, tripropylene glycol dipropyl isopropyl ester, hydrogen terminated silicone oil and trifluoropropyl trimethoxy silane are introduced to prepare modified hydrogen terminated silicone oil, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane is further adopted to modify the modified hydrogen terminated silicone oil to prepare functionalized hydrogen terminated silicone oil, the functionalized hydrogen terminated silicone oil has more reactive active sites, and the functionalized hydrogen terminated silicone oil is introduced into the ink, so that the wear resistance, the stability and the hardness of the ink are obviously improved, and the bonding strength is improved; the compatibility of the functionalized hydrogen-terminated silicone oil with petroleum resin and modified alkyd resin is improved; the glossiness, the adhesive force, the stability and the hardness of the environment-friendly ink can be obviously improved, so that the environment-friendly ink can be stored for a long time; the environment-friendly ink provided by the invention has the advantages of no solvent volatilization in the film forming process, high environment-friendly degree, small influence on human bodies and environment, and capability of being used in a printing process to obtain a printed matter with higher printing quality.
Detailed Description
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.
Hydrogen-terminated silicone oil, CAS: 70900-21-9, purity: 98% of the total weight of the product, purchased from Wuhan mountain Yao concoct chemical Co.
Tripropylene glycol di-isopropyl ester, CAS: 42978-66-5, purity: 98% from Hubei Xinming Titai chemical Co.
Trifluoropropyltrimethoxysilane, CAS: 429-60-7, purity: 98% of the total weight of the composition, available from Suzhou Zhongbo chemical technology Co.
Tert-butyl catechol, CAS: 27213-78-1, purity: 99 percent of the total weight of the product, purchased from Hubei Qifei pharmaceutical chemical Co.
2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, CAS: 3388-04-3, purity: 99% of the total amount of the components obtained from Bailey chemical Co., Ltd.
Monobutyl maleate dibutyl tin, CAS: 66010-36-4, purity: 98 percent of the total weight of the product, purchased from Kaita chemical Co., Ltd.
Example 1
A printing process comprising the steps of:
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 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 to ensure that the thickness of the ink layer of the ink is 45 mu m, 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, wherein the 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
| Gloss value | |
| Example 1 | 86.5 |
| Example 2 | 86.1 |
| Example 3 | 85.6 |
| Example 4 | 81.9 |
| Example 5 | 81.3 |
| Example 6 | 83.2 |
| Example 7 | 78.9 |
| Example 8 | 75.6 |
| Example 9 | 76.7 |
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 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 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.
Example 10
A printing process comprising the steps of:
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 environment-friendly ink on the cylindrical intaglio, and performing test printing and drying operation on a test printed matter; judging whether the environment-friendly ink needs to be prepared again or the specification of the columnar gravure needs to be adjusted according to the obtained environment-friendly ink forming effect and the printing quality; if the environment-friendly 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 environment-friendly ink proportion;
q4 printing: and smearing the environment-friendly 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 to ensure that the thickness of the ink layer of the environment-friendly ink is 45 mu m, then placing a printed matter on the plate surface of the columnar intaglio, and then applying pressure to print the environment-friendly ink on the columnar intaglio onto the printed matter, wherein the printing process is finished.
The preparation method of the environment-friendly 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, 5 parts by weight of hydrogen-terminated silicone 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 environment-friendly 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 11
Essentially the same as example 10, except that: and the hydrogen-terminated silicone oil is replaced by the functionalized hydrogen-terminated silicone oil.
The preparation method of the functionalized hydrogen-terminated silicone oil comprises the following steps: mixing tripropylene glycol dipropionate, hydrogen-terminated silicone oil, trifluoropropyltrimethoxysilane, isopropanol solution of chloroplatinic acid and tert-butyl catechol, heating to 120 ℃, reacting for 14 hours at the rotating speed of 600r/min, removing volatile matters by reduced pressure distillation after the reaction is finished, and drying to obtain the modified hydrogen-terminated silicone oil, wherein the mass ratio of the tripropylene glycol dipropionate to the hydrogen-terminated silicone oil to the trifluoropropyltrimethoxysilane to the isopropanol solution of chloroplatinic acid to the isopropanol solution of the tert-butyl catechol is 1.2:1:0.5:20:0.3, and the mass ratio of the isopropanol solution of the chloroplatinic acid is 1gH2PtCl6·6H2Adding O into 35mL of isopropanol, and uniformly mixing; uniformly mixing modified hydrogen-terminated silicone oil, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and monobutyl maleate dibutyltin, heating to 90 ℃, reacting for 12 hours at the rotating speed of 600r/min, centrifuging, taking precipitate, and drying to obtain the functionalized hydrogen-terminated silicone oil, wherein the mass ratio of the modified hydrogen-terminated silicone oil, the 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and the monobutyl maleate dibutyltin is 1:3: 1.
Test example 3
(1) And (3) hardness testing: the environmental protection inks obtained in examples 10 to 11 were subjected to hardness tests with reference to GB/T6739-2006 paint film hardness determination by the color paint and varnish pencil method.
TABLE 3 hardness and stability of eco-friendly inks
| Hardness of | |
| Example 10 | 1H |
| Example 11 | 2H |
(2) And (3) stability testing: the inks of examples 10-11 were sealed and placed in a 50 ℃ oven for 7 days without delamination and thickening of the inks.
Claims (10)
1. The preparation method of the environment-friendly ink is characterized by comprising the following steps: the method 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, 3-8 parts by weight of hydrogen-terminated silicone oil/functionalized hydrogen-terminated silicone oil and 5-8 parts by weight of modified alkyd resin, and then stirring at the temperature of 105 ℃ and 115 ℃ at 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 environment-friendly ink.
2. The method for preparing the environmentally friendly ink according to claim 1, wherein: the preparation method of the functionalized hydrogen-terminated silicone oil comprises the following steps: mixing tripropylene glycol dipropionate, hydrogen-terminated silicone oil, trifluoropropyltrimethoxysilane, isopropanol solution of chloroplatinic acid and tert-butyl catechol, heating to 125 ℃ at the temperature of 100 ℃ and reacting at the rotating speed of 700r/min for 12-20h, removing volatile matters by reduced pressure distillation after the reaction is finished, and drying to obtain the modified hydrogen-terminated silicone oil, wherein the mass ratio of the tripropylene glycol dipropionate to the hydrogen-terminated silicone oil to the trifluoropropyltrimethoxysilane to the isopropanol solution of the chloroplatinic acid to the tert-butyl catechol is (0.8-2) to (0.1-0.5) to (15-20) to (0.1-0.5), and the mass ratio of the isopropanol solution of the chloroplatinic acid is 1gH to2PtCl6·6H2Adding O into 35mL of isopropanol, and uniformly mixing; uniformly mixing modified hydrogen-terminated silicone oil, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and dibutyltin maleate, heating to 80-100 ℃, reacting at the rotating speed of 500-700r/min for 10-15h, centrifuging, taking precipitate, and drying to obtain the functionalized hydrogen-terminated silicone oil, wherein the mass ratio of the modified hydrogen-terminated silicone oil, the 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and the dibutyltin maleate is 1 (3-6) to (0.5-2).
3. The method for preparing the environmentally friendly ink according to claim 1, wherein: the vegetable oil is at least one of castor oil and cottonseed oil.
4. The method for preparing the environmentally friendly ink according to claim 1, wherein: the anti-drying agent is at least one of catechol and 2-methoxy-4-methylphenol.
5. The method for preparing the environmentally friendly ink according to claim 1, wherein: 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.
6. The method for preparing the environmentally friendly ink according to claim 5, wherein: the sulfonamide is at least one of N-methyl-N-nitroso-p-toluenesulfonamide and p-aminotoluene o-sulfonanilide.
7. The method for preparing the environmentally friendly ink according to claim 5, wherein: the method is characterized in that: the anti-aging agent is at least one of coco dimethyl tertiary amine and dioctylalkyl methyl tertiary amine.
8. An environment-friendly ink is characterized in that: the environment-friendly ink is prepared by the method for preparing the environment-friendly ink as claimed in any one of claims 1 to 7.
9. Use of the environmentally friendly ink of claim 8 in a printing process.
10. The printing process method is characterized by comprising 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 environment-friendly ink as defined in claim 8 on the cylindrical intaglio plate, and performing test printing and drying operations on a test printed matter; judging whether the environment-friendly ink needs to be prepared again or the specification of the columnar gravure needs to be adjusted according to the obtained environment-friendly 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 environment-friendly ink ratio;
q4 printing: and smearing the environment-friendly ink on the whole plate surface of the columnar intaglio, scraping the redundant environment-friendly 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 environment-friendly ink on the columnar intaglio onto the printed matter, wherein the printing process is finished.
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